Nanomaterials as catalysts for CO2 transformation into

value-added products: A review

Yakubu Adekunle Alli, Peter Olusakin Oladoye, Onome Ejeromedoghene,
Owolabi Mutolib Bankole, Oyekunle Azeez Alimi, Elizabeth Oyinkansola
Omotola, Clement Ajibade Olanrewaju, Karine Philippot, Adeyemi Adeleye,
Adeniyi Sunday Ogunlaja

To cite this version:

Yakubu Adekunle Alli, Peter Olusakin Oladoye, Onome Ejeromedoghene, Owolabi Mutolib
Bankole, Oyekunle Azeez Alimi, et al.. Nanomaterials as catalysts for CO2 transformation into
value-added products: A review. Science of the Total Environment, 2023, 868, pp.161547.
�10.1016/j.scitotenv.2023.161547�. �hal-03955576�

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 1 Nanomaterials as Catalysts for CO2 Transformation into Value-added Products: A

2 Review

3 Yakubu Adekunle Allia,b**, Peter Olusakin Oladoyec, *, Onome Ejeromedoghened,

4 Owolabi Mutolib Bankolee, Oyekunle Azeez Alimif, Elizabeth Oyinkansola Omotolag,

5 Clement Ajibade Olanrewajuc, Karine Philippota, Adeyemi S. Adeleyeh, Adeniyi

6 Sunday Ogunlajae

a
7 Laboratoire de Chimie de Coordination du CNRS, UPR8241, Universite´ de Toulouse,

8 UPS, INPT, Toulouse cedex 4 F-31077, France.

b
9 Department of Chemical Sciences, Faculty of Science and Computing, Ahman Pategi

10 University, Km 3, Patigi-Kpada Road , Patigi, Kwara State 243105, Nigeria

c
11 Department of Chemistry and Biochemistry, Florida International University, 11200

12 SW 8th St, Miami, FL, 33199, USA

d
13 School of Chemistry and Chemical Engineering, Southeast University, 211189

14 Nanjing, Jiangsu Province, P. R. China

e
15 Department of Chemistry, Nelson Mandela University, Port Elizabeth, South Africa
f
16 Research Center for Synthesis and Catalysis, Department of Chemical Sciences,

17 University of Johannesburg, PO Box 524, Auckland Park, Johannesburg 2006, South

18 Africa
g
19 Department of Chemical Sciences, Tai Solarin University of Education, Ijebu Ode,

20 Ogun State, Nigeria

h
21 Department of Civil and Environmental Engineering, University of California, Irvine,

22 CA 92697-2175, USA

23 **
Corresponding author’s e-mail address: [email protected]
24 **
Corresponding author’s address: LCC-CNRS, Université de Toulouse, CNRS, UPS,
25 205 Route de Narbonne, BP44099, 31077 CEDEX 4 Toulouse, France

1
26 Corresponding author’s e-mail address: [email protected]
*

27 *
Corresponding author’s address: Department of Chemistry and Biochemistry, Florida
28 International University, 11200 SW 8th St, Miami, FL, 33199, USA
29
30 **
Corresponding author’s e-mail address: [email protected]
31 **
Corresponding author’s address: LCC-CNRS, Université de Toulouse, CNRS, UPS,
32 205 Route de Narbonne, BP44099, 31077 CEDEX 4 Toulouse, France
33 Abstract

34 Carbon dioxide (CO2) is the most important greenhouse gas (GHG), accounting for

35 76% of all GHG emissions. The atmospheric CO2 concentration has increased from 280

36 ppm in the pre-industrial era to about 417.86 ppm, and is projected to reach 570 ppm by

37 the end of the 21st century. In addition to reducing CO2 emissions from anthropogenic

38 activities, strategies to adequately address climate change must include CO2 capture. To

39 promote circular economy, captured CO2 should be converted to value-added materials

40 such as fuels and chemical feedstock. Due to their tunable chemistry (which allows

41 them to be selective) and high surface area (which allows them to be efficient),

42 engineered nanomaterials are promising for CO2 capturing and/or transformation. This

43 work critically reviewed the application of nanomaterials for the transformation of CO2

44 into various fuels, like formic acid, carbon monoxide, methanol, and ethanol. We

45 discussed the literature on the use of metal-based nanomaterials, inorganic/organic

46 nanocomposites, as well as other routes suitable for CO2 conversion such as the

47 electrochemical, non-thermal plasma, and hydrogenation routes. The characteristics,

48 steps, mechanisms, and challenges associated with the different transformation

49 technologies were also discussed. Finally, we presented a section on the future outlook

50 of the field, which includes recommendations for how to continue to advance the use of

51 nanotechnology for conversion of CO2 to fuels.

52 Keywords: CO2 based fuels, nanomaterials, global warming, catalysts

2
53 Table of contents

54 1. Introduction

55 2. Nanomaterials for CO2 conversion

56 3. Routes of CO2 conversion

57 3.1 Photocatalytic transformation of CO2

58 3.1.1 Single metal nanoparticles

59 3.1.2 Metal/metal oxide-based composites

60 3.1.3 Metal oxide/mesoporous oxides

61 3.1.4 Inorganic/organic nanocomposites

62 3.1.4.1 Metal-organic frameworks (MOF) nanomaterials

63 3.1.4.2 Metal-free nanomaterials

64 3.2 Electrochemical transformation of CO2

65 3.3 Photo-electrochemical (PEC) reduction of CO2

66 3.4 Photothermal heterogeneous catalysts for the hydrogenation of CO2

67 3.5 Thermochemical transformation of CO2

68 3.6 Non-thermal plasma (NTP) catalysis

69 4. Fuels generated from CO2 conversion

70 4.1 Formic acid

71 4.2 Carbon monoxide

72 4.3 Methanol

73 4.4 Ethanol

74 4.5 Methane

75 4.6 Formaldehyde

76 4.7 Hydrogen

77 4.8 Olefins and gasoline

3
 78 5. Conclusions and future outlook

79

80 1. Introduction

81 One of the primary environmental concerns today is climate change. Indicators of

82 climate change include global warming, increased frequency and intensity of natural

83 disasters and extreme weather events such as wildfires which was responsible for the

84 loss of ~$650 billion between 2016 to 2018, extreme droughts in Europe, heatwaves in

85 USA, and hurricanes in other parts of the world (Mustafa et al., 2020). Climate change

86 is mainly attributed to increased emission of greenhouse gases into the atmosphere

87 (Cassia et al., 2018; Solomon et al., 2010, 2009), which has led to the global surface

88 temperature of 0.88°C (1.58°F) in September 2022 which is above the average for the

89 20th century of 15.0°C (59.0°F), tying September 2021 as the sixth warmest for

90 September in the 143-year record. In addition, global CO2 levels was 280 ppm in the

91 pre-industrial era; it has now increased to 417.86 ppm as at October 19, 2022 according

92 to the Global Monitoring Laboratory (daily global CO2 trend) and it is projected to

93 reach 570 ppm by the end of the 21st century (Mustafa et al., 2020).

94 In order to ameliorate global warming and other climate change indicators, it is

95 imperative that emission of CO2 is controlled, and the excess atmospheric CO2 is

96 captured. Several strategies exist for achieving atmospheric CO2 reduction. For

97 instance, afforestation is effective for CO2 emission reduction and sequestration

98 (Halder et al., 2014; Jansen et al., 2015; Li et al., 2013; Mondal et al., 2012). More so,

99 various governmental and inter-governmental policies have been implemented to also

100 reduce the emissions of CO2 by putting taxes on carbon sources and fossil fuels (Atsbha

101 et al., 2021; Herzer, 2022; Omoregbe et al., 2020; Peiseler & Cabrera Serrenho, 2022).

102 Chemical CO2 conversion is also effective but is a herculean task due to the

4
103 characteristic thermodynamic stability of CO2 molecule. The stability of CO2 arises

104 from its structure (O=C=O) and possession of double covalent bonds with two oxygen

105 atoms (Ateka et al., 2022). The carbon in CO2 is extremely inactive and is kinetically

106 inert owing to its occurrence at the highest oxidation state in CO2 (Wang et al., 2022).

107 As a result, the transformation of CO2 to useful fuels and/or chemicals demands the

108 input of substantial amount of energy to cleave the C-O bond (Pawelec et al., 2021; Sha

109 et al., 2020)

110 The energy requirement for CO2 conversion is met through three major routes: (i) the

111 use of (nanomaterial-based) catalysts with active sites, (ii) the application of high

112 pressure and/or temperature, and (iii) application of energy from carbon-neutral and

113 renewable energy sources (Kamkeng et al., 2021). There are a number of technological

114 approaches that can be employed to execute transformation of CO2. In terms of using

115 catalysts for CO2 transformation, the processes and/or mechanisms involved may be

116 photocatalytic, electrocatalytic, thermal or non-thermal etc., to lower the energy barrier

117 and create alternative pathway for the catalytic CO2 reduction (Ateka et al., 2022). For

118 example, in photo-catalyzed transformation using titanium dioxide (TiO2; a common

119 photo-catalyst) as a catalyst, upon irradiation, a photo hole-electron pair is generated,

120 which interacts with CO2 and H2O molecules to produce hydrocarbons and other value-

121 added products. This is feasible only by appropriate catalyst selection, doping and

122 conditions (Low et al., 2017). Scheme 1 presents the various value added-products of

123 CO2 transformation covered in this synthesis.

5
124

125 Scheme 1: Products obtained from the transformation of CO2

126 A number of comprehensive, systematic and/or critical reviews on the transformation

127 of CO2 have been published (Kamkeng et al., 2021; Low et al., 2017; Mustafa et al.,

128 2020; Pawelec et al., 2021; Sha et al., 2020; Wang et al., 2011; Wu et al., 2017).

129 Although a large proportion of them are detailed with respect to application and

130 transformation of CO2, recent advances in technologies for CO2 conversion have not

131 been sufficiently covered by the existing reviews. In addition, the technical challenges

132 facing the real-world implementation of these technologies are yet to the

133 comprehensively explored and presented. Therefore, this synthesis on CO2 conversion

6
134 to valued-added products attempts to provide current and comprehensive understanding

135 on nano-enabled CO2 conversion, routes of CO2 conversion, fuels generated from CO2

136 conversion, application, technical issues and economic implications of transformation

137 of CO2 into hydrocarbon fuels. The review also elaborates the research gaps that need

138 to be filled.

139 2. Nanomaterials for CO2 conversion

140 Nanomaterials have gotten a lot of attention in the research world because of their

141 fascinating small size (1-100 nm), which is responsible for their improved functionality

142 (Afolabi et al., 2022; Alli et al., 2022, 2021). In this regard, the use of nanomaterials

143 for direct transformation of CO2, to renewable organic fuels and other feedstocks has

144 become a promising solution to simultaneously mitigate the global energy crisis and

145 climatic change. Due to the thermodynamic stability, fully oxidized nature, and

146 inertness of CO2, various nanoscale catalysts have been developed to activate CO2

147 molecules into low (C1) and high hydrocarbon (C1-C9) molecules. Figure 1 depicts

148 possible catalytic pathways for CO2 transformation to fuels and chemical products.

149 They include thermocatalytic reduction of CO2/H2 to produce CH4/CO, electrocatalytic

150 transformation of CO2/H2/electron to C1-C9 hydrocarbons, cycloaddition of CO2 with

151 epoxide to form cyclic and polycarbonates, and the emerging photocatalytic reduction

152 of CO2/H2O to CH4, CHOOH, CH3OH, etc. The nature and kinds of nanomaterials for

153 conversion of CO2 also play a vital role in product selectivity to get carbon-containing

154 fuels, in addition to process parameters such as solvent effects, reaction temperature,

155 H2/CO2 ratios, and partial pressure condition of CO2. The nanomaterials for catalytic

156 conversion of CO2 are range from plasmonic metal nanoparticles and metal oxides-

157 based composites to metal-free nanoporous materials including carbon nanostructures

7
158 such as grapheme oxide (GO) reduced grapheme oxide (rGO) and carbon nanotubes

159 (CNT), silica, alumina, covalent organic polymers, etc.

160

161 Figure 1: Pathways for catalytic conversions of CO2 to various feedstocks

162 3. Routes of CO2 conversion

163 3.1 Photocatalytic transformation of CO2

164 The natural process of photosynthesis, in which plants change CO2 and H2O into

165 oxygen and carbohydrates when exposed to sunlight, served as the inspiration for

166 photocatalytic CO2 reduction. This process transforms solar energy into chemical

167 bonds, which are then stored (carbohydrates). It combines light and dark reactions with

168 water oxidation and carbon dioxide reduction (or CO2 fixation) reactions. The process

169 of photocatalytic transformation of CO2 into value added particularly using

170 semiconductor or metal complex as catalyst can be divided into four steps: (i)

171 absorption of light greater or equal to the band gap (ii) Separation of valence band (CB)

172 and conduction band (CB) (iii) migration of electrons from the VB to CB and migration

8
173 of electrons to the surface of cocatalyst (iv) adsorption and activation of CO2 by the

174 photogenerated electrons (Kovačič et al., 2020)(Figure 2).

175 To understand the kinetic and thermodynamic point of view, the formal reduction

176 potentials for the reactions connected to the photoreduction of CO2 (at pH 7) is

177 presented in Figure 12a. Due to their extremely high negative reduction potentials

178 [E(CO2/CO2•-) = -1.85 V vs NHE] in relation to the CB edges of many semiconductors,

179 one-electron reduction processes of CO2, such as the generation of CO2 •, are not

180 practical (Lingampalli et al., 2017). A highly negative reduction potential results from

181 the conversion of C's sp2 to sp3 hybridization. Reduction potentials for HCOOH,

182 HCHO, CH3OH, and CH4 production are minimal (-0.81, -0.48, -0.38, and -0.246 V)

183 (Figure 12b) and positive relative to CB edges of various semiconductors. Proton

184 coupled electron transfer (PCET), in which electron transfer to CO2 is accompanied

185 with proton transfer, is thus preferable (Kovačič et al., 2020; Lingampalli et al., 2017).

186 A good number of works has been done recently to functionalize semiconductors and

187 it’s like as novel and effective photocatalysts. Various single and composites

188 nanomaterial have been reported for photocatalytic transformation of CO2. This section

189 critically survey the scattered literatures

190

191 Figure 2: (a) Energy diagram for CO2 reduction and water oxidation on a

192 semiconductor. b) A schematic representation of the overal photocatalytic reaction

9
193 process, demonstrating elements that may influence photocatalytic performance.

