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Article history:
Received 1 March 2014
Received in revised form
9 August 2014
Accepted 17 September 2014
Available online 1 November 2014
Alarming carbon dioxide emissions and its detrimental environmental impacts (e.g. climate change and
global warming) are the major consequences of the undue reliance of the modern civilization on fossil
fuels. Long-term solutions to address these issues are based on developing sustainable alternatives for
the human energy thirst. However, the versatilities offered by the carbonaceous fuels have still
preserved their popularity as the main source of energy for a wide variety of applications. After decades
of practicing conventional carbon capture and storage, researchers believe the ultimate solution of
realistically facing with CO2 sequestration problem is the chemical conversion of carbon dioxide to
valuable products. However, substantial development of state-of-the-art materials remains the major
bottleneck of such technologies. Graphene, as the rising star of the materials world in 21st century, offers
game-changing prospects towards a more sustainable future for fossil-fuel-based economies. This twodimensional planar sheet of sp2-bonded carbon atoms is the most widely studied nanomaterial since its
discovery in 2004. Here we aim to highlight various aspects of graphene research in carbon dioxide
capture and conversion from materials viewpoint. After presenting an overview of the most common
and effective synthesis and doping/functionalization methods, the application of graphene and its
derivatives in CO2 capture and conversion is discussed in detail. Catalytic, electrocatalytic and
photoelectrocatalytic use of graphene-based compounds could potentially revolutionize some of the
current techniques for CO2 transformation to valuable chemical commodities. CO2 to graphene
conversion pathways are also covered extensively in this review paper as another intriguing relation
of graphene with CO2.
& 2014 Elsevier Ltd. All rights reserved.
Keywords:
CO2
Carbon capture and conversion
Graphene
Catalysis
Electrocatalysis
Photoelectrocatalysis
Contents
1.
2.
3.
4.
5.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1516
Graphene synthesis overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1517
2.1.
Scalable top-down production techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1518
2.2.
Chemical doping/functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1520
2.2.1.
Doping (condensed matter). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1520
2.2.2.
Functionalization (chemical synthesis) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1522
CO2-assisted graphene production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1525
Graphene-assisted CO2 capture. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1527
4.1.
CO2 capture background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1527
4.2.
Graphene-based sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1527
Graphene-assisted CO2 conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1531
5.1.
CO2 conversion background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1531
5.2.
Catalytic reduction of CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1532
5.2.1.
Hydrogen-assisted CO2 reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1532
5.2.2.
Methane-assisted CO2 reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1533
http://dx.doi.org/10.1016/j.rser.2014.09.022
1364-0321/& 2014 Elsevier Ltd. All rights reserved.
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5.3.
Electrocatalytic reduction of CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4.
Photoelectrocatalytic reduction of CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6. Concluding remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
Energy and environmental issues are two of the major challenges facing modern civilization by the mid-century [1]. From this
perspective, fossil fuels are double-edged swords that require a
delicate balance between their benets and drawbacks. On one
hand, they are unquestionably versatile energy supplies; where oil
and natural gas supply close to 90% of our current energy needs,
making so many industrial activities economically feasible [2]. The
adaptabilities offered by the carbonaceous fuels have still preserved their popularity as the main source of energy for a wide
variety of applications. Firstly, they are available in a wide range of
physical formats (gas, liquid and solid) spreading almost all over
the world. Secondly, myriad of technological advances are made
with respect to their implementation for various applications in
different scales. Thirdly, owing to high energy density and portability, their superior properties as fuels in transportation industry
cannot be overstated [3]. On the other hand, the increasingly
alarming climate change issues have occurred due to notable
amounts of carbon dioxide emissions from undue consumption
of fossil fuels [4]. Burning each gram of carbon in fossil fuels
releases more than 3.5 g of carbon dioxide (CO2), accumulation of
which is now approaching 1 Tt in the atmosphere [5]. In order
to limit the consequent global mean temperature increase by
2.02.4 1C, the world-wide CO2 emission must be reduced
5080% by 2050 versus that of 2000 [6,7].
