A review of g-C3N4 based catalysts for

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& Anand Kumar
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A review of g-C3N4 based catalysts for direct

methanol fuel cells

Afdhal Yuda, Anand Kumar*

Department of Chemical Engineering, Qatar University, P O Box 2713, Doha, Qatar

highlights

g-C3N4 based MOR catalyst with noble metals and non-noble metals are presented.

Synthesis methods and photo/electro-catalytic properties of g-C3N4 are described.

Structural modifications and doping of g-C3N4 can lead to better performance.

CO poisoning is a major challenge, and catalysts tolerant to CO are discussed.

Challenges faced in MOR and critical points for future research are proposed.

article info abstract

Article history: Direct methanol fuel cells (DMFC) possess numerous advantages for powering portable
Received 2 November 2020 mobile devices. However, there are still major challenges in their development and
Received in revised form commercialization that originates from the anode catalyst responsible for methanol
26 December 2020 oxidation reaction. This has motivated researchers to find a cost effective and durable
Accepted 12 January 2021 catalyst material for methanol oxidation. Recently, carbon-based 2-D graphitic carbon
Available online xxx nitride (g-C3N4) has been found to have good potentials to catalyse alcohol oxidation re-
actions in fuel cells. This review provides a summarized information of previously devel-
Keywords: oped g-C3N4-containing-electrocatalysts based on the active sites present (e.g., non-metals,
Direct methanol fuel cells noble metals, and non-noble metals) for methanol electro-oxidation to compare their
g-C3N4 catalysts electrocatalytic performance. It also consists of brief examination of their structure,
Carbon based electrocatalysts description of different synthesis methods and post-synthesis treatments, and evaluation
of their properties that contributes to their resulting performance. The review then con-
cludes with the details of challenges and possible solutions that enable DMFC to be a
reliable source of energy in the future.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

continuous usage. As a result, significant attention has been

Introduction
The growth of industrialization has resulted in an increased
demand for energy globally. Since energy generation is mostly
dependent on using pollutant-producing fossil fuels, there are
serious environmental problems on a global scale with its
given towards investigating novel systems for energy preser-
vation and transformation, such as DMFCs, in recent years
due to it being highly efficient and low emitter of pollutants. In
DMFCs, the electrocatalyst system is one of its crucial
component that determines the operation of the fuel cell [1].