194 Reproduced with the permission from (Shen et al., 2020). Copy right 2020 Willey

195 Library

196 3.1.1 Single metal nanoparticles

197 Plasmonic metal nanoparticles (NPs) such as Au, Ag, and Cu have a large optical

198 extinction cross section and the ability to absorb significant visible light which accounts

199 for up to 40% of solar irradiation to catalyze a wide range of photochemical reactions.

200 As a result, , they offer several advantages over other conventional catalysts like Pt, Pd,

201 Ru, and Rh, whose localized surface plasmon resonances (LSPRs) fall in the UV region

202 of the solar spectrum. A single silver nanoparticles (AgNPs) photocatalyst was excited

203 in a microfluidic reaction cell filled with CO2 led to CO2 reduction reaction CO2RR, to

204 CO and HCOOH. The synergy between photoexcited CO2 and catalytic active sites,

205 which is not clearly understood at the molecular level, was evidenced by in-situ

206 surface-enhanced Raman spectroscopy (SERS) (Kumari et al., 2018). The SERS was

207 used to physi-sorb CO2 on nanoparticles, LSPR-triggered CO2 activation to HOCO*

208 (intermediate), followed by transformation of HOCO* to multiple products (H2, CO,

209 HCOOH, HCHO and CH3OH), (see Figure 3). The real-time monitoring of CO2RR

210 activity by SERS shows that plasmonic AgNPs are selective for CO and HCOOH, with

211 CO being the predominant product. On polyvinylpyrrolidone (PVP)-capped plasmonic

212 AuNP-photocatalyst, photoexcited LSPR induced a multi-electron and multi-proton

213 reduction of CO2 to C1 (methane) and C2 (ethane) hydrocarbons, without formation of

214 CO (Yu et al., 2018). The CO2RR was conducted in isopropyl alcohol (IPA) saturated

215 CO2-aqueous solution to prevent h+/e- recombination during photoredox reaction, and

216 the CO2RR selectively produced CH4 (6.8 NP-1) and C2H6 (5.6 NP-1) after 10 h of light

217 irradiation. The results show that catalytic and selectivity of plasmonic gold

10
218 nanoparticles (AuNPs) for CO2 transformation to C1 and C2 is modulated by laser

219 excitation wavelength (photon energy), and photon flux (light intensity). Thus, the CH4

220 production rate increased with decreasing excitation wavelength and with overall 8e-

221 process (8H+ + CO2 → CH4 + 2H2O), while C2H6 production was only observed at

222 lower excitation wavelength with 14e- process (14H+ + 2CO2 → C2H6 + 4H2O). Zeng

223 et al. (Zeng et al., 2021) embedded uniformly distributed plasmonic CuNPs into a

224 triphenothiazine benzene ring (TPB) for photocatalytic CO2 reduction to CO, H2 and

225 CH4. CO evolution rates over TPB-Cu increased as the wt% of Cu bonded to TBP units

226 increased, and CuNPs with 1wt% content yielded a CO evolution rate 3.2 times higher

227 than bare CuNPs. Interestingly, the evolution rates of H2 and CH4 on TPB-Cu remained

228 relatively constant, implying that incorporating plasmonic CuNPs into TPB increased

229 the directional selectivity for CO formation over H2 and CH4. Plasmonic cupper NPs

230 conjugated with TBP could provide a large contact area for hot electron migration,

231 opening new doors for energy and carbon cycle processes.

11
232

233 Figure 3: Representative SERS spectra that capture specific adsorbates or products

234 observed in photocatalytic CO2 reduction on Ag NPs. Specific species captured include

235 (a) physisorbed CO2, (b) HOCO* reaction intermediate, (c) carbon monoxide or CO, (d)

236 formate ion or HCOO-, (e) carbonate or CO2− −

3 , (f) bicarbonate or HCO3 ., adsorbed

237 hydroxide or OH*, and H2, and (g) Histogram of prevalence by the number of catalytic

238 NPs on which each type of species was observed. Reproduced with permission from the

239 American Chemical Society from ref. (Kumari et al., 2018).

240 3.1.2 Metal/metal oxide-based composites

241 In order to overcome the limitations of single-component plasmonic metal

242 photocatalysts and to expand their light harvesting to UV region, researchers have

12
243 turned to multi-component semiconductors for a variety of applications. Decoration of

244 metal oxide semiconductors with transition or plasmonic metals has been a huge

245 success. Both plasmonic and transition metals on semiconductors can help harness UV

246 and visible light by reducing energy band gaps, which play key roles in CO2 activation

247 and intermediates stabilization for CO2RR.

248 For many years, the selective absolute conversion of CO2 to CO has been a source of

249 contention. In 2020, Nguyen et al. (Nguyen et al., 2020) constructed air-stable Z-

250 scheme photocatalysts composed of Ag-decorated reduced titanium oxide/tungsten

251 hybrid nanoparticles (TiO2/WO3-AgHNPs) for CO2 reduction to CO (100%, without

252 byproducts) and with an evolution rate of 1166.72 μmol g-1 h-1 after 7 h of light

253 illumination. On one hand, the plasmonic Ag (1wt% Ag) increased the photocatalytic

254 electron reaction rate up to 2333.44 μmol g-1 h-1, and facilitated intense absorption light

255 in the visible region of the catalysts due to its strong LSPR effect. The presence of Ti 3+

256 states in the catalysts, on the other hand, facilitated the physisorption, stabilization, and

257 reorientation of the intermediates formed during CO2 reduction. Other gas products

258 such as CH4 and H2 were produced in the absence of Ag deposition, suggesting the

259 importance of using plasmonic Ag to achieve the formation of only CO.

260 Zhang et al. (Zhang et al., 2021) reported p-type Cu2O photocatalysts with phase

261 structures of 100 (100Cu2O) and 111 (100Cu2O) modified with Pd nanoparticles for

262 CO2RR activities. The well-matched band alignments between Pd and 100Cu2O

263 increased the work functions (Ws) of the 100Cu2O-Pd composite, resulting in an

264 enhanced photocatalytic CO generation at a production rate of 0.13 μmol/g.h, which is

265 3.0 times higher than bare 100Cu2O nanoparticles. Pd nanoparticles (in 100Cu2O-Pd)

266 promoted efficient photoexcited electrons by acting as a photoinduced hole scavenger,

267 and also improved photostability of 100Cu2O-Pd by reducing photocorrosion.

13
268 However, 111Cu2O-Pd composites lacked electron-hole mobility due to mismatched

269 band structures between 111Cu2O and Pd species, resulting in lower work function and

270 poor photocatalytic CO2RR compared to 100Cu2O-Pd composites, emphasizing the

271 importance of crystal surface structure and matched band structure construction for

272 selective CO2RR to CO.

273 Wang and co-workers demonstrated LSPR photo-assisted electron migration from

274 plasmonic CuNPs to ZnO via metal-support interfaces in Cu/ZnO catalysts for CO2

275 reduction to MeOH (Wang et al., 2019). In the photothermal process, the rate of MeOH

276 formation was 2.13 μmol/g. min, compared to 1.38 μmol/g. min recorded in pure

277 thermal process, and the apparent activation energy decreased from 82.4 to 49.4 kJ mol-
1
278 . The rate-determining step in the thermal process was the formation of reaction

279 intermediates (*HCOO, *

HCOOH, and *
H2COOH species), followed by the

280 hydrogenation of *HCOOH to MeOH. Formation of MeOH in photothermal process

281 followed the same reaction pathway as thermal process, with the exception that induced

282 hot electrons on CuNPs accelerated the conversion of intermediates to product

283 (MeOH). Under visible light irradiation, the product selectivity over Cu/ZnO remained

284 relatively constant and the decreased activation energy had no effect. Small amounts of

285 Pt nanoparticles have also been used as co-catalyst on ZnMn2O4 nanorods as visible-

286 light-driven catalysts for promoting CO2 reduction to produce methane, as was the case

287 in other studies (Alhaddad and Shawky, 2021) (see Figure 4a). The wt% of Pt species

288 on ZMO nanorods influenced the catalytic activity and selectivity of Pt/ZMO catalysts,

289 with 1.5% Pt/ZMO exhibiting the best photocatalytic performance for CO2RR activity

290 (Figure 4b). Band connection and surficial interactions between Pt species and ZMO

291 nanorods with optimal Pt/ZMO at 1.5% Pt enhanced selective reduction of CO2 to

292 MeOH with an evolution rate of 1,906 μmol/g within 9 h.

14
293

294 Figure 4: (a) Photocatalytic generation of methanol over Pt/ZMO nanocomposites at

295 different illumination time, and (b) impact of Pt content in Pt/ZMO composite for a

296 dose of 1.0 g/L for each within 9 h of light illumination. Reproduced from (Alhaddad

297 and Shawky, 2021) with permission.

298

299 V, Cr, and Co loaded on TiO2 were studied for CO2RR to produce H2, C1 and C2+.

300 Higher photoconversion rates were observed compared to pristine TiO2, which were

301 found to be sensitive to the metal concentrations and TiO2 crystallite size modification

302 (Ola and Maroto-Valer, 2015). After 4 h of illumination, 1wt% Co-TiO2 demonstrated

303 the highest photoconversion rates of 62.91 μmol/gcath for H2 and 26.12 μmol/gcath for

304 MeOH (Figure 5). Ni-modified CeO2, MgO, α-Al2O3 and TiO2 NPs were studied for

305 CO2 methanation, and the effects of the solid supports were elucidated (Tada et al.,

306 2012). CO2 methanation pathways followed two steps: (i) reaction of CO2 and H2 at the

307 meta/metal oxide interfaces to afford CO through reverse water gas shift reaction (CO2

308 + H2 → CO + H2O), and (ii) prompt methanation of CO with H2 (CO + 3H2 → CH4 +

309 H2O) at low temperature via the Fisher–Tropsch synthesis (FTs). CeO2 has the highest

310 number of CO2 adsorption sites and exhibits the highest CO2 methanation with near-

311 unity CH4 selectivity. Li and co-workers showed that partially oxidized metallic Fe NPs

15
312 (Fe and FeOx) deposited on MgO-Al2O3 and then reduced under H2 at different

313 temperatures photothermally hydrogenated CO2 into C1 and C2+ hydrocarbons (Li et al.,

314 2021). The Fe-500 sample (reduction performed at 500°C) showed the highest CO2

315 conversion and excellent selectivity for C2+ hydrocarbons with 0% CO. The FeOx phase

316 promotes CO2 reduction to CO via RGSW reaction and modulates the electronic

317 properties of Fe phase to suppress CH2 and CH3 hydrogenation, thus enhancing C2+

318 hydrocarbon formation.

319

320 Figure 5: Irradiation time profile of 1 wt%Co–TiO2 for CO2 reduction to fuels.

321 Reproduced from (Ola and Maroto-Valer, 2015) with permission.

322

323 The conjoining of metal, e.g. Ag and narrow band semiconductor e.g. InS2 has been

324 reported to improve photocatalytic reduction of CO2 activity. Recently, a quaternary

325 nanocomposite (AgCuInS2) deposited on a graphene-TiO2 based material presented

326 excellent photoreduction activity of carbon dioxide in H2O with the formation of

327 mostly methanol, formaldehyde and formic acid. AgCuInS2 combined with TiO2

328 semiconductors (AgCuInS2−TiO2) absorb photon energy, which led to the excitation of

329 electrons from valence band (VB) to conduction band (CB), creating electron−hole

330 pair, and the graphene act as electron assimilates (Figure 6).

16
331

332

333 Figure 6: Mechanism of photocatalytic CO2 reduction. Re-used with permission from

334 (Otgonbayar et al., 2020). Copyright (2021) American Chemical Society.

335 3.1.3 Metal oxide/mesoporous oxides

336 Many metal-functionalized mesoporous aluminas and silicas have been studied as

337 catalysts for CO2 hydrogenation to CO via RWGS or CO methanation by Fischer

338 Tropsch (FT) reactions. In terms of activity and selectivity, mesoporous materials with

339 high Brunauer-Emett-Teller (BET) surface areas are important features for CO2

340 adsorption and conversion (Petrovic et al., 2021). The nature of metal species

341 immobilized on porous oxides also influences the CO2RR selectivity for either CO or

342 CH4. Deposition of Ni on CaO-Al2O3 showed CO2 conversion with 81% selectivity to

343 CH4; however, lower performance of the Ni-based catalyst in the subsequent

344 methanation reaction (due to partial oxidation of Ni fractions) suggests that a better

345 approach for CO2RR on metal/mesoporous materials is required (Mutz et al., 2015).

346 Addition of La as a second metal to Ni/-Al2O3, enhanced direct CO2 methanation (CO2

347 + H2 → CO + H2O) via the Sabatier reaction, increasing the CO2 conversion rate to

348 CH4 from 42% to 80.3% (Rahmani et al., 2019). CO2 methanation over mono and

17
349 bimetallic catalysts was temperature, feedstock (H2/CO2 ratio), and gas hourly space

350 velocity (GHSV) sensitive. CO2 was transformed into CO as a result of the RWGS

351 reaction which occurred at higher GHSV values (between 6000-18,000 mL/(gcath)),

352 350oC, and 3.5 H2/CO2 ratio, resulting in decreased CH4 selectivity. In contrast, Bashiri

353 and coworkers demonstrated that lowering the GHSV from 2000 to 1250 nml/min over

354 a Ni-promoted iron catalyst on HZSM5-Al2O3 (Fe-Ni/HZSM5-Al2O3) increased CO2

355 methanation significantly (Bashiri et al., 2018). The results also show that adding

356 HZSM5 to Al2O3 increases the rate of CO2 conversion to light hydrocarbons, CO, and

357 CH4 by 15.53%, indicating that combined supports have the potential to improve CO2

358 conversion activity and selectivity.

359

360 Figure 7: (a) Proposed reaction pathways on Cu/fumed-SiO2 and CuNi/fumed-SiO2

361 surface (b) Activation energy calculation for CO2 conversion reaction over Cu/fumed-

362 SiO2 and CuNi/fumed-SiO2. Reproduced from (Kumar et al., 2022) with permission.

363

364 Mesoporous siliceous materials are valuable supports because of their large number of

365 active sites for supporting various metal ions to catalyze CO2RR to renewable

366 feedstocks. Single Cu-based catalytic systems are not suitable for direct CO2

18
367 hydrogenation to either CH4 or CH3OH because they lead preferentially to the

368 formation of CO via RWGS reaction. For example, CuNi/fumed-SiO2 showed

369 enhanced activity and selectivity for CO, as well as a tendency for methanation to CH4

370 via interaction of CO and neighboring H, whereas Cu/fumed-SiO2 showed only

371 selectivity to CO due to decomposition of adsorbed formate intermediates to CO,

372 Figure 7a (Kumar et al., 2022). The incorporation of Ni increases the system's catalytic

373 active sites and lowers the activation barriers for CO2RR to CO and CH4, Figure 7b.