Long-term solutions to address the aforementioned problems
are based on the development of sustainable alternatives for
quenching the ever-increasing human energy thirst. Meanwhile,
in the current fashion of runaway fossil fuel intakes, CO2 reduction
strategies particularly from large-scale energy consumers (e.g.
power stations and cement works) rely mainly on three proposed
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generic solutions for CO2 capture and storage (CCS): pre- and postcombustion capture, and oxy fuel combustion [8,9]. Afterwards,
the puried CO2 is sent for physical storage options such as
deep ocean sequestration [10], geological storage [11], limited
industrial uses (e.g. mineral processing and soda companies)
[12], etc. However, researchers believe that storing CO2 somewhere other than atmosphere is not the permanent solution to the
problem [13,14]. In fact, the long term ecological and environmental impacts of using the earth as a gigantic reservoir for carbon
dioxide are not well-understood [10,15]. The potential hazards of
CO2 leakage to the earth surface remarkably increases the risk of
this approach [16,17]. It also imposes signicant nancial burdens
on the industrial rms from expensive CO2 capture equipment to
hefty sequestration costs ultimately translated into higher prices
for the end-users [18,19].
Based on the facts mentioned, chemical transformation of CO2
can be the realistic solution to the CO2 sequestration concerns;
which could ultimately lead to the utopia for fossil-fuel-based
economies with taking full advantage of the carbonaceous fuels
while minimizing their negative environmental impacts. This
approach of recovering CO2 in order to synthesize useful products
is capable of sustainable reduction of carbon emissions, and is
known as carbon capture and conversion (CCC) [20]. The economic
advantages of producing valuable chemicals from CO2 provide
further incentives for major emitters to move towards this
direction.
The author has recently published a critical review paper on the
state-of-the-art CCC technologies, addressing more efcient material development as the main bottleneck in this eld of research
[21]. Graphene, as the rising star of the materials world in 21st
century, offers game-changing prospects towards a more sustainable future for fossil-fuel-based economies. This two-dimensional
Fig. 1. Graphene, the mother of all carbon dimensions with myriad of applications (right, Reprinted with permission from Ref. [22], Copyright 2011, American Physical
Society).
Nomenclature
NMP
NPD
ARPES
APCVD
Eg
CCC
CCS
CMS
CNT
CCM
CVD
DRM
CB
DFT
DOS
DMF
ERC
EF
FLG
FWHM
f-HEG
GCMC
GO
GN
G-silica
GMNO
GIC
HOMO
HRTEM
HEG
IGCC
1-methyl-2-pyrrolidone
4-nitrophenyl diazonium
angle-resolved photoemission spectroscopy
atmospheric pressure chemical vapor deposition
band-gap energy
carbon capture and conversion
carbon capture and storage
carbon molecular sieve
carbon nanotube
catalytic combustion of methane
chemical vapor deposition
CO2 reforming of methane
conduction band
density functional theory
density of states
dimethylformamide
electrochemical reduction of carbon dioxide
Fermi energy
few-layer graphene
full-width at half-maximum
functionalized hydrogen exfoliated graphene
grand canonical Monte Carlo
graphene oxide
graphene sheets
graphene-based mesoporous silica
graphene-Mn3O4 hybrid
graphite intercalation compound
highest occupied molecular orbital
high-resolution transmission electron microscopy
hydrogen exfoliated graphene
integrated gasication combined cycle
LDH
LUMO
MOF
OFET
ORR
POM
PGNB
PES
PECVD
PANI
PEI
PPy
PS
PT
PC
rGO
RWGS
RTIL
SWCNT
SEG
sccm
H0
S0
G0
SMR
g
SOCl2
TiNS
TEM
VB
WE
XPS
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Fig. 2. Graphene production pathway via effective reduction of the mono-layered graphene oxide sheets. Reprinted with permission from Ref. [81], Copyright 2011, WileyVCH.
hydrazino-alcohols [89]. This derivative then reacts further, converting to an amino-aziridine moiety which goes through thermal
elimination of di-imide to form a double bond [77]. Stable aqueous
suspensions of rGOs were obtained via pH adjustments
using ammonia solutions during reduction with hydrazine [90].
However, without surfactant-assisted stabilization, rGOs tend to
agglomerate in organic solvents due to their hydrophobicity
[77,88].
Sodium borohydride (NaBH4), as another promising reductive
agent, is reported to be more effective in removal of GO's oxygencontaining groups compared to hydrazine [86]; although borohydride is prone to hydrolysis by water [69]. The resulting rGOs show
lower sheet resistances of 59 k/m2 (comparing with 780 k/m2
for a hydrazine-reduced sample under similar circumstances), and
higher C:O ratios of 13.4:1 (compared to 6.2:1 for hydrazine) [86].
Other GO chemical reduction pathways include the use of hydroquinone [91], gaseous hydrogen (after thermal expansion) [92],
strong alkaline solutions [93], and solvothermal methods [94].
