Available online at www.sciencedirect.

com Current Opinion in

ScienceDirect Green and Sustainable Chemistry

Green hydrogen production by water electrolysis:

Current status and challenges
Bahman Amini Horri1 and Hasan Ozcan1,2

Abstract 2050. While renewables’ share of electricity generation

The scientific and industrial communities worldwide have is increasing globally, the power supply sector still needs
recently achieved impressive technical advances in developing on-demand access to green hydrogen and other reliable
innovative electrocatalysts and electrolysers for water and and clean fuels to balance the grid. Produced from sus-
seawater splitting. The viability of water electrolysis for com- tainable resources (water and renewables), it can also
mercial applications, however, remains elusive, and the key contribute to decarbonising part of the industrial and
barriers are durability, cost, performance, materials, transportation sectors.
manufacturing, and system simplicity, especially with regard to
running on practical water sources like seawater. This article, Green hydrogen can be produced by a variety of tech-
therefore, primarily aims to provide a concise overview of the nologies, including water electrolysis, microbial elec-
most recent disruptive water-splitting technologies and mate- trolysis, photoelectrochemical and photocatalytic water
rials that could reshape the future of green hydrogen production. splitting, solar thermochemical water splitting, direct
Starting from water electrolysis fundamentals, the recent ad- water thermolysis, and arguably some biomass gasifica-
vances in developing durable and efficient electrocatalysts for tion, pyrolysis, and reforming processes [1e5]. Among
modern types of electrolysers, such as decoupled electrolysers, these, electrocatalytic water splitting, driven by
seawater electrolysers, and unconventional hybrid electrolysers, renewable power, is one of the most promising tech-
have been represented and precisely annotated in this report. nologies for sustainable hydrogen production with a
Outlining the most recent advances in water and seawater minimal carbon footprint, which can be implemented
splitting, the article can help as a quick guide in identifying the with various types of electrolysers, mainly including
gap in knowledge for modern water electrolysers while pointing alkaline, proton-exchange membrane (PEM), solid
out recent solutions for cost-effective and efficient hydrogen oxide, and anion-exchange membrane (AEM) electro-
production to meet zero-carbon targets in the short to near term. lysers [6e10]. Table 1 represents a summary of the
rough characteristics of these electrolysers. Among all,
alkaline electrolysers are the most mature with relatively
Addresses
1
School of Chemistry and Chemical Engineering, University of Surrey, low efficiency; therefore, other technologies are being
Guildford, GU2 7XH, UK developed to replace alkaline technology. PEM and
2
Faculty of Engineering and Natural Sciences, Ankara Yıldırım Beyazit AEM are more efficient and compact than alkaline
University, Ankara, 06010, Turkiye electrolysis, while they require expensive materials,
Corresponding author: Horri, Bahman Amini ([email protected].
resulting in higher capital expenses. SOEC is the most
uk) efficient technology, but the major issue is that it han-
dles high-temperature operations and is the most
Current Opinion in Green and Sustainable Chemistry 2024, expensive.
47:100932
This review comes from a themed issue on Chemistry for Climate In conventional water electrolysis, hydrogen and oxygen
(2024) are simultaneously produced in an integrated single-cell
Edited by Borhane Mahjoub comprised of two electrodes (cathode and anode)
Available online 3 May 2024 separated by a membrane in the middle (Figure 1a).
For complete overview of the section, please refer the article
Water electrolysis in these electrolysers is usually
collection - Chemistry for Climate (2024) performed in an alkaline or acidic environment to
https://doi.org/10.1016/j.cogsc.2024.100932
enhance the cell’s charge transfer properties. The
cathodic hydrogen evolution reaction (HER) and the
2452-2236/© 2024 The Author(s). Published by Elsevier B.V. This is an
open access article under the CC BY license (http://creativecommons.
anodic oxygen evolution reaction (OER) involved in the
org/licenses/by/4.0/). alkaline and acidic electrolyte environments are well-
known and can be found elsewhere [11].
Keywords
Green hydrogen production, Water electrolysis, Decoupled water split-
Precious-metal-based electrocatalysts containing plat-
ting, Seawater electrolysis, Hybrid electrolysers. inum, palladium, iridium, ruthenium, etc., are currently
the most common electrode materials for developing
Introduction highly efficient and (arguably) durable water-electrolysis
Green hydrogen is recognised as one of the key energy cells. However, using these materials is not commercially
vectors to achieve the ‘Net Zero Emissions’ targets by

www.sciencedirect.com Current Opinion in Green and Sustainable Chemistry 2024, 47:100932

2 Chemistry for Climate (2024)

Table 1

Rough characteristics of the conventional water electrolysis techniques (modified from IRENA [27]).