374 Mesoporous Cu/SiO2 doped with Ga and/or Zn had greater catalytic activity for direct

375 CO2 reduction to MeOH than undoped Cu/SiO2 (Paris et al., 2020).

376 The strong promoting effects of dopants restricted the occurrence of RWGS reaction

377 for CO formation while increasing selectivity for MeOH one. Both dopants provide

378 more active sites on the catalysts, lowering the activation barrier of MeOH synthesis

379 compared to CO formation, so methanol formation was preferred over CO formation.

380 When mesoporous TiO2/SiO2 was irradiated with visible light without Cu species, CO

381 was the main product of photo-transformation of CO2/H2O (Li et al., 2010). Cu

382 deposition on TiO2/SiO2 improved photoreduction of CO2 to CO, and CH4 selectivity

383 increased as well, peaking at 0.5wt% optimum Cu specie on TiO2/SiO2 (Figure 8). XPS

384 allowed to identify the deposited Cu species as Cu2O, which acts as a photoexcited

385 electron sink, limiting the recombination of photoinduced holes and excited electrons

386 and thus enhancing multi-electron photoredox reactions for CO2 to CO and CH4. Fu et

387 al. designed photocatalytic systems based on CoO and Co3O4 nanoparticles to convert

388 CO2 to CO using bare CoONPs, CoO/s-SiO2, CoO/s-SBA-15, and Co3O4/s-SBA-15 (Fu

389 et al., 2019). Under similar photoredox conditions, CoO/s-SBA-15 exhibited the best

390 activity for CO2RR to CO with 85% selectivity at 14,147 μmol/hg after 2.5 h.

391 Interfacial interactions between porous silica -OH groups and reaction substrates

19
392 enhance sorption and photocatalytic CO2 reduction to CO over CoO/s-SBA-15 catalyst

393 system.

394

395 Figure 8: (a) Peak production rates of CO and CH4 on various TiO2-containing

396 catalysts, and (b) Peak production rates of CO and CH4 as a function of Cu loading in

397 Cu/TiO2–SiO2 catalysts. Reproduced from (Li et al., 2010) with permission.

398 3.1.4 Inorganic/organic nanocomposites

399 3.1.4.1 Metal-organic frameworks (MOF) nanomaterials

400 MOFs are recognized as catalytic systems of choice for CO2RR conversion to

401 renewable energy feedstocks due to the large panel of surface functionalities and

402 geometries, porosity as well as the possible customization these materials offer

403 specifically for CO2 capture and utilizations (CCUs). Architectural flexibility and ease

404 of structural modification of MOFs through insertion of different metal ions (or metal

405 clusters) together with interconnection of multidentate organic linkers with different

406 functionalities are notable strategies to improve performance of MOF-based

407 photocatalysts for CO2 reduction (Ejeromedoghene et al., 2022). Wang and coworkers

408 investigated the photocatalytic conversion of CO2 to formate over a variety of amino-

409 functionalized and unfunctionalized Fe-based MOFs. They found that amine-

20
410 functionalized Fe-based MOFs outperformed their respective parent MOFs in this

411 transformation. NH2-MIL-101(Fe), a framework composed of FeO clusters and 2-

412 aminoterephthalic acid (H2ATA) ligands prepared in dimethylformamide (DMF),

413 exhibits the best catalytic activity, to generate HCOO- at the evolution rate of 178

414 µmol/g (Wang et al., 2014). Mechanistic pathways for enhanced activities include

415 excitation of NH2 functionality, electron transfer to the Fe center and direct excitation

416 of Fe-O cluster (Scheme 2). Wei et al. reported visible-light induced CO evolution

417 from CO2RR over a series of UiO-based MOFs photocatalysts modified with different

418 functional groups (F, NH2, OCH3, CH3) (Wei et al., 2019). They observed an influence

419 of the electron-withdrawing and electron-donating character of the introduced

420 functional groups, CO evolution following the order UiO-68-F < UiO-68-NH2 < UiO-

421 68-CH3 < UiO-68-OCH3. The superior performance of UiO-68-OCH3 was attributed to

422 the pronounced charge separation efficiency of OCH3. Crake et al. investigated

423 applicability of titanium dioxide/carbon nitride (TiO2/CNNS) nanosheet

424 nanocomposites in photoreduction of CO2 (Crake et al., 2019). They found that

425 TiO2/CNNS possessed improved CO2 conversion and adsorption when compared to the

426 individual materials used to make the composites (> 10 times). In addition, it was

427 reported that the composite material with more {001} TiO2 facets was the most

428 catalytically active and this is attributed to enhanced charge transfer at the TiO2/CNNS

429 heterojunction interface. Previously, Crake et al (Crake et al. 2017) coupled NH2-UiO-

430 66 onto pre-formed TiO2 nanosheets via in situ process to develop TiO2/NH2-UiO-66

431 heterojunction with permanent pore sizes and exposed catalytic actives sites for

432 enhance CO2 uptake and photoreduction of adsorbed CO2 to CO under UV-visible

433 light. The evolution rate of CO2-to-CO conversion over the bound nanocomposite was

434 1.9 times more than that of pure TiO2. Interestingly, the photoreduction efficiency of

21
435 mechanically blended TiO2 and NH2-UiO-66 is comparable to pure TiO2, proving that

436 in situ growth method was necessary for the enhanced catalytic activity. Transient

437 absorption spectroscopy confirmed that the increased photoactivity of TiO2/NH2-UiO-

438 66 was due to the efficient charge transfer at the interface of heterojunction.

439

440 Scheme 2: Dual excitation pathways over amino-functionalized Fe-MOFs for

441 photocatalytic reduction of CO2 to formate. Reproduced from (Wang et al., 2014) with

442 permission.

443 Besides the use of MOFs with multidentate linkers and different functional groups,

444 multi-metallic MOFs can also offer improved stability and overall catalytic efficiency

445 for CO2 reduction in comparison to monometallic counterparts. Different MOFs with

446 multi-metallic nodes have been explored for CO2RR. For instance, bimetallic ZnCu

447 MOF-74 outperformed monometallic Cu-MOF-74 when used as catalysts in methanol

448 synthesis (Stolar et al., 2021). Selectivity for MeOH formation increased by 4.7 times

449 upon incorporation of Zn into Cu-MOF-74 (c-ZnCU-MOF-74), and this value

450 increased further to a factor of 8.3 upon amorphization of c-ZnCU-MOF-74. The

451 findings highlight the significance of using heterometal nodes and amorphous MOF to

452 get improved activity and selectivity. Fe-N-TiO2/CPO-Cu MOF nanocomposites were

453 fabricated where CPO-Cu-27MOF is supported on 0.12%Fe-0.5%N-codoped TiO2

22
454 leading to effective photocatalytic reduction of CO2 (khalilzadeh and Shariati, 2019).

455 Reduction efficiency of Fe-N-TiO2/CPO-Cu can be tuned by varying the amount of

456 CPO-Cu-27 (CPO) in composites from 8 to 65wt.%, and the Fe-N-Ti@50CPO sample

457 with 50wt% CPO yields the highest conversion of CO2 to methane. The performance

458 achieved is ca. 1.7 times higher than in the case of CO2 methanation over Fe-NTiO2.

459 Liu et al. reported visible-light-driven CO2 to CO conversion on hollow transition

460 metal NPs-based MOFs (Liu et al., 2021). Their results show that Co-MOF-3 with two

461 stacked piezoelectric phononic crystal nanoplates had a 2.5-fold higher CO2

462 photoreduction efficiency than Co-MOF-1 with single nanoplate ( Figure 9). The Co-

463 MOF-3 homojunction system demonstrated a high CO2 to CO conversion rate with

464 100% selectivity, outperforming most of the previously reported semiconductors for

465 this reaction.

466 Polyoxometalates-based MOFs (POMOF) composites have also been studied for

467 CO2RR due to POM's unique ability to act as nodes or pillars, and more importantly, as

468 high-efficiency catalytic sites in the MOF cages to adsorb reactants and improve MOF

469 acidity, stability, and redox activity. Li et al. (Li et al., 2019) reported the use of a

470 reductive POM and a hydrophobic fluorine-containing ligand to fabricate a stable

471 POM-based MOF (NNU-29) composite as an effective CO2 photoconversion catalytic

472 system. The presence of a hydrophobic ligand improves the chemical stability of NNU-

473 29 and reduces H2 generation due to water attack to some extent, resulting in 98%

474 selectivity for CO2 reduction to HCOOH in aqueous solution after 16h of light

475 irradiation. Wang et al. (Wang et al., 2021) recently proposed SO3H-MIL-101-Cr

476 (SO3H-MOF) supported silicomolybdic acid (SMA) as a host-guest composite for CO2

477 photoreduction. Pristine POM and MOF have negligible CO2-to-CO activity compared

478 to SO3H-MOF. CO formation over POMOF composite, on other hand, achieved a

23
479 remarkable yield of 829.46 mol/g and selectivity of 93.2%. The superior reductive

480 activity of POMOF was attributed to increased CO2 affinity for silicomolybdic acid

481 (SMA) and synergy between POF and MOF, resulting in enhanced charge carrier

482 separation.

483

484 Figure 9: (a) Schematic view for the hollow Au/Ag directed formation of Co-MOF-3

485 nanocomposites. (b) Evolution of CO and H2 as a function of reaction time during the

486 CO2 reduction under visible-light irradiation for Co-MOF-1 and Co-MOF-3

487 photocatalysts. (c) Stability of Co-MOF-3 during the continuous CO2 reduction

488 process. Reproduced with permission from ref. (Liu et al., 2021). Copyright 2021

489 Nature.

490 3.1.4.2 Metal-free nanomaterials

491 The high cost of production of metal-based nanomaterials, their susceptibility to

492 deactivation in catalytic systems, environmental concerns about toxicity (Fall et al.,

493 2022; Keller et al., 2017), and more often than not, their moderate catalytic

494 performance in terms of activity and selectivity, have limited their use in CCUs.

495 Graphene oxides, fullerenes, and graphitic carbon nitrides have recently emerged as

496 valuable metal-free platforms for CO2RR preparation, chemical inertness, and natural

497 abundance (Yang et al., 2022). These materials are frequently used as a standalone

498 material or in combination with other non-metal semiconducting materials to improve

499 their CO2RR performance (Shen et al., 2020). Several reports have shown that GO can

24
500 act by itself as a photocatalyst for CO2 reduction either by adapting its method of

501 preparation or through UV-Vis light-induced activation of pristine GO (Kuang et al.,

502 2020). Hsu et al. (Hsu et al., 2013) studied the effect of volume of H3PO4 used as a

503 mild oxidizer to prevent overoxidation of pristine GO on the CO2RR performance.

504 Their results show that modified GOs have increased visible light absorption and

505 improved CO2 photoreduction to MeOH compared to pristine GO. The CO2-to-MeOH

506 conversion rate of GO-3 with excess H3PO4 was found 6-fold higher than with pure

507 TiO2. Kuang et al. (Kuang et al., 2020) reported on the photoreduction of CO2 to CO

508 over GO activated either by UV or simulated sunlight. GO activated by simulated-

509 sunlight provided the highest CO2 reduction efficiency, with a CO yield of 1.3-fold

510 higher than the UV-activated GO and nearly 3 times higher than with pristine GO. The

511 observed efficiency is due to light-induced increased defects and restoration of large π-

512 conjugative systems. Compared to GO, reduced-GO (rGO) are superior solid supports

513 for other semiconducting materials due to their high thermal and electrical conductivity.

514 Yang et al. supported quinacridone (QA) NPs on rGO nanosheets through H-bonding

515 and with different rGO contents and observed that this metal-free photocatalysts

516 allowed photoreduction of CO2 to CO and CH4 under UV light (Yang et al., 2019). The

517 sample containing 2% rGO had the highest CO2 reduction efficiency and selectivity for

518 CO and CH4 due to the synergistic effects of QA as a photosensitizer and rGO as an

519 electron acceptor to promote effective charge separation.

520 Based on the number of published articles on photocatalysis, graphitic carbon nitride

521 (gCN) materials is the highest promising among the reported carbon-based materials

522 for photoreduction of CO2, due to its facile tunable synthetic routes, structural

523 maneuverability, and tailorable morphology. However, they are limited due to their

524 narrow visible light absorption window, low specific surface area, poor electrical

25
525 conductivity, and rapid recombination of photoexcited excitons (Shi et al., 2018). A

526 variety of strategies, including structural modification via elemental doping, the

527 attachment of a semiconducting motif, functional group modulation of gCN, and others,

528 can significantly improve the photocatalytic CO2 reduction (Alaghmandfard and

529 Ghandi, 2022). Nonmetals like P, O, B, S, and N have become popular as interstitial or

530 substitutional dopants on gCN for CO2 photoreduction and other photocatalytic

531 reactions.

532 Arumugam and coworkers synthesized a series of porous gCN doped with various

533 nonmetals (B, O, P, and S) for photoreduction of CO2/H2O to gaseous fuels

534 (Arumugam et al., 2022) among which S-doped gCN showed the highest CO2-to-CH4

535 conversion rate compared to others. Imaging studies showed that bare g-C3N4 has a

536 thin-layered structure with irregular porosity, whereas S-doped g-C3N4 has a denser

537 structure with a homogenous distribution of S atoms on the g-C3N4 matrix, suggesting

538 that S atom can act as an electron sink for improved activity. Doping of S atoms into g-

539 C3N4 did not enhance the surface area or modify the energy band gap of g-C3N4; rather,

540 the remarkable boost in photoreduction efficiency was due to charge separation and

541 migration processes. Mo et al. demonstrated that hydrothermal treatment of melamine

542 and hydroxylammonium chloride precursors structurally transformed bulk g-C3N4 from

543 an irregular morphology into a supramolecular hydrogen-bonded network intermediate;

544 and that subsequent heating of the intermediate under NH3 atmosphere led to the

545 formation of porous TCN(NH3) nanotubes with a 1D tubular structure. The structural

546 transition from bulk gCN to 1D tubular structure was confirmed using XRD, FTIR,

547 SEM, and TEM. The CO2-to-CO conversion rate of porous TCN(NH3) nanotubes was

548 17 and 15 times that of bulk g-C3N4 and TiO2, respectively. Tubular structure of

549 TCN(NH3) has permanent porosity and a large surface area, which enhances solar light

26
550 utilization and spatially resisted photoinduced charge recombination, resulting in a

551 better photoreduction efficiency than bulk g-C3N4. Huang et al. (Huang et al., 2015)

552 successfully photoreduced CO2 to CH4 and MeOH over bulk g-C3N4 and amine-

553 functionalized g-C3N4, which was prepared by heating g-C3N4 in monoethanolamine

554 (MEA) solution. Both pure and functionalized g-C3N4 have a 2D lamellar structure

555 with equal porosity, indicating that the amine functionalization has no effect on g-C3N4

556 morphology. The functionalized g-C3N4 heated in an oil bath for 5 hours had the

557 highest CO2 to fuel conversion rate. The CO2 photoreduction efficiency over amine-

558 functionalized g-C3N4 was significantly higher than pristine g-C3N4 due to the

559 enhanced adsorption and destabilization of CO2 by amine functional groups.