While hydrogen-assisted GO reduction was proved to be promising (C:O ratio of 10.814.9:1), hydroquinone and alkaline solutions
did not emerge as effective as hydrazine and sodium borohydride
based on semi-quantitative results [69].
Nonetheless, most of the reported chemical production techniques use harsh oxidizers (e.g. H2SO4/KMnO4), and an excess of
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Fig. 3. Electrochemical approaches of (a) oxidation, intercalation and exfoliation (negative ions are shown in red color), and (b) reduction, intercalation and exfoliation to
produce single and multilayer GN akes (positive ions are shown in deep blue color). Reprinted with permission from Ref. [52], Copyright 2013, Elsevier. (a) Positive current
to produce "oxidised" GN akes and (b) Negative current to produce "non-oxidised" GN akes. (For interpretation of the references to color in this gure legend, the reader is
referred to the web version of this article.)
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leads to the intercalation of anions (or cations) from the electrolyte. The intercalation process prompts structural expansion in the
graphite matrix which was reported as blisters in early investigations [107]. This has been suggested to yield ultrathin GNs when
high voltages are applied to the graphitic electrodes in sulfuric
acid [101], and KOH solutions [108] at the anode and cathode,
respectively. Nonetheless, the exact exfoliation mechanism is still
debated, and more exhaustive experiments are required to verify
the described pathways illustrated in Fig. 3.
Due to limitations imposed by water electrolysis in aqueous
electrolytes, non-aqueous solvents or mixtures of aqueous with
non-aqueous components are generally employed to provide a
wider electrochemical window [103105]. Accordingly, amongst
anodic electro-exfoliations, large anions of PF6 , and/or BF4 in
ionic liquids have shown remarkable tendency to intercalate
graphite electrodes, yielding gram-scale quantities of carbon
nanostructures especially GN akes [105,106]. Air- and moisturestable room temperature ionic liquids (RTILs), salts of large organic
cations with relatively bulky inorganic counter-ions, are molten
salts with melting points close to room temperature [109,110].
Owing to low vapor pressure, high chemical and thermal stability,
solvating capability, non-ammability with potential recyclability,
RTILs have received much interest as green solvents in organic
synthetic processes to replace classic, toxic and volatile molecular
solvents [111,112]. Consequently, ILs are extensively used as a
reaction medium for the fabrication of conducting polymers and
nanoparticles [113116]. Additionally, their tunable physicochemical properties enable in-situ functionalization of GNs which is the
most important approach for expanding the graphene applications
throughout many key research themes [117,118].
Among the cationic electro-exfoliation reports, lithium
co-intercalation with propylene carbonate (PC) has been proposed
for high-yield production of few-layer graphene (FLG) ( 470%)
[103]. The process resembles the destructive effects of PC as a
molecular solvent on the graphitic electrodes in lithium-ion
batteries [119,120]. Intercalation of tetraalkylammonium cations
from 1-methyl-2-pyrrolidone (NMP) solutions is also reported
with signicant exfoliation rates as a viable choice for GN synthesis with low energy consumption and ease of operation [121].
In any case, a subsequent sonication treatment is suggested to
have complementary role in improving the quality of the electrosynthesis products particularly with boosting the exfoliation of the
expanded akes into the ultrathin sheets [103,106,121].
2.2. Chemical doping/functionalization
Any effort toward tailoring graphene characteristics by inserting external atoms or molecules to its sp2 network falls into
chemical doping/functionalization category. Physicists and chemists look at this subject from quite different perspectives, which
we have aimed to combine them here. Physicists are mostly
inclined to view this from electronic point of view, where any
external impurities can affect the band structure of graphene,
therefore focusing on the doping concept [122,123]. This is also
paraphrased as the adatom phenomenon for creating new body
states that do not appear in pure graphene [124,125]. On the other
hand, chemists are more interested in such modications for
functionalization and improving the processability of graphene;
hence they tend to discuss the concept from chemical synthesis/
activation approach [117,118]. This has often caused confusion
with misplacing the related categorizations which we tried to
address here.