Technology readiness level Mature/commercialised R&D

(TRL)

Electrolysis technology Alkaline electrolysis Proton exchange Solid oxide Anion exchange
(AE) membrane (PEM) membrane (SOM) membrane (AEM)
electrolysis electrolysis electrolysis

Schematic diagram and

operating principle

Operating temperature,  C 70–90 50–80 600–1000 40–60

Operating pressure, bar ~Atmospheric <40 <5 <35
Nominal voltage, V 1.8–2.4 1.8–2.2 0.80–1.6 1.4–2.0
Nominal current density, A/ 0.2–0.5 0.6–3.0 0.1–3.9 0.2–2.0
cm2
Type of Electrolyte/ KOH solution Generic PEMs Yttria-Stabilised Generic AEMs (DVB
membrane (25–30 wt.%) (PFSA) zirconia (YSZ) or polymers)
gadolinium-doped
ceria (GDC)
Commercial separator Zirfon™, Nafion™ YSZ/GDC Pellets Fumatech™
polysulfone, and
polyphenylene
sulphide polymers
Common types of cathode/ Nickel-coated Iridium/platinum Nickel-YSZ/LSM Nickel foam or
anode electrocatalysts perforated stainless (lanthanum strontium carbon cloth
steel manganite)-YSZ
Cell nominal efficiency 50–80 50–83 80–100 52–67
(HHV), %
Specific energy 5.0–5.9 5.0–6.5 3.7–3.9 Unknown
consumption, kWh/Nm3
Hydrogen purity, % 99.5–99.9998 99.9–99.9999 99.9 99.9–99.9999
Stack lifetime, h <90,000 <20,000 <20,000 <5000
Stack cost, USD/kW) 270 400 >2000 Unknown

viable due to their high cost and scarcity [12e14]. Given these concerns, the scientific and manufacturing
Moreover, as an environmentally friendly approach, con- communities have devoted a remarkable effort to
ventional water electrolysis seems relatively simple to developing highly active, durable, and stable electro-
implement at low-to medium-scale production capac- catalysts based on the abundantly available non-precious
ities; however, it has yet to reach efficiency standards, metals and carbon-based electrocatalysts in the past few
secure freshwater accessibility, and economised renew- years. In addition, as seawater is abundantly available on
able supply that would satisfy the desirable levelised cost our planet, many research studies in water splitting have
of hydrogen production at the industrial scale. For redirected to membrane-less and decoupled electrolysis
instance, the required energy consumption of water cells to handle electrocatalytic seawater splitting. Hence,
splitting is 39.4 kWh per kg of hydrogen generated and this article aims to concisely highlight the most recent
for a USD 50 MWh per kWh electrical energy cost, the advances in the past couple of years in developing inno-
contribution of electrical energy cost to the levelised cost vative electrocatalysts and contemporary electrolysis cell
of hydrogen will be USD 1.97/kg alone, which is not designs capable of efficiently splitting water and
competitive with conventional techniques [15e17]. seawater.

Current Opinion in Green and Sustainable Chemistry 2024, 47:100932 www.sciencedirect.com

 Green hydrogen technology: current state & future Amini Horri and Ozcan 3

Figure 1

Basic operating principle for conventional and unconventional water electrolysis approaches: (a) conventional membraned water electrolysis based on
porous electrocatalysts, (b) simplified decoupled two-step water electrolysis based on a stagnant soluble redox mediator, (c) simplified membraneless
water electrolysis based on nickel electrocatalyst coated on a stainless-steel mesh, (d) schematic hybrid water electrolysis for electrooxidation
(upgrading) of biomass resourced anions.

Innovative water-splitting technologies density of 10 mA/cm2 with a HER overpotential of 71 mV,

