Process Safety and Environmental Protection 116 (2018) 262–286

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep

Review on synthesis of 3D graphene-based configurations and their

adsorption performance for hazardous water pollutants
Billie Yan Zhang Hiew a , Lai Yee Lee a,∗ , Xin Jiat Lee a , Suchithra Thangalazhy-Gopakumar a ,
Suyin Gan a , Siew Shee Lim a , Guan-Ting Pan b , Thomas Chung-Kuang Yang b ,
Wee Siong Chiu c , Poi Sim Khiew d
a
Department of Chemical and Environmental Engineering, University of Nottingham Malaysia Campus, Jalan Broga, 43500, Semenyih, Selangor, Malaysia
b
Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, 1 Zhongxiao E. Rd. Sec. 3, Da’an District, Taipei City
106, Taiwan, ROC
c
Low Dimensional Materials Research Centre, Department of Physics, Faculty of Science, University of Malaya, 50603, Kuala Lumpur, Malaysia
d
Center of Nanotechnology and Advanced Materials, Faculty of Engineering, University of Nottingham Malaysia Campus, Jalan Broga, 43500 Semenyih,
Selangor, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: Water pollution is a global health and environmental issue affecting all life forms. The treatment of
Received 22 October 2017 water polluted by dyes, heavy metals and pharmaceuticals is a major challenge to operators of wastew-
Received in revised form 14 January 2018 ater treatment facilities. Adsorption technology functions effectively in removing these pollutants using
Accepted 11 February 2018
specific adsorbents. Graphene oxide (GO) and its three dimensional (3D) configurations are new carbon-
Available online 15 February 2018
based adsorbents. With superiorly large surface area, high porosity and large variety of functional groups,
these materials have been tested for their potential application in wastewater treatment. This review
Keywords:
focuses on the synthesis methods of 3D graphene-based structures and their adsorption performance
Graphene oxide
3D graphene-based structures
of dyes, heavy metals and pharmaceuticals. Various synthesis methods have been successfully devel-
Adsorption oped demonstrating the feasibility of configuring graphene into porous 3D networks. These methods
Pharmaceuticals can be categorised into direct synthesis and solution-based methods. The 3D graphene structures por-
Dyes trayed relatively high adsorption capacities for the three pollutant groups. Their adsorptive properties
Heavy metals were influenced by characteristics of pollutant, adsorbent surface and process parameters. The major
adsorption mechanisms of the 3D graphene-based structures were identified to be hydrogen bonding,
electrostatic, ␲-␲ and hydrophobic interactions. This review indicated that 3D graphene configurations
are promising solutions for practical application of carbon nanomaterials in wastewater treatment.
© 2018 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction pollutants and the adsorption efficiency varied with the type of
adsorbent, as illustrated in Table 1 based on the respective adsorp-
The proportional increase in industrial, agricultural and domes- tion capacity. Of these adsorbents, carbon nanomaterials exhibited
tic activities arising from the growing human population has led comparatively high adsorption capacity possibly due to their high
to elevated levels of hazardous chemicals such as synthetic dyes, porosity, specific surface area and surface chemical functionalities.
heavy metals and pharmaceutical residues in the environment over Recent research have demonstrated the potential application of low
the years. Such pollutants have been reported to cause toxicosis dimensional carbon nanomaterials such as graphene (Zhu et al.,
accumulation and carcinogenic effects on human beings (Ahmed 2017), carbon nanotube (Patiño et al., 2015) and fullerene (Chen
et al., 2015; Álvarez-Torrellas et al., 2017; Peng et al., 2017). To et al., 2016b) as highly effective adsorbents for capturing numer-
mitigate the effects of water pollution, various water purification ous water pollutants. Specifically, graphene which was discovered
technologies have been developed. Among them, adsorption is an by Novoselov et al. (2004) has attracted significant research inter-
attractive option as it offers relatively simple and low cost opera- ests for its potential utilisation in various fields such as engineering,
tion. A wide range of adsorbents have been used to remove these medical, material synthesis, electronics, energy and environment.
Structurally, graphene is a sheet of sp2 hybridised carbon atoms,
arranged in a honeycomb-like lattice with a thickness equivalent to
∗ Corresponding author. the diameter of an atom (Meyer et al., 2007). Graphene is made up
E-mail address: [email protected] (L.Y. Lee). of pure carbon whereby each carbon atom is attached to another

https://doi.org/10.1016/j.psep.2018.02.010
0957-5820/© 2018 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286 263

Table 1
Adsorbents used for the removal of different dyes, heavy metals and pharmaceutical residues.

Adsorbent Pollutants qm (mg/g) Reference

Biomass
Coffee residue Cu2+ 70.0 Kyzas (2012)
Luffa acutangula peel Malachite green 69.64 Ng et al. (2016)
Litchi peel waste Cr6+ 101.1 Ali Khan Rao et al. (2012)
Cortaderia selloana flower spikes Methylene blue 114.3 Yu et al. (2017b)
Fish scales waste Acid Blue 113 145.3 Ooi et al. (2017)
Clays
Aluminium pillared clay Hg2+ 49.75 Eloussaief et al. (2013)
Bentonite Phenol 66.67 Hank et al. (2014)
Safi decanted clays Malachite green 88.70 Elmoubarki et al. (2015)
Polymer matrix
Porous ␤-cyclodextrin polymer Bisphenol-A (BPA) 88.0 Alsbaiee et al. (2016)
Alginate beads U6+ 237.15 Yu et al. 2017b)
Activated carbon Cu2+ 43.47 Demiral and Güngör (2016)
Methylene blue 199.6 Djilani et al. (2015)
Cephalexin 233.1 Nazari et al. (2016)
Biochar Pb2+ 20.87 Lee et al. (2017)
Pb2+ 102.0 Park et al. (2016)
Naproxen 290.0 Jung et al. (2015)
Carbon nanomaterial
Carbon nanotube Red 159 208 ± 9 Vuono et al. (2017)
Pb2+ 117.65 Tofighy and Mohammadi, (2011)
Ciplofloxacin 206.0 Yu et al. (2016)
Graphene oxide Cd2+ 44.64 Xue et al. (2016)
Atenolol 116.0 Kyzas et al. (2015)
Proflavine 186.56 Bhattacharyya et al. (2017)

Note: qm – maximum adsorption capacity.

carbon atom in the same planar via covalent bonding. The single-
sheets of graphene are linked by van der Waals force. The presence 1600
of aromatic rings, free ␲-␲ electrons and vacant reactive sites at the
edges of graphene structure contributes to the remarkable char- 1400
acteristics of graphene which enable its diverse applications such
1200
as bio-sensing, electronic devices, composite material reinforce-
ment, energy storage and adsorption (Adán-Más et al., 2017; Chen 1000
et al., 2016a; Chia et al., 2014; Liu et al., 2012b; Minitha et al., 2017;
800
Novoselov et al., 2004; Wang et al., 2017a; Wang et al., 2017d).
Graphene can be represented in different forms which include 600
graphene sheets, graphene oxide (GO) and reduced graphene oxide
400
(rGO) as illustrated in Table 2. Due to its lower production cost,
GO is recently one of the most widely explored carbon nanoma- 200
terials in wastewater remediation by adsorption technology. GO
is the product of oxidation of graphene sheets and the oxida- 0
2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017
tion process significantly alters its physicochemical properties. The
incorporation of oxygen-containing functional groups to the car-
bon structure lowers the electronic and mechanical properties of Fig. 1. Number of publications with terms ’graphene adsorption’ available between
2005 and 2017. Extracted from Scopus database on 31/12/2017.
GO as compared to graphene (Table 2) (Gómez-Navarro et al., 2008;
Sreeprasad and Berry, 2013; Suk et al., 2010). The introduced oxy-
gen functionalities increases the hydrophilicity of GO such that it is
readily dispersed and forms stable colloidal suspension in aqueous together into three-dimensional (3D) configuration. This approach
media. Other remarkable properties such as enormous surface area can prevent the restacking of individual graphene sheets into
(∼2630 m2 /g), better colloidal stability than other carbon materi- macro-scale aggregates during adsorption process (He et al., 2013a;
als and high aspect ratio for modification, have made GO a feasible Wang et al., 2013a). The 3D graphene structures enabled the GO
material for applications in adsorption and surface reaction. Fig. 1 intrinsic properties to be incorporated into the bulk volume and
demonstrates the rising trend in research interests related to GO improved the practical application of the nanomaterial.
and its derivatives in adsorption processes (Konicki et al., 2017a; Graphene-based foams (Speyer et al., 2017), sponges (Wu et al.,
Kyzas et al., 2015; Lingamdinne et al., 2016; Liu et al., 2016a; Robati 2016), aerogels (Liu et al., 2017a) and hydrogels (Gan et al., 2015)
et al., 2016; Rostamian and Behnejad, 2016; Wang and Chen, 2015). are some of the 3D graphene-derived structures reported in cur-
Despite having excellent adsorption performance, several dis- rent literature. Today, a number of researchers have utilised the
advantages have hindered the use of GO in practical engineering unique properties of these 3D configurations in adsorption pro-
applications, and this included the difficulty in separating nano- cesses and demonstrated that they possessed superior adsorption
sized adsorbent (nanosorbent) particles from the liquid phase, capability as compared to commercially available adsorbents. For
necessary additional process to treat exhausted nanosorbent, par- instance, Jayanthi et al. (2016) has developed GO foam to remove
ticle agglomeration and high manufacturing cost (Liu et al., 2012a). organic dyes such as malachite green, rhodamine B and acri-
To overcome these challenges, increasing research efforts have flavine, exhibiting Langmuir maximum adsorption capacities of
been devoted to tailor and bind the individual graphene sheets 460.0, 351.4 and 235.4 mg/g, respectively, at 37 ◦ C. The sulphur-
doped graphene sponge prepared by Zhao et al. (2015b) showed
264 B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286

Table 2
Chemical structure and properties of graphene-based materials (Gómez-Navarro et al., 2008, Lee et al., 2008, Park and Ruoff, 2009, Sreeprasad and Berry, 2013, Suk et al.,
2010).

Material Graphene GO rGO

Chemical structure

C:O ratio No oxygen 2–4 8–246

Young’s modulus (GPa) 1000 200 250
Electron mobility (cm2 /V s) 10000–50000 Insulator 0.05–200
Production cost High Low Low