560

561 Figure 10: Schematic view and mechasism of CN/CTF heterostructure for

562 photocatalytic CO2 reduction. Reproduced with permission from ref. (He et al., 2022).

563

564 gCN has also been decorated with COFs and carbon dots (CDs) to fabricate metal-free

565 composites for improved visible-light-induced CO2 reduction. He et al. (He et al.,

566 2022) reported for the first-time gCN/covalent triazine framework (2D/2D CN/CTF)

567 heterostructures for CO2 photoreduction. The TEM micrograph of CN/CTF reveals an

568 overlaying lamellar structure of CN superimposed on an irregularly stratified

27
569 morphology of CTF, validating successful formulation of 2D/2D CN/CTF

570 heterostructure. The optimal CN/CTF heterostructure is up to 25.5 and 2.5-fold more

571 efficient in photoreduction of CO2 to CO than CTF and CN, respectively. The enhanced

572 reduction efficiency of CN/CTF was attributed to a lower probability of hole-electron

573 recombination due to [Co(bpy)3]2+, which acts as electron harvester to accelerate

574 charges separation, cleaving O=C=O to selectively produce CO (Figure 10). Wang et

575 al. (Wang et al., 2022) reported van der Waals interfacial bonding between N-deficient

576 gCN and Tp-Tta COF, demonstrating exceptional stability and selectivity for CO2

577 photoreduction to CO. DFT calculations and EPR analysis confirmed the strong

578 electronic coupling between gCN and Tp-Tta COF, which was responsible for

579 improved photoreduction efficiency of the composite via large active sites for CO2

580 capture and, an accelerated S-scheme charge separation system. Wang et al. (Wang et

581 al., 2020) described carbon nanodots (CDs) electrostatically bounded to the surface of

582 protonated gCN which demonstrated an excellent metal-free bifunctional photocatalysts

583 to promote selective reduction of CO2 to nearly 100% methanol. Structural elucidation

584 reveals that the boundaries and edges of CN nanosheets, which possess a graphene-like

585 structure, were coherently decorated by graphitic structure of mCDs, indicating strong

586 electrostatic interactions between the two phases, which may have enhanced the

587 composite's charge transfer process. In contrast, the amorphous structure of sCD was

588 barely located in the phase structure of CN/sCD composite following heterojunction
m
589 formation, indicating weak interaction between the two phases. CD features near-

590 crystallized graphitic structures, whereas sCD is composed of amorphous carbons;

m
591 hence, the photocatalytic functions of CD/CN and sCD/CN are notably distinct.

592 According to this study, mCD/CN photoreduces CO2 to 6e- product MeOH (Figure

593 11a), while sCD/CN favors formation of 2e- product CO (Figure 11b). The authors

28
 m
594 attributed the improved CD/CN reduction efficiency to the hole-accepting role of
m
595 CD, which led to electron accumulation on CN surface and facilitated a multi-electron

596 reduction process to produce MeOH with near-unity selectivity (Figure 11c).

597

m
598 Figure 11: Photocatalytic activity of (a) CD/CN for methanol formation, and (b)

599 CD/CN for CO formation measured under visible light (λ > 420 nm). (c) Schematic
s

600 diagram of photocatalytic CO2 reduction by the mCD/CN and sCD/CN. Reproduced

601 with permission from ref (Wang et al., 2020). Copyright 2020 Nature.

602 Apart from all the aforementioned examples, this section also surveyed other

603 recent/relevant research works on photocatalytic transformation of CO2 (see Table S1

604 in the supplementary information)

605

606 3.2. Electrochemical transformation of CO2

607 The electrochemical transformation of CO2 to value added fuels has received

608 considerable attention in recent years owing to its plethora benefits including energy

609 production, storage, and others. The conversion process is located at the interface

610 between the solid catalyst surface and the electrolyte, as is the case with all

611 electrochemical reactions. A compact layer of ions next to the electrode, followed by a

612 diffusion layer of solvated ions, can be used to describe the interface's structure (Rosen

613 and Hod, 2018). The more the potential an electroactive species has, the more the

29
614 distance it can travel to the interface, and its relative orientation to the interface are all

615 influenced by the bilayer structure which is thus essential for the rate and efficiency of

616 the electrochemical CO2RR. Electrochemical CO2RR can produce useful chemicals and

617 fuels including formaldehyde, CO, formic acid, ethylene, ethanol, methane, and

618 methanol, depending on the electrical voltage supplied to the electrode (Chen et al.,

619 2020).

620 The methods most frequently used for electroreduction of CO2 are cyclic voltammetry

621 (CV) and linear sweep voltammetry (LSV). The catalytic performance can also be

622 evaluated using chronoamperometry. These CO2 conversion operations are typically

623 carried out at a specific reaction rate and ambient conditions of temperature and

624 pressure (Nielsen et al., 2018). A coupled proton electron transfer that results in the

625 protonation of the oxygen atom O (eq 1) or the carbon atom C (eq 2) triggers the

626 adsorption of CO2 on the electrode surface (eq 4) (Nielsen et al., 2018; Zhu et al.,

627 2014). As such, this process requires the use of a large potential, which results in

628 competing reactions such as the hydrogen evolution reaction (HER). In lieu of the

629 above, integration of a catalyst in the system allows to reduce the overpotential and

630 activate CO2 conversion. In general, a heterogeneous catalyst deposited on the

631 electrode surface or a homogeneous catalyst dissolved in solution are used in

632 electrocatalytic CO2 transformation. These catalysts will allow for a faster electron

633 transfer coupled with protons, resulting in the observed products HCOOH (eq 2 and eq

634 3) or CO (eq 5 and eq 6) (Yin et al., 2019).

635 * + CO2 + H+ + e- → *OCHO (Eq 1; a slow step)

636 *OCHO + H+ + e- → *HCOOH (Eq 2; a fast step)

637 *HCOOH → * + HCOOH (Eq 3)

30
638 * + CO2 + H+ + e-→ *COOH (Eq4; a slow step)

639 *COOH + H+ + e- → *CO + H2O (Eq 5; a fast step)

640 *CO → * + CO (Eq6)

641 As shown in Figure 12, various studies using different metal electrodes modified with

642 catalysts such as Sn, In, Au, Ag, Pd, Bi, Co, Mo, and others have been reported. As the

643 other side reactions (i.e. HER) can be almost suppressed, these materials exhibit

644 significant catalytic properties for the CO2 transformation (Lu et al., 2019).

645 Furthermore, they present an extremely low energy barrier for the formation of the

646 intermediate, which must then be protonated at the carbon or oxygen atom before being

647 converted to formate or carbon monoxide.

648

31
649 Figure 12: Overview of some typical Au, Ag, Pd, Sn, and Ni-based nanocatalysts for

650 electrochemical reduction of CO2 to CO. All potentials are contrasted with an electrode

651 made of reversible hydrogen (RHE). NP stands for nanoparticle, whereas FE stands for

652 faradic efficiency. Reprinted with the permission from (Yin et al., 2019). Copyright

653 (2019) Elsevier.

654 Yang et al also investigated the CO2RR on Ag, Pd, and Ag@Pd nanocubes. Pd

655 nanocubes led to CO with high selectivity as a result of Pd turning into Pd hydride

656 (PdH) during CO2RR (Yang et al., 2022). In contrast, Ag@Pd makes the formation of

657 PdH more difficult due to inhibited production of CO from the intermediate *HOCO

658 which thus adjusts the reaction pathway towards HCOOH. The authors concluded that

659 Ag nanocubes have high selectivity for H2 with no phase transition during CO2RR.

660 Li et al. (Z. Li et al., 2022) studied electrochemical CO2RR to formate, which not only

661 has the potential to reduce the issue of global warming brought on by CO2, but also has

662 the potential to be exploited for energy storage as intermittent renewable energy. A

663 bimetallic BiSn nanomaterials were electrodeposited on copper mesh and tested as

664 electrocatalysts for the conversion of CO2 to formate. The resulting electrodes

665 demonstrated excellent catalytic activity at 1.0 V vs. RHE, with a partial current density

666 of 34.0 mA/cm2 and an astonishingly high faradaic efficiency of roughly 94.8%. The

667 production of formate at a remarkable rate of 634.3 mol/cm2h -significantly higher than

668 most rates previously reported- is noteworthy. The quick electron transfer of BiSn

669 nanomaterials also contributed in the creation of the CO2•- intermediate. Additionally,

670 they produced a metastable metal oxide/metal interface that helped to stabilize the

671 CO2•-intermediate and suppress the HER side reaction. The pathway connected to the

672 OCHO• intermediate was improved because of the optimized electronic structure of

32
673 BiSn, promoting the conversion of CO2 to formate. According to these results, Bi/Sn

674 bimetallic catalysts are a viable option for very effective CO2 reduction.

675 In contrast, the conversion of CO2 to CO and formate is less difficult than CO2RR to C-

676 H hydrocarbons, which are more significant scientifically and technologically but are

677 more difficult to manage. Concerning the synthesis of ethylene, Cu and Cu2O are

678 regarded as the most common and effective electrocatalysts for CO2RR. Multi-carbon

679 oxygenates, such as ethanol (the primary product), acetate, and n-propanol, can also be

680 produced in an alkaline electrolyte at -0.25 to -0.5 V vs RHE with a total EF of 57 %

681 (Li et al., 2014).

682 In order to achieve a lofty ultra-high selectivity of 82.4% for ethylene in an H-cell

683 system with good catalytic stability and material durability of 100 h, Sultan et al.

684 (Sultan et al., 2022) presented a completely redesigned electrocatalyst consisting of

685 Al2CuO4 nanosheets uniformly coated with CuO nanoparticles (CuAl-1: CuO/Al2 CuO

686 4 -23) by phase. They found that Cu (CuAl-1) permitted high surface CO intermediate

687 coverages and improved CO adsorption for C-C coupling to *OCCO, a generation of

688 CO intermediate, and Cu (CuAl-1) also enabled high surface coverages of CO

689 intermediates.

690 Cu catalysts for CO2RR can produce a wide range of hydrocarbons at a high catalytic

691 activity. For selective CO2RR, Yin et al. (Yin et al., 2019) used a catalyst based on

692 copper nitride (Cu3N) nanocubes (NC). With a FE of 60%, a mass activity of 34 A/g, a

693 C2H4/CH4 molar ratio over than 2000, and strong selectivity and stability of CO2RR

694 towards ethylene at -1.6 V vs. RHE, their 25 nm Cu3N NCs showed good performance.

695 This lacks of product selectivity is a significant barrier to the use of these catalysts for

33
696 selective CO2RR, and more research on the application of these substitute catalysts is

697 required for increased hydrocarbon yield.

698 In a related piece of study, Liu and coworkers noted the formation of exceptional

699 oxygen-rich ultrathin CuO nanoplate arrays that spontaneously transform into Cu/Cu2O

700 heterogeneous surfaces after CO2RR (Liu et al., 2022). The electrocatalyst displayed a

701 high ethylene energy efficiency of 84.5%, steady electrolysis for 55h, and a total cell

702 ethylene energy efficiency of 27.6% at 200 mA.cm-2 in a flow cell with a neutral KCl

703 electrolyte. A density functional theory (DFT) investigation of the mechanism,

704 highlighted that stable nanostructures, stable Cu/Cu2O interfaces, and improved

705 adsorption of the intermediate *OCCOH can enhance selectivity and amount of C2H4

706 produced.

707 Wang et al. developed CuBi NPs that showed a CH4 FE as high as 70.6% at 1.2 Vs

708 RHE. According to their study, adding Bi NPs to the matrix (CuBi NPs) significantly

709 boosted the FE when compared to regular Cu NPs by almost 25 times (Wang et al.,

710 2020). DFT studies showed that alloying Cu with Bi lowers the energy required for the

711 rate-determining phase of *COH production, which provides an additional explanation

712 for the enhanced performance.

713 In addition to the aforementioned systems, other metal-based nanomaterials have been

714 investigated towards the production of hydrocarbon via the electrochemical reduction

715 of CO2, which are outlined in Table 1 below.

34
716 Table 1. Selected examples of electroactive metal nanoparticles for converting CO2 into hydrocarbon products

Nanoparticles FE (%) Current overpotent Products Remarks Reference

ial vs
Density
RHE (V)
(mA/c

m2 )

Dibenzyldithioc 100 ± 1 - -0.8 CO The hydrophobic (L. Souza and H.

arbamate nature of B. Lima, 2021)

functionalized dibenzyl moites

AuNPs permit CO2 to

pass through

C3N4/Cu2O-FeO 84.4 - -0.24 CO The interfacial (Woyessa et al.,

nanocomposites interaction 2021)

between g-C3N4

35
 and CU2O-FeO

are responsible

for the efficient

CO2 reduction to

CO

CuxAuy 48 - -0.5 to 0.7 EtOH The selectivity (Zhu et al., 2019)

of EtOH is
nanowire
attributed to the
arrays
synergistic effect

of morphology

Iron dispersed 80 - -0.57 CO with small Fe-N4 increased (Zhang et al.,

on graphene traces of CH4 CO2 activation 2018)

doped with resulting from

nitrogen the incorporation

36
 of trace Fe atoms

to graphene

matrices

ZnIn2S4/silver - - - CO and H2 Au NPs favor H2 (P. Li et al.,

(gold)/tetra(4- generation, 2022)

carboxyphenyl) whilst Ag NPs

porphyrin serve as a

iron(III) promoter for

chloride hybrids interfacial charge

transfer from

ZnIn2S4 to the

FeTCPP.