* Corresponding author.
E-mail address: akumar@qu.edu.qa (A. Kumar).
https://doi.org/10.1016/j.ijhydene.2021.01.080
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Yuda A, Kumar A, A review of g-C3N4 based catalysts for direct methanol fuel cells, International Journal of
Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.01.080
2 international journal of hydrogen energy xxx (xxxx) xxx
Commonly, nanoparticles (NPs) of platinum (Pt) and
platinum-alloys can demonstrate good performance as an
anode electrocatalyst material. However, due to Pt being
expensive, limited in supply, and poor poison tolerance its use
for commercial purposes has declined. Hence, the focus of
many researchers has recently been towards minimizing the
use of Pt and instead implement other metals, such as palla-
dium, or supporting platinum on carbon or alternative support
materials [2e4]. Palladium has been chosen as one of the
alternative metals because of its relatively lower cost and
exceptional activity for electrocatalytic oxidation and carbon
monoxide resistivity in comparison to catalysts that are based
on platinum [5e7]. Nonetheless, the electrocatalytic activity of
palladium is still low and the stability is not high enough to be
used in the commercialization of DMFCs [8,9]. Carbon based
materials have shown exceptional promise as support mate-
rials for electrocatalytic applications [10,11]. The types of
carbon support material suitable for dispersing metal nano-
particles include carbon nanotubes (CNTs) [12], carbon black
[13], graphene [7,14], and carbon nanofibers [15], and they
possess advantageous properties such as good conductor of
electricity and great stability [16]. Vulcan XC-72R carbon black
is amongst the most extensively used carbon materials to
support active metals in various electrocatalytic applications.
This is because the material is widely available, cheap, pos-
sesses large surface area and the necessary pore structure,
and high electrical conductivity [16]. There are still, however,
disadvantages presented by Vulcan carbon support, including
insufficient resistivity towards corrosion [17]. Various
methods could be undertaken to enhance the surface of
chemically inert carbon materials and to add microspores.
One of them is through performing chemical activation that
utilizes activating agents in the form of alkali hydroxides to
pull in microspores with small distribution and enlarge their
surface areas. Surface modification is also a common tech-
nique to minimize corrosion and this could be attained by
functionalizing the surface with carboxylates, sulfonates,
steric polymer/oligomer, and tertiary amines [18,19]. Another
approach is to alter pure carbon by heteroatom-doping of the
respective materials that can help achieve significantly better
performance [20]. Studies performed recently have shown
that it is conductive to modify carbon chemical reactivity and
electronic structures to achieve improved catalytic perfor-
mance. So far the development in doping of carbon with
heteroatoms include the addition of phosphorous, nitrogen, or
boron-doped carbon black [21e23], nitrogen and sulfur-
codoped graphene [24e26] etc. Examples of structural modi-
fication or hybrid structures include carbon nanotubes
[27e29], or graphene [30e32], and carbon nitride-graphene
hybrids [33e35] etc. Doping of carbon with nitrogen atoms
resulted in an improvement of the chemical activity of the
surface and modification of the surface characteristics such as
basicity, polarity, heterogeneity, and adsorption capability
[36]. It is also important to note that introducing heteroatoms
into carbon frameworks can assist in removing absorbed
poisoning intermediates, which could further ensure that the
active sites are highly exposed to promote catalytic reactions
[37,38]. In a study performed by Baglio et al., a highly active
Please cite this article as: Yuda A, Kumar A, A review of g-C3N4 based catalysts for direct methanol fuel cells, International Journal of
Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.01.080
catalyst containing nitrogen and carbon was developed using
an iron precursor (Fe-N-C catalyst) [39]. The purpose of the
work was to not only avoid the usage of high cost platinum
group metals, but also to minimize the inefficiency of oxygen
reduction reaction (ORR) on cathode catalyst when permeated
alcohols (e.g., methanol and ethanol) adsorb on the active
sites of the catalyst. Based on Density Function Theory (DFT)
calculations, it was observed that Fe-N2C2 and Fe-N4 active
sites present on the synthesized catalyst preferably adsorb
oxygen with greater energy than to adsorb ethanol, methanol
to carry out partial ethanol oxidation products (0.73e1.16 eV
stronger adsorption). Sites related to nitrogen and carbon such
as pyridinic and graphitic nitrogen are much less selective
towards ORR. Graphitic carbon nitride, or g-C3N4, another
carbon material that is rich in nitrogen, that is an allotrope of