In the most general classication, any impurity introduced to
graphene can interact in two major states. First, the impurity can
disrupt the sp2 network and cause sp3 defect regions via bonding
with graphene. This is something which is typically associated
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Fig. 4. (A) Left: the electronic structure of the sp2 bonded graphene. Right: zoom-in of the Dirac point where valance and conduction bands intersect. Reprinted with
permission from Ref. [129], Copyright 2009, American Physical Society. (B) Ambipolar electric eld effect in single-layer graphene (the position of the Dirac point and the
Fermi energy (EF) are shown in the insets as a function of gate voltage). Reprinted with permission from Ref. [130], Copyright 2007, Nature Publishing Group. (C) A schematic
diagram for the Dirac point and the Fermi level positions as a function of doping; where the upper panel is n-type doped, pristine and p-type doped free-standing graphene
(ac), and the lower section illustrates n-type doped, pristine and p-type doped epitaxial graphene grown on silicon carbide (SiC) (df). Reprinted with permission from Ref.
[131], Copyright 2008, American Chemical Society.
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effect transistors (OFETs) has exhibited competitive work functions similar to those for Ag and Cu [194,195]. Moreover, the
analogous molecular structure of graphene and organic semiconductors like pentacene affords strong interactions amongst
them, lowering the carrier injection barriers, thus improving the
device overall performance (Fig. 6d).
Other applications have also been reported including use of
nitrogen-doped graphene as an efcient metal-free electrocatalyst
for oxygen reduction reaction (ORR) in fuel cells (Fig. 7) [196,197],
and graphene doping with thionyl chloride (SOCl2) for achieving high
electrical conductivities [198]. More practical applications are anticipated to emerge soon due to the rapid progress on graphene
research. This is further elaborated in the upcoming sections relating
doping to graphene competence for CO2 capture and conversion.
Fig. 5. Raman shift trends for the graphene's G band upon interaction with (a) 1 M
solutions of monosubstituted benzenes, and (b) with various concentrations of
aniline and nitrobenzene. Reprinted with permission from Ref. [165], Copyright
2008, Royal Society of Chemistry.
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Fig. 6. (a) Linear dependency of chemically induced charge transport, n, to various concentration, C, of NO2. Lower inset: graphene characterization by the electric eld
effect. (b) Changes in resistivity, , at zero-band-gap point of graphene induced by exposure to various diluted gases (1 ppm). The positive (negative) sign of changes indicate
electron (hole) doping. (c) Constant mobility of charge carriers in graphene with increasing chemical doping. The parallel shift is caused by a negligible scattering effect of the
charged impurities induced by chemical doping. Reprinted with permission from Ref. [42], Copyright 2007, Nature Publishing Group. (d) Schematic of charge transfer at the
F4-TCNQ/graphene interface. Reprinted with permission from Ref. [141], Copyright 2007, American Chemical Society.
Fig. 7. (a) Metal-free nitrogen-doped graphene as an efcient electrocatalyst for oxygen reduction reaction. Reprinted with permission from Ref. [144], Copyright 2013, Royal
Society of Chemistry. (b) Schematic illustration of various types of nitrogen-doped graphene (gray for the carbon, blue for the nitrogen, and white for the hydrogen atom).
A possible defect structure is shown in the middle of the ball-stick model. Reprinted with permission from Ref. [182], Copyright 2010, American Chemical Society. (For
interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
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Fig. 8. As-prepared graphite oxide dispersions in water and 13 organic solvents by bath ultrasonication for 1 h. Top: Dispersions immediately after sonication. Bottom:
Dispersions three weeks after sonication. The yellow color of the o-xylene sample is due to the solvent itself. Reprinted with permission from Ref. [211], Copyright 2008,
American Chemical Society. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
Fig. 9. Variations in the proposed model structures for the GO sheets regarding the presence (left, Reprinted with permission from Ref. [212], Copyright 1998, American
Chemical Society) or absence (right, Reprinted with permission from Ref. [213], Copyright 2009, Nature Publishing Group) of carboxylic acids on basal plane edges.
In contrast with noncovalent interactions, covalent functionalization involves rehybridization of sp2 carbon atoms through the
graphene network into the sp3 conguration, associating with the
loss of electronic conjugation (equivalent to substitutional doping)
[234]. This is mainly due to the rigorous interactions of the dopant
with the honeycomb graphene, and it is often irreversible. Such
strong surface modications can be achieved in a variety of ways
including nucleophilic substitution, electrophilic addition, condensation, and combinatory addition; which most of them use
GO as the starting material [235237].
Briey, the epoxy functionalities of GO are the target groups for
the nucleophilic substitution reaction. It involves attacking amine
(single bond NH2) groups of the organic modiers, bearing a lone
pair of electrons, to the GO's epoxy groups. Comparing with other
techniques, nucleophilic substitution is more facile and takes place
at room temperature in an aqueous medium. Thus, it has emerged
as a promising scalable production method for GNs functionalized
with all types of aliphatic and aromatic amines, amino acids,
amine-terminated biomolecules, ionic liquids, low molecular
weight polymers, and silane compounds [235246].