Cu nanocrystals - -1.74 -0.95 n-propanol The increased (Ren et al., 2015)

activity of the Cu

37
 nanocrystals

toward the

production of n-

propanol was

linked to the

number of defect

sites on their

surface.

Composite of 64 2.6 -0.4 CO The dispersion (Miao et al.,

ZrO2 of ZrO2 NPs 2019)

nanoparticles with oxygen

anchored on N- vacancies on the

doped carbon N-C responsible

sheets for the improved

electrochemical

38
 performance

Cu nanowires 60, 17.4, - -1.1 H2, ethylene, CO Cu nanowire (Ma et al.,

8 and 2 and ethene, arrays can be 2016a)

respectively tuned to

systematically

controlling

hydrocarbon

formation via the

electrochemical

reduction of

CO2.

Mesoporous 98 60 -0.81 CO The dispersive (Du et al., 2022)

carbon modified Ni nanoparticles

CNT anchored and N-doping

39
 by Ni NPs active sites of

mesoporous

carbon is good

for selective

reduction of CO2

to CO.

C-supported Bi 93 ± - -1.6 HCOO- The electrode (Ávila-Bolívar et

NPs 2.5% deactivates after al., 2019)

about 70 h (in 3-

h electrolysis

experiments at

different

potentials).

717 FE - Faradaic Efficiency; EtOH – Ethanol; FETCPP - Tetra(4-carboxyphenyl)porphyrin iron(III) chloride; HCOO- - Formate ion; NPs –Nanoparticles; AuNPs –

718 Gold nanoparticles

40
719 In the quest for additional electro-active nanoparticles for CO2 reduction, non-metal

720 NPs have been explored in order to speed up the reaction rate and increase the

721 selectivity for products. For instance, boron phosphide NPs were shown by Mou et al.

722 (Mou et al., 2019) to function remarkably as a non-metal electrocatalyst for the highly

723 selective electrochemical conversion of CO2 to CH3OH. In comparison to RHE in 0.1

724 m KHCO3, this catalyst achieves a high FE of 92% for CH3OH at 0.5 V. According to

725 DFT calculations, B and P synergistically facilitate the binding and activation of CO2,

726 and the *CO + *OH to *CO + *H2O pathway, with a free energy change of 1.36 eV, is

727 the rate-determining step for the CO2RR. Liu et al. (Liu et al., 2022) reported B/N-

728 doped sp3/sp2 hybridized nanocarbon, which consists of extremely small carbon NPs

729 with an sp3 carbon core surrounded by a sp2 carbon shell, as an effective electrocatalyst

730 for CO2 to ethanol reduction at relatively low overpotentials. They claim that CO2

731 reduction occurs during the synthesis of ethanol and acetate at 0.5 0.6 V (vs. RHE),

732 with ethanol accounting for 51.6% - 56.0% of the total reduction. Due to the combined

733 effects of sp3/sp2 carbon and B/N doping, there is a strong ethanol selectivity.

734 To perform electrocatalytic CO2 reduction to liquid ethanol and acetone, Yuan and

735 colleagues presented their findings. Yuan and colleagues used five pyridine derivatives,

736 including pyridoxine, 4-hydroxypyridine, 4-aminopyridine, 8-hydroxyquionline, and 5-

737 amino-1,10-phenanthroline, to functionalize graphene oxide (GRO) surfaces (Yuan et

738 al., 2018). Surprisingly, the greatest catalyst for electrochemical CO2 conversion is

739 pyridoxine-modified GRO sheets with a pyridinic N concentration of 2.32% and an

740 overall FE of 45.8%. Furthermore, the CO2 reduction potentials of the other four

741 pyridine derivatives functionalized GO varied with respect to ethanol and acetone. Li

742 and colleagues described non-metal nanoporous S-doped and S,N-codoped carbons as

743 catalysts for electrochemical transformation CO2 (Li et al., 2016). The team found that

41
744 S,N-doped carbon has greater FE for conversion to CO and CH4 compared to S-doped

745 counterpart. The former revealed a maximum FE of 11.3% and 0.18%. for CO and CH4

746 production, respectively. The S,N-nanoporous carbon was better at decreasing the

747 overpotential of the reduction process.

748 Two-dimensional (2D) boron nitride nanosheets or meshes (BNs) doped with beryllium

749 have been the subject of research by Azofra and coworkerss (Azofra et al., 2016).

750 According to their mechanistic study, adding electron-deficient Be atoms to the 2D

751 network significantly lowered the energy barriers for CO2 fixation and the initial steps

752 in hydrogenation. As a result of the exceptionally large hole created on the Be-doped

753 surface environment, CO2 was spontaneously absorbed (in terms of the Gibbs free

754 binding energy).

755 Despite all the accomplishments in CO2RR, it is worth to mention that high progress is

756 still needed in the design of catalysts based on metal and non-metal for achieving a

757 more performant CO2 electrocatalytic transformation. The main challenge being the

758 energy requirement for reducing CO2 (due to its stability), an electrochemical potential

759 [E°] of 1.9 V vs normal hydrogen electrode (NHE) at pH. Furthermore, due to the high

760 reactivity of the one-electron reduction product (CO2•-), regulating product selectivity is

761 difficult. When a multi-electron process is combined with proton-coupled electron

762 transfer, the potential for CO2 reduction is greatly reduced, resulting in a variety of

763 products depending on the number of electrons involved (Maeda, 2019). Finally, the

764 quantum yield and current density reported thus far are extremely low, particularly for

765 C2+ products, making commercial production extremely difficult. As a result, extensive

766 and intensive research is required to overcome all of the aforementioned challenges.

767 3.3 Photo-electrochemical (PEC) reduction of CO2

42
768 Photoelectrochemical (PEC) conversion of CO2 can be described as a procedure

769 mimicking the artificial photosynthesis technique. This method has been employed for

770 the conversion of CO2 to formate, formaldehyde, formic acid, methane, methanol, and

771 ethanol (Kumaravel et al., 2020).This technique combines electrocatalytic and

772 photocatalytic systems in which photogenerated electrons are transferred to the

773 electrode surface under an applied electric field, thus reducing CO2 in the process

774 (Nandal et al., 2022).

775 During the 80s, Fisher et al. (Fisher and Eisenberg, 2002)and Inoue et al. (Inoue et al.,

776 1979) studied the electrocatalytic reduction reactions that gave rise to studies of photo-

777 electrocatalytic reduction of CO2 on selected semiconductors. However, an extensive

778 study using various metals and metal oxides requires large over potentials and suffers

779 from hydrogen evolution (Benson et al., 2009; Qiao et al., 2014; Shen et al., 2015).

780 Since then, it has become a promising technique for CO2 conversion. In 2020, Arai et

781 al. (Arai et al., 2010) reported the PEC conversion of CO2 into HCOOH using a p-InP-

782 Zn photocathode which has been modified with a Ru polymer. The conversion was

783 achieved in the presence of visible light/ solar energy. Similarly, Kumaravel and his

784 coleagues (Kumaravel et al., 2020) also synthesized a range of fuels and chemicals

785 (Formic acid, methanol, ethanol, methane and ethane) from CO2. They employed a

786 catalyst-embedded microfluidic PEC reactor for the synthesis. The catalyst was

787 activated in the presence of visible light irradiation. The schematic of the conversion is

788 presented in Figure 13

43
789

790 Figure 13: PEC Conversion of CO2 into value-added product using solar irradiation.

791 Adapted with permission from reference (Kumaravel et al., 2020). Copyright [2020],

792 [American Chemical Society].

793

794 According to a recent study by Karim et al. (Rezaul Karim et al., 2018), single electron

795 reduction of CO2 to •CO2 occurs at -1.90 V vs NHE at pH = 7 in aqueous solution at 25

ο
796 C under 1 atm pressure. The 2e- pathway of CO2 reduction produces CO (E = -0.53 V

797 vs NHE) and formate (E = -0.61 V vs NHE) while the 6e- pathway leads to the

798 production of methanol (E= -0.38 V vs NHE) (Qiao et al., 2014; Rezaul Karim et al.,

799 2018). The band varies depending on the type of metal coordination as shown in

800 Figure 14.

801 In the electrochemical process, ultraviolet radiation on the semiconductor photocatalyst

802 activates the metal center, thus forming an oxidation-reduction environment. During

803 this process, electrons get excited from the VB to CB, leaving behind positive holes

804 that oxidize water on the surface to form OH- radicals with strong oxidative

805 decomposing power. Excited electrons from the CB get accepted by CO2 to form •CO2

806 radicals that react with the intermediate products of the oxidative reactions forming one

807 or more of the products in Table 2 depending on the bandgap of the photocatalysts

808 (Ekambaram et al., 2007). Metal oxides present desirable bandgap and bandgap edge

44
809 positions, and their electronic structure plays a major role where the VB is fully filled

810 by electrons and the CB is empty.

811 Table 2: The oxidation-reduction potential at pH=7 vs NHE and half-cell reactions

812 (Ekambaram et al., 2007)

Reactants Products EMF

CO2 + 2e− → •
CO2 -1.90
•
CO2 + 2H++ 2e− → HCOOH -0.61
•
CO2 + 2H++ 2e− → CO + H2O -0.53
•
CO2+ 4H++ 4e− → HCHO + H2O -0.48
•
CO2 + 6H++ 6e− → CH3OH + H2O -0.38
•
CO2 + 8H++ 8e−→ CH4+ 2H2O -0.24

2H2O + 4H+→ O2 + 4H+ +0.81

H+ + 2e− → H2 -0.42

813

814 Therefore, the integration of electrocatalysis and photocatalysis generates a unique

815 synergistic photo-electrochemical catalysis system (Huang et al., 2017; Rezaul Karim

816 et al., 2018). The catalytic activity of a photocatalyst towards CO2 reduction depends

817 on its band gap and appropriate positioning of the conduction and valence bands

818 (Handoko and Tang, 2013). Doping semiconductors have extensively been explored in

819 the literature to enable visible-light-activated photocatalysis and the usage efficiency of

820 solar light. Several published studies have used titanium for photocatalytic applications

821 for organic compound decompositions due to its ability to oxidize organic and

822 inorganic substances in water and air through a redox reaction (Xie et al., 2018). TiO2

823 and ZnO absorb ultraviolet light of the solar spectrum due to their large bandgap’s

45
824 energy (~380 nm and ~360 nm respectively) (Liu et al., 2010). The bandgap (the

825 distance between the valence band and conduction band) of each semiconductor

826 determines are shown in Figure 14, it shows the relationship between the bandgap and

827 EMF at pH 7. Several alternative semiconductors such as Fe2O3, ZnO, WO3, SrTiO3,

828 NaTaO3, CdS, Ag3PO4, BiPO4 and g-C3N4 have been reported to have promising

829 electro-photocatalytic performance (Kubacka et al., 2011; L. White et al., 2015; Liu et

830 al., 2010; Wang et al., 2009).

831

832 Figure 14: Band gap energy of various semiconductors (Wang et al., 2009). Copy right

833 2019

834 More recently, Nandal et al. (Nandal et al., 2022) performed a selective conversion of

835 CO2 into ethanol via a PEC method (see Figure 15). The catalytic systems involve a

836 mixture of Graphene oxide/Copper oxide and a copper-based MOF (GO/CuxO, Cu-

837 MOF). The catalytic system was solar-driven and activated in the presence of sunlight.

838 They reported an ethanol yield of 162 µM cm-1. Most researchers believe that the PEC

839 reduction technique is not only efficient, but it is also greener and sustainable. Other

46
840 PEC for CO2 reduction surveyed in this section are listed in the supplementary file

841 (Table S2)

842

843 Figure 15: PEC reduction of CO2 to ethanol. Adapted with permission from reference

844 (Nandal et al., 2022). Copyright [2022], [Elsevier].

845 3.4 Photothermal heterogeneous catalysts for the hydrogenation of CO2

846 The hydrogenation of CO2 is gaining significant impetus in scientific investigations

847 considering the large amount of CO2 generated by the industrial processes and the

848 associated environmental degradation. It facilitates the production of clean fuels and

849 hydrocarbons such as CO, CH4, and C2+ products (Fan and Tahir, 2022). The

850 hydrogenation reaction can proceed via thermal catalysis, photocatalysis, and

851 photothermal catalysis. While thermal and photocatalytic processes require the action

852 of heat and light energies respectively, the photothermal catalytic approach combines

853 both in a single reaction system. In photothermal catalytic systems, the CO2

854 transformation reaction is driven by light energy into a thermally inspired catalytic

855 reaction system or utilizing the photoinduced thermal effect of a catalyst. The light

856 energy initiates a photoinduced redox reaction and a photoinduced thermally driven

857 reaction (Oladoye et al., 2021). For instance, the exposure of a transition metal oxide-

858 based catalyst to a sufficient amount of light energy causes an excitation of photons that

859 produces electron-hole pairs in the conduction band (CB) and valence band (VB)

47
860 (Figure 16). These highly energetic electrons enter the anti-bonding orbitals of the

861 reactants and activate the reactant molecules to stimulate a redox reaction. In other

862 instances, the absorbed photon could be converted into heat energy (Liu et al., 2022).

863 At an activated temperature, the active sites on the surface of the photothermal catalytic

864 material could induce a thermally driven catalytic reaction. Several semiconducting

865 metal oxides with tunable porosity and defective active sites have been designed for the

866 hydrogenation of CO2 into different hydrocarbon-based fuels (Table 3).