carbon nitride, has been reported to have high structural
stability with potential to be use in photocatalysis, heteroge-
neous catalysis, and fuel cells [40,41]. Apart from an ultrahigh
nitrogen content it also has other interesting properties that
include ideal 2D structure, remarkable thermal and chemical
stability that can be utilized in areas of water splitting with
metal-free catalysts [42e47], organic pollutant degradation
[48e50], CO2 fixation [51,52], and so on. In addition, it has a
matrix that could offer coordination to various metals because
of the nitrogen rich polymeric semiconductor system (C/
N ¼ 0.75, a heterocyclic macrocycle structure with N-C-N-
bonding pattern) [19-25], that behaves as Lewis basic sites
(different amino groups). The unique characteristics leaves g-
C3N4 with plenty of reactive sites for the formation of metal/g-
C3N4 hybrids. Therefore, g-C3N4 might not only function as a
template, but also as a support to anchor metal nano-
structures, which is an advantageous addition to its photo-
active ability to achieve improved performance. Nevertheless,
g-C3N4 performance towards electrochemical reactions is still
not satisfactory because of its poor electrical conductivity [53].
Hence, many research studies have recently been concen-
trated towards combining g-C3N4 with other suitable electro-
catalytic materials to achieve exceptional properties leading
to better electrochemical performance. Its use together with
platinum metal as an electrocatalyst for methanol oxidation
reaction has also shown an enhancement in electrocatalytic
ability relative to bare platinum nanoparticles [54]. Further
enhancement was also observed upon visible light irradiation
for methanol electro-oxidation and could be attributed to the
synergistic effects of photocatalytic and electrocatalytic abil-
ity in addition to efficient interfacial charge transfer in the
hybrid system.
There are some recent reviews on the development of
methanol electro-oxidation catalysts [55], however a focused
review on g-C3N4 based 2-dimensional materials is lacking.
This review paper has been made to provide more information
on the subject, where it will first look at the structures and
properties of g-C3N4 that makes them a suitable electro-
catalyst material. It will then look at the various synthesis
methods that could be implemented to develop g-C3N4, and
the results of different research studies involving the utiliza-
tion of g-C3N4 as an electrocatalyst material for methanol
oxidation reaction (MOR).
 international journal of hydrogen energy xxx (xxxx) xxx
Understanding the structures of g-C3N4
The term, “graphitic carbon nitride”, is used to refer to a large
group of materials that has various structural and chemical
properties. Much of the recent publications have referred to
these family of materials as “g-C3N4” compounds, however
almost none of the materials involved have the ratio of 3 to 4
for C to N. Commonly, they instead contain considerable
concentrations of hydrogen and other elements, that include
oxygen. The layers of graphite are also possibly incomplete
and the sheet-like regions are less likely to be planar [56].
There are other categories of graphitic carbon nitride mate-
rials that have been discovered and the first group is related to
graphitic carbon, graphene-like carbons or carbon nanotubes
(CNTs). They are those that are synthesized by involving ni-
trogen to a degree that reaches up to a few atomic percent
[57,58] and have metallic characteristics [58,59]. This group is
better termed as N-doped carbon instead of graphitic carbon
nitrides and their implementation as support materials for
electrocatalysts started in the 1980s [60,61]. The carbonaceous
materials were pyrolyzed along with precursors that contain
nitrogen. Since the beginning of their use, different produc-
tion techniques have been developed and through these ap-
proaches support materials were produced that could
potentially enhance the catalytic performance by combining
both transition metal and support [38,62e65].
Compounds with a range of polymeric or graphitic ar-
rangements make up the largest category of true carbon
nitride compounds. These compounds are generated from
condensation reactions of easily available precursors, that
include melamine, urea, or dicyandiamide, that takes place
after thermal treatments in the temperature scale of
500e700  C [66]. They could precisely be called as compounds
of gCNH whose structures are generally built from linked units
of heptazine (tri-s-triazine, or C6N7). When low temperature
ranges are used for synthesis, these polyheptazine (PHs)
become imperfectly assembled ribbon-like shapes, similar to
those established in Liebig’s melon [67]. They are ended
laterally by groups of eNH2- and -NH- (Fig. 1a) [68]. With rising
synthesis temperatures, the condensation extent increases
with a drop in ammonia-containing components and units