Electrocatalysts for water-splitting which is close to that of platinum-based electrocatalyst
Nevertheless, the high cost, scarcity, and lack of dura- (54 mV). Zhu et al. [23] have synthesised a fast-charge
bility of precious metals can considerably hinder their transfer Co5.47N/MoN-based heterostructure nano-
practical implementation in the water electrolysis in- sheets on nickel foam that showed a low overpotential of
dustry [18e21]. In the past few years, numerous non- 82 and 288 mV for HER and OER at a current density of
precious metals and carbon-based electrocatalysts 10 mA cm 2, respectively. The progress of non-precious
(including transition-metal borides, carbides, phos- transition metal-based 2D layered materials, including
phides, sulphides, borides, oxides, single-atom catalysts, exfoliation synthesis methods for dichalcogenides,
and doped carbon catalysts) have been reported to double hydroxides, and graphitic carbon nitride, has been
improve the water splitting efficiency in various types of recently reviewed [24e26]. The current modifications
electrolysis technologies industry. mainly focus on the electrodes’ structural and spatial
properties through the compositional and surface engi-
In this regard, Lin et al. [22] have recently reported the neering approaches to improve the thermodynamic effi-
preparation of FeNi2P 3D-oriented nanosheet electro- ciency of water electrolysis, which is primarily hindered
catalyst on carbon cloth and tested its performance in an by the intrinsically sluggish kinetics of both HER and
alkaline solution (KOH, 1 M), which resulted in a current OER reactions.

www.sciencedirect.com Current Opinion in Green and Sustainable Chemistry 2024, 47:100932

4 Chemistry for Climate (2024)

Decoupled water-splitting and membraneless assembly was proposed by Wang et al. [36] and tested as a
electrolysis approaches microbial cell. However, this cell showed a comparably
The spatial design of conventional electrolysis funda- low current density of 4.95 mA/cm2 and a hydrogen
mentally introduces a few operational challenges, production rate of w34 L/L/D. Combining decoupled
including membrane degradation, the inevitable gas and water splitting and membrane-less electrolysis, Vanags
electrolyte crossover through the thin membrane layer, et al. [37] proposed a hybrid amphoteric electrolysis
product purification, and potential safety risks. Redox using auxiliary electrodes of HxWO3 and NiOOH in
mediator-assisted electrolysis (decoupled water- spatially separated acid and alkaline cells, respectively.
splitting, Figure 1b) and membraneless electrolysis The average efficiency of the proposed membraneless
(Figure 1c) are a couple of revolutionary spatial re- decoupled amphoteric electrolysis was w71%, higher
designs that have received extensive consideration in than that observed from a typical decoupled electrolysis.
the past few years. The levelised cost of hydrogen production in
membraneless electrolysis can be as low as w2 USD/kg
Since 2013, when Symes and Cronin [28] introduced when integrated with renewables at scale [38]. The
the disruptive concept of decoupled water splitting, membraneless electrolysis operates based on the fluid-
several soluble and solid redox mediators have been dynamic forces to separate hydrogen and oxygen gases
proposed for various operation schemes. Ma et al. [29] and, therefore, can comparably offer more scalability,
have recently reviewed the current status and chal- lower cost, and versatility operation, particularly for
lenges of solid-state redox mediators in decoupled water seawater electrolysis, which will be briefly reviewed
electrolysis. Inspired by rechargeable batteries, nickel below.
hydroxide (Ni(OH)2) is the most common inorganic
solid redox mediator to separate the hydrogen and Seawater electrolysis
oxygen generation in alkaline water electrolysis. In Seawater represents about 97% of our planet’s total
terms of organic redox mediators, Wu et al. [30] have water, implying a desirable, secure, and sustainable
reported a notable work by synthesising a phenazine- source of hydrogen production and an alternative to
based compound and tested its performance for the highly purified freshwater. However, it cannot be
acidic two-step decoupled electrolysis cell, which directly supplied to the conventional membraned elec-
showed a rate performance of 186 mAh/g at the current trolysis cells due to its accompanying natural organic and
density of 30 A/g in 3000 cycles. The thermo- inorganic species, particularly chloride ions, which can
electrochemical redox-mediated decoupling system is interfere with hydrogen and oxygen evolution reactions.
another exciting idea proposed by Wei et al. [31]. In this Given the flexibility offered by the membraneless
work, a temperature-dependent mediator (based on iron electrolysis cell, i.e., their operation with a single elec-
cyanide anions) was used to convert low-grade heat into trolyte solution, they can be potentially applied for
thermopower to improve hydrogen production in a direct seawater splitting using stable electrodes with
decoupled electrolysis cell, which resulted in gaining high selectivity towards HER and OER.
1.9 mV/K toward water splitting. Integrating the
photovoltaic and decoupled water electrolysis cells is One pathway to retard chlorine evolution is to convert it
another approach recently studied to improve the solar- efficiently into soluble hypochlorous acid (HClO) using
to-hydrogen (STH) conversion efficiency, with the a selective chloride oxidation reaction (ClOR) electro-
highest efficiency reported to be 24.4% while this can catalyst at the anode surface. In this regard, Liang et al.
reach up to 30% [32,33]. [39] proposed using a ternary titanium-based electro-
catalyst (Pt0.06Ru0.24Ti0.7Ox) to drive the ClOR and
Membraneless microfluidic electrolysis is another simultaneously retarding ORR. They applied this elec-
emerging topic in green hydrogen production that has trocatalyst in a membraneless cell containing seawater at
attracted considerable interest in the past few years. pH 8.2, which showed a Faradaic efficiency of w100% at
Swiegers et al. [34] have reported a concise track record the current density of 800 mA/cm2 over 500 h operation
of this technology since patenting in the early 1990s. time. Another inspiring approach has been recently
Manzotti et al. [12] recently reviewed the characteristics proposed by Gu et al. [40], which is based on intro-
of membrane-less electrolysis and compared various ducing a “hard Lewis acid” film on the catalyst surface to
spatial architectures. Regarding spatial architectures, assist localising the water-splitting reaction by capturing
Samir De et al. [35] have reported an integrated cell the hydroxyl anions (OH ) forming around the catalyst.
design consisting of three parallel microchannels sepa- They applied this method for chromium (III) oxide
rated by porous electrodes. Their microfluidic cell (Cr2O3)-based electrocatalysts, which resulted in
showed a current density of 747 mA/cm2 at 2.5 V with achieving 500 mA/cm2 at 1.87 V and 60  C for 100 h;
99.35% faradaic efficiency. Another stimulating architec- however, they claimed that the method could be a
ture design with an integrated compact electrode generic strategy for various types of catalysts without