867

868 Figure 16: Scheme of the photothermal catalytic CO2 reduction

48
869 Table 3: Examples of photothermal catalysts for the hydrogenation of CO2 in fuels and hydrocarbons

Photothermal Light Reaction Selective products Conversion Comments References

catalyst source conditions rate

(mmol·g-1·h-1)

Pd/ZnO Visible light Low CH3OH Localized SPR of Pd (Wu et al.,

pressure (12 contributed to the high yield of 2019)

bar) methanol

AuPt@UiO-66- 300 W Xe 150°C, 4 h CO 1451 Synergetic effect of plasmonic (Wang et

NH2 lamp Au, doped active Pt, and al., 2022)

encapsulation structure leading

to the production of

metal@MOF gives good

hydrogenation performance

49
120 μm- 300 W Xe Pressure (1 CO 1780 Strong light-absorption ability (Shen et

SiNCs@Co arc lamp bar), power over the entire solar spectrum al., 2022)

nanoarray intensity due to the combination of the

(2.5 W light-trapping effect of the

cm−2) nanoarray structures and the

SPR of Co NPs increases the

conversion rate

Ni/TiO2−xHx 300 W Xe Gas flow CH4 Abundant defects such as (Y. Li et

lamp rate at 500 oxygen vacancies, active al., 2022)

mL hydrogen species, and Ni active

sites enhance the performance

min−1 and
of the catalyst
purged for

10 min

Nb2C- 300 W Xe 36-sun CO 8.5 mol·g-1·h-1 Ni NPs greatly enhance the (Wu et al.,

50
nanosheet- arc lamp illumination activation of H2 and accelerate 2021)

supported Ni without CO2 hydrogenation reactions;

NPs external formation of Ni−H is vital for

heating CO2 conversion

Fe3O4 Xenon light 4 h of CO 11.3 Fe-carbide and other Fe-based (Song et

source irradiation catalysts show excellent light- al., 2020)

θ-Fe3C CHx 10.9
(200−1000 to-heat conversion performance

nm) and good light-harvesting

properties

α-MoC and β- 300 W 130 °C, 5 h CO and CH4 25.8 mL·g-1·h- dissociation of light-promoted (Zhao et
1
Mo2C mixed xenon lamp surface intermediate (formate al., 2021)

phases species) was responsible for the

enhanced activity of

photothermal catalytic CO2

51
 hydrogenation

Pd2Cu alloy UV-Vis (350 150 °C C2H5OH 4.1 Pd active sites utilize the (Elavarasan

dispersed TiO2 to 750 nm) electrons and hydrogenate the et al.,

*CO to *HCO, which is a key 2022)

step in the conversion process

SNAs support 300 W Xe Pressure (1 CO 0.433 Photoexcited electron-hole pairs (D. Zhang

on Co bar), power in the SNAs might be involved et al.,

arc lamp
intensity in the catalytic process 2021)

(2.5 W

cm−2)

Co@AAO Sunlight Power CO 1666 A dual-pass AAO with a large (D. Lou et

intensity channel size facilitates gas al., 2021)

(2.5 W diffusion and thus boosts

cm−2) photothermal catalytic

52
 performance

Au/CeO2 Xe lamp 623 K CO Positive effect of light on CO2 (B. Lu et

transformation is associated al., 2019)

with the hydrogen dissociation

step.

870 SPR-Surface plasmon resonance; MOF-Metal organic frameworks; SiNCs-Silica nanocones, NPs-Nanoparticles, SNA-Silicon

871 nanowires arrays, AAO-Anodic aluminum oxide

53
872 3.5 Thermochemical transformation of CO2

873 The thermochemical transformation of CO2 is an interesting strategy that has been gainfully

874 explored for the reduction, splitting, or reforming of CO2 to fuels/products such as carbon

875 monoxide, methanol, methane, and dimethyl ether in the presence of suitable catalysts (Fuqiang

876 et al., 2017; Roy et al., 2018). Although, there are many high-temperature thermochemical

877 energy conversion processes for energy storage, energy conversion and water splitting reactions

878 (Ali et al., 2020; Cheng et al., 2021; Lorentzou et al., 2014; Wu et al., 2018), the solar-induced

879 thermochemical cyclic method is been emphasized as an outstanding approach for the efficient

880 conversion of CO2 (Table 4). This approach has produced intriguing results from several the

881 experimental tests/designs conducted in different solar reactor models, which has given rise to

882 more intensified research and technology development in this field (Guene Lougou et al., 2020).

883 Many studies have shown that the solar thermochemical CO2‐transformation is a promising

884 solution for solar energy harvesting and storage using materials like Fe‐Ni alloy embedded in a

885 perovskite (Hu et al., 2021), Ca- and Al-doped nSmMnO3 perovskite (Gao et al., 2022), and

886 ZrO2-supported NiFe2O4 (Shuai et al., 2021), to convert CO2 into CO with a 99% conversion rate

887 of 381 mL g−1 min−1 at 850°C, high conversion of 595.56 mmol/g, and 37.89 mL of CO yield in

888 46 min, respectively. Meanwhile, Ni-doped CaCO3 transformed 86.6% of CO2 into syngas along

889 with CH4 in a fixed bed photo-reactor (Teng et al., 2022). The solar thermochemical process

890 follows a two-step dissociation approach wherein the first step is an endothermic process that

891 involves the production of O2 by partially reducing a perovskite or metal oxide (MO) to a non-

892 stoichiometric oxide with the assistance of high-temperature solar heat (Eq. 7). The second step

893 usually occurs at low temperature via an exothermic process. At this stage, the reduced

54
894 perovskite or MO is oxidized with H2O and/or CO2 giving rise to the formation of H2 and/or CO

895 (Eq. 8-9), together with the stoichiometric oxide (Chen et al., 2022; Nair and Abanades, 2018).

896 MO + solar heat → MOred + O2 (7)

897 MOred + CO2 → MOox + CO (8)

898 CO2 + solar heat → CO + ½O2 (9)

899 In the same vein, the photo-thermochemical (PTC) model produces photoinduced oxygen

900 vacancies on the surface of the MO catalyst after exposure to UV-light energy (Eq. 10). Further,

901 the oxygen vacancies are used to reduce CO2 at temperatures below 873 K, thereby producing

902 CO and O2 (Eq. 5) (Xu et al., 2017, 2016).

903 2MxOy → 2MxOy-1 + O2 (Photochemical step) (10)

904 2MxOy-1 + CO2 (g) → MxOy + CO (Thermochemical step) (11)

905 By exploring the Fisher Tropsh (F-T) technology, solar-assisted MOs can also afford carbon-free

906 alternative fuels i.e. production of H2 that can be used directly as a fuel or converted into other

907 value-added chemicals (Figure 17) (G. Takalkar and Bhosale, 2019). Besides, other

908 heterogeneous catalysts that change dynamically during the thermochemical reactions as well as

909 possessing catalytic active sites and definite reaction pathways have been identified for CO2

910 transformation (Feng et al., 2021). For example, the loading of IrOx onto LaFeO3 almost double

911 the maximal CO release rate and increases the maximal O2 evolution rate 0.5 times i.e. a 5-fold

912 CO production (Jiang et al., 2016); meanwhile, the sol-gel synthesized CoxFe3−xO achieved

913 higher CO generation rate via CO2 splitting (Takalkar and Bhosale, 2019).

55
914

915 Figure 17: Solar-assisted thermochemical process for the production of hydrogen and syn gas by

916 the F-T approach. Reproduced from (Takalkar and Bhosale, 2019). Copyright 2019 Elsevier Ltd

917 Table 4: Some investigations on solar-assisted thermochemical transformation of CO2

Fabricated Product(s) Condition Conversion rate References

thermochemical of the

material process

NiFe2O4@SiC CO 1073–1273 K 18.1 %, 410 (Jiang et al., 2022)

μmol/g

Ni-phyllosilicate H2 and CO 100 h of 90.4 %, 120.90 (Shi et al., 2023)

@CeO2 irradiation and 136.84 mmol

56
 gcat min−1

CeO2- H2 and CO 1400 oC 5.1 mL/g (Haeussler et al.,

2020)

Zn/ZnO Syngas 900-2300 K 31.5-52.1% (Loutzenhiser and

Steinfeld, 2011)

Ni-ferrite CO or 1100-1400 oC 0.07 mmol/g (Lorentzou et al.,

2014)
CO/H2

NiFe2O4@Alumina Fuels and 1300 K, 0.5 98.22% (Guene Lougou et

support chemicals atm, and al., 2020)

0.4 m/s

La1-xCaxMnO3 H2 and CO 1000-1400 oC 137.5 μmol/g (Dey et al., 2015)

(1.6-fold

increase)

Ceria pellets H2 1400 oC 2.3 mL.g−1.min−1 (Abanades and

Haeussler, 2021)

Porous ceria CO 2.8−3.8 kW 4.56 ± 0.12 mL (Furler et al., 2012)

and 1400 to g−1

1600 °C

LaCo0.7Zr0.3O3 CO 1000 C to 75% (Wang et al., 2020)

1300 °C, flow

57
 rate of 40 sccm

918

919 3.6 Non-thermal plasma (NTP) catalysis

920 Non-thermal plasma (NTP) catalysis is an auspicious technology that is gaining significance in

921 C1 chemistry. It has been postulated as an effective alternative to conventional thermal catalysis

922 due to the unique interplay between the plasma and heterogeneous catalyst. Thus, this approach

923 could overcome the kinetic limitation of conventional thermal catalysis without the need for any

924 external heat sources (Parastaev et al., 2018). Typically, this process employs an electric

925 discharge of partially ionized gas made up of electrons possessing average electron energy in the

926 range of 1-10 eV (Chen et al., 2020c). These electrons have the capacity to activate stable C1

927 molecules as well as denature their bonding structures in the gaseous phase under moderate

928 conditions, thereby producing atoms, ions, and vibrationally-excited reactive species (Mehta et

929 al., 2019). The NTP catalytic approach has the potential of accelerating many energy-intensive

930 and kinetically and/or thermodynamically limited heterogeneous catalytic reactions such as CO 2

931 hydrogenation (Song et al., 2022), water–gas shift reaction (Xu et al., 2019), hydrocarbon

932 reformation (Wu et al., 2018) and CO2 splitting (Chen et al., 2019), amongst others.

933 In Chen et al. (Chen et al., 2020a) Ni NPs supported on silicalite-1 zeolites with suitable active

934 sites and pore structures were comparably investigated in CO2 hydrogenation under the thermal

935 and NTP conditions. The comparative investigation showed that the hierarchical meso-

936 microporous structures and the associated well-dispersion of Ni species were highly beneficial to

937 the catalysis under the NTP conditions, especially at relatively high voltages. Using a dielectric

938 barrier discharge (DBD) reactor at 150°C, Zeng and Tu (Zeng and Tu, 2017) showed that the

939 presence of Ni in the reactor and injection of argon (up to 60%) in the reaction promotes the

58
940 conversion of CO2 to CO and CH4 (selectively, 85%) and the energy efficiency of the plasma

941 process. In the reactor, Ar decelerates the breakdown voltage of the feed gas and accelerates

942 charge transfer through the reactor. Furthermore, the NTP-activated hydrogenation of CO2 in the

943 presence of Ru/MgAl layered double hydroxide catalysts (having low activation energy)

944 provided ∼84 % of CH4 yield at relatively low temperatures (Xu et al., 2020). In another

945 approach, a MOF-supported Ni catalyst (15Ni/UiO-66) presented 99% selectively towards the

946 conversion of CO2 to CH4 under NTP conditions and the catalyst was still stable after 20h of

947 reaction (H. Chen et al., 2020b). The experimental investigations of Nizio et al. (Nizio et al.,

948 2016) revealed that ceria and zirconia-promoted Ni-containing hydrotalcite-derived catalysts

949 could yield high CH4 under NTP conditions and temperatures < 330 °C.

950 4. Fuels generated from CO2 conversion

951 The discovery and development of efficient technologies for the catalytic transformation of CO2

952 is an exciting area of research (Ramírez-Valencia et al., 2021) as, in parallele of lowering the

953 atmospheric CO2, this would allow the access to essential chemicals and fuels such as formic

954 acid (HCOOH), methanol (CH3OH), carbon monoxide (CO), ethanol (CH3CH2OH) and methane

955 (CH4), among others, that are presently produced from fossil resources. Figure 18 describes the

956 potential products that could be derived from CO2 conversion.

59
957

958 Figure 18: Potential products from CO2 conversion (Ramírez-Valencia et al., 2021).

959

960 4.1 Formic acid

961 Among the myriad of products accessible from CO2, formic acid is a valuable intermediate

962 chemical and also used in the domain of energy for reversible hydrogen storage (Figure 19)

963 (Moret et al., 2014). Formic acid is of great importance in textile industries, pharmaceuticals and

964 food companies dues to its acidic nature and reducing properties (Afshar, 2014). In particular,

965 the leather and tanning industries are one of the largest global consumers of formic acid (Pérez-

966 Fortes et al., 2016). Other critical applications of formic acid include preservatives and

967 antibacterial agents in animal feeds (Anadón et al., 2006). Therefore, formic acid is a highly

968 valued product with little or no alternative.

60
969

970 Figure 19: Reversible hydrogenation of CO2 to formic acid (Li et al., 2002)

971 Several synthetic methods for the conversion of CO2 to formic acid have been explored. This

972 includes biochemical, photochemical, electrochemical, microwave-assisted, photosynthetic and

973 catalytic reduction (Asiri and Lichtfouse, 2020; Hu et al., 2013; Lu et al., 2014; Scibioh and

974 Viswanathan, 2004; Yadav et al., 2012). Catalytic conversion of CO2 to formic acid was first

975 reported by Inoue (Inoue et al., 1976) in 1976. Since then, CO2 has become an attractive starting

976 molecule for the synthesis of formic acid. Compared to other methodologies, the catalytic

977 reduction method offers higher selectivity to targeted product, thus minimizing the risk of

978 unwanted CO as a byproduct that may poison the fuel. However, the selectivity of the preferred

979 product depends on the reduction method and the nature of the catalyst used.

980

981 Weilhard et al. reported the synthesis of formic acid from CO2 feedstock using an ionic liquid as

982 an alternative to expensive precious metal-based catalytic systems (Weilhard et al., 2021). As

61
983 shown in Scheme 3, the synthetic strategy consists of a mixture of CO2 and H2 in 1:1 molar ratio.

984 The catalytic system consists of a homogeneous mixture of 1-butyl-2,3-dimethylimidazolium

985 acetate (BMMI.OAc) and Scandium(III) trifluoromethanesulfonate (Sc(OTf)3. They reported a

986 very high catalytic efficiency with turnover numbers (TON) and turnover frequency (TOF) of 8 x

987 105 and 2.1 x 104 h-1, respectively.

988
Dioxane/water

989 CO2 + H2 → HCOOH (12)

BMMI.OAc/ (Sc(OTf)3

990

991 Moret et al. (Moret et al., 2014) applied a ruthenium-based homogeneous catalytic system to

992 convert CO2 feedstock into formic acid directly. The catalytic conversion was performed

993 following the catalytic life cycle described in Figure 20. The reaction was performed at 40 °C

994 using a mixture of water and dimethyl sulphoxide (DMSO) as the solvent.