with sheet-like appearance start to develop graphitic ar-
rangements. The procedure, in theory, can be extended to the
graphitic carbon nitride (g-C3N4) composition (Fig. 1b) [68],
although this has not been performed [56,66]. Instead, the
limiting stoichiometries obtained until now amidst gCNH
material have been near to the constitution of C2N3H. Another
category of carbon nitride system to note is constructed from
independent rings of triazine (C3N3) that are connected by
groups of -NH- or eN ¼ . These layers of polytriazine imide
(PTI) offer an alternative way of generating infinite sheets of
graphite with the C3N4 compositions (Fig. 1c and d) [68].
Initially they were synthesized in the form of nanocrystal via
chemical vapour deposition (CVD) method [69,70]. Afterwards,
graphitic carbon nitride based on triazine of crystalline form
(TGCN, Fig. 1c) was found during the synthesis of molten salt
that was deposited on the surface of the melt phase or the
reaction vessel walls [68,71]. It was also observed that the
layers in this material contain C6N6 voids that are stacked
Please cite this article as: Yuda A, Kumar A, A review of g-C3N4 based catalysts for direct methanol fuel cells, International Journal of
Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.01.080
3
with a pattern of AB or ABC [68,71]. In addition, its bandgap
was determined to be 2.7 eV. The polytriazine imide group of
crystalline graphitic carbon nitride materials grow by the
involvement of heteroatoms that include Li, H, Cl and Br
within the system, that are inserted during production pro-
cess in a molten salt (e.g., LiCl:KBr) or via high temperature-
high pressure approaches [32,72e75]. Larger (C12N12) ring
voids are present in these materials inside the layers, with
bromide or chloride ions occupying the spaces between the
layers or the void sites. -NH- groups link the units of triazine
that decorate the void sites’ interior, and the hydrogens can be
partially or completely substituted by cations of Liþ. More Liþ
species can also be present between the layers (Fig. 1d and e)
[68,74,76].
Properties of g-C3N4
Chemical stability
Like graphite, the presence of stacking with van der Waals
bonds that are optimized in the middle of carbon nitride single
layers renders it insoluble in many solvents. There was also
no noticeable reactivity or solubility of carbon nitride in reg-
ular solvents such as alcohols, H2O, THF, DMF, toluene, and
diethyl ether [77]. The stability as well as the durability of
graphitic carbon nitride in organic solvents was previously
analysed by dispersing a powder of carbon nitride in acetone,
H2O, C2H5OH, acetonitrile, pyridine, CH2Cl2, glacial acetic acid,
DMF, and an aqueous solution of sodium hydroxide of 0.1 M
concentration for a duration of 30 days. The dispersed carbon
nitride samples were next dried at a temperature of 80  C for
10 h and then measurement of their IR spectra was taken for
comparison with the fresh material. Results of IR spectra of
the samples that were soaked were observed to be unaltered.
There were, however, two exceptions and one of them was
that the treatment of g-C3N4 in molten alkali metal hydroxides
caused the hydrolysis of the structure. The other observation
made was that treatment in concentrated acids resulted in a
sheet-like dissolution to generate a colloidal distribution [78],
that is nevertheless completely reversible.
Thermal stability
Performing thermal gravimetric analysis, or TGA, on graphitic
carbon nitride has indicated that this substance is remarkably
robust and remained non-volatile up to a temperature of
600  C, even during exposure to air. A strong endothermal peak
also appeared at a temperature of 630  C at which there was
also successive complete loss of weight. This reveals that the
fragments’ thermal decomposition and vaporization began at
the temperature value previously mentioned. In a study per-
formed by Gillan, carbon nitride was sealed in evacuated silica
ampoules and was then positioned within a temperature
gradient [77]. Observations from the study showed that a very
slow rate sublimation of carbon nitride occurred at 450  C and
escalated greatly at 650  C. Carbon nitrides were then
completely decomposed at 750  C and left no residue. From this
analysis, the thermal stability observed is amongst the highest
for an organic material (greater than the ordinary high-
4 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 1 e Structural motifs observed in g-C3N4 (a) Liebig’s melon that consists of chains with zig-zag pattern of units of
heptazine (tri-s-triazine) connected by linking nitrogens and adorned on their edges by groups of N-H, (b) C3N4 layer that is
fully condensed based on units of heptazine, (c) C3N4 layer that is totally condensed built from units of triazine, (d)
Foundation of PTI based on units of triazine rings, connected by bridges of N-H and (e) Side elevation of PTI. Licl that is fully
occupied [68].