Current Opinion in Green and Sustainable Chemistry 2024, 47:100932 www.sciencedirect.com

 Green hydrogen technology: current state & future Amini Horri and Ozcan 5

further tailoring the catalysts and electrolysis cell ar- production rate of w2525 L/h.m2 with an average Faradic
chitecture. Lyu and Serov have briefly reviewed the efficiency (FEH2) of 98.93%. In another notable work,
“cutting-edge methods” for enhancing the OER selec- Wang et al. [56] applied ultra-thin CoNi0.2P nanosheets
tivity in direct seawater electrolysis [41]. The emerging on nickel foam as an electrocatalyst to assist simultaneous
materials, cell architecture, and advances of direct HER and biomass oxidation reactions which showed a
seawater splitting have also been well-reviewed in a few lower integral potential (1.24 V) at the current density of
reports [42e45]. Despite the potential benefits of 50 mA/cm2 compared to the traditional cells (1.53 V).
direct seawater electrolysis, several concerns, including
electrode corrosion, precise mechanisms of reactions, Conclusion and outlook
and the impact of impurities, should yet be addressed; Driven by renewables, hydrogen production by water
these can be found elsewhere [40]. electrolysis will be crucial to decarbonising our envi-
ronment and transitioning to a net-zero emission
Hybrid and unconventional water splitting economy. Emerging electrocatalysts, innovative elec-
Electrolytic water splitting purely driven by renewable trolysis approaches, and modern electrolysers’ archi-
electric power is one of the most promising approaches tecture designs created a significant driving force again
to producing green hydrogen; however, the efficiency of towards direct seawater electrolysis, particularly based
the process is predominantly restricted by the thermo- on membraneless and decoupled water electrolysis;
dynamically unfavoured reactions at the surface of however, to introduce these technologies to the
electrodes. Moreover, the traditional improvement market, the research community still need to address
strategies, such as architectural and spatial design ap- the challenges associated with electrodes’ degrada-
proaches, compositional and structural improvements, tions, potential safety issues of the inevitable O2/H2
electrocatalysts’ functional layers, and other engineering crossover, and certainly establishing accurate and
modifications, have their own limits in enhancing the standardised protocols for screening long-term reli-
overall efficiency of the electrolytic water splitting ability of these electrolysis technologies. Another
method. This gap, however, can be addressed by challenge of membraneless electrolysis cells to address
developing efficient hybrid water-splitting systems is their comparably lower voltage efficiency at high
(Figure 1d) and unconventional electrolysis strategies. operating current densities, mainly due to the large gap
Such technologies are addressed here to present effi- required between two electrodes, which is usually
cient alternatives to conventional water splitting using much thicker than that of PEM and AEM membranes.
novel ideas that can produce cost-effective and The progress in direct seawater electrolysis technology
competitive hydrogen. could have been accelerated by developing highly
active and stable non-precious electrocatalysts oper-
Recently, the traditional water electrolysis domain has ating at a near-neutral pH condition (pH of w8.0) to
experienced numerous revolutionary ideas to tackle its retard chlorine evolution reaction. Overall, unconven-
deficiencies by implementing a variety of approaches, tional and hybrid water-splitting technologies have the
such as incorporating a thermodynamically favoured potential for highly efficient and cost-effective
organic or biomass oxidation step rather than the elec- hydrogen production yet require further research and
trolytic sluggish OER, replacing the HER with a water development. Materials availability, technology readi-
reduction step using reducible metal particles, or ness, and funding opportunities are low in the short
coupling the electrolysis with a free source of excess heat term. However, its potential will attract more attention
(nuclear heat), etc. The unconventional enhancement in the near term when the global hydrogen ecosystem is
approaches for solar-driven water-splitting technology well established.
based on plasmonic, thermoelectric, and magnetic effects
have been recently reviewed [46]. Based on the review, Declaration of competing interest
the H2 generation rate can be significantly increased with The authors declare that they have no known competing
the plasmonic effect, as an example, yet further explo- financial interests or personal relationships that could
rations on pH-dependent mechanisms are needed. The have appeared to influence the work reported in this
potential benefits of hybrid electrolysis compared to article.
conventional methods have attracted remarkable
consideration by the scientific and manufacturing com-
munities in the past few years [20,47e53]. In particular, Data availability
Horri and Gu [54] have recently reported a novel No data was used for the research described in the
thermochemical-electrochemical looping approach for article.
water splitting that can deliver hydrogen production with
90% efficiency. In this regard, Yi et al. [55] have recently Acknowledgements
reported a hybrid acidealkali electrolysis cell based on We are grateful for financial support from the University
Co2P nanocatalysts that showed a maximum hydrogen of Surrey.