Cu2+ adsorption capacity (228 mg/g) that was 40 times better then sified into three groups, namely toxic metals, precious metals and
activated carbon. Chen et al. (2017b) have successfully assem- radionuclides. Intensive industrial activities such as electroplating,
bled a novel 3D agar-GO composite aerogel for methylene blue fertiliser manufacture, painting, cadmium-nickel battery manufac-
dye sequestration, portraying remarkably large adsorption per- ture, smelting, alloy fabrication and mining, have caused severe
formance (578 mg/g). In another study on ciprofloxacin removal heavy metal pollution of the aquatic environment (Kula et al., 2008;
by sodium alginate-GO hydrogel beads, the highest adsorption Vunain et al., 2016). The build-up of heavy metals such as nickel
capacity achieved was 86.1 mg/g (Fei et al., 2016). These studies (Ni), cadmium (Cd), lead (Pb), chromium (Cr), manganese (Mn),
demonstrated a remarkable research breakthrough on the utili- zinc (Zn), iron (Fe) and copper (Cu), can pose lethal damages to the
sation of GO or graphene-based materials in physical form of 3D human body and the ecosystem as they are highly toxic and non-
structure which can be a practical engineering configuration for biodegradable (Karatas, 2012; Monferran et al., 2012). The health
control of contaminants level in wastewater. hazards of heavy metals are summarised in Table 4 (Wang and
Chen, 2006; Volesky and Holan, 1995). Precious metals such as pal-
ladium (Pd), platinum (Pt), silver (Ag), gold (Au) and ruthenium (Ru)
1.1. Pharmaceutical pollutants
have high commercial value as they are rare in nature (Das, 2010).
Uranium (U), thorium (Th), radium (Ra) and americium (Am) are
The worldwide consumption of pharmaceutical compounds has
some of the examples of radionuclides which are present in metal
been predicted to increase continuously due to the extensive usage
form, beta emitter and gross alpha particle, and they emit radia-
in various fields such as medicine, aquaculture, livestock farming
tion. Radioactive effects from these metals are lethally dangerous
and human daily life (Khan et al., 2017, Wang and Wang, 2016). The
and toxic to all living organisms. Thus, the discharge of wastewa-
annual production of pharmaceutical products was estimated to be
ter containing heavy metals needs to be regulated to safeguard the
higher than 20 million t and this figure is increasing to meet the high
environment and human health. To regulate emissions to the envi-
demands for medical drugs (Wang and Wang, 2016). Pharmaceuti-
ronment, many countries have imposed specific discharge limits for
cal compounds can be classified based on their specific functions as
the heavy metals such as the Malaysia effluent discharge standards,
shown in Table 3. It has been reported that approximately 30–90%
United States Environmental Protection Agency (USEPA) maximum
of the pharmaceutical compounds remained in human and ani-
contaminant level, World Health Organisation (WHO) guideline
mal bodies, while the remaining active compounds were excreted
standard and China integrated wastewater discharge standards, as
as pollutants to the environment (Rivera-Utrilla et al., 2013). As
shown in Table 4.
such, pharmaceutical residues have been recognised as one of the
emerging anthropogenic pollutants containing different biologi-
cally active compounds used intensively in medicine and personal
1.3. Dye pollutants
care products (Khan et al., 2017). These pharmaceutical residues
were detected not only in surface waters, but also in ground water,
Synthetic dyes are widely used as the colouring agent in
soil and drinking water (aus der Beek et al., 2016). Generally, the
numerous industries such as textile, paint, cosmetic and pigment
pharmaceutical residues entered the surface water through direct
manufacturing sectors (Liu et al., 2011). The worldwide production
effluent discharge from hospitals, veterinary, wastewater treat-
of dyes has been reported to be more than 700,000 t per year (Ajmal
ment plants, pharmaceutical industries and residential areas. The
et al., 2014, Lee et al., 2015, Natarajan et al., 2017). Due to the com-
residues further enter the ground water from the process efflu-
plexity of chemical structure, the classification of synthetic dyes is
ent of domestic sewage and wastewater treatment plants (Khan
often adapted from their application or ionic charge. The classifi-
et al., 2017, Mompelat et al., 2009, Wang and Wang, 2016). Although
cation depicted in Table 5 divides the synthetic dyes into anionic,
the concentration of pharmaceutical residues in water body is very
cationic and non-ionic dyes. Generally, non-ionic dyes such as vat
low (ranging from ng/L to mg/L), they can affect the water quality
and disperse dyes are insoluble in water, but soluble in organic
and ecosystem negatively due to their inherent resistance towards
solvents whereas ionic dyes are readily soluble in water. The ionic
biodegradation and toxicity accumulation (Al-Khateeb et al., 2014).
dyes are further categorised into cationic and anionic dyes. All basic
Therefore, the concentration of pharmaceutical residues in water
dyes are known as cationic dyes, while anionic dyes are made up
sources needs to be controlled.
of three categories which are acid, direct and reactive dyes. Dur-
ing dye manufacture, 10–15% of the substance is released along
1.2. Heavy metal pollutants with the contaminated water (Ajmal et al., 2014, Natarajan et al.,
2013). The inefficiency of wastewater treatment facility has caused
Heavy metals are generally referred to as dense metals or metal- dyes to enter the environment. Contamination of water systems by
loids with atomic weight ranging from 63.5 to 200.6 Da and specific the dyes is easily detected from colouration of the receiving water
gravity >5 g/mL (Järup, 2003; Vunain et al., 2016). They can be clas- body, even if their concentration was <1 mg/L (Natarajan et al.,
 B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286 265

Table 3
Classification and main property of pharmaceutical pollutants (Wang and Wang, 2016).

Classification Function Example Molecular weight (g/mol) pKa

Antibiotics Eliminate bacteria Sulfamethoxazole 253.3 5.70

Trimethoprim 290.3 7.12
Ofloxacin 261.4 5.97
Ciprofloxacin 331.3 6.09
Sulfadiazine 250.3 6.36
Tetracycline 444.4 3.30
Oxytetracycline 460.4 3.27
Anticonvulsants Mood stabiliser and treat mood Carbamazepine 236.3 2.30
disorder Primidone 218.3 –
Mephobarbital 246.3 7.80
Antidepressants Correct chemical imbalances of Diazepam 284.7 3.40
neurotransmitter in brain and treat Doxepin 279.4 –
depression Oxazepam 286.7 10.9
Antineoplastic Control or kill neoplastic cells Epirubicin 543.5 9.17
Methotrexate 454.4 4.70
Tamoxifen 371.5 8.87
Beta (␤) blockers Inhibit hormone adrenaline and the Atenolol 266.3 9.60
neurotransmitter noradrenalin Metoprolol 267.4 9.60
Propranolol 259.3 9.42
Sotalol 272.4 –
Diagnostic Enhancement of vascular on magnetic Iopromide 791.1 –
contrast media resonance (MR) Iomeprol 777.1 –
Diatrizoate acid 613.9 1.13
Hormones Regulate rate of metabolism, control of Estrone 270.4 10.91
sexual development, keep homeostasis Testosterone 288.2 19.09
17-␤ Estradiol 272.4 10.08
Lipid regulators Regulate triglycerides and cholesterol Clorfibric acid 214.6 3.15
in blood Gemfibrozil 250.3 4.50
Clofibrate 242.7 −4.90
Nonsteroidal Reduce pain and inflammation Diclofenac 296.1 4.15
anti-inflammatory Naproxen 230.3 4.15
drugs (NSAIDs) Ibuprofen 206.3 4.91
Ketoprofen 254.3 4.45
Salicylic acid 138.1 2.97
Paracetamol 151.2 9.38

Table 4
Health hazards and discharge limits of heavy metals (Carolin et al., 2017; DOE, 1974; Drake and Hazelwood, 2005; MEP, 1998; USEPA, 2009; WHO, 2011).

Heavy metal Health hazard Threshold limit (mg/mL)

Malaysia effluent Malaysia effluent U.S. EPA WHO Guideline China integrated
discharge discharge Maximum Standard wastewater
Standard A(a) Standard B(b) Contaminant discharge
Level (MCL) standard

Cd Renal failure, itai-itai disease, birth defects, 0.010 0.020 0.005 0.003 0.10
anaemia, carcinogenic
Pb Kidney failure, loss of voluntary muscle 0.100 0.500 0.015 0.010(P) 1.0
function
Cr (III) Genotoxic, alopecia 0.200 1.000 – – 1.5(T)
Cr (VI) Genotoxic, alopecia 0.050 0.050 0.100(T) 0.050(T)(P) 0.5
As Gastrointestinal symptoms, death, 0.050 0.100 0.010 0.010(P) 0.5
melanosis, hepatomegaly
Ni Anaphylaxis, lung cancer, red blood cells 0.200 1.000 – 0.070 1.0
loss, nephrotoxic
Mn Neurotoxic, sleep dysfunctions 0.200 1.000 0.050(S) 0.400(H) –
Zn Dizziness 1.000 1.000 5.000(S) 3.000(N) –
Sn Metabolism disruption, carcinogenic 0.200 1.000 – – –
Hg Kidney disease, death, muscle movement 0.005 0.050 0.002 0.006 0.05
impairment, gum inflammation
Cu Liver and kidney disease, cancer, stomach 0.200 1.000 1.300 2.000 –
irritation
Fe Blood creatinine, kidney damage 1.000 5.000 0.300(S) 0.300(N) –
Ag Argyria, argyrosis, respiratory damage – – 0.100(S) – 0.5
␣ photon emitter Carcinogenic, genetic damage, infertility – – 15 pCi/L 0.5 Bq/L 1 Bq/L
␤ photon emitter Carcinogenic, genetic damage, infertility – – 4 mrems/year 1.0 Bq/L 10 Bq/L
226
Ra Carcinogenic, genetic damage, infertility – – 5 pCi/L(R) 1.0 Bq/L –
228
Ra Carcinogenic, genetic damage, infertility – – – 0.1 Bq/L –
U Change in bone structure, carcinogenic, – – 0.030 0.030(P) –
nephritis

Note: (a) = Effluent discharged of upstream water intake, (b) = downstream effluent discharge, (T) = Total chromium, (S) = Secondary MCL, (R) = Combined total of 226
Ra and
228
Ra, (P) = Provisional guideline, (H) = Health-based guideline, (N) = non-formal guideline, Bq = Becquerel, Ci = Curie, rems = Roentgen equivalent in mammals.
266 B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286

Table 5
Classification, property and example of dyes adapted from (Hunger et al., 2004). .

Class Type of dye Chemical groups Property Substrate Example

Anionic Acid Azo, anthraquinone, xanthene, Water soluble and anionic Wool, nylon, silk, inks, leather Acid blue 113, acid red 183,
nitro and triphenylmethane. and paper. indigo carmine, acid fuschin,
acid yellow 17 and acid black 2
Direct Azo, oxazine, phthalocyanine Anionic, water soluble Nylon, leather, cotton, Congo red, direct red 23, direct
and stilbene. regenerated cotton blue 86, direct orange 39 and
direct red 81 .
Reactive Azo, oxazine, formazan, Covalent binding of reactive Wool, cotton, silk and textile Reactive black 5, reactive green
anthraquinone and sites with functional groups of 19, reactive blue 4 and reactive
phthalocyanine. substrate under the effect of red 120
heat and pH
Cationic Basic Azo, hemicyanine, cyanine, Water soluble, release of Inks, paper, polyesters, treated Crystal violet, methylene blue,
azine diphenylmethane, coloured cations in solution, nylon, medicine as antiseptics. basic fuschin, malachite green,
xanthene, acridine and and show biological activity for rhodamine 6G and Orange 2
oxazine. certain dyes.
Non-ionic Disperse Azo, benzodifuranone, Non-ionic, insoluble in water. Cellulose acetate, acrylic fibres, Disperse red 1, disperse orange
anthraquinone, nitro and polyester, polyamide and 37 and disperse yellow 1
styryl. plastics.
Vat Indigoids and anthraquinone. Insoluble in water, soluble in Cellulose fibre, wool and cotton Vat black 8, vat green 9, vat
sodium hydrogen sulphite, blue 4 and vat yellow 20
then spent on reoxidised and
fibre