995

996 Figure 20: Catalytic cycle and hydrogenation of CO2 into formic acid over [HRu(PTA)4Cl]

997 They reported that the catalytic system is highly sustainable than the existing routes. In addition,

998 it is highly recyclable and gives a higher yield of the target product. More recently, Mubarak et

62
 999 al. (Mubarak et al., 2022) published a greener approach via photocatalytic transformation of CO2

1000 into formic acid. The catalytic procedure involves the breaking down of CO2 into valuable

1001 chemicals in the presence of sunlight and Ag-doped TiO2 NPs. This catalytic system iss highly

1002 selective with HCOOH as the single product, formic acid being obtained at a yield of 193 μM

1003 cm-2 h-1.

1004 4.2 Carbon monoxide

1005 In the series of products derived from CO2, carbon monoxide (CO) is one of the most critical

1006 chemicals and feedstock. It is a primary raw material along with H2 gas for syngas production

1007 via Fischer-Tropsch synthesis to produce liquid fuels (Zeng et al., 2018). It is also valuable for

1008 the metallurgical industries (Liu et al., 2017). Most of the efforts concerning CO2 reduction into

1009 CO efforts can be listed in two major categories, namely thermochemical reduction and

1010 electrochemical reduction (Porosoff et al., 2016). CO2 being a very stable molecule, it requires a

1011 very high temperature (> 1200 °C) to decompose to CO (Equation 13). Therefore, this procedure

1012 is not thermodynamically favorable and must be catalytically driven.

1
1013 CO2(g) → CO(g) + 2O2(g) ∆𝐻 = 279.8 𝑘𝐽/𝑚𝑜𝑙 (13)

1014 Various catalytic materials have been employed to reduce the energy cost of the catalytic

1015 conversion of CO2 to CO. For example, Au nanocatalysts have shown tremendous potential in

1016 converting CO2 to CO with a remarkable selectivity (Qi et al., 2019). Qi et al. (Qi et al., 2021)

1017 reported a successful electrochemical conversion of CO2 to CO over Au nanocatalyst. Wen et al.

1018 (Wen et al., 2018) used a nanoporous Au leave electrocatalyst prepared by a de-alloying

1019 technique to reduce CO2 to CO, achieving a very high catalytic efficiency to CO (90% FE).

1020 While gold-based catalysts are the most successful catalysts for the conversion of CO2 to CO, the

1021 high cost of Au may prevent large-scale industrial applications (Ma et al., 2016b) which requires

63
1022 to find low-cost alternative catalysts. Metallic Ag is gaining considerable attention for CO2

1023 conversion because of its significantly lower cost compared to Au and also high selectivity to

1024 CO (Ma et al., 2016b). This has been demonstrated by Ma et al. (Ma et al., 2016b) who

1025 developed a Ag-based electrocatalyst comprising oxide-derived nanostructure silver (OD-Ag)

1026 and polycrystalline Ag. The proposed reduction mechanism is described in Scheme 3. The

1027 obtained catalytic efficiency was 80% Faradic efficiency which is comparable to the results

1028 obtained with Au electrocatalysts.

1029

1030

1031 Scheme 3: Mechanism of the conversion of CO2 to CO via electrochemical reduction proposed

1032 by (Ma et al., 2016b).

1033 Dong et al. (Dong et al., 2021) reported the use of low-cost ZnOHF nanorods as a substitute to

1034 expensive Au and Ag metals for the reduction of CO2 to CO by electrochemical reduction. They

1035 obtained a CO Faraday efficiency of 76.4% with the CO current density of 57.53mA/Cm 2. It is

1036 worth mentioning that the catalytic efficiency of this Zn-based catalyst is not as high as Au and

1037 Ag-based ones, but the price is significantly lower which may open avenues for a large-scale

1038 electrochemical reduction of CO2 to CO.

1039 4.3 Methanol

64
1040 The conversion of CO2 to MeOH has been drawing tremendous attention lately because of the

1041 vast applications of methanol (Olah, 2013). Methanol is a multipurpose chemical feedstock

1042 (Offermanns et al., 2014) for producing various value-added products and fuel. The current

1043 production rate of methanol is 98 million metric tons per year (Kajaste et al., 2018). It is also an

1044 important hydrogen carrier. The various applications and Carbon cycle of methanol are described

1045 in Figure 21.

1046

1047 Figure 21: Main applications of methanol in industry

1048 Considering the vast application of methanol (Figure 16), conversion of CO2 to MeOH is a

1049 crucial research area. The production of methanol has been dominated by the conversion of

1050 syngas (a mixture of CO and H2) and CO2 (Nieminen et al., 2019). From the mechanistic point of

1051 view, the synthetic pathway may occur through direct CO2 hydrogenation (eq 14) or via reverse

1052 water gas shift (RWGS) (eq 15) followed by CO hydrogenation (eq 16) (Gaikwad et al., 2020).

65
1053 A challenge often characterized by this synthetic procedure is that it is performed at very high

1054 temperature and pressure (Bertau et al., 2014). In addition, it also suffers from poor selectivity

1055 and low yield (Jadhav et al., 2014).

1056 To improve this procedure, various homogeneous and heterogeneous catalytic hydrogenation

1057 reactions as well as thermocatalysis, photocatalysis, electrocatalysis, and enzymatic catalysis

1058 have been explored with promising results (Navarro-Jaén et al., 2021).

1059 CO2 + 3H2 ⇌ CH3OH + H2O → ΔH = -40.9 kJ mol-1 (14)

1060 CO2 + H2 ⇌ CO + H2O → ΔH = +49.8 kJ mol-1 (15)

1061 CO + 2H2 ⇌ CH3OH → ΔH = -90.7 kJ mol-1 (16)

1062 Conventionally, methanol production from syngas is usually catalyzed by a Cu-based

1063 heterogeneous catalyst at 513-533K temperature and 50-100 bar pressure (Bart and Sneeden,

1064 1987). It is worth mentioning that Cu alone exhibits a very low activity; to enhance the activity,

1065 the Cu catalyst is usually tethered on support or promoters such as Al2O3, ZnO, and ZrO2. In

1066 most cases, the synergy between the Cu catalyst and the promoters only achieves a conversion of

1067 approximately 30% due to a fast deactivation of the Cu catalyst (Navarro-Jaén et al., 2021).

1068 Although the activity is low, Cu-based catalysts are very cheap thus justifying their

1069 predominance in methanol synthesis. However, the growing demand for methanol induced

1070 emergence of new ideas for converting CO2 to methanol.

1071 For instance, Pd-based heterogeneous catalytic systems have been used to improve the synthesis

1072 of methanol. Díez-Ramírez et al. (Díez-Ramírez et al., 2016) reported the application of Pd/ZnO

66
1073 catalyst to convert CO2 to methanol under atmospheric conditions, observing a low conversion

1074 rate due to the side reactions from coke formation and water from the (RWGS) reaction (eq 15).

1075 Various attempts have been made to suppress side reactions from the (RWGS) reaction.

1076 Fiordaliso et al. (Fiordaliso et al., 2015) reported the use of supported Pd-Ga bimetallic catalysts,

1077 specifically, GaPd2/SiO2 for converting CO2 to methanol, at low CO2 pressure, and with a MeOH

1078 production rate of 0.12 mol%. Although the catalytic activity of this GaPd2/SiO2 was better than

1079 in previous studies, the major drawback is the Pd cost, thus limiting practical applications.

1080 Ahmad et al. (Ahmad and Upadhyayula, 2019), developed an efficient, cheaper bimetallic

1081 catalyst Ga3Ni5 for CO2 conversion and compared their results with those of Fiordaliso et al.

1082 (Fiordaliso et al., 2015). The activity of the Ga3Ni5 catalyst was found to be higher under the

1083 same experimental conditions, showing a MeOH conversion rate of 38.85 µmol gcat-1 min1

1084 coupled to an impressive selectivity of 94 %.

1085 While Ga, Zn, Cu, Al, Pd, Ni, Pt-based catalysts have been widely tested for MeOH synthesis,

1086 To motivate a cost-effective catalyst, scientists are considering an alternative to Pt and noble

1087 metals. For instance, CeO2-based catalyst is getting attention due to its abundant oxygen and
4+ 3+
1088 reversible valence charges (Ce and Ce ) (F. Wang et al., 2016). This potential was

1089 demonstrated by Chang et al. (Chang et al., 2021), who applied a CeO2-based catalyst Cu/ZnO–

1090 CeO2 to convert CO2 to methanol.

1091 Perovskites have been also identified as low-cost approach for CO2 conversion to methanol. This

1092 is described by Zhan et al. (Zhan et al., 2014), who employed a perovskite-based catalyst to

1093 produce methanol from CO2. They reported an excellent catalytic efficiency with impressive

1094 stability of the prepared catalyst.

67
1095 Apart from heterogeneous-based catalytic systems, homogeneous catalysts have been also

1096 reported for methanol synthesis from CO2. Kothandaraman et al. (Kothandaraman et al., 2016)

1097 developed a Ru-based homogeneous catalytic system that showed a very good yield (79 %) in

1098 methanol. In addition, this catalyst also shows excellent recyclability with over five runs without

1099 a significant loss in activity. Zhou et al. (Zhou et al., 2022) published the use of a ruthenium

1100 pincer complex [RuH2(Me2PCH2SiMe2)2NH(CO)] which led to a good catalytic efficiency from

1101 the density functional theory (DFT) data.

1102 Application of enzymes to reduce CO2 to methanol is also getting considerable attention. Zhang

1103 et al. (Z. Zhang et al., 2021) reported the enzymatic conversion of CO2 to methanol in the

1104 presence of nicotinamide adenine dinucleotide (NADH). The enzyme was immobilized on

1105 porous a MOF (ZIF-8) to improve CO2 concentration. The prepared NADH/ZIF-8 composite

1106 was placed in the bio-electrochemical cell. The methanol conversion rate was 822 μmol g-1 h-1,

1107 and the catalytic system was found stable and environmentally friendly.

1108 4.4 Ethanol

1109 Ethanol is a valuable chemical in our daily life. In contrast to methanol, ethanol has some distinct

1110 advantages, such as higher energy density, lower toxicity, and transportation safety (D. Wang et

1111 al., 2016). As a result of these advantages, it intervenes in a wide range of domestic and

1112 industrial applications, including chemical raw material for chemical synthesis, in disinfectants,

1113 pharmaceuticals and cosmetics, plasticizers, polishes and dyes (An et al., 2021). In addition to its

1114 domestic and industrial applications, ethanol is a necessary fuel and hydrogen carrier (Pang et

1115 al., 2019). The United States are the world largest ethanol producer, accounting for 59% of

1116 global production. This is followed by brazil with 28% while the rest of the world accounts for

1117 13% (Figure 22).

68
1118

1119

1120 Figure 22: Ethanol production in various countries for the year 2020 (Cooper et al., 2021).

1121

1122 The high energy density and the compatibility of ethanol with existing and modern combustion

1123 engines make it a vital fuel. Ethanol is usually produced from the fermentation of starch and

1124 cellulose feedstock (Ali et al., 2022; Wang et al., 2021). With the population and increasing

1125 demand for food, the search for an alternative strategy for ethanol synthesis is highly urgent.

1126 That’s why hydrogenation of CO2 to ethanol has drawn a lot of attention.

1127 Several catalytic systems have been used for CO2 conversion to ethanol, notably Pt, Co, Fe, and

1128 Cu systems (Zheng et al., 2019). Cu-based catalysts have been used for hydrogenating CO2 to

1129 ethanol due to their success in converting CO2 to methanol; however, the selectivity to ethanol is

1130 very low (Cao et al., 2016). Recently, it has been found out that ethanol selectivity can be

1131 improved by using Cu1 instead of Cuo. Despite this success, the Cu-catalyst suffers from long-

1132 term use due to instability under the reaction conditions and operating conditions.

1133 Other catalytic systems have been tested to improve the selectivity and yield of ethanol from

1134 CO2, including Pt-based catalysts and their alloys; while good yield was obtained with these

69
1135 catalysts, the high cost of the catalytic materials is an issue that limits their practical application

1136 (Choi and Liu, 2009). Lou et al. (Y. Lou et al., 2021) successfully applied a Pd/CeO2 catalyst to

1137 convert CO2 to ethanol. They reported a space yield time of 45.6 g ethanol gPd-1 h-1. Together with

1138 an excellent selectivity of 99.2 %. Zhang et al. (F. Zhang et al., 2021) reported the application of

1139 supported sodium-modified Rh NPs in zeolite to hydrogenate CO2 to ethanol that showed a CO2

1140 conversion rate of 10 % and a selectivity of 24% to ethanol. Zheng et al. (Zheng et al., 2019)

1141 reported the conversion of CO2 to ethanol using a LaCo1-xGaxO3 composite perovskite catalyst

1142 with a very good catalytic CO2 conversion of 9.8% and a 88.1% selectivity to ethanol.

1143 Another challenge is catalyst separation from the product and recyclability; therefore, extensive

1144 research efforts are is devoted to develop effective and highly reusable catalysts in order to

1145 address this challenge.

1146 4.5 Methane

1147 Methane (CH4) is a C1 compound primarily used as fuel. Moreover, it is also used as a feedstock

1148 for chemical synthesis, especially as a synthetic natural gas and is also a major source of

1149 hydrogen storage (Koytsoumpa and Karellas, 2018). Therefore, the hydrogenation of CO2 to

1150 methane is an effective strategy for CO2 capture, utilization and conversion to valuable

1151 chemicals. Catalytic hydrogenation is the most widely studied route for CO2 conversion to

1152 methane (Koytsoumpa and Karellas, 2018). This procedure is called methanation or Sabatier

1153 reaction (Lu et al., 2016) as it was first reported in 1902 by Sabatier et al. (Sabatier, 1902).

1154 According to the literature, two possible mechanisms have been proposed. The first mechanism

1155 is direct methanation (eq 17) which involves the reaction of CO2 and H2 with a nominal ratio of

1156 1:4, respectively, while the second mechanism is the reaction of CO and H2 in a ratio of 1:3

1157 respectively (equation 2) (Dias and Perez-Lopez, 2021). As shown in equations 17 and 18, the

70
1158 conversion of CO2 to methane is a highly exothermic reaction which can proceed at a relatively

1159 lower temperature. However, given the thermodynamic stability of CO2 molecules due to the

1160 presence of delocalized  bonds, the conversion of CO2 to methane remains a serious challenge

1161 at a lower temperature (Álvarez et al., 2017).