www.sciencedirect.com Current Opinion in Green and Sustainable Chemistry 2024, 47:100932

6 Chemistry for Climate (2024)

References 18. Wang M, Ma W, Tan C, Qiu Z, Hu L, Lv X, Li Q, Dang J:

Papers of particular interest, published within the period of review, Designing efficient non-precious metal electrocatalysts for
have been highlighted as: high-performance hydrogen production: a comprehensive
evaluation strategy. Small 2023, 2306631.
* of special interest 19. Yu H, Wu L, Ni B, Chen T: Research progress on porous
* * of outstanding interest carbon-based non-precious metal electrocatalysts. Materials
2023, 16:3283.
1. Fallah Vostakola M, Salamatinia B, Amini Horri B: A review on
20. Deng C, Toe CY, Li X, Tan J, Yang H, Hu Q, He C: Earth-
recent progress in the integrated green hydrogen production
abundant metal-based electrocatalysts promoted anodic re-
processes. Energies 2022, 15.
action in hybrid water electrolysis for efficient hydrogen
2. Chatenet M, Pollet BG, Dekel DR, Dionigi F, Deseure J, Millet P, production: recent progress and perspectives. Adv Energy
Braatz RD, Bazant MZ, Eikerling M, Staffell I: Water electrolysis: Mater 2022, 12, 2201047.
from textbook knowledge to the latest scientific strategies and
21. Lv X-W, Tian W-W, Yuan Z-Y: Recent advances in high-
industrial developments. Chem Soc Rev 2022, 51:4583–4762.
efficiency electrocatalytic water splitting systems. Electro-
3. Olabi AG, Abdelkareem MA, Mahmoud MS, Elsaid K, chem Energy Rev 2023, 6:23.
Obaideen K, Rezk H, Wilberforce T, Eisa T, Chae K-J, Sayed ET:
22. Lin S, Yu Y, Sun D, Meng F, Chu W, Huang L, Ren J, Su Q, Ma S,
Green hydrogen: pathways, roadmap, and role in achieving
* Xu B: FeNi2P three-dimensional oriented nanosheet array
sustainable development goals. Process Saf Environ Protect
bifunctional catalysts with better full water splitting perfor-
2023, 177:664–687.
mance than the full noble metal catalysts. J Colloid Interface
4. Ozcan H, El-Emam RS, Horri BA: Thermochemical looping Sci 2022, 608:2192–2202.
technologies for clean hydrogen production–Current status Using a one-step phosphating synthesis method, the authors reported
and recent advances. J Clean Prod 2023, 382, 135295. a unique self-supported 3D nickel-based electrocatalyst showed an
OER overpotential of 210 mV, which is ~30% less than that of the
5. Zainal BS, Ker PJ, Mohamed H, Ong HC, Fattah IMR, precious-metal electrocatalyst based on Ruthenium (RuO2).
Rahman SMA, Nghiem LD, Mahlia TMI: Recent advancement
and assessment of green hydrogen production technologies. 23. Zhu J, Du Q, Arif Khan M, Zhao H, Fang J, Ye D, Zhang J: 2D
Renew Sustain Energy Rev 2024, 189, 113941. * porous Co-Mo nitride heterostructures nanosheets for highly
effective electrochemical water splitting. Appl Surf Sci 2023,
6. Shiva Kumar S, Lim H: An overview of water electrolysis 623, 156989.
technologies for green hydrogen production. Energy Rep The authors reported heterogeneous nanosheets of nitrogenated Co-
2022, 8:13793–13813. Mo electrocatalyst showed a comparably lower overall electrical po-
tential for water electrolysis (1.69 V to at a current density of 50 mA/
7. Niblett D, Delpisheh M, Ramakrishnan S, Mamlouk M: Review of cm2)
next generation hydrogen production from offshore wind
using water electrolysis. J Power Sources 2024, 592, 233904. 24. Lakshmi KS, Vedhanarayanan B, Lin T-W: Electrocatalytic
hydrogen and oxygen evolution reactions: role of two-
8. Shih AJ, Monteiro MC, Dattila F, Pavesi D, Philips M, da Silva AH, dimensional layered materials and their composites. Electro-