2017). The dye molecules absorb and deflect sunlight entering the process (Singh et al., 2016). The reduction process could eliminate
water body, hindering the photosynthesis rate of aquatic plants. a large fraction of the oxygen content, yielding a C:O ratio between
Prolonged exposure to synthetic dyes can result in skin irritation, 8:1 to 246:1. However, a complete reduction of GO was still not pos-
respiratory problem and cancer (Yagub et al., 2014). Synthetic dye sible. The reduction process could also alter the chemical structure
molecules are designed and made to be resistant against wash- of GO. During reduction, the GO sheets underwent changes in car-
ing water, chemicals, heat and ultraviolet light, making them very bon vacancies and residual oxygen content which resulted in the
difficult to be treated by standard wastewater treatment facilities. deformation of hexagonal carbon chains into pentagonal or hep-
The special properties of the abovementioned pollutants have tagonal carbon structures (Gómez-Navarro et al., 2010). Hence, the
caused conventional wastewater treatment methods to be inef- reduction process could only produce GO derivatives with mechan-
fective in removing them from the aquatic environment. For ical and electronic properties which were a fraction of those of
example, anaerobic digester is ineffective in removing pharma- pure graphene (Table 2). The insights and data gathered on the
ceutical residues, particularly antibiotics, due to the bacterial synthesis pathways of graphene-based materials could contribute
resistance of antibiotics during the digesting process (Wang and to the development of graphene-based composites for wastewater
Wang, 2016). From literature, adsorption technology using 3D treatment (Lü et al., 2013; Peng et al., 2017; Perreault et al., 2015).
graphene structures showed excellent adsorptive performance
towards certain pollutants, implying its promising potential in a
practical nanosorbent system for commercial wastewater facilities 2.1. Synthesis of GO
in the future. Additionally, the use of 3D graphene structures in
wastewater treatment has currently expanded to a strong research The preparation of GO from pristine graphite generally involved
field for green and sustainable technology development, and a crit- chemical oxidation and exfoliation, which can be extended to pro-
ical review is timely to highlight the current trends and future duce rGO through reduction processes, as illustrated in Fig. 2.
developments. This review entails the compilation of studies con- A number of synthesis routes of GO have been developed
ducted on the application of 3D graphene structures in adsorption between the years 1859 and 1958, and these included Brodie
field between the years 2008 and 2017. Furthermore, the review method (Brodie, 1859), Staudenmaier method (Staudenmaier,
focuses on the synthesis pathways of GO and 3D graphene struc- 1898), Hoffmann method (Hofmann and König, 1937) and Hum-
tures, adsorption affinity and mechanism, as well as regeneration of mers method (Hummers and Offeman, 1958) as well as their
spent graphene-based adsorbents to provide essential data for the modified and improved versions (Fig. 3). The major issues with
development and commercialisation of GO and its 3D composites Brodie method were its long reaction time which ranged from 72
for wastewater treatment. to 96 h, and the release of toxic gaseous by-products. Stauden-
maier improved the Brodie method by increasing the acidity level
of the reaction using concentrated sulphuric acid (H2 SO4 ) which
2. Synthesis of GO and 3D graphene-based structures resulted in a single reaction vessel system. Nonetheless, Stauden-
maier method was also time-consuming and produced explosive
As previously mentioned, GO has high specific surface area, chlorine dioxide. Over the years, Hoffmann reduced the risk level
and contains epoxy and hydroxyl groups on the basal plane, and of the synthesis process by using non-fuming nitric acid (HNO3 ).
carboxylic functional group at the edge of the sheets, which con- In 1958, an alternative approach was introduced by Hummers
tribute to its hydrophilicity and high negative charge density. These and Offeman for the oxidation of graphite which is widely known
distinctive properties of GO attracted much chemical functionalisa- as Hummers method (Hummers and Offeman, 1958). This method
tion work from researchers worldwide. As such, GO is recognised involved reacting graphite powder with acids (HNO3 and H2 SO4 ),
as the precursor for devising graphene-based composite materi- followed by intercalating with alkali metals (KClO3 , KMnO4 and
als for various applications. GO can also be a relatively low cost NaNO3 ) into the graphitic layers of graphite, dissembling the layers
starting material for the synthesis of rGO through several reduc- into smaller pieces (Singh et al., 2016). The intercalation of oxygen-
tion techniques such as reduction with reducing reagents, thermal containing functional groups could increase the lattice distance of
annealing, microwave-assisted reduction and photo-reduction the graphite from 0.34 to 0.8–1.0 nm (Franklin, 1951; Peng et al.,
 B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286 267

Fig. 2. Typical processes involved in the synthesis of GO and rGO from pristine graphite. Adapted from (Peng et al., 2017) with permission from Elsevier.

1859 1898 1937 1958

Brodie Staudenmaier Hoffman Hummers
method method method method

Graphite + KClO3 Graphite Graphite Graphite + NaNO3

+ H2SO4 + H2SO 4 Ice bath
Oxidation Ice bath Ice bath + H2SO 4
+ HNO3 + HNO 3 + HNO 3 at 0oC
for 3-4 days at 0oC at 0 oC
at 60oC (fuming) (fuming) (non-fuming)
Suspension
Suspension Suspension
+ KMnO4
Graphite oxide Oxidation for (below 20oC)
Oxidation for + KClO3
+ KClO3 3-4 days at
4 cycles of 3-4 days at (slowly at
(slowly at room Graphite oxide
oxidation + H2O room 0oC)
0oC) temperature Increase
process temperature
temperature + H2O
Graphite oxide
Graphite oxide to 98oC
Graphite oxide + H2O Graphite oxide
(free of salt and acid) + H2O + HCl (free of salt and acid)
+ HCl (remove SO42-)
Vacuum (remove SO 42-) + H2O2
dried at Exfoliation (remove MnO4-
100oC Graphite oxide Graphite oxide and MnO2)
(free of salt and acid) (free of salt and acid)
GO Clean Graphite oxide
Vacuum Vacuum
Exfoliation Exfoliation Vacuum dried Exfoliation
dried dried
at 40oC
GO GO GO

Fig. 3. General synthesis routes of GO.

2016a; Schniepp et al., 2006). The increase in interlayer distance production yield and lower production cost albeit the random dis-
in graphite oxide could be beneficial for exfoliation of graphite tribution of pore structure. In the following sections, both synthesis
oxide to obtain GO through sonication or mechanical stirring due to approaches will be reviewed.
weakening of van der Waal forces between the adjacent graphitic
layers (Cai and Song, 2007; Zhu et al., 2010). Hummers and its mod-
2.2.1. Direct synthesis
ified methods are the most preferred methods for the synthesis of
2.2.1.1. Chemical vapour deposition (CVD). Graphene synthesis by
GO nowadays (Gan et al., 2015; Wu et al., 2016; Zhao et al., 2015b).
CVD is a process where a carbon source is decomposed on a metal
substrate to form a single layer or few layers of graphene sheet (Gao
2.2. Synthesis of 3D graphene-based structures and Zhao, 2013; Sutter, 2009). 3D graphene structure with con-
trolled layers and sizes can be produced by CVD on pre-fabricated
In literature, many terminologies have been used to describe 3D metal framework (Li et al., 2013b; Sha et al., 2016; Yavari et al.,
the 3D graphene-based structures such as foam, network, hydro- 2011). Nickel and copper substrates have been applied for the
gel, aerogel, monolith, bead and sponge (Adhikari et al., 2012; synthesis of 3D graphene structures. It was reported that the pri-
Branca et al., 2015; Chen et al., 2017b; Zhang et al., 2014c; Zhuang mary growth mechanisms of graphene on nickel substrates were
et al., 2016). The synthesis methods of the 3D configurations can be adsorption and incorporation of carbon atoms within the substrate,
largely classified into two categories, namely direct synthesis from and precipitation of carbon atoms from the substrate upon cool-
carbon sources and solution-based synthesis. The overview on the ing (out-diffusion) (Memon et al., 2013). Although surface growth
synthesis of 3D graphene-based structures is illustrated in Fig. 4. is one of the growth mechanisms on nickel substrate, the car-
For each of the synthesis classes, two different approaches bon dissolution-precipitation is more dominant, and thus several
including template-assisted and template-free methods are avail- layers of graphene structure can be deposited on the metal frame-
able for fabrication of 3D graphene-based structures. The direct work, thereby strengthening the stability of the structure. Hence,
synthesis approach offers better control of pore size, pore den- nickel substrate is the most preferred substrate for synthesising
sity and pore size distribution development in the 3D structures. 3D graphene foam. On copper substrate, the formation of graphene
However, it is associated with relatively high manufacturing cost. was governed purely by surface growth which resulted in lower
In contrast, the solution-based synthesis method provides bene- carbon solubility (Bhaviripudi et al., 2010; Memon et al., 2013).
fits such as elemental functionalisation, potential scalability, higher Hence, only a single layer of graphene is deposited on the tem-
268 B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286

3D graphene-based structures
synthesis

Solution based
Direct synthesis
synthesis

Template- Template-
Template-free Template-free
assisted assisted
• Chemical vapour • Sugar blowing • Template-assisted • GO assembly by
deposition (CVD) technique freeze drying reduction process
• Carbonisation of polymer • Plasma enhanced CVD • Template-assisted

Fig. 4. Overview on the synthesis of 3D graphene-based structures.

plate making it difficult to support the interconnected 3D network skeleton at 1000 ◦ C, followed by etching of the nickel with 1 M
of graphene. This type of structure breaks down easily during FeCl3 /0.2 M HCl, and finally freeze drying. A relatively high density
handling (Chen et al., 2011; Shehzad et al., 2016). Apart from (22–100 mg/cm3 ) graphene foam was reported which was larger
using metal substrates, other materials such as metal oxides, metal than that of nickel foam (∼1 mg/cm3 ). Moreover, Li et al. (2013b)
nanostructures and metallic salts were used as templates for the also investigated the effect of growth time (0.5–10 min) on the mor-
synthesis of 3D graphene structures (Ago et al., 2012; Chang Goo phology and density of the graphene foam. It was reported that
et al., 2011; Wang et al., 2013b; Zhou et al., 2013). the density of the graphene foam increased linearly with growth
The first 3D graphene foam made by CVD on nickel-based tem- time. When the growth time was more than 3 min, many graphite
plate was reported by Chen et al. (2011). In their work, the nickel microspheres were formed as time progressed, suggesting a fast
substrate was pyrolysed with methane gas (CH4 ) as the carbon and efficient growth of graphene layer. At 10 min, the deposited
source at 1000 ◦ C and atmospheric pressure. Polymethyl methacry- graphene layers with a density of 100 mg/cm3 was strong enough
late (PMMA) film was formed on the surface of the 3D graphene to avoid collapsing without the nickel support (Li et al., 2013b).
foam to support the structure and prevent it from disintegrating
when nickel was etched with hydrochloric acid (HCl). Finally, the 2.2.1.2. Carbonisation of polymeric structure. Carbonisation of
PMMA was dissolved with hot acetone to produce free-standing organic-based framework is a relatively simple technique for syn-
graphene foam. The graphene foam produced had a specific sur- thesis of carbon rich materials. In this process, 3D polymeric
face area of ∼850 m2 /g, interlayer spacing of 0.34 nm and porosity structures such as highly cross-linked framework, hydrogel or aero-
of ∼99.7% (Chen et al., 2011). gel are subjected to thermal annealing (carbonisation) to synthesise
Several process parameters such as the type of carbon source, a 3D graphene-based structure. This approach was demonstrated
framework structure and template material were studied to estab- by Patil et al. (2016) for the development of 3D carbon foam from
lish their influences on the formation of graphene-based foam. For poly-HIPE polymeric structure for supercapacitor application. In
example, Cao et al. (2011) used ethanol as the carbon source to their work, the poly-HIPE was sulphonated and pyrolysed at 850 ◦ C
prepare a graphene foam with lattice spacing of 0.21 nm at atmo- to produce a 3D graphitic configuration with a specific surface area
spheric pressure. The effects of template material on the synthesis of 389 m2 /g and open voids of 14 ␮m, interconnected by 4 ␮m win-
of graphene foam have also been investigated by a number of dows in monolithic structure (Patil et al., 2016). A novel elastic
researchers. A graphene foam derived from nickel-copper catalytic carbon foam with ultrahigh porosity (99.6%), high specific surface
template with pore sizes varying from 5 to 100 ␮m was devel- area (268 m2 /g) and ultralight weighted or low density (5 mg/cm3 )
oped by Ning et al. (2014). Ning and co-workers synthesised the 3D was developed by Chen et al. (2013a) through direct carbonising
graphene nano-mesh by CVD on porous MgO template using CH4 of melamine foam at 800 ◦ C. Their results demonstrated that the
gas as the carbon source. The graphene nano-mesh was reported to elastic carbon foam was able to absorb 148–411 times of its own
possess a specific surface area of 1654 m2 /g and pore size of 10 nm weight, depending on the density of the specific organic solvents
(Ning et al., 2011). Another 3D graphene structure with a pore (Chen et al., 2013a). This direct carbonisation technique enabled the
size of 95 nm was developed using anodic Al2 O3 ceramic template fabrication of 3D porous graphene monolithic structure with high
(Zhou et al., 2013). Shi et al. (2016a) used a scalable seashell-based specific area, large voidage, light weighted and excellent adsorption
CVD template for graphene foam formation, and the developed 3D properties.
foam was used in oil-water separation. The sacrificial template was
obtained from calcination of scallop shell (CaO template). The 3D 2.2.1.3. Sugar blowing technique. The sugar blowing method has
graphene foam was synthesised using CH4 as the carbon source and been reported in literature for the preparation of a 3D graphene
diluted HCl as the etching agent. The graphene foam developed structure. This technique was inspired by the traditional food art
from the shell had an average pore size of 300 nm and a branch of ‘blown sugar’ in which a mixture of glucose and NH4 Cl was
width of 1 ␮m. It also had high adsorption capacities for various heated. The molten syrup was gradually polymerised and the gas
organic liquids such as ethanol, DMSO, n-hexane, pump oil, bean released chemically by NH4 Cl blew the glucose-derived polymer
oil and petrol (Shi et al., 2016a). Metallic salt was used as a cata- into a number of bubbles. The generation of the gas caused the
lyst and template precursor to synthesise graphene foam (Li et al., bubble walls to become thinner, and the polymeric fluid and small
2013b). In this study, a 3D nickel support structure was initially molecules were removed from the polymer walls. The ultrathin
formed by annealing NiCl2 ·6H2 O at 600 ◦ C under the flow of H2 - graphitic bubble networks were formed from the carbonisation of
Argon gas mixture, followed by a mixture of water vapour-HCl. the polymeric wall at high temperature. The 3D structure produced
The 3D graphene foam was produced by CVD growth on the nickel by this method is known as 3D strutted graphene, and the synthe-
sis process is illustrated in Fig. 5 (Wang et al., 2013c). The strutted
 B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286 269

Fig. 5. Strutted graphene synthesis by sugar blowing technique. Reprinted from (Wang et al., 2013c) with permission from Nature Communication.