Electrophilic substitution occurs when an electrophile agent
displaces a hydrogen atom. Impulsive insertion of aryl diazonium
via reduction of 4-nitrophenyl diazonium (NPD) tetrauoroborate
is a prominent example for such electrophilic reactions with
graphene surface [247]. Stable dispersions of functionalized GNs
in organic solvents have also been obtained via electrophilic
substitution of aryl diazonium salt on the surface of surfactantwrapped graphene [248,249].
In condensation reaction, two molecules (or functional groups)
combine to form one single molecule with a loss of entropy.
It occurs when isocyanate, di-isocyanate, and amine compounds
form amides and carbamate ester linkages with GO body.
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issues, several studies have examined preparing functionalized GNs directly from graphite in a one-step process using,
for instance, ionic liquids and surfactants via direct liquidand electro-exfoliation methods [102,106]. Nonetheless, the
bottom line is that all the related studies have appreciated the
effectiveness of graphene functionalization in preventing GNs
agglomeration in various solvents, and affording more physicochemical properties for a broad range of applications.
Fig. 10. TEM images of few-layer graphene obtained from magnesium combustion
with CO2. (a) Graphene nanosheets with an average length of 50100 nm.
(b) Larger size graphene sheets with average lengths of 300 nm. (c) Crystalline
GNs with an average length of 200 nm. (d) High-resolution TEM image of few-layer
graphene with the number of layers ranging from 37. Inset: the electron
diffraction pattern of GNs. Reprinted with permission from Ref. [258], Copyright
2011, Royal Society of Chemistry.
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Fig. 11. Graphene CVD growth on copper foils via catalytic activation of CO2.
(a) Schematic diagram. (bf) SEM images of graphene domains development on
copper foils with 200 sccm H2 and different ow rates of CO2 (330 sccm) after
30 min of growth time. (g) The characteristic length of the domains as the function
of CO2 ow rates. Reprinted with permission from Ref. [262], Copyright 2013, Royal
Society of Chemistry.
Fig. 12. Formation of graphene oxide nanocomposites from carbon dioxide using
ammonia borane with representative TEM micrograph showing curled and stacked
akes. Reprinted with permission from Ref. [277], Copyright 2012, American
Chemical Society.
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Fig. 13. (a) Hydrogen sorption isotherms at 1 atm and 77 K. (b) Carbon dioxide sorption isotherms. (c) Binding energies of a single molecule on a graphene supercell as a
function of distance with various adsorption orientations (shown in insets) for hydrogen (upper panel) and carbon dioxide (lower panel). Reprinted with permission from
Ref. [328], Copyright 2008, American Chemical Society.
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Fig. 14. (a) CO2 and N2 adsorption isotherms at 273 K on nanographenes ( for CO2, for N2), edge sites (solid curve), and basal planes (dashed curve), and (b) snapshots.
Reprinted with permission from Ref. [329], Copyright 2012, American Chemical Society.
materials also displayed selectivity towards CO2 adsorption compared to H2, N2, Ar or CH4. Fig. 15 represents the described
recyclability and gas selectivity for the NG7 samples (979.6 m2 g 1
surface area), which showed the highest CO2 uptakes (NG7 stands
for chemical activation at 700 1C).
N-doped porous carbons are also synthesized via chemical
activation of polypyrrolegraphene composites using KOH solutions [364]. Polypyrrole (PPy) is an environmentally benign basic
CO2 sorbent with excellent thermal stability and can be easily
produced in large scales [365]. However, the low surface area
along with costly nature of PPy have constrained its application for
CO2 capture at the industrial level. In this regard, interfacing PPy
with graphene substantially increases its surface area, and the
resulting composites have also exhibited a high adsorption capacity for aqueous mercury [366]. After chemical activation, nitrogen
was found to be doped within the porous carbon rather than the
graphene matrix. The PPyGN nanomaterials showed a selective
and reversible adsorption for CO2 (4.3 mmol g 1) over N2
(0.27 mmol g 1) at 298 K and 1 bar [364]. The scalability of the
synthesis method and excellent recyclability of the N-doped
porous carbons make them highly competitive for practical
applications.