Vos RE, Ojha K, Park S, van der Heijden O: Water electrolysis. chim Acta 2023, 447, 142119.
Nat Rev Methods Prim 2022, 2:84.
25. Kou Z, Wang K, Liu Z, Zeng L, Li Z, Yang B, Lei L, Yuan C, Hou Y:
9. Nagappan S, Karmakar A, Madhu R, Dhandapani HN, Roy SS, Recent advances in manifold exfoliated synthesis of two-
Kundu S: Tuning the active sites and optimizing the d-spacing dimensional non-precious metal-based nanosheet electro-
value in CoFe-LDH by ex situ intercalation of guest anions: an catalysts for water splitting. Small Struct 2022, 3, 2100153.
innovative electrocatalyst for overall water splitting reaction.
Catal Sci Technol 2023, 13:6377–6391. 26. Li C, Bao Y, Liu E, Zhao B, Sun T: Recent advances of modified
Ni (Co, Fe)-Based LDH 2D materials for water splitting. Mol-
10. Singha Roy S, Karmakar A, Madhu R, Nagappan S, N ecules 2023, 28:1475.
Dhandapani H, Kundu S: Three-dimensional Sm-doped
NiCu-LDH on Ni foam as a highly robust bifunctional elec- 27. Irena I: Green hydrogen cost reduction: scaling up electrolysers to
trocatalyst for total water splitting. ACS Appl Energy Mater meet the 1.5 C climate goal. Abu Dhabi: International Renewable
2023, 6:8818–8829. Energy Agency; 2020.
11. Lide DR. CRC handbook of chemistry and physics, vol. 85. CRC 28. Symes MD, Cronin L: Decoupling hydrogen and oxygen evo-
Press; 2004. lution during electrolytic water splitting using an electron-
coupled-proton buffer. Nat Chem 2013, 5:403–409.
12. Manzotti A, Robson MJ, Ciucci F: Recent developments in
membraneless electrolysis. Curr Opin Green Sustain Chem 29. Ma Y, Wu K, Long T, Yang J: Solid-state redox mediators for
2023, 40, 100765. decoupled H2 production: principle and challenges. Adv
Energy Mater 2023, 13, 2203455.
13. Sutra P, Igau A: Emerging earth-abundant (Fe, Co, Ni, Cu)
molecular complexes for solar fuel catalysis. Curr Opin Green 30. Wu K, Li H, Liang S, Ma Y, Yang J: Phenazine-based com-
Sustain Chem 2018, 10:60–67. * pound realizing separate hydrogen and oxygen production in
electrolytic water splitting. Angew Chem 2023, e202303563.
14. Kim HJ, Kim HY, Joo J, Joo SH, Lim JS, Lee J, Huang H, Shao M, The authors reported a novel phenazine-based solid-state redox
Hu J, Kim JY: Recent advances in non-precious group metal- mediator for acidic decoupled water splitting that showed a high spe-
based catalysts for water electrolysis and beyond. J Mater cific capacity (290 mAh/g) and comparably a long cycle life (3000
Chem A 2022, 10:50–88. cycles).
15. Vanags M, Iesalnieks M, Je 
 kabsons L, Zukuls A, Sutka A: Two- 31. Yang W, Qiu Y, Bao J, Luo C, Zhao Q: Thermo-electrochemical
step decoupled electrolysis approach based on pseudoca- redox-mediated decoupling of water splitting for improving
pacitive WO3 auxiliary electrode. Int J Hydrog Energy 2023, 48: H2 production. Ind Eng Chem Res 2023.
20551–20561.
32. Wu T, Hu Y, Li M, Han B, Liang Z, Geng D: Enabling efficient
16. Terlouw T, Bauer C, McKenna R, Mazzotti M: Large-scale decoupled alkaline water electrolysis using a low-cost
hydrogen production via water electrolysis: a techno- sodium manganate solid-state redox mediator. Int J Hydrog
economic and environmental assessment. Energy Environ Sci Energy 2023.
2022, 15:3583–3602.
33. Lv F, Qin Z, Wu J, Pan L, Liu L, Chen Y, Zhao Y: Decoupled
17. Lange H, Klose A, Lippmann W, Urbas L: Technical evaluation * water electrolysis driven by 1 cm2 single perovskite solar cell
of the flexibility of water electrolysis systems to increase yielding a solar-to-hydrogen efficiency of 14.4%. Chem-
energy flexibility: a review. Int J Hydrog Energy 2023, 48: SusChem 2023, 16, e202201689.
15771–15783.