Fig. 6. Green synthesis of xanthan gum/GO hybrid aerogel by ISISA. Reprinted from (Liu et al., 2017b) with permission from Elsevier.

graphene with an average width of 3.5 ␮m graphitic skeleton, den- with or without additional chemical binders before freeze drying
sity of 3 mg/cm3 and specific surface area of 1005 m2 /g, was used (He et al., 2013b; Hong et al., 2015; Jayanthi et al., 2016; Li et al.,
for high power density supercapacitors application (Wang et al., 2015; Ma et al., 2016). In this process, the formation of ice crys-
2013c). Likewise, the strutted graphene fabricated by Jiang et al. tals provided the structural support for the 3D graphene structure,
(2015) had a specific surface area of 710 m2 /g and pore sizes of and the morphological properties and porosity of the structure
2–10 ␮m. were dependent on the freezing temperature and temperature
gradient (Abarrategi et al., 2008; He et al., 2013b). During freeze
2.2.1.4. Plasma-enhanced CVD (PECVD). A direct PECVD approach drying, the GO sheets were ejected and entrapped between the
without sacrificial templates has been used to construct 3D neighbouring ice crystals, yielding highly oriented inter-connected
graphene-based structure (Bo et al., 2011; Vasudev et al., 2013; Yu GO-composite layers that formed a solid 3D graphene-based
et al., 2011). This method utilised a non-thermal radio frequency structure (Shehzad et al., 2016). However, the pore structure of
plasma to radicalise a monomer, generating chemical reactive the graphene configuration fabricated by ISISA was inconsistent
species to form uniform coatings and depositing the coated species throughout the structure which was attributed to the local differ-
vertically to construct a 3D structure (Vasudev et al., 2013). In 3D ences in freezing time and the temperature gradient applied onto
graphene structure development, conductive substrates such as Ni, the template during the synthesis process.
Cu, Au or stainless steel were often used together with CH4 as the In literature, many chemical additives were used to fabricate 3D
carbon source to produce graphene foam without the assistance of graphene-based structures by ISISA, and these included chitosan
template. In general, the 3D graphene structure developed by this (He et al., 2011; Yu et al., 2013), polyvinyl alcohol (PVA) (Dai et al.,
technique is highly cross-linked with uniform and robust graphene 2016; Fu et al., 2017; Tan et al., 2016), carboxylmethyl cellulose (Liu
films. The graphene layers are firmly adhered to the substrates et al., 2016b; Zhang et al., 2014c) and gum (Sahraei and Ghaemy,
with many vacant active sites on the edges of the graphene sheets, 2017; Yu et al., 2015b). Typically, the process involved mixing of
which render them suitable for surface-related applications such GO suspension with the chemical additive solution. The homo-
as adsorption, bio-sensing and catalysis (Vasudev et al., 2013; Yu geneous mixture of GO-composite solution was frozen overnight
et al., 2011). prior to freeze drying or drying by super critical CO2 to form 3D
graphene aerogel. For instance, Liu et al. (2017b) have success-
2.2.2. Solution-based synthesis fully demonstrated the green development of xanthan gum-GO
2.2.2.1. Template-assisted freeze drying. Template-assisted freeze hybrid aerogel by mixing 5 mL GO dispersion (0.002 g/mL) with
drying or ice-template is the process which utilises the rapid 5 mL of xanthan gum solution (0.01 g/mL). The resultant mixture
freezing of aqueous dispersion containing amphiphilic polymers was subjected to freezing at −40 ◦ C for 1 h before freeze drying
to construct a porous 3D structure. This process is also termed as for 8 h as illustrated in Fig. 6 (Liu et al., 2017b). From their find-
the ice-segregation-induced-self-assembly (ISISA) (Shehzad et al., ings, the freezing temperature played an important role in the
2016). GO was first incorporated into the aqueous media either formation of porous structure. The aerogel which was frozen at
270 B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286

Fig. 7. Synthesis of rGO aerogel by freeze drying.

lower temperature (−40 ◦ C) displayed an oriented hierarchical thin sion of GO in aqueous media. Due to strong electrostatic repulsion
sheet structure and the formation of networks connecting the co- force in GO dispersion, the 2D GO sheets form a stable colloidal
aligned and pores channel was also observed. Conversely, for the system hindering the self-assembly of GO into 3D structure. Several
sample which was frozen at higher temperature (−10 ◦ C), the thick- methods have been proposed to overcome this problem, and one of
ness of the GO composite sheets increased and the aerogel had a them is the reduction of GO either by chemical or thermal treatment
disoriented structure. The orientation of the aerogel also affected (He et al., 2013a; Yang et al., 2013). In-situ reduction of GO by chem-
the adsorption performance as the reported adsorption efficiency ical additives is a potential approach for fabrication of 3D graphene
for rhodamine B and methylene blue dyes of the aerogel frozen structure. The mechanism for chemical reduction of GO is governed
at −40 ◦ C were higher than that at −10 ◦ C. The volume per unit by sol-gel chemistry. The process involved elimination of the oxy-
mass of the developed aerogel was reported to range from 52.7 genated functional groups from the GO, triggering gelation of the
to 63.2 cm3 /g, indicating the XG/GO aerogel had a tunable poros- GO sheets into a 3D form known as rGO hydrogel. A large variety of
ity (Liu et al., 2017b). The ISISA or template-assisted freeze drying reducing agents have been tested and these included acids (Wang
is one of the most commonly used techniques for synthesis of 3D et al., 2017b; Zhang et al., 2010), hydrazine (Gao et al., 2010; Park
graphene structure as the process has relatively straightforward et al., 2011), metal or metal oxides (Chua and Pumera, 2014; Pei
steps. and Cheng, 2012), reducing salts (Bo et al., 2014) and plant extracts
(Firdhouse and Lalitha, 2014; Lee and Kim, 2014). In typical chemi-
cal reduction process, the reducing agent was introduced to the GO
2.2.2.2. Template-assisted hydrothermal process. Template-assisted
dispersion and subsequently heated to complete the reduction pro-
hydrothermal synthesis involves the use of porous foam-like
cess. During reduction, the reaction vessel was left to stand without
template and the 3D graphene structure is obtained through
stirring to enable stacking of graphene layers in an orderly arrange-
hydrothermal process (Yin et al., 2014). The foam template used
ment. The properties of the developed 3D graphene structure were
can be either metallic or polymeric foam. In the fabrication pro-
dependent on the type of reducing agent used. It was reported that
cess, the templates were soaked in GO dispersion and the soaked
mild reducing agent such as l-ascorbic acid, could assist in the con-
template was subjected to hydrothermal process for deposition of
struction of more uniform and stable graphene structure in water
GO sheets on the templates wall. After chemically reducing the GO,
(Abdolhosseinzadeh et al., 2015; De Silva et al., 2017; Zhang et al.,
the template skeleton was removed to obtain the graphene-based
2010). The stability of the rGO hydrogel could be attributed to the
structure. Typically, the removal of metallic template was achieved
formation of hydrogen bonds between the oxidised ascorbic acid
by chemical etching whereas polymeric template was eliminated
and residual oxygen functional groups, as well as the disruption of
by solvent dissolution or thermal decomposition. In this synthe-
␲-␲ stacking between the rGO hydrogel which prevented agglom-
sis method, the quality of 3D graphene foam is poorer than that
eration (De Silva et al., 2017). Recently, green reducing agents such
fabricated by CVD due to stacking of multi-layered GO sheets. Fur-
as plant derived extracts (tea leaves, spinach leaves and Roselle
thermore, this method is associated with higher manufacturing
flower) were investigated as alternative reagents for GO reduction.
cost due to the sacrifice of the template support at the end of the
It was reported that the plant extracts could effectively reduce GO
process, and the higher difficulty in controlling the morphologi-
(Chu et al., 2014; Suresh et al., 2015; Wang et al., 2011).
cal properties of the final product. Yin et al. (2014) has developed a
Hydrothermal reduction process is commonly used to reduce
rGO/ZnO foam by immersing nickel foam into GO suspension before
GO to initiate the self-assembly of GO under high temperature
transferring into autoclave for hydrothermal treatment at 90 ◦ C for
and pressure environment. In this method, a fixed concentra-
16 h. The rGO foam was then etched with 2 M HCl and dialysed with
tion of GO dispersion was heated in a Teflon-lined hydrothermal
deionised water to remove excess acid residue and metal ions. The
reactor to form the hydrogel. During hydrothermal process, the
ZnO nanorods was then deposited on the rGO foam by contacting
reduction of GO was achieved through elimination of carboxylic
the rGO foam with aqueous solution containing 25 mM zinc nitrate
groups which significantly reduced the electrostatic repulsion in
hydrate and 25 mM hexamethylenetetramine (HMTA) at 90 ◦ C for
the GO dispersion. This phenomena triggered the self-assembly
6 h. It was reported that the rGO/ZnO foam was densely packed with
of graphene-based hydrogel through the ␲-␲ deposition of GO
ZnO nanorods with diameters between 40 and 60 nm and lengths
sheets at the graphene basal planar (Shehzad et al., 2016). The
within 1–2 ␮m. Several works on synthesis of 3D graphene struc-
feasibility of adjusting the pores morphology of hydrogel through
tures by this method have been reported in literature (Ghosh and
hydrothermal process was demonstrated by altering GO concen-
Das, 2015; Huang et al., 2012; Xie and Zhan, 2015).
tration, hydrothermal reaction time or addition of metallic catalyst
(Zhu et al., 2016). The hydrothermal reduction also offers a pos-
2.2.2.3. Assembly of GO by reduction process. The assembly of 2D GO sibility for elemental functionalisation onto the graphene lattice
sheets into 3D graphene-based structures is initiated from disper-
 B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286 271