temperature polymers, polyimides, and aromatic polyamides).
It is also important to consider that carbon nitride’s stability
rather differs from one preparation technique to another, as
found in the literature [72,73,77,79,80], and this could be due to
different degrees of polymerization.
Optical and photo-electrochemical properties
UV/Vis absorption and photoluminescence experiments have
previously been used to investigate the optical characteristics
of carbon nitride. Based on calculations performed theoreti-
cally, carbon nitride of polymeric form is an ordinary semi-
conductor that has a band gap reaching 5 eV, which depends
on the structural variants or adatoms [81]. In fact, carbon
nitride commonly demonstrates a pattern of absorption of an
organic semiconductor that has a bandgap adsorption that
appears strongly at approximately 420 nm. This is in line with
the pale yellow colour it presents that has been reported
earlier by various authors [82e84].
An important point to note is that synthesis approach,
precursors utilized, and the condensation temperature
applied could have a slight impact on carbon nitride’s ab-
sorption edge. This may be because of the distinct local
structure, defects, and packing that are formed throughout
the production or alteration process [83,85]. Different alter-
ations of carbon nitride, for instance, may cause a blue-shift
(by either protonation [78] or doping with sulfur [86]) or red-
shift (by copolymerization with barbituric acid [87] and by
boron and fluorine doping [88]) of the adsorption edge.
Reports have also been made on several photoluminescent
species and some were able to demonstrate blue region
emission. It appears that there is a high dependence of pho-
toluminescence spectrum towards the condensation degree
as well as the packing in the middle of layers [79,84,89,90].
Conventional polymeric carbon nitride has, in many cases,
exhibited intense blue photoluminescence at ambient tem-
perature. It was established that the luminescence spans over
a wide range of 430e550 nm and showed a maximal value at
around 470 nm.
With an electronic band structure that is satisfactory,
carbon nitride has become a potential material for use in
systems that harvest and convert solar energy (e.g., photo-
electrochemical cells). It is also known that photocurrent was
determined even by bulk graphitic carbon nitride when radi-
ated with visible light (wavelength of greater than 420 nm)
[87]. Carbon nitride’s high level of chemical and thermal sta-
bility improves the stability of photoelectrochemical cells in
presence of oxygen. In addition, it is possible to tune graphitic
carbon nitride’s electronic band structure by nanomorphology
alteration or by doping and this helps in the enhancement of
photocurrent. For instance, carbon nitride with mesoporous
structure (mpg-C3N4) can usually assist in boosting the ca-
pacity to harvest light due to its multiple scattering effect and
large surface area, and hence demonstrated a rise in photo-
current [91]. Other types of modification that can increase the
photocurrent include protonation and doping [87].
Even though carbon nitride modification can partially
enhance the photocurrent, it is still presently considered to be