Current Opinion in Green and Sustainable Chemistry 2024, 47:100932 www.sciencedirect.com

 Green hydrogen technology: current state & future Amini Horri and Ozcan 7

The authors reported an efficient photovoltaic cell integrated with a 44. Gao F-Y, Yu P-C, Gao M-R: Seawater electrolysis technolo-
decoupled water electrolyser based on the Prussian blue analogue gies for green hydrogen production: challenges and oppor-
(PBA) sodium nickel-hexacyano-ferrate (NaNiHCF) electrocatalyst, tunities. Curr Opin Chem Eng 2022, 36, 100827.
which showed comparably lower activation energy with reaching a
solar-to-hydrogen efficiency of 14.4%. 45. Hausmann JN, Schlögl R, Menezes PW, Driess M: Is direct
seawater splitting economically meaningful? Energy Environ
34. Swiegers GF, Hoang AL, Hodges A, Tsekouras G, Lee C-Y, Sci 2021, 14:3679–3685.
Wagner K, Wallace G: Current status of membraneless
water electrolysis cells. Curr Opin Electrochem 2022, 32, 46. Wang K, Huang D, Li X, Feng K, Shao M, Yi J, He W, Qiao L:
100881. Unconventional strategies to break through the efficiency of
light-driven water splitting: a review. Electron 2023, 1:e4.
35. Samir De B, Singh A, Ji Dixit R, Khare N, Elias A, Basu S:
Hydrogen generation in additively manufactured membrane- 47. Behera S, Ganguly S, Loha C, Mondal B, Ghosh S: Critical role
less microfluidic electrolysis cell: performance evaluation of interface design in acceleration of overall water splitting
and accelerated stress testing. Chem Eng J 2023, 452, 139433. and hybrid electrolysis process: state of the art and per-
spectives. Energy Fuels 2023.
36. Wang L, Linowski K, Liu H: Scalable membrane-less microbial
electrolysis cell with multiple compact electrode assemblies 48. Li D, Tu J, Lu Y, Zhang B: Recent advances in hybrid water
for high performance hydrogen production. Chem Eng J 2023, electrolysis for energy-saving hydrogen production. Green
454, 140257. Chem Eng 2023, 4:17–29.