through doping. Du et al. (2014) have successfully synthesised The first cross-linking agent reported in literature was polyvinyl
nitrogen-doped rGO structures for high performance lithium ion alcohol (PVA) by Bai et al. (2010). It was found that the gelation
battery anode by hydrothermal process. In their work, the nitrogen- between GO and PVA was governed by hydrogen bonding between
doped rGO was formed by hydrothermal treatment of a mixture of the functional groups (hydroxyl, epoxy and carboxyl groups) on
melamine and GO suspension in a Teflon-lined autoclave at 180 ◦ C the GO surface and the hydroxyl-rich PVA chains. One notable find-
for 6 h (Du et al., 2014). From their work, the nitrogen-doped rGO ing from their work was that gelation of GO-PVA hydrogel was a
exhibited Type IV adsorption isotherm indicating the existence of reversible process made possible by tuning the pH of the system. In
mesopores within the structure with a Brunauer-Emmett-Teller their research, the hydrogel was formed at pH < 7, but remained in
(BET) specific surface area of 146.0 m2 /g. In addition, the hydrother- aqueous form at pH > 7. This sol-gel transition of GO-PVA hydrogel
mal process can be extended to solvothermal process by replacing occurred due to insufficient binding force between the molecules
the water with organic solvents (Dubin et al., 2010; Liu et al., under high pH condition. The hydrogel produced under acidic con-
2016e; Wang et al., 2009). This method enables the use of chem- dition was found to be much stronger than that prepared under
icals which are soluble in organic solvents for functionalisation of elevated pH condition. This was attributed to reduction of GO
the 3D graphene structures. sheets through acidification which facilitated the ␲-␲ stacking of
graphene sheets (Bai et al., 2010). The development of GO-PVA
2.2.2.4. Freeze drying. Freeze drying is commonly practised to hydrogel was also reported by other researchers for applications
eliminate the water molecules trapped inside the structure of rGO such as adsorbent, material reinforcement and wound dressing
hydrogel to produce an orderly configured aerogel (He et al., 2016; (Fan et al., 2016; Huang et al., 2014; Li et al., 2014; Zhang et al.,
Worsley et al., 2012; Wu et al., 2012). The preparation of rGO 2011a).
aerogel from GO sheets involved three key steps as illustrated in Apart from PVA, various chemicals were reported to be effective
Fig. 7. Generally, the GO sheets are transformed into rGO hydrogel cross-linkers for the construction of 3D graphene-based structures
through reduction process, followed by freezing of the hydrogel such as polymers (poly(N-isopropylacrylamide), polypyrrole and
to crystallise the water molecules. The water crystals act as the polyaniline), polysaccharide-based materials (chitosan, sodium
pore forming agent. Finally, the solidified water molecules are sub- alginate, carboxylmethyl cellulose and cyclodextrin), bivalent and
limated under vacuum condition to form a 3D porous rGO aerogel. trivalent metal ions (Ni2+ , Mg2+ and Fe3+ ) (Bai et al., 2011; Chen
The porous microstructure of the 3D graphene-based aerogel is et al., 2017a; Chen et al., 2013c; Khodaverdi et al., 2014; Li et al.,
highly dependent on the nature of hydrogel, freezing conditions 2013c; Lin et al., 2016; Luan et al., 2015; Moussa et al., 2015; Park
and temperature gradient. Zhang et al. (2011c) have prepared a et al., 2008; Zhang et al., 2014a; Zhao et al., 2015a). The type of
mechanically strong and highly conductive graphene-based aero- cross-linking mechanisms formed between the GO and cross-linker
gel for electrochemical application. The 3D graphene aerogel was depends on the cross-linking chemical used (Sui et al., 2013). For
produced by adding l-ascorbic acid into aqueous GO suspension. example, the cross-linking mechanism between chitosan and GO
Upon stirring and heating, the mixture was allowed to stand for was reported to be nucleophilic addition mechanism as the epoxy
at least 16 h for construction of rGO hydrogel. The hydrogel was groups in GO were cross-linked with the amino groups of chitosan
then purified and subjected to freezing and freeze drying to form (Han et al., 2011; Shao et al., 2013). Huang et al. (2015) hypoth-
the graphene-based aerogel. In their research, Zhang et al. (2011c) esised that the GO sheets and polyethyleneimine (PEI) film were
investigated two types of sublimation system which included cross-linked through electrostatic interaction and covalent bond-
freeze drying and super-critical CO2 drying. They reported that ing between the epoxy groups of GO and the primary amine groups
the graphene aerogel made by super-critical CO2 drying exhib- of PEI. The cross-linked GO-PEI film was more mechanically stable
ited remarkable mechanical properties as it could withstand 14000 in water as no brownish yellow colouration leached out from the
times its own weight than that prepared by freeze drying (3300 film after 6 h of oscillation at 120 rpm (Huang et al., 2015).
times its own weight). The aerogel prepared by super-critical CO2 Additionally, cross-linking assembly offers the flexibility in
showed a BET surface of 512 m2 /g which was higher than that of making different 3D graphene structures such as beads. The devel-
aerogel prepared by freeze drying (11.8 m2 /g) (Zhang et al., 2011c). opment of 3D graphene beads has received worldwide attention
Wan et al. (2016) have also investigated the influence of reduc- as an alternative practical structure for fixed bed packing and drug
ing agents (vitamin C (VC), ethanediamine (EDA) and ammonia) carriers (Bao et al., 2016; Ouyang et al., 2015; Platero et al., 2017;
on the formation of graphene aerogel by hydrothermal technique. Rasoulzadeh and Namazi, 2017). Generally, the GO beads were
The specific surface areas for graphene aerogels reduced by VC, synthesised by injecting droplets of GO dispersion and chemical
EDA and ammonia were reported to be 661, 440 and 1089 m2 /g, additives (such as chitosan, sodium alginate or carboxylmethyl cel-
respectively (Wan et al., 2016). However, the highest mechanical lulose) mixture into a cross-linking agent (such as CaCl2 , NaOH,
strength was demonstrated by the VC-reduced graphene aerogel. boric acid or cetyltrimethylammonium bromide). The formed
The researchers further reported that the surface roughness could beads were then washed to remove excess cross-linker molecules.
be governed by the pH values which were determined by the func- Sahraei et al. (2017) developed a novel magnetic PVA-modified
tional groups of reducing agents. The pH of the mixed solutions of gum tragacanth-GO hydrogel beads for the removal of heavy met-
VC-GO, EDA-GO and ammonia-GO before hydrothermal reduction als (lead and copper) and dyes (crystal violet and congo red).
were 3.4, 11 and 10.4, respectively. The acidic condition promoted The Fe3+ functionalised beads displayed high regeneration effi-
agglomeration and fragmentation of graphene sheets during reduc- ciency, bio-compatibility and chemical stability. Additionally, they
tion process whereas the basic condition favoured the production could be easily separated from the liquid phase. The functional-
of larger graphene sheets with thin morphology (Fan et al., 2008; isation of beads with Fe3+ introduced magnetism property and
Wan et al., 2016; Xu et al., 2015). additional chemical functional groups to the beads, and these fea-
tures assisted in the solid-liquid separation as well as enhanced the
2.2.2.5. Cross-linking assembly. Cross-linking induced assembly is removal of pollutants through electrostatic interactions between
based on the addition of different chemicals to promote gelation of the adsorbent and adsorbates. The magnetic beads of spherical
the GO dispersion, construction and strengthening of the 3D struc- shape reportedly had an average diameter of 3.0 mm, a spe-
tures through chemical or physical cross-linking. In this approach, cific surface area of 283.84 m2 /g and an average pore diameter of
the chemical additives act as pore forming agent and introduce new 0.42767 nm (Sahraei et al., 2017).
functional groups to the 3D graphene structure.
272 B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286

3. Adsorption performance of 3D graphene structures such as PVA, gums, chitosan and sodium alginate not only offered
extra functionalities to the adsorbent, but they also improved the
3.1. Adsorption technology mechanical properties and water stability of the adsorbents which
are crucial in the development of an adsorbent to prevent disinte-
Adsorption is a surface phenomenon where accumulation of a gration upon contact with aqueous media.
species at the interface of two phases (solid-liquid or solid-gas) One notable finding from this comparison is that the 3D
is through physical or chemical interaction. The species attached graphene-based structures have higher adsorption capacities than
at the interface is termed as ‘adsorbate’ while the solid on which the 2D GO. The 3D structures possessed properties such as higher
˛
adsorption occurs is known as ‘adsorbent’ (Dabrowski, 2001). Phys- porosity and additional functionalities which induced mechanisms
ical interaction between the adsorbent and adsorbate is called such as hydrogen bonding and physical adsorption (pore entrap-
physisorption while chemical interaction is called chemisorp- ment) to enhance the adsorption capacities (Kim et al., 2015; Gupta
tion. Generally, physisorption is characterised by weak attraction and Khatri, 2017). For instance, the adsorption capacities of mala-
forces between the adsorbate and adsorbent, and the prominent chite green dye onto the 3D graphene structures were remarkably
physical interactions include van der Waal’s, hydrogen, polarity, high in comparison to that of pristine GO. The adsorption capacity of
dipole–dipole and ␲–␲ bonds. For chemisorption, the adsorption malachite green dye increased according to the following adsorbent
is governed by strong interaction between the adsorbate and adsor- types: pristine GO (27.16 mg/g) < 3D GO foam (321 mg/g) < rGO
bent surface through electron exchange. As such, physisorption is powder (476.2 mg/g) < nitrogen-sulphur (N-S) co-doped graphene
a reversible process while chemisorption is an irreversible process hydrogel (738.1 mg/g). The main adsorption mechanism of the
(Yagub et al., 2014). uptake of malachite green dye by GO was electrostatic force, but
Adsorption technology has been widely applied in wastewater additional mechanisms such as ␲-␲ and hydrophobic interactions,
treatment because of its flexibility and non-complicated process, as well as physisorption were observed for the dye uptake by the
as well as its relatively low capital and operating costs. It also does 3D structures. The N–S co-doped graphene hydrogel developed by
not generate toxic secondary sludge when adsorbent regeneration Shi et al. (2016b) was found to exhibit BET specific surface area
is being practised (Tan et al., 2015; Yagub et al., 2014). The efficiency of 41.4 m2 /g. It displayed Type IV adsorption isotherm which sug-
of the system is influenced by operating parameters such as mass gested that the hydrogel was a mesoporous structure in which
of adsorbent, concentration of adsorbate, process temperature, pH multi-layer adsorption and capillary condensation occurred at rel-
and contact time (Ahmed, 2017a; Ahmed, 2017b; Anastopoulos and atively low and high adsorbate pressures, respectively (Jang et al.,
Kyzas, 2014; Da’na, 2017; Ihsanullah Abbas et al., 2016; Peng et al., 2015). Barrett-Joyner-Halenda (BJH) analysis was carried out in
2017). order to determine the pore size distribution of the hydrogel. A
The primary challenges of adsorption process are the selection cumulative pore surface area of BJH (45.56 m2 /g) and total pore
of promising feasible adsorbent from a wide range of commer- volume (0.095 cm3 /g) were reported, signifying both mesopores
cial materials and identification of adsorption mechanism of the and macropores existed in large quantities in the graphene-based
adsorbent-adsorbate species. The type of adsorption mechanism structure which could be the sorption sites (Shi et al., 2016b).
is strongly influenced by the adsorbent textural and morpho- Furthermore, the reduction of GO showed an improvement
logical characteristics such as type of surface functional groups, in adsorption capacity as compared to pristine GO. The forma-
specific surface area, porosity and surface charge. Some of the tion of rGO contributed a conjugate aromatic structure adsorbent
reported adsorption mechanisms include ionic exchange, com- which trapped the adsorbate species via ␲-␲ interaction (Sharma
plexation, chelation, electrostatic interaction, hydrogen bonding, et al., 2013; Xiao et al., 2016). Zhuang et al. (2016) investigated
precipitation, hydrophobic interaction and neutralisation (Yagub the effect of GO reduction on GO-alginate beads for methylene
et al., 2014). In the subsequent sections, the adsorption perfor- blue dye sequestration. In their work, the GO-alginate beads were
mance of 3D graphene-based structures for removal of hazardous known as single network nanocomposite beads (GAS) and the rGO-
pollutants such as synthetic dyes, heavy metals and pharmaceuti- alginate beads as double network nanocomposite beads (GAD).
cal pollutants, are discussed along with the associated adsorption It was reported that GAD showed a higher adsorption capac-
mechanisms. ity (2300 mg/g) than GAS (1840 mg/g). The reported adsorption
mechanisms for GAD included electrostatic interaction, hydrogen
3.2. Adsorption of dyes onto GO and 3D graphene-based bonding and ␲-␲ interaction based on FTIR analysis. The GAD was
structures also reported to have a higher specific surface area (37.6 m2 /g)
and better thermal stability than GAS (3.4 m2 /g). The surface mor-
The performance of an adsorbent can be assessed by several cri- phology of GAD was rougher than GAS which could provide extra
teria; a key criteria is the adsorption capacity which represents the potential binding sites for the adsorbate species (Zhuang et al.,
mass of adsorbate uptake by unit mass of adsorbent. Adsorption 2016).
equilibrium modelling generally provides a quantitative bench-
mark to study the adsorption capacity of different adsorbents under 3.3. Adsorption of heavy metals onto GO and 3D graphene
different process parameters. Meanwhile, adsorption kinetic mod- structures
elling is often used to evaluate the adsorption time and mechanism.
The adsorption of various dyes onto GO and 3D graphene struc- GO and its 3D derivatives have been demonstrated to adsorb
ture are displayed in Table 6. Here, it can be seen that GO and heavy metals effectively. The maximum adsorption capacities of
3D graphene structures are effective adsorbents for removal of different heavy metals on GO and the 3D graphene-based struc-
different dyes, exhibiting comparatively large adsorption capaci- tures are summarised in Table 7. The uptake of the heavy metals
ties. The mechanism of dyes uptake by GO and the 3D structures varied with the GO composite type, pH condition, process tem-
was driven mostly by electrostatic and ␲-␲ interactions between perature and concentration of the heavy metals. As evident from
the adsorbent and adsorbate. Generally, the adsorption equilibrium Table 7, the mechanism of heavy metals adsorption onto GO and
and kinetic of the dyes-GO and dyes-3D graphene structure systems its 3D configurations was mainly due to surface complexation, ionic
were well described by Langmuir and pseudo-second-order (PSO) exchange and electrostatic interaction. Data modelling suggested
models, respectively, suggesting that monolayer adsorbates were that the adsorption systems generally involved monolayer deposi-
attached onto the active sites by chemisorption. Chemical additives tion of the heavy metals on the adsorbents which were controlled
Table 6
Adsorption capacity and mechanism of different dyes onto GO and 3D graphene-based structures.