As the latest follow up to the abovementioned line of research,
S-doped microporous carbon materials, obtained by the chemical
activation of polythiophene (PT) grafted rGOs, were examined for
CO2 adsorption [367]. With a signicant CO2 uptake of
4.5 mmol g 1 at 298 K and 1 atm, the S-doped samples showed
remarkable selectivity over N2, CH4 and H2 with a stable recycling
adsorption capacity of 4.0 mmol g 1 [367]. The microporosity
(0.6 nm pore size), surface area (1567 m2 g 1), and oxidized S
content of the porous carbon ( 6.5 wt%) were found to be the
determining factors for the remarkable CO2 adsorption resulted
from chemical activation at 700 1C. Noticeably, S-doped chemically
activated graphene reached higher CO2 adsorption values than
those for N-doped materials prepared and examined under similar
conditions [367].
Successful synthesis of graphene-based mesoporous silica
(G-silica) sheets is reported recently with sandwich-like structure
and high surface area [368]. Conning GNs within individual porous
silica sheets enables the end product to have broader applications
particularly in ultrafast energy storage [368,369]. It was found that
G-silica sheets can serve as an effective host for immobilizing
polyethyleneimine (PEI), as another amine-rich compound (denoted
as PEI-G-silica) [370]. The resulting PEI-G-silica sheets not only
had an ultrathin structure with high PEI surface density, but
also exhibited superior thermal conductivities originated from GNs
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Fig. 15. (a) Recycling of the NG7 composite material, and (b) its selectivity towards CO2 adsorption over Ar, N2, H2 and CH4. NG7 stands for chemical activation at 700 1C.
Reprinted with permission from Ref. [358], Copyright 2013, IOP Science.
1531
Fig. 16. (a) Schematic of the LDH-GO hybrids for CO2 capture. (b) Average CO2 uptakes as a function of GO content at 573 K and P(CO2) 0.2 bar. Reprinted with permission
from Ref. [376], Copyright 2012, American Chemical Society.
Fig. 17. Absolute CO2 uptakes of C60 intercalated graphite versus g at 298 K with equimolar compositions of: (a) CH4/CO2 mixture; (b) N2/CO2 mixture. (c) Snapshots of pure
gas adsorption in C60 intercalated graphite at 298 K and 6 MPa (top for top view, and bottom for side view). Reprinted with permission from Ref. [388], Copyright 2010,
American Chemical Society.
1532
Fig. 18. Appropriate reactions that can lead to a negative Gibbs free energy change
for organic synthesis using CO2 as a co-reactant.
Fig. 19. Ideal carbon-neutral energy cycle via coupling carbon capture technologies
with renewable carbonaceous fuel production from CO2 upon successful graphene
utilization.
Scheme 6. Reverse water-gas shift reaction (RWGS) as the main bottleneck of CO2
hydrogenation.
1533
and di-oxide to methane are 0.01% and 0.07% for pure GO and its
composite with metal oxides (in this case iron and vanadium),
respectively. Increasing the temperature up to 100 1C is projected
to afford the total conversion of CO/CO2 [421]. The calculated
reaction rates compete fairly with more expensive catalysts
(platinum- and ruthenium-based), but in terms of yield per gram
(or cm2) by far outweigh the costly rivals due to the superior
surface over weight ratios of GO [421]. Fig. 20 illustrates the
optimized atomic structure and energy costs of initial (a, d),
intermediate (b, e) and nal (c,f) stages of CO2 to HCOOH conversion using pure graphene oxide (ac) as well as GO hybrids with
metal oxides (df).
5.2.2. Methane-assisted CO2 reduction
Three major classes based on transition metals are broadly
examined as catalysts for carbon dioxide reforming with methane
[425427]: (i) non-noble metals (Ni, Co and Fe), (ii) noble metals
(Ru, Rh, Pd, Pt, Ir), and (iii) transition metal carbide catalysts. Noble
metallic nanoparticles are highly resistant to coke formation (the
main catalyst deactivator here) [428]; however, their costly nature
remains the limiting factor. Ni-based materials have shown the
closest performance comparing with the noble metals, incurring
intense attention due to their non-preciousness and earth abundance. However, they still suffer from rapid coke formation and
subsequent catalyst deactivation which is mostly linked with the
methane cracking reaction [429,430]. In such situations, the
adsorbed oxygen atoms on the surface are supposed to eliminate
the deposited carbon and release CO as the result. However, this
does not occur efciently on the surface of non-noble metals such
as Ni due to the insufcient oxygen adsorption and/or severe
solubility/diffusivity of carbon in the metal. There have been a
number of studies to address the oxygen activation issue via
surface engineering of the catalyst. For instance, it is reported that
metal oxide composites such as CeO2/ZrO2 [431], Y2O3/ZrO2 [432],
TiO2/ZrO2 [428], and Nb2O5/ZrO2 [433] as the carriers can improve
the catalytic performance relative to the pure oxides. Moreover,
the most recent studies have revealed that synthesizing NiO
MgOZrO2 alloys inhibit the coke formation process on Ni1 more
effectively under dry reforming conditions [425].