Please cite this article as: Yuda A, Kumar A, A review of g-C3N4 based catalysts for direct methanol fuel cells, International Journal of
Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.01.080
 international journal of hydrogen energy xxx (xxxx) xxx
rather low. This is supposed to be the result of the presence of
grain boundary defects as well as the lack of ability to generate
bigger domain sizes with the present synthesis strategy.
Mechanism of methanol oxidation reaction on g-
C3N4 catalysts
The mechanism described in this section is based on that
proposed by Zhu et al. in which they utilized an ultrathin 2-
dimensional g-C3N4 nanosheet as a support for ultrasmall
platinum nanoclusters [54] (Fig. 2). It was observed that the
electrode modified with the as-prepared Pt/g-C3N4 demon-
strated better electrocatalytic performance for methanol
oxidation reaction in comparison to bare platinum nano-
particles. Much higher performance was also observed when
the modified electrode was irradiated with visible light.
In a traditional electrocatalytic methanol oxidation process
involving platinum nanoparticles, the particles would serve as
active sites on which methanol molecules would be electro-
oxidized to carbon dioxide. With the introduction of ultra-
thin g-C3N4 as a support, the aggregation of platinum during
the synthesis process could be avoided to help in forming
small platinum nanoparticles. This also improves the
adsorption of target molecules due to the 2-dimensional
structures. Furthermore, upon visible light irradiation
(>400 nm), the graphitic carbon nitride could be excited to
generate electrons (e CB) in the conduction band (CB) and holes
(hþ
VB) in the valence (VB) [92e95]. Therein, the holes possess an
oxidative ability and could react with OH/H2O adsorbed on
the surface to produce strong oxidative hydroxyl radicals
(∙OHs) [96e99]. The methanol molecules being adsorbed on
the catalyst surface could also be oxidized in presence of the
hydroxyl radicals as in photocatalytic methanol oxidation
reaction [96e99]. Generally, the pairs of hole and electron will
quickly recombine and only some portion of the holes could
be utilized. During the interfacial charge transfers between
photoexcited g-C3N4 nanosheets and platinum nanoclusters,
the photoexcited electrons will first transfer to platinum and
then flow to the circuit under external electric field. This is
what prevents the charges from recombining.
Fig. 2 e Representation of the synergistic photocatalytic
(PC) and electrocatalytic (EC) influence of the Pt/g-C3N4
modified electrode for methanol oxidation reaction (in the
presence of visible light) [54].
Please cite this article as: Yuda A, Kumar A, A review of g-C3N4 based catalysts for direct methanol fuel cells, International Journal of
Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.01.080
5
The group also examined the EIS of the synthesized Pt/g-
C3N4 nanosheets modified electrode in different range of po-
tentials in both the presence and absence of light. The ex-
amination further provided a proof of the suggested
synergistic effect and the photo-catalysis aspect of the
methanol oxidation reaction. It was established that from a
potential of 0.60 V to 0.40 V the diameters of the impedance
arcs (DIA) significantly reduced with increasing potential
value in darkness (Fig. 3a). This signifies that at a lower po-
tential there are more active sites available for methanol
oxidation reaction as a result of CO intermediate species
removal by oxidation (CO is generated from methanol dehy-
drogenation [100,101]). With increasing potential value, from
0.40 V to 0.20 V, the DIA also increased because of catalyst
poisoning and oxidation at relatively higher value of poten-
tials (Fig. 3b). However, there is a sudden reverse trend
observed in the arc to the second quadrant at a potential of
0.15 V. This pattern is due to CO oxidative removal from the
surface of the catalyst and regeneration of the active sites.
Further increase in the potential from 0 V to 0.15 V caused
the arcs to adjust to normal positive behaviour gradually with
a large DIA (Fig. 3c). The observed behaviour is due to the
carbon monoxide intermediate species being absent while the
platinum might be covered by platinum oxides that inhibits
methanol oxidation [100].
Upon light illumination on the Pt/g-C3N4 electrode, smaller
DIAs were generated at the same potential values (Fig. 3d).
This is an indication that the methanol oxidation reaction
charge-transfer resistance (Rct) during the photo-assisted
process is relatively smaller. The arc reversing to the second
quadrant previously observed also occurred at 0.20 V, a
comparatively lower value than that observed in absence of
light, as the applied potential is continuously increased
(Fig. 3e). A more negative onset potential of negative imped-
ance seen during visible light illumination suggested that
removal of CO species by oxidation on the surface of the
modified electrode is much easier [102]. In addition, from a
potential of 0 V to 0.15 V (Fig. 3f), the arcs adjusted to normal
positive behaviour gradually with a large DIA, while the ten-
dency of the arc to turn back towards the first quadrant at
0.10 V was more apparent. Furthermore, based on the
Nyquist plots obtained by the research team, the DIAs at the
entire range of potential were smaller than those seen in the
absence of light. This indicates that in presence of light there
is lesser charge-transfer resistance, due to the effective
interfacial charge transfer on Pt/g-C3N4, which further leads to
improved photo-electrocatalytic performance towards meth-
anol oxidation reaction.
Various g-C3N4 preparation and modification
techniques
Carbon nitrides are commonly synthesized by direct
condensation organic precursors that contain nitrogen. Ex-
amples of these precursors include thiourea, urea, dicyan-
diamide, melamine, cyanamide, and guanidine
hydrochloride. They are bulk materials that are characterized
by small surface areas that are often less than 10 m2 g1.
Providing well-controlled porosity of nanoscale level in the
6 international journal of hydrogen energy xxx (xxxx) xxx
Fig. 3 e Nyquist plots of the electrode modified with Pt/g-C3N4 in a solution of 1 M methanol and 1 M KOH at electrode
potential values ranging from ¡0.6 V to 0 V (aec) in the absence of light and (def) under visible light illumination [54].
bulk carbon nitride is necessary for practical applications in