Adsorbent Adsorbate Co (mg/L) T (◦ C) m (mg) pH t (min) qm (mg/g) Isotherm model Kinetic model Mechanism Reference

GO Basic Yellow 28 10–50 20–60 40 3–11 10–240 68.5 Langmuir PSO Electrostatic interaction, Konicki et al. (2017a)
hydrogen bonding
Basic Red 46 10–50 20–60 40 3–11 10–240 76.9 Langmuir PSO Electrostatic interaction, Konicki et al. (2017a)
hydrogen bonding
Acid Orange 8 10–50 20–60 40 3–11 10–240 29 Langmuir PSO Electrostatic interaction, Konicki et al. (2017b)

B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286
hydrogen bonding
Direct Red 23 10–50 20–60 40 3–11 10–240 15.3 Langmuir PSO Electrostatic interaction, Konicki et al. (2017b)
hydrogen bonding
Proflavine 6 15–40 6–25 mg/L 8.5 0–130 – Freundlich PSO Electrostatic interaction, Bhattacharyya et al.
hydrogen bonding (2017)
Malachite green 25 20 - 35 20 3–9 10–120 27.16 Langmuir PSO Electrostatic interaction Robati et al. (2016)
Methylene blue 25–125 RTP – 3–12 0–90 135.1 Langmuir PSO Electrostatic interaction. Minitha et al. (2017)
Methyl orange 25–125 RTP – 3–12 0–90 66.7 Langmuir PSO Electrostatic interaction Patiño et al. (2015)
Acid blue 22 1–2 mM 18–35 – 4–9 5–120 4.273 mmol/g Langmuir PSO Electrostatic interaction Sharma et al. (2013)

3D GO foams Rhodamine B – 37 3 4–9.2 0–480 446 Langmuir PSO Electrostatic interaction, Jayanthi et al. (2016)
␲–␲ interaction, electron
transfer
Malachite green – 37 3 4–9.2 0–480 321 Langmuir PSO Electrostatic interaction, Zhang et al. (2009)
␲–␲ interaction, electron
transfer
Acriflavine – 37 3 4–9.2 0–480 228 Langmuir PSO Electrostatic interaction, Ihsanullah Abbas et al.
␲–␲ interaction, electron (2016)
transfer
GO/chitin nanofibril Methylene blue 12–108 30 20 – – 173.3 Langmuir – Cation–anion interaction, Ma et al. (2016)
composite foam ␲–␲ interaction
N-S co-doped graphene Malachite green 40–220 20–40 8 3–10 720 738.1 Langmuir PSO ␲–␲ interaction, Shi et al. (2016b)
hydrogel electrostatic interaction,
hydrophobic interaction
3D GO/alginate beads Methylene blue 0.05–3.5 mmol/L 20 ± 0.5 30 4–9 1440 4.25 mmol/g Langmuir – ␲–␲ interaction, Platero et al. (2017)
electrostatic interaction.
Methylene blue 1–3000 25 – 8 1440 1840 Langmuir PSO ␲–␲ interaction, Zhuang et al. (2016)
electrostatic interaction.
3D graphene aerogel Rhodamine B 100 30–50 5 – 600 280.8 Langmuir PSO ␲–␲ interaction, hydrogen Liu et al. (2017a)
bonding
Xanthan gum/GO aerogel Rhodamine B – – 5 – 1440 244.36 Langmuir PSO – Liu et al. (2017b)
Methylene blue – – 5 – 1440 290.57 Langmuir PSO – Liu et al. (2017b)
PVA-supported GO Congo red 40 – – – 2880 36.7%* – – Hydrogen bonding, ␲–␲ Dai et al. (2016)
aerogel interaction.
Methylene blue 25 – – – 2880 96%* – – Electrostatic interaction, Dai et al. (2016)
hydrogen bonding, ␲–␲
interaction.

273
 274
Table 6 (Continued)

Adsorbent Adsorbate Co (mg/L) T (◦ C) m (mg) pH t (min) qm (mg/g) Isotherm model Kinetic model Mechanism Reference

Anionic Basic fuchsin 100–400 0–40 5–65 2.6–8.9 0–3300 1034.3 Langmuir PSO Hydrogen bonding, Yang et al. (2015)
polyacrylamide/GO intermolecular force, ␲–␲
aerogel interaction

B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286
rGO powder Malachite green 50–200 30–50 50 3.7–9.0 0–600 476.2 Langmuir PSO Electrostatic interaction, Gupta and Khatri
␲–␲ interaction, pores (2017)
trapping
Acid blue 22 1–2 mM 18–35 – 4–9 5–120 6.256 mmol/g Langmuir PSO Electrostatic interaction, Sharma et al. (2013)
␲–␲ interaction
Magnetic graphene Methylene blue 50–400 25 5 2–12 5–420 526 Langmuir PSO Electrostatic interaction Yu et al. (2015a)
sponge
Ionic liquid–GO sponge Direct red 80 25–00 23 0.1–1 g/L 2–10 2.5–90 500 Langmuir PSO Electrostatic interaction, Zambare et al. (2017)
(mimGO) ␲–␲ interaction
Zeolitic imidazolate Malachite green 0–100 20–40 3–20 2.2–7 0–240 3300 Langmuir PSO Electrostatic interaction, Abdi et al. (2017)
framework-GO ␲–␲ interaction, Lewis
(ZIF-GO) acid-base interaction,
hydrogen bonding,
hydrophobic interaction
3D rGO/alginate beads Methylene blue 1–3000 25 – 8 1440 2300 Langmuir PSO ␲–␲ interaction, Zhuang et al. (2016)
electrostatic interaction,
hydrogen bonding
Cetyltrimethylammonium Acid red 265 25–150 25–50 0.01–0.1 1–10 0–210 510.67 Langmuir PSO ␲–␲ interaction, Yusuf et al. (2017)
bromide (CTAB) electrostatic interaction,
intercalated graphene van der Waals interaction
composite
Acid orange 7 25–150 25–50 0.01–0.1 1–10 0–210 355.89 Langmuir PSO ␲-␲ interaction, Yusuf et al. (2017)
electrostatic interaction,
van der Waals interaction
3D rGO macrostructure Acid red 1 50–300 – – 7 0–90 277.01 Langmuir PSO ␲–␲ interaction, Kim et al. (2015)
electrostatic interaction,
hydrogen bonding
Methylene blue 50–300 – – 7 0–90 302.11 Langmuir PSO ␲–␲ interaction, Kim et al. (2015)
electrostatic interaction,
hydrogen bonding

Note: Co – initial concentration of adsorbate, T – temperature, m – adsorbent dosage, t – contact time, qm – maximum adsorption capacity based on highest R2 on Langmuir isotherm fitting, RTP – room temperature, PSO –
pseudo-second-order kinetic model.
‘–’ denotes unavailable/not applicable, ‘*’ denotes removal percentage.
Table 7
Adsorption capacity and mechanism of different heavy metals onto GO and 3D graphene–based structures.

Adsorbate Adsorbent Co (mg/L) T (◦ C) m (mg) pH t (min) qm (mg/g) Isotherm model Kinetic model Mechanism Reference
3+
As Iron oxide/GO nanocomposite 0.1–1200 23 2.4 2–10 15–1440 147 Langmuir PSO Complexation, electrostatic Su et al. (2017)
interaction
Magnetite-GO composite – 25 3 4–10 0–1440 42.9 Langmuir PSO Complexation, electrostatic Yoon et al. (2016)
interaction
Magnetite-rGO composite – 25 3 4–10 0–1440 29.8 Langmuir PSO Complexation, electrostatic Yoon et al. (2016)
interaction
As5+ Iron oxide/GO nanocomposite 0.1–1200 23 2.4 2–10 15–1440 113 Langmuir PSO Complexation, electrostatic Su et al. (2017)

B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286
interaction
3D Fe3 O4 /graphene aerogels 0.5–30 25 2 7 720 40.05 Langmuir PSO – Ye et al. (2015)
Magnetite GO encapsulated in 10–200 20 5 g/L 3–10 0–1440 6.859 Langmuir PSO Electrostatic interaction, Vu et al. (2017)
alginate beads chemical interaction
Cd2+ GO – – 10 2–8 0–120 30.8 Langmuir PSO Electrostatic interaction, Bian et al. (2015)
ionic exchange
3D sulfonated rGO aerogel – 25 1 2–9 0–1440 234.8 Langmuir PSO Cation exchange, Wu et al. (2015)
electrostatic interaction
Modified gum tragacanth/GO 20–100 25 5–30 2–6 0–3600 112.5 Langmuir PSO Electrostatic interaction, Sahraei and Ghaemy, (2017)
composite hydrogel chelation, ionic exchange
GO/zirconium phosphate 5–400 – 100 1–8 0–400 232.4 Freundlich PSO Chemical interaction, Pourbeyram (2016)
(GO-Zr-P) nanocomposite electrostatic interaction
Cr6+ Nanoscale zerovalent iron 15–35 RTP 20 3–13 0–180 21.72 Langmuir PFO Electrostatic interaction Li et al. (2016)
decorated graphene
nanosheets (NZVI/GNS)
3-aminopropyltriethoxysilane- 50–200 10–55 20 2–8 5–480 215.2 Langmuir PSO Electrostatic interaction, He et al. (2017)
functionalized GO hydrogen bonding,
(AS-GO) electron transfer, chelation
Magnetic 5–50 30–50 100 1–7 – 67.66 Langmuir PSO Electrostatic interaction, Li et al. (2013a)
cyclodextrin-chitosan/GO complexion, electron
composite transfer, physisorption
Magnetite GO encapsulated in 10–200 20 5 g/L 3–10 0–1440 14.90 Langmuir PSO Electrostatic interaction, Vu et al. (2017)
alginate beads chemical interaction
Poly(m- 50–250 RTP 10 2–9 0–90 502.5 Langmuir PSO Electrostatic interaction, Wang et al. (2017e)
phenylenediamine)/rGO/nickel reduction of Cr6+ to Cr3+
ferrite magnetic adsorbent
Amino functionalised GO – 25–45 0.2 g/L 1–8 0–300 123.4 Langmuir PSO Electrostatic interaction, Zhao et al. (2016)
decorated with Fe3 O4 chemical reduction by
nanoparticle electron transfer
Cu2+ GO/chitosan aerogel 1.92–32 30 5 2–7 720 25.4 Langmuir PSO Physisorption, Yu et al. (2013)
GO/zirconium phosphate 5–400 – 100 1–8 0–400 328.6 Freundlich PSO Chemical interaction, Pourbeyram (2016)
(GO-Zr-P) nanocomposite electrostatic interaction
GO – 25 2 2–8 0–120 294 mmol/g Langmuir PSO Electrostatic interaction Sitko et al. (2013)
GO membranes 5–100 30 4 2–7 0–50 72.6 Langmuir PSO Ionic exchange, Tan et al. (2015)
electrostatic interaction
Poly-allylamide 10–210 20 10 1–6 0–350 349 Langmuir PSO Surface complexation, Xing et al. (2015)
hydrochloride/GO composite metal coordination,
(PAH/GO) electrostatic interaction

275
 276
Table 7 (Continued)

Adsorbate Adsorbent Co (mg/L) T (◦ C) m (mg) pH t (min) qm (mg/g) Isotherm model Kinetic model Mechanism Reference

Hg2+ Magnetic polypyrrole-GO 20–100 27–47 0.01–0.09 g/L 2–10 20–720 400 Langmuir PSO Ionic exchange, hydrogen Zhou et al. (2017)
nanocomposite (PPy-GO) bonding, electrostatic
contact
Thymine-grafted rGO – 25–45 – 2–6 0–180 128 Langmuir PSO Coordination of NH with Liu et al. (2016d)
complexes Hg2+ , chelation.
GO foam 50 ␮g/L 21 1–20 mg/L 3–9 0–2880 35 Langmuir PSO Chemical interaction, ionic Henriques et al. (2016)
exchange
Graphene-diatom silica aerogel 50–400 21 10 2–10 0–90 >500 Langmuir PSO Physical trapping, Kabiri et al. (2015)
electrostatic interaction,