37. Vanags M, Kulikovskis G, Kostjukovs J, Jekabsons L, 49. Yao D, Zhang Y, Zhang S, Wan J, Yu H, Jin H: Hybrid water

* * Sarakovskis A, Smits K, Bikse L, Sutka A: Membrane-less electrolysis with integrated and cascading reactions by two-
amphoteric decoupled water electrolysis using WO3 and Ni dimensional electrocatalysts. J Mater Chem A 2023.
(OH)2 auxiliary electrodes. Energy Environ Sci 2022, 15:
50. Veeramani K, Janani G, Kim J, Surendran S, Lim J, Jesudass SC,
2021–2028.
Mahadik S, Kim T-H, Kim JK, Sim U: Hydrogen and value-added
The authors demonstrate a membraneless decoupled amphoteric
products yield from hybrid water electrolysis: a critical
electrolyser where, for the first time, both alkaline and acid half-cells
review on recent developments. Renew Sustain Energy Rev
were integrated into operation using spatially separated WO3 and
2023, 177, 113227.
Ni(OH)2 auxiliary electrodes.
51. Zhao H, Yuan ZY: Progress and perspectives for solar-driven
38. Manzotti A, Quattrocchi E, Curcio A, Kwok SCT, Santarelli M,
water electrolysis to produce green hydrogen. Adv Energy
Ciucci F: Membraneless electrolyzers for the production of
Mater 2023, 13, 2300254.
low-cost, high-purity green hydrogen: a techno-economic
analysis. Energy Convers Manag 2022, 254, 115156. 52. Li W, Tian H, Ma L, Wang Y, Liu X, Gao X: Low-temperature
water electrolysis: fundamentals, progress, and new strate-
39. Liang N-N, Han DS, Park H: Membraneless unbuffered
* gies. Mater Adv 2022, 3:5598–5644.
seawater electrolysis for pure hydrogen production using
PtRuTiOx anode and MnOx cathode pairs. Appl Catal B Envi- 53. Wang HY, Sun ML, Ren JT, Yuan ZY: Circumventing chal-
ron 2023, 324, 122275. lenges: design of anodic electrocatalysts for hybrid water
The authors prepared a direct seawater electrolysis cell with a electrolysis systems. Adv Energy Mater 2023, 13, 2203568.
platinum-based chloride oxidative anode and a MnOx chloride reduc-
tion inhibitive cathode to completely shift chlorine and oxygen revolu- 54. Horri BA, Gu S: A continuous process for sustainable production
tion reaction to form HClO, which showed an outstanding Faradaic * * of hydrogen. Google Patents; 2021.
efficiency of 100%. The authors reported the first hybrid thermochemical-electrochemical
cycle for sustainable hydrogen generation based on the chemical
40. Guo J, Zheng Y, Hu Z, Zheng C, Mao J, Du K, Jaroniec M, looping principle using a Zn/ZnO redox pair. The technology is highly
* * Qiao S-Z, Ling T: Direct seawater electrolysis by adjusting the efficient (above 90%) and is currently undertaken for commercialisation
local reaction environment of a catalyst. Nat Energy 2023, 8: by Clean Hydrogen Ltd. in the UK with the trade name SurreyH2.
264–272.
Introducing a hard Lewis acid layer (based on Cr2O3) on transition 55. Yi L, Shao P, Li H, Zhang M, Liu X, Wang P, Wen Z: Hybrid acid/
metal oxide catalysts, for the first time, the authors reported direct * alkali electrolysis toward industrial-scale H2 generation and
electrolysis of actual seawater that showed long-term stability at sulfite oxidation conversion. Chem Eng J 2023, 467, 143462.
500 mAcm2 with a maximum 1.0 A cm/2 at 1.87 V @ 60  C, which is an The authors reported a hypotoxic molten-salt-assisted method to
outstanding record. synthesise nanostructured Co2P electrocatalyst for developing a hybrid
acid-alkali electrolyser for sulphite removal and H2 generation, which
41. Lyu X, Serov A: Cutting-edge methods for amplifying the has potential applications for environmentally benign sulphur removal
oxygen evolution reaction during seawater electrolysis: a processes.
brief synopsis. Ind Chem Mater 2023, 1:475–485.
56. Wang X-H, Zhang Z-N, Wang Z, Ding Y, Zhai Q-G, Jiang Y-C,
42. Jin H, Xu J, Liu H, Shen H, Yu H, Jaroniec M, Zheng Y, Qiao S-Z: * Li S-N, Chen Y: Ultra-thin CoNi0.2P nanosheets for plastics
Emerging materials and technologies for electrocatalytic and biomass participated hybrid water electrolysis. Chem
seawater splitting. Sci Adv 2023, 9, eadi7755. Eng J 2023, 465, 142938.
The authors reported an ultrathin CoNi0.2P nanosheet on nickel foam for
43. Malek A, Lu X, Shearing PR, Brett DJL, He G: Strategic com-
hybrid electrolysis to directly upgrade the hydrolysate of polyethylene
parison of membrane-assisted and membrane-less water
terephthalate and co-generation of hydrogen at a low potential (1.35 V).
electrolyzers and their potential application in direct
seawater splitting (DSS). Green Energy Environ 2023, 8:
989–1005.

www.sciencedirect.com Current Opinion in Green and Sustainable Chemistry 2024, 47:100932