As mentioned in earlier sections, metal-free carbonaceous
materials have recently gained a signicant ground with their
low cost, high temperature stability, and the absence of sulfur
poisoning [434437]. They are also strong absorbers of microwave (i.e. highly heated under microwave radiation) [438440].
As the result, improved yields for dry reforming are achieved by
microwave heating of carbon-based catalysts compared to the
conventional heating methods, with an optimum temperature
ranges between 700 and 800 1C [436]. The better outcome via
microwave heating is attributed to the presence of microplasmas
within the porous carbon which act both as catalyst and as
microwave receptor (C/MR), thus boosting the homogeneous and
heterogeneous catalytic reactions [436,441,442]. In this situation, dry reforming mechanism is proposed to be a combination
of the catalytic methane decomposition (Scheme 7), and the CO2
gasication (Scheme 8) [441,443]. CH4 decomposition takes
place on the active sites of C/MR, and the nature of these
centers has been suggested to fall into the following categories:
Fig. 20. Optimized atomic structure and energy costs of initial (a, d), intermediate
(b, e) and nal (c,f) stages of CO2 to HCOOH conversion using pure graphene oxide
(ac) as well as GO hybrids with metal oxides (df). Reprinted with permission
from Ref. [421], Copyright 2013, Scientic Research.
1534
Scheme 10. Competitive reduction of water to hydrogen as the main issue for CO2
electroreduction.
1535
Fig. 21. (a) Model structure of porphyrin-like functionalized metalGN composite. The central metal is coordinated to four adjacent nitrogen atoms, creating a porphyrin
ring attached to the graphene network. (b) Comparison of density of states projected onto the d orbitals of the Pt atom at the porphyrin ring center, and the Pt surface atom
in Pt(111) surface. Reprinted with permission from Ref. [470], Copyright 2013, American Chemical Society.
Fig. 22. Photocatalytic CO2 reduction by water using PtTiO2: (a) photo-excitation
of the electronic band structure of the semiconductor, and (b) migration of photoinduced electronhole pairs to the photocatalyst surface for driving redox
reactions.
Scheme 12. CO2 reduction half-reaction as the heart of carbon dioxide photocatalytic conversion.
1536
photocatalytic performance of TiO2 (or any other suitable semiconductor) especially by boosting charge separation [498,499].
Photo-excited electrons in the CB of TiO2 are delocalized via swift
migration to graphene, which keeps them reasonably distant from
recombination with the localized holes generated on TiO2 surface
[500]. Charge transport efciency on graphene surface is also vital
to preserve the reactivity power of electrons for driving CO2
reduction reasonably [481,501]. Additionally, it is recently
reported that graphene can elevate the conduction band of WO3
toward more effective CO2 reduction into hydrocarbon fuels under
visible light irradiation [479].
The inuence of lattice defects in honeycomb graphene on the
photocatalytic reduction of CO2 is investigated using two major
solution-based GN synthesis techniques (rGOs and solvent exfoliated) [502]. It was revealed that the TiO2GN composites prepared with solvent exfoliated graphene (SEG) exhibit higher
activities due to lesser defects and more enhanced electron
mobility. Comparing with unsupported TiO2, the optimized TiO2
GN hybrids led to 7-fold improvement in the photoreduction of
CO2 [502].
Moreover, the dimensionality role of the carbon nanomaterial
as the support on the photoreduction of CO2 with TiO2-based
nanosheets (TiNS) is studied by comparing two photocatalysts of
SEGTiNS and SWCNTTiNS [503]. As the result, SEGTiNS nanocomposites afforded 73.5% more CH4 production compared to
SWCNTTiNS [503]. Such improvements were attributed to more
compatible electronic and physical coupling of 2D SEG with TiNS
comparing with 1D SWCNT. This intimate interconnection through
Fig. 23. Schematic of TiO2-graphene hybrids for more efcient photoexcited charge
separation during photocatalytic conversion of CO2 to methane/methanol.
SEGTiNS nanostructure suppresses recombination of the photogenerated pairs more effectively [503].