B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286
chemical bonding by
functional group
Ni2+ Porous GO/carboxymethyl 40–300 20–50 100 7 1–60 – Freundlich PSO Chelation Wu et al. (2014)
cellulose/sawdust
Glycerine-functionalised GO 10–25 10–35 20 – 10–70 36.63 Langmuir PSO – Najafi et al. (2015)
GO/cellulose membrane 1–20 25 – 1–8 15–180 14.3 Langmuir PSO Electrostatic interaction, Sitko et al. (2016)
chelation, complexation
Fe3 O4 /rGO nanocomposite 20–100 25 100 2–7 0–240 76.34 Langmuir PSO Electrostatic interaction, Vuong Hoan et al. (2016)
protonation and ionisation
Pb2+ Carboxymethyl cellulose 100 20 30 2–12 0–240 19.19 Langmuir PSO Electrostatic interactions, Liu et al. (2016b)
sodium/GO hydrogel surface complexation, ionic
microparticles exchange
EDTA/GO 5–300 25 10–25 2–8.2 3–120 479 Langmuir PSO Electrostatic interaction, Madadrang et al. (2012)
ionic exchange, surface
complexation
GO 10.37–259.25 30 – 5 5–180 766.8 Langmuir PSO Surface complexation Peng et al. (2016b)
GO/zirconium phosphate 5–400 – 100 1–8 0–400 363.4 Freundlich PSO Chemical interaction, Pourbeyram (2016)
(GO-Zr-P) nanocomposite electrostatic interaction
3D graphene/␦-MnO2 aerogel 1–200 25 65 2–6 0–200 643.3 Langmuir PSO Ionic exchange, Interlayer Liu et al. (2016c)
trapping, complexation,
interaction
GO-wrapped magnetic 50–400 30 – 2–7 0–1400 255.6 Langmuir PSO Chelation, electrostatic Hu et al. (2017)
composite interaction, covalent
bonding
Polymer based GO magnetic 2.5–10 20–35 4 3–7 0–1400 73.52 Langmuir Electrostatic attraction and Ravishankar et al. (2016)
nano-sorbent chelation
U6+ GO/amidoxime hydrogel – RTP 10 2–12 0–360 398.4 Langmuir PSO Chelation, hydrogen Wang et al. (2016)
bonding, electrostatic
interaction
GO 0.04–0.6 mM RTP 0.1 g/L 1–10 0–1440 299 Langmuir PSO Surface complexation, Li et al. (2012)
electrostatic interaction
rGO 0.04–0.6 mM RTP 0.1 g/L 1–10 0–1440 47 Langmuir PSO Surface complexation, Li et al. (2012)
electrostatic interaction
GO-activated carbon felt 0–50 RTP 10 1–11 0–60 298 Langmuir PSO Electrostatic interaction, Chen et al. (2013b)
composite surface complexation
Bovine Serum Albumin-coated 50–600 25 10 3–10 0–300 389 Langmuir PSO Coordination, electrostatic Yang et al. (2017)
GO (BVA-GO) interaction, intraparticle
diffusion

Note: Co – initial concentration of adsorbate, T – temperature, m – adsorbent dosage, t – contact time, qm – maximum adsorption capacity, RTP – room temperature, PSO – pseudo-second-order kinetic model.
‘–’ denotes unavailable/not applicable.
 B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286 277

by chemisorption, as proven from the best-fit of data to Langmuir nificantly improved. For instance, the 3D sulfonated rGO aerogel
isotherm and PSO kinetic models. constructed by Wu et al. (2015) exhibited remarkable Cd2+ adsorp-
Generally, GO has a strong adsorption affinity towards differ- tion capacity (234.8 mg/g) as compared to GO (139.9 mg/g) and
ent heavy metals due to the existence of reactive oxide functional activated carbon (23.5 mg/g). The aerogel was synthesised through
groups including hydroxyl and carboxyl groups. The affinity of GO freeze drying of a mixture of rGO aqueous dispersion and diazo-
towards divalent heavy metals increased in the following order: nium salt solution from sulfanilic acid. The sulfonation process
Zn2+ > Cd2+ > Cu2+ > Pb2+ (Sitko et al., 2013). The affinity order was introduced extra -SO3 H functional groups into the rGO surface.
in good agreement with the electronegativity and stability constant The findings of zeta potential suggested that the 3D aerogel was
trends of the resulted metal hydroxide (Dastgheib and Rockstraw, negatively charged over pH ranging from 2 to 10, favouring the
2002, Peng et al., 2017). The higher the electronegativity of heavy adsorption of positively charged heavy metals (Wu et al., 2015).
metal, the stronger the attraction force between the cationic metal The incorporation of metal oxide into GO has been carried out
and anionic GO surface. The standard reduction potential (elec- to produce effective adsorbents for heavy metal decontamination
tronegativity) for Pb2+ , Cu2+ , Cd2+ and Zn2+ were reported to be (Liu et al., 2016c; Vuong Hoan et al., 2016; Ye et al., 2015). Liu et al.
−0.1262, −0.3419, −0.4030 and −0.7618 V, respectively, which (2016c) reported a highly efficient 3D graphene-␦-MnO2 aerogel
supported the above affinity sequence (Haynes and Handbook, for Pb2+ , Cd2+ and Cu2+ removal. Manganese, oxygen and carbon
2010). were determined to be uniformly distributed in the 3D graphene-
The formation of metal complexes through surface complex- based structure, and K+ was successfully incorporated into the
ation between the cationic metal and anionic functional groups structure. The unique layer of ␦-MnO2 offered additional uptake
on the GO surface (e.g. OH and COOH) is one of the adsorp- capability, from surface to bulk adsorption, through ionic exchange
tion mechanisms, and the speciation of heavy metal complexes is with the pre-inserted K+ (Liu et al., 2016c). It was also reported
determined by the stability constant. The general equations for the that adsorption of Pb2 resulted in the disappearance of Mn O lat-
formation of metal hydroxide and metal acetate are represented by tice vibration bands. The maximum adsorption capacities of Pb2+ ,
the following equations: Cd2+ and Cu2+ onto the 3D graphene-␦-MnO2 aerogel were 643.62,
250.31 and 228.46 mg/g, respectively. The results indicated that
M n+ + OH − ↔ M(OH)n (1) incorporation of metal oxide to the 3D graphene-based structure
M n+ + CH3 COOH − ↔ M(CH3 COOH)n (2) was an effective functionalisation approach to enhance the adsorp-
tion performance (Liu et al., 2016c).
where M is the metal species and n is the heavy metal valency.
The first stability constant of the above metal hydroxide (log 3.4. Adsorption of pharmaceuticals on GO and 3D graphene
K1 = 7.82, 7.0, 4.17 and 4.4 for Pb2+ , Cu2+ , Cd2+ and Zn2+ , respec- structures
tively) and metal acetate (log K1 = 2.52, 2.16, 1.5 and 1.5 for
Pb2+ , Cu2+ , Cd2+ and Zn2+ , respectively) complexes were in good Various studies have indicated that GO and its derivatives are
agreement with the aforementioned heavy metal ions affinity effective adsorbents for sequestrating pharmaceuticals in aqueous
(Dean, 1990). Similar findings have been reported by Gu and media. Table 8 summarises the maximum adsorption capacities
Fein (2015). Sitko et al. (2016) studied the selectivity of dif- of different pharmaceuticals on GO and the 3D graphene-based
ferent divalent heavy metals by GO-cellulose membrane and structures. The tabulated data showed that several adsorption
found that the adsorption capacity increased in the following mechanisms were involved in the pharmaceuticals uptake, with
order: Co2+ > Zn2+ > Ni2+ > Cu2+ > Cd2+ > Pb2+ . GO-zirconium phos- the main mechanisms being hydrogen bonding, ␲-␲, hydropho-
phate (GO-Zr-P) nanocomposite and 3D graphene-␦-MnO2 aerogel bic and electrostatic interactions (Fei et al., 2016; Liu et al., 2014;
demonstrated different heavy metal affinity order which was as fol- Liu et al., 2016a; Wang et al., 2017c). As observed in Table 8, the
lows: Cd2+ > Zn2+ > Cu2+ > Pb2+ and Cu2+ > Cd2+ > Pb2+ , respectively adsorption equilibrium and kinetic of the different pharmaceuti-
(Liu et al., 2016c; Pourbeyram, 2016). Generally, GO and its 3D cals on GO and its 3D derivatives were mostly best correlated to
structures have strong affinity towards Pb2+ . The overall adsorp- Langmuir and PSO kinetic models. The adsorption of pharmaceuti-
tion capacity of the 3D graphene structure has been significantly cal residues such as antibiotics and nonsteroidal anti-inflammatory
improved as compared to the pristine GO. However, there is no drugs (NSAIDs) using GO and its 3D structures have been commonly
apparent trend to predict the order of heavy metal affinity by GO investigated by other researchers. To date, however, there are lim-
and its derivatives because the chemical functional groups avail- ited reports on the adsorption of antidepressants, anticonvulsants,
able on their structures are dependent on the functionalisation antineoplastic and diagnostic contrast media onto GO and its 3D
process and chemical reagent used. Nonetheless, it is important derivatives.
to understand the selectivity of adsorbent to synthesise a suitable The morphological and internal properties of adsorbents con-
nanosorbent for wastewater treatment. tribute significantly to the pharmaceuticals adsorption as different
The adsorption performance of GO for U6+ was shown to be bet- functionalities in the adsorbents can result in different adsorption
ter than that of rGO, as evident from the higher adsorption capacity mechanisms (Khan et al., 2017). This was evident from adsorp-
of GO (299 mg/g) than rGO (47 mg/g) (Li et al., 2012). From the tion of tetracycline on magnetic GO sponge as reported by Yu
study, the chemical functional groups in the adsorbents played a et al. (2017a). The developed magnetic GO sponge was able to
vital role in the sequestration of U6+ in aqueous medium. It was achieve a maximum adsorption capacity of 473 mg/g, ∼50% greater
reported that the GO contained functional groups such as hydroxyl, than that of the GO material developed by Gao et al. (2012). The
carbonyl and carboxyl groups, while the rGO contained mainly non- incorporation of Fe3 O4 nanoparticles into the GO matrix intro-
oxygenated carbon (Li et al., 2012). The functional groups of GO duced superparamagnetic property to the GO sponge enabling
contributed to the negatively charged surface to attract the cationic solid-liquid separation by magnetism. The magnetic GO sponge was
U6+ through electrostatic interaction. The same trend was observed prepared by lyophilising the mixture of GO and Fe3 O4 nanoparti-
in adsorption of Pb2+ onto GO and rGO, and the reported maximum cles through co-precipitation. According to Yu et al. (2017a), the
adsorption capacities were 766.8 and 413.22 mg/g, respectively Fe3 O4 nanoparticles were responsible for the increase in adsorption
(Peng et al., 2016b; Wang et al., 2014). However, through chem- capacity of tetracycline as the nanoparticles prevented restacking
ical functionalisation and construction of 2D GO sheets into 3D of GO sheets during lyophilisation and adsorption process. The per-
structure, the heavy metals adsorption performance could be sig- formance of the magnetic GO sponge was compared with other
 278
Table 8
Adsorption capacity and mechanism of pharmaceuticals onto GO and 3D graphene-based structures.