1162 CO2 + 4H2 ⇌ CH4 + 2H2O ΔH = -165 kJ mol-1 (17)

1163 CO + 3H2 ⇌ CH4 + H2O ΔH = -206 kJ mol-1 (18)

1164 To overcome this challenge and permit activation of CO2 at lower temperatures, highly active

1165 catalytic materials with good selectivity to methane and low deactivation must be developed.

1166 CO2 methanation has been performed with transition metals such as Co, Ni, Fe, Cu, Ru, Rh, and

1167 Pd (Y.-T. Li et al., 2022). However, due to the cost and limited availability, these noble metals

1168 are not widely employed for methane synthesis, especially on an industrial scale. Therefore, a

1169 new generation of low-cost and efficient catalysts have been investigated for methanation

1170 reaction. Among them, Ni, Fe, and Co-based catalysts have been widely studied because of their

1171 low cost and catalytic efficiency for CO2 methanation. Ni-based catalytic materials are the most

1172 studied for CO2 methanation due to their low cost and availability (Fukuhara et al., 2017). Dias

1173 et al. (Dias and Perez-Lopez, 2021) reported the conversion of CO2 to Methanol using Ni/SiO2

1174 catalyst promoted by Fe, Co, and Zn. They obtained a very high CO2 conversion (73 %) and

1175 excellent selectivity (98.5 %) to methane.

1176 It is generally believed that catalytic behavior depends on several factors, such as surface

1177 properties, metal support interaction, etc. Researchers are currently developing further catalytic

1178 supports to enhance the performance of catalytically active metal species. This was recently

1179 demonstrated by Li et al. (Y.-T. Li et al., 2022) who used a metal-organic framework (MOF) as a

1180 support to enhance the catalytic activity of NiFe for the hydrogenation of CO2 to methane. MOFs

71
1181 are highly porous coordination polymers that are characterized by high surface areas. As a result,

1182 they can enhance the catalytic activity in comparison to other traditional supports.

1183 Li et al. (Y.-T. Li et al., 2022) obtained a very high CO2 conversion (72.3 %) and impressive

1184 selectivity (99.3 %) with the NiFe/MOF catalytic material. Similarly, Hu et al. (Hu et al., 2022)

1185 also established the role of metal-support interaction using Ni supported on CeO2 nanofibers.

1186 The oxygen vacancy enhanced the catalytic efficiency of Ni in CeO2. The prepared catalyst

1187 recorded 82.3 % conversion of CO2 at low temperatures (250 oC - 300 oC). In addition, they also

1188 reported impressive stability of the catalyst up to 60h. This result can be attributed to synergistic

1189 effects between the Ni NPs and the CeO2 nanofibers.

1190 4.6 Formaldehyde

1191 The ease of availability of CO2 has provided an opportunity for energy production and

1192 commodity products for the economy. Among other compounds which could be generated from

1193 CO2 is formaldehyde (FMD). Formaldehyde, with the chemical formula HCHO, is a substance

1194 that has gained wide usage by millions of people, directly or indirectly, across the globe due to

1195 its versatility (Rauch et al., 2019; Subasi 2020; Usanmaz et al., 2002). Generally, FMD is

1196 produced industrially via three stages. These include the production of synthesis gas (a mixture

1197 of water gas, carbon(iv) oxide and hydrocarbons) by steam reforming natural gas, synthesis of

1198 MeOH, and the generation of FMD through the partial oxidation of MeOH (Bahmanpour et al.,

1199 2015). All these methods are energy-intensive procedures (Heim et al., 2017; Nguyen et al.,

1200 2020). Moreover, during these processes, CO2 was contained in most of the products formed

1201 (Lervold et al., 2021), leading to increased pollution.

1202

72
1203 In a bid to curb the emission of CO2, scientists have developed methods that could possibly

1204 convert CO2 into useful products. Of these methods is the production of FMD (Friedlingstein

1205 2015; Sümbelli et al., 2019). Although the generation of FMD from CO2 is quite challenging,

1206 frantic efforts are being made to overcome this fall-out as CO2 is resistant to chemical changes

1207 (Rauch et al., 2019). One of those efforts is the conversion of CO2 at ambient temperature

1208 yielding the formation of FMD. The CO2 reacts with triphenylsilane in the presence of a

1209 magnesium catalyst, resulting in an intermediate product formed, known as bis(silyl)acetal. This

1210 product is then converted to FMD in the presence of cesium fluoride (Eq 19) (Rauch et al.,

1211 2019).

eq 19

1212

1213 Another way that allows to convert CO2 into FMD is the hydrogenation process, which different

1214 researchers have debated to be dependent on the catalytic system (heterogeneous or

1215 homogeneous) involved (Dang et al., 2019; Nguyen et al., 2020; Studt et al., 2015). The most

1216 prevalent catalysts used for this reaction are heterogeneous Cu-based, such as Cu-ZnO-Al2O3

1217 (Kobl et al., 2016) or Pt-promoted Cu/SiO2 (Lee et al., 2001). This latter converts CO2 to FMD at

1218 150oC for 120 min at 600 kPa. However, Lee and co-partners indicated some issues encountered

1219 with this catalyst (Lee et al., 2001). Moreso, a mesoporous graphitic carbon nitride (g-C3N4)

1220 material with specific crystallinity and surface area, has been shown to have a significant effect

1221 on the conversion of CO2 to FMD. Since this discovery other photocatalytic mesoporous

1222 nanomaterials have been explored for the photocatalytic reduction of CO2 (Park et al., 2012; Xu

1223 et al., 2013).

73
1224 4.7 Hydrogen

1225 Aside from FMD, a critical commodity product is hydrogen, being also a fuel, that could be

1226 generated from CO2 via a process called carbon dioxide reforming. This process, represented on

1227 equation 20, consumes CO2 and methane (CH4), two greenhouse gases. This process requires

1228 high temperature, and as such, it is highly endothermic and also favored by low pressure (Wang

1229 et al., 1996).

1230 CO2 + CH4 → 2CO + 2H2 ∆𝐻(298) = 247 𝑘𝐽/𝑚𝑜𝑙 eq 20

1231 Fan and coworkers reported this process has been catalyzed over a Ni-Co/MgO-ZrO2

1232 nanomaterial, (Fan et al., 2011). The effect of Ni-based catalysts on the CO2 reforming of

1233 methane had earlier been investigated by Takano et al., (1994). This process produces green

1234 hydrogen a quality of hydrogen which is otherwise generated via the electrolysis of water using a

1235 renewable energy source (Acar and Dincer 2022; Luo et al., 2022). This process could solve the

1236 problem of CO2 emission during hydrogen production from classical techniques (Madadi

1237 Avargani et al., 2022). However, there is a fall-out associated with the production of green

1238 hydrogen via the method mentioned above; it involves the release of carbon(ii)oxide as a by-

1239 product. Although CO has a significant value as a fuel and is crucial in manufacturing other

1240 chemicals, it has been known over the years for its highly hazardous nature (Prockop and

1241 Chichkova 2007; Rose et al., 2017; Wu and Juurlink 2014) and toxicity. Studies should focus

1242 more on the production of hydrogen from CO2, as this process is not well explored. This will go

1243 a long way in tackling the issue of global warming.

1244 4.8 Olefins and gasoline

1245 The hydrogenation of CO2 into high molecular weight hydrocarbons such as lower olefins and

1246 gasoline has become increasingly popular due to the necessity to use non-fossil carbon resources

74
1247 as alternative to fossil oil for a sustainable production of liquid fuels and chemicals (Jiao et al.,

1248 2016; Yang et al., 2017; Zhong et al., 2016). This process requires input energy to form C-H

1249 bonds and to break C=O bonds (Dang et al., 2019) and efficient catalysts.

1250 Processes based on different catalysts and producing unique products distribution have been

1251 developed in the past decades. A commonly used process is Fischer-Tropsch synthesis (FTS) that

1252 yields typically straight-chain hydrocarbons controlled by the Anderson–Schulz–Flory (ASF)

1253 product distribution, which restricts to C2-C4 hydrocarbon fraction of about 56.7% selectivity for

1254 desired lower olefins (C2= - C4=) with 29.2% of undesired CH4 selectivity (Scheme 4). If

1255 selective formation of lower olefins and low CH4 formation can be achieved by proper catalyst

1256 modification and optimization of reaction conditions (Chen et al., 2015; Liu et al., 2015; Lu et

1257 al., 2014; Zhong et al., 2016; Zhou et al., 2015) achieve high selectivity for lower olefins and

1258 high stability, requires to develop new catalysts that operate away from Anderson–Schulz–Flory

1259 (ASF) distribution (Numpilai et al., 2017; Visconti et al., 2017; Zhang et al., 2015).

1260

1261 Scheme 4. Typical Reaction processes related to reduction of Syngas to hydrocarbons through

1262 Fischer-Tropsch synthesis and methanol-to-Olefins Technology. (Adapted without change from

1263 (Cheng et al., 2017)

75
1264 In recent years, significant progress in the development of new catalysts that increase the

1265 selectivity of product formed has been made. For instance bifunctional catalysts such as

1266 oxide/zeolite have been shown to increase selectivity for lower olefins (C2=–C4=) with significant

1267 inhibition of CH4 formation (Jiao et al., 2016; Li et al., 2019; Liu et al., 2017). Bifunctional

1268 catalysts typically consist of oxides and zeolites, which activate CO2 and catalyze C-C coupling,

1269 respectively. In a recent work Gao et al. obtained 80% C2=–C4= selectivity with ~ 4% CH4

1270 inhibition among all hydrocarbons using In-Zr composite based oxides and SAPO-34 zeolites

1271 (Gao et al., 2018; Dang et al., 2018). In addition, CO selectivity over the bifunctional catalysts

1272 could be jacked up to 85 % during CO2 reduction to lower olefins at high temperature reversed

1273 water-gas shift (RWGS).

1274 Moreover, the CO selectivity could be reduced if In2O3 is further modified by Zr and Zn

1275 promoters (Gao et al., 2017). The reduction of CO2 to hydrocarbons over bifunctional catalysts

1276 involves hydrogenation of CO2 to CHxO species or intermediates on the oxygenated sites of the

1277 oxide component as the first step, and the migration of the intermediates to the zeolite

1278 component where they are transformed into various hydrocarbons at the acid sites of the zeolite

1279 (Cheng et al., 2017; Gao et al., 2017). The transport of the CHxO intermediates plays a crucial

1280 role in suppressing the undesired RWGS side reaction and achieving a high selectivity and it can

1281 be improved by acid treatment of the zeolite crystals. The performance of bifunctional catalysts

1282 with and without acid treatment for In2O3-ZnZrOx/SAPO-34 composite is summarized in Table

1283 5. The maximum of C2=–C4= selectivity is 85 % among all hydrocarbons with 1.6 % CH4.

1284 Moreover, the decrease of zeolite crystal size (Dang et al., 2019) and shortening of the diffusion

1285 path of the methanol intermediates should favor the formation of lower olefins over the

1286 composite catalyst (Jiao et al., 2018; Yang et al., 2017).

76
1287 Table 5: Performance of In2O3-ZnZrOx and SAPO-34 as bifunctional catalysts prior to and after

1288 treatment with nitric acid (Dang et al., 2019)

Entr Catalyst type Selectivity CO2 Hydrocarbon distribution

y conversion

(%)

HC CO C 2 =- C2o-C4o C5+ CH4

C4 =

1. In2O3- 17.0 44.2 55.8 85.0 11.1 2.3 1.6

ZnZrOx/SAPO-

34-S-a

2. In2O3- 17.9 45.0 55.0 79.6 13.9 5.2 1.3

ZnZrOx/SAPO-

34-S

3. In2O3- 17.0 46.6 53.4 84.5 11.0 3.3 1.2

ZnZrOx/SAPO-

34-S-H-a

4. In2O3- 17.4 45.9 54.1 79.0 16.5 3.3 1.2

ZnZrOx/SAPO-

34-H

5. In2O3- 17.2 46.2 53.8 80.6 15.2 2.9 1.3

ZnZrOx/SAPO-

77
 34-C-a

6. In2O3- 18.1 47.5 52.5 76.8 19.2 2.7 1.3

ZnZrOx/SAPO-

34-C

1289 5. Conclusions and future outlook

1290 Information gathered from recent literature confirms that continuous efforts are being made to

1291 reduce CO2 in the environment. However, most articles are focused on its conversion to

1292 hydrocarbons, mainly methane, and other organic compounds, such as ethanol, methanol, and

1293 methanoic acid. Only limited articles were published on CO2 reduction to either FMD (mostly as

1294 intermediates) or hydrogen. Thus, more reaction pathways that yield these products should be

1295 investigated. There are some challenges involved in CO2 conversion into useful products, which

1296 should be considered. These include but are not limited to the production of harmful gases like

1297 CO, technological feasibilities in terms of more research as regards more-efficient conversion

1298 techniques, instability and low selectivity of the conversion products, and insufficient basic

1299 understanding of the catalytic processes (Sharma et al., 2022). Having pointed out these fall-outs,

1300 it is worth mentioning that scientists and other stakeholders should consider the project of CO2

1301 conversion as germane because it technically solves the problem of global warming and, in turn,

1302 impacts the economy of the worldwide system.

1303 The use of nanomaterials-based technologies for the transformation of CO2 is a relatively new

1304 area that scientists have to continue to explore. Unarguably, the demonstrated suitability,

1305 selectivity and applicability of nanomaterials for producing hydrocarbons and valued-added

1306 chemicals (methanol, ethanol, formic acid, formaldehyde, etc) have made nanomaterials

78
1307 promising systems for the transformation of CO2 into various fuels. The research findings so far

1308 are quite intriguing at the laboratory scale. However, the extension of these findings to industrial

1309 scale would be highly phenomenal. It is therefore recommended and/or suggested industrially

1310 suitable, and applicable catalyst (nanomaterials) be developed to selectively and efficiently

1311 transformed atmospheric CO2 to value-added products.

1312

1313

1314

1315

1316

1317 Funding

1318 This research exercise received no external funding

1319 Acknowledgements

1320 Alli, Y.A. would like to seize this opportunity to appreciate CNRS-Laboratory of Coordination

1321 Chemistry and Prof. Karine Philippot for providing him with laboratory space and enabling

1322 environment for postdoctoral research activities. Also, Oladoye, P.O. would like to appreciate

1323 Prof. Yong Cai for providing him with laboratory space and enabling environment for his

1324 doctoral research activities.

1325

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