Robust hollow spheres composed of alternating TiNS and GNs
(GTi0.91O2) are recently fabricated via a layer-by-layer deposition
method with dramatic improvements in photocatalytic CO2 conversion rates [480]. Compared to the conventional synthesis
procedures for TiO2graphene nanocomposites by impregnation
of TiO2 nanoparticles on the graphene surface, GTi0.91O2-based
samples showed a 9-fold enhancement in the photoreduction of
CO2 [480]. This was mainly linked to three key aspects of: (i) the
extreme thinness of Ti0.91O2 nanosheets which allows rapid charge
transfer to the surface; (ii) the compact pile of ultrathin TiNS with
GNs that enables fast interface electron exchange between the two
components and increases the lifetime of electronhole pairs; and
(iii) the hollow structure that acts as a photon-collector and
renders maximum absorption of multi-scattered incident light.
Fig. 23 depicts the schematic of TiO2graphene hybrids for more
efcient photoexcited charge separation during photocatalytic
conversion of CO2 to methane/methanol.
Graphene oxide has also emerged as a promising photocatalyst
for CO2 to methanol conversion [478]. The modied Hummers
method was used for the synthesis of the GO-based photocatalysts
with the enhanced catalytic activities [504]. CO2 conversion rates
of up to 0.172 mol g 1 h 1 were achieved under visible light,
which was reported to be six-fold higher than the results for the
pure TiO2. The wide and tunable band gap of GO via controlling
the oxygenated functional groups unprecedentedly rendered
noticeable photocatalytic activities for CO2 to methanol conversion. Only a small fraction of oxygenated groups in GO was lost
and slightly affected the initial methanol formation before reaching the rate stabilization region (up to 2 h). Fig. 24a illustrates the
underlying mechanisms of photocatalytic CO2 reduction to
methanol on GO.
The stoichiometric carbon-to-oxygen atomic ratios in GO
determine the electronic structure and band gap properties of this
semi-insulating material with a wide band gap [505,506]. Studies
suggest covalent functionalization of GO basal plane with the
epoxide and hydroxyl groups, while proposing the presence of
carboxyl functional groups at the edges (see more in Section 2.2.2)
[209,507]. Thus, owing to several types of oxygenated functional
groups on different locations, GO can undergo a series of complex
covalent/noncovalent interactions with the neighboring molecules. The diversity of surface components also provides a blended
2D network of sp2 and sp3 bonded atoms in GO, which ultimately
results in a specic band gap depending on the sp2/sp3 domain
ratios [118,508]. Consequently, based on the disruption severity of
the graphene sp2 network with sp3 defects, the resulting material
Fig. 24. (a) Schematic illustration of the underlying mechanisms for photocatalytic CO2 reduction to methanol on GO. (b) Photocatalytic methanol formation rates via
different graphene oxide samples (GO-1, GO-2, GO-3) comparing with TiO2. Reprinted with permission from Ref. [478], Copyright 2013, Royal Society of Chemistry.
6. Concluding remarks
This review paper presented the latest theoretical and experimental studies on versatilities of graphene and its derivatives for
carbon capture and conversion. Imposing effective CO2 remediation strategies as one of the top urgencies of 21st century requires
state-of-the-art materials development and graphene could play a
game-changing role in this regard. The author did not overlook
theoretical studies as they offer numerous key guidelines for
future material synthesis and development based upon graphene
heterostructures.
The overview of the most common and effective preparation,
doping/functionalization methods was presented along with
detailed discussions on the current and potential applications of
graphene and its derivatives for CO2 capture and conversion.
In addition to the extraordinary CO2 capture capability of
graphene-based materials, their catalytic, electrocatalytic and
photoelectrocatalytic use were elaborated, accompanied by some
of the key DFT investigations. CO2-assisted graphene production is
another intriguing pathway for carbon dioxide chemical transformation, which was covered extensively in this review paper. In
fact, it represents a high interconnectivity between multidisciplinary branches of research on materials for energy and environment
applications.
Finally, there is no doubt that solutions to climate change are in
debt of CO2 annihilation. The worldwide budget to encourage
industries' actions toward efciency improvements, process modications, CCS, and so forth is not sufcient for achieving globally
set visions of hindering the accelerated warming. Without promoting economically oriented CCC technologies, the CO2 regulation mission will fail. Subsequently, without introducing more
cutting-edge materials and processes for CO2 chemical conversion,
the entire concept cannot emerge viably.
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