Adsorbate Adsorbent Co (mg/L) T (◦ C) m (mg) pH t (min) qm (mg/g) Isotherm model Kinetic model Mechanism Reference

Antibiotics
Sulfamethoxazole 3D cellulose nanofibril/GO 20–160 25–45 0.25–2 0.0 g/L 2–12 0–180 302.7 Langmuir PSO Electrostatic attraction, Yao et al. (2017)
hybrid aerogel p-␲, ␲–␲ interactions,
hydrogen bonding,
physical adsorption

B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286
GO nanosheets – 25–45 10 3–11 0–240 122 Redlich-Peterson PSO ␲–␲ interaction, Rostamian and
and Koble-Corrigan electrostatic interaction Behnejad, (2016)
Tetracycline Magnetic GO sponge 50–1000 0–55 5 2–12 60–2880 473 Langmuir PSO ␲–␲ interaction, hydrogen Yu et al. (2017a)
bonding, electrostatic
interaction
GO 8.33–333.33 4–45 – 3–11 15–150 313.5 Langmuir PSO ␲–␲ interaction, cation-␲ Gao et al. (2012)
bonding, electrostatic
interaction
Magnetic GO doped with 10–100 20–40 5–100 2–10 1–180 65.78 Langmuir PSO Electrostatic and ␲–␲ Rashidi Nodeh and
strontium titanium interaction, hydrogen Sereshti, (2016)
trioxide nanoparticle bonding
Ciprofloxacin Sodium alginate/GO 10–150 25 20 2–12 0–170 h 86.12 Langmuir PSO ␲–␲ interaction Yao et al. (2017)
hydrogel beads
GO/calcium alginate – RTP 0.25–2.0 g/L 3–9.3 0–1440 66.25 Langmuir PSO Ionic exchange, surface Wu et al. (2013)
bio-composite fibres complexation, electrostatic
interaction
Long TiO2 nanotube/GO 1–200 25 10 7 1440 181.8 Langmuir – ␲–␲ interaction, hydrogen Zhuang et al. (2015)
hydrogel bonding and electron
transfer
Doxycycline GO/cellulose nanofibril – 25 8 – – 469.7 Langmuir PSO ␲–␲ interaction, hydrogen Wang et al. (2017c)
hybrid aerogel bonding, electrostatic
interaction
Anticonvulsants
Carbamazepine rGO 6–100 25 – 2–12 7 day 115 Dubinin-Ashtakhov - Hydrogen bonding, Liu et al. (2014)
electrostatic interaction,
␲–␲ interaction
GO-C 5–220 RTP 0.5–2.0 g/L 3–11 0–1440 110 Freundlich PSO ␲–␲ interaction, Cai and
electrostatic interaction Larese-Casanova,
(2014)
Beta blocker
Atenolol GO 10–150 25–65 10 2–10 0–1440 116 Langmuir PSO Electrostatic and ␲–␲ Kyzas et al. (2015)
interaction, hydrogen
bonding
Propranolol GO 10–150 25–65 10 2–10 0–1440 67 Langmuir PSO Electrostatic and ␲–␲ Kyzas et al. (2015)
interaction, hydrogen
bonding
 Dorzolamide GO and acrylic acid grafted 0–500 25–65 20 3–9 0–1440 334 Langmuir- PSO Electrostatic and polar Kyzas et al. (2014)
chitosan Freundlich interaction, hydrogen
bonding, Lewis acid-base,
amide formation

B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286
Hormones
17-␤ Estradiol Few-layered GO 1–16 25–65 3 3–12 15–720 149.4 Langmuir PSO Hydrogen bonding, ␲–␲ Jiang et al. (2016)
nanosheets interaction
␤-cyclodextrin/ poly – 25–50 5 4.2–10.1 0–1440 85.80 Langmuir PSO Hydrogen bonding, ␲–␲ Jiang et al. (2017)
(l-glutamic acid) interaction, hydrophobic
supported magnetic GO effect, electrostatic
interaction
Superparamagnetic 1–10 – 0.5 g/L 3–11 20–720 106.38 Langmuir PSO Hydrogen bonding, ␲–␲ Bai et al. (2017)
amino-functionalised GO interaction, electrostatic
nanocomposite* interaction
Lipid regulators
Clorfibric acid GO 1–2000 25 5 3–11 5–120 994 Langmuir PSO Hydrogen bonding, ␲–␲ Zhang et al. (2014b)
interaction, electrostatic
interaction
NSAIDs
Diclofenac GO 10–100 20 0.1 g/L 3–11 0–1440 500 Langmuir PSO Hydrophobic, ␲–␲ Nam et al. (2015)
interaction, electrostatic
interaction
rGO 20–200 25 30 8–10 0–480 59.67 Liu* PSO ␲–␲ interaction, Jauris et al. (2016)
electrostatic interaction
High surface area graphene 20 8–50 0–40 2–11 0–60 19.3 **
– PSO ␲–␲ interaction, Al-Khateeb et al. (2017)
nanoplatelets electrostatic interaction
Naproxen High surface area graphene 20 8–50 0–40 2–11 0–60 17.8** – PSO ␲–␲ interaction, Al-Khateeb et al. (2017)
nanoplatelets electrostatic interaction
Paracetamol Porous 0.03.0.41 mmol/L 25 5 4–10 0–72 h 350.6 ␮mol/g Freundlich PSO ␲–␲ interaction, Shan et al. (2017)
GO/decafluorobiphenyl electrostatic interaction,
(DFB) composite hydrophobic interaction
Ketoprofen rGO 6–100 25 – 2–12 7 day 62.5 Dubinin-Ashtakhov - Hydrogen bonding, Liu et al. (2014)
electrostatic interaction,
␲–␲ interaction
Ibuprofen GO nanoplatelets 2–10 25–40 0.50–1.25 g/L 2–10 180 3.24 Langmuir PSO Electrostatic interaction Banerjee et al. (2016)

Note: Co – initial concentration of adsorbate, T – temperature, m – adsorbent dosage, t – contact time, qm – maximum adsorption capacity, RTP – room temperature, PSO – pseudo-second-order kinetic model.
‘–’ denotes unavailable/not applicable.

279
280 B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286

Table 9
Regeneration conditions for elution of dyes, heavy metals and pharmaceuticals from GO and its 3D structures.

Adsorbate Adsorbent Eluting agent Desorption cycle Desorption efficiency (%) Reference

Synthetic dyes
Methylene blue Magnetic GO/PVA composite gel 0.1 M HCl 5 >85 Cheng et al. (2015)
Chrysoidine Y Magnetic GO-Fe3 O4 nanocomposite 0.1 M HCl 5 86.6 Hao et al. (2015)
Malachite green N-S co-doped graphene hydrogel – 6 ∼100 Shi et al. (2016b)
Heavy metals
Cu2+ Porous chitosan-gelatin/GO monoliths HNO3 6 81 Zhang et al. (2011b)
Pb2+ GO/zirconium phosphate (GO-Zr-P) 3 M HCl 5 90 Pourbeyram (2016)
nanocomposite
As3+ Graphene modified by iron-manganese 0.1 M NaOH and 0.1 M 4 >90 Zhu et al. (2015)
binary oxide (FeMnOx /rGO) NaClO
PPs
Tetracycline 3D cellulose nanofiber (CNF)/GO 5 wt.% NaOH 10 78.9 Yao et al. (2017)
hybrid aerogel
17-␤ Estradiol Few-layered GO nanosheets 4 wt.% NaOH and acetone 5 94.14 Jiang et al. (2016)
Dorzolamide GO and acrylic acid grafted chitosan Deionised water at acidic 10 90 Kyzas et al. (2014)
(GO/CSA) condition (pH = 3)

magnetic graphene derivatives (Lin et al., 2013, Rashidi Nodeh and 4. Regeneration of GO and 3D graphene-based structures
Sereshti, 2016). It was found that the larger the Fe3 O4 nanoparti-
cle, the more Fe3 O4 nanoparticles of the same size were required to An effective adsorbent should not only exhibit high adsorption
avoid GO re-stacking during functionalisation. Yu et al. (2017a) also capability, but also display high desorption efficiency. This is to
compared the surface functionalities of their magnetic GO sponge regenerate exhausted adsorbents for re-use in the adsorption pro-
(modified by citric acid) with GO-Fe3 O4 nanoparticles (modified cess. This approach could assist in the reduction of overall operating
by NH2 ) prepared by Lin et al. (2013). The positively charged NH2 cost and elimination of secondary solid waste formation. Desorp-
caused the Fe3 O4 nanoparticles to be attached tightly to the exist- tion performance and regeneration efficiency of an adsorbent are
ing oxygenated groups on the GO surface, hindering the formation hence crucial for the application of GO and its derivatives in large-
of hydrogen bonds between the tetracycline and the sorption sites, scale wastewater treatment. Several regeneration methods such as
and hence a reduction in adsorption capacity was observed. The steam treatment, electrochemical treatment, temperature change,
drying method applied during the synthesis stage could also affect pressure swing and chemical eluting agents have been applied to
the adsorption performance of the GO composite. As a comparison, regenerate exhausted adsorbents (Lata et al., 2015). The majority of
Lin et al. (2013) prepared a GO composite through hydrothermal the studies reported that the regeneration of GO and 3D graphene
process while Yu et al. (2017a) utilised lyophilisation to prepare structures using chemical eluting agents (acid, base and organic
a magnetic GO sponge. The hydrothermal process resulted in the solvent) was effective. Table 9 summarises the regeneration param-
reduction of GO which caused serious stacking of the GO sheets and eters for GO and 3D graphene-based structures for the pollutants
subsequently lowered the adsorption capacity. of interest in this review.
A 3D cellulose nanofiber (CNF)-GO hybrid aerogel developed The selection of an appropriate eluting agent is one of the
by Yao et al. (2017) demonstrated a remarkably high adsorption keys to achieving good recovery and good desorption efficiency
capacity (302.7 mg/g) for sulfamethoxazole in comparison with of an adsorbent. For instance, Zhu et al. (2015) have attempted
other adsorbents such as GO nanosheets (122 mg/g, Rostamian to regenerate graphene modified by iron-manganese binary oxide
and Behnejad, 2016), functionalised multi-walled carbon nanotube (FeMnOx -rGO) from As3+ using a mixture of 0.1 M NaOH and 0.1 M
(118.58 mg/g, (Song et al., 2016)) and activated carbon (42.5 mg/g, NaClO as the eluting agent. The regeneration efficiency of this
(Akhtar et al., 2011)). The CNF-GO aerogel had a porous microstruc- system was reported to be >90% after 4 adsorption-desorption
ture network of pore sizes varying from nano- to macro-scale, cycles. Sahu et al. (2017) reported that a desorption efficiency of
enhancing the adsorption capacity. The BET surface area and pore ∼81% was achieved for regeneration of organically modified silica-
volume of the aerogel were 97.5 m2 /g and 0.4 cm3 /g, respectively magnetite rGO (ORMOSIL-Fe3 O4 -rGO) composite using 0.1 M HNO3
The BJH analysis suggested that the CNF-GO aerogel had uni- (Sahu et al., 2017). One notable finding was reported by Kyzas
formly distributed mesopores of 0.2 nm pore size (Yao et al., et al. (2014) on desorption of dorzolamide from GO and acrylic
2017). These morphological properties indicated the CNF-GO aero- acid-grafted chitosan nanocomposite (GO-CSA). The regeneration
gel possessed high surface area. The 3D aerogel also exhibited efficiency of GO was compared to that of GO-CSA using deionised
removal efficiency greater than 69% for six different antibiotics. The water as the eluting agent at pH 3. After 10 adsorption-desorption
adsorption efficiency of the antibiotics increased in the following cycles, the removal efficiencies of GO and GO-CSA were 15% and
order: quinolones (128.3 mg/g) < sulphonamides (227.3 mg/g) < ␤- 90%, respectively, showing a distinctive difference in dorzolamide
lactams (230.7 mg/g) < macrolides (291.8 mg/g) < chloramphenicol removal performance of these two materials. The decrease in subse-
(418.7 mg/g) < tetracyclines (454.6 mg/g) (Yao et al., 2017). Addi- quent adsorption efficiency could be due to progressive saturation
tionally, the CNF-GO matrix contained numerous hydroxyl groups of adsorbent by dorzolamide or material degradation under the
which facilitated the pharmaceuticals uptake through hydrogen extreme pH condition (Kyzas et al., 2014). Therefore, a systematic
bonding. The ␲-␲ stacking of CNF-GO enabled ␲-␲ electron donor- investigation on other regeneration conditions such as type of elut-
acceptor (EDA) interaction to attract unsaturated double bond or ing agent, pH, temperature, adsorption-desorption cycle number
conjugate structure of the antibiotics molecules (Yao et al., 2017). and desorption time are necessary in adsorbent development to
reduce the replacement cost of exhausted adsorbent.
 B.Y.Z. Hiew et al. / Process Safety and Environmental Protection 116 (2018) 262–286 281

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