areas of a single catalyst or a support substrate of co-catalysts
(e.g., heterojunctions) to improve its use to a large scale. The
creation of mesoporous system and the enhancement of
specific surface area are vital to properly adjust the physico-
chemical properties and upgrade the photocatalytic perfor-
mance [103]. Reports from analysis in the past indicate that
the mesoporous g-C3N4 was first attained by the performance
of duplication or nanocasting on matrices of mesoporous sil-
ica that are notable for producing the corresponding nano-
structures of carbon [104e106]. Several experiments were
performed after gaining inspiration from this hard template
method to discover new approaches for g-C3N4 alteration.
These new techniques include the ultrasonic dispersion
technique [48], the soft template method [107e109], the
chemical functionalization technique [80,86,87,110], and the
acidic solution impregnation method [78,111]. The strategies
mentioned are also useful in modifying the electronic prop-
erties as well as the texture and surface chemical properties.
Nanoporous g-C3N4 synthesis methods
Materials with porous characteristics are particularly attrac-
tive for use as heterogeneous catalysts or as a component for
catalytic reactions that convert energy because of their vast
surface areas and accessible porosity [112e117]. Graphitic
carbon nitride with mesoporous features (meso-g-C3N4) is a
potential material for producing metal-free catalysts. It is
because it displays distinctive semiconductor properties in
addition to large surface area and available crystalline pore
walls to assist with the transfer of mass. Relative to the bulk
graphitic carbon nitride, the material could demonstrate
greater porosity that could reach 1.25 cm3 g1, larger specific
surface area that could reach a value of 830 m2 g1, larger
quantities of active sites as well as higher size- or shape-
selectivity that overall improve the catalytic performance.
Approaches that are vital to synthesize graphitic carbon
Please cite this article as: Yuda A, Kumar A, A review of g-C3N4 based catalysts for direct methanol fuel cells, International Journal of
Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.01.080
nitride with mesoporous arrangement include the templating
strategy which can either be the hard-templating methods (of
nanocasting) or the soft-templating methods (or self-
assembly). Through these techniques, a continuous meso-
porous g-C3N4 structure possessing spherical or cylindrical
mesopores and their inverse duplicates could be achieved.
Mesoporous g-C3N4 e soft-templating synthesis method
Formation of mesoporous array using this technique is
attainable through cooperative construction of molecules of
amphiphilic surfactant and guest species that are directed by
the likelihood of decreasing interfacial energy. The compo-
nents of the organic templates, as well as their properties are
essential to produce mesoporous structures. Hence, they are
also identified as structure-directing agents (SDAs). This
method is usually performed in hydrothermal environment
that is achievable through evaporation induced self-assembly
(EISA).
To be precise, ionic liquids (ILS) or surfactants (e.g., P123,
Triton X-100, F127, Brij76, Brij58, and Brij30) have also been
utilized as soft templates for synthesizing meso-g-C3N4 by
dicyandiamide self-polymerization reaction [118] to obtain
various specific surface areas and pore structures. It is
important, however, to note that only certain pyrolysis design
and template pathways could be used to produce the desired
mesoporous arrangements as the template components could
decompose before graphitic carbon nitride could be formed.
Moreover, some carbon residue could still be left over in the
final products from the templating polymers that could seri-
ously minimize the nitrogen content of the resulting materials
further affecting their catalytic performance. A study reported
by Shen and team described the generation of bimodal mes-
oporous g-C3N4 that possesses pores of 3.8 nm and a diameter
of between 10 and 40 nm when Triton X-100 template and
precursors of glutaraldehyde and melamine were used [119].
The resulting meso-g-C3N4 surface has a polar nature that
could enhance the immobilization of Candida rugosa lipase,
 international journal of hydrogen energy xxx (xxxx) xxx
and further assist in maintaining its thermal stability and
catalytic activity.
Mesoporous g-C3N4 e hard-templating synthesis method
With this technique nanostructured graphitic carbon nitride
with nanowires or nanospheres features can be duplicated by
making use of primary nanopores in the template of silica to
synthesize a replica arrangement that is stable. The final g-
C3N4 of nanoporous form, that is an inverse duplicate of the
template of silica, is extracted after extracting the template
with aqueous HF or NH4HF2. However, this method is not
environmentally friendly and is unsafe. When SBA-15 was
used as a hard template and carbon tetrachloride (CCl4) and
ethylenediamine ((CH2-NH2)2) were used as precursors in a
nanocasting method, the generated final product was an or-
dered mesoporous carbon nitride (meso-CN) [120,121]. Fea-
tures of the product included 140 m2 g1 specific surface area,
2-dimensional hexagonal ordered mesostructures with
approximately 2.9 nm pores, and 0.16 cm3 g1 pore volume.
Furthermore, the ratio of carbon to nitrogen could be modified
from a value of 4.5 to 3.5 by stepping up the weight ratio of
(CH2-NH2)2 to CCl4 from 0.3 to 0.9. The same technique could
also be applied to synthesize 3-dimensional cubic meso-
carbon nitride structures when a hard template of SBA-16
silica is used [122]. Duplication using a hard template of
mesoporous silica IBN-4 could help in producing meso-carbon
nitride nanoparticles of about 150 nm. The product synthe-
sized in this way could demonstrate greater C/N atomic ratio
of 2.3 than those synthesized with KIT-6 and SBA-15 tem-
plates. The reason could be due to the IBN-4 template
magnified pore size that assists its impregnation with ethyl-
enediamine [123].
Examples of other C- and N-rich organic compounds that
could be utilized to produce highly condensed meso-g-C3N4
include melem (C6N7(NH2)3), melamine (C3N3(NH2)3), dicyan-
diamide ((CN-NH2)2), cyanamide (CN-NH2), and ammonium
dicyanamide (NH4(N(CN)2)) [82,106,124e126]. Antonietti et al.
fabricated a disordered form of meso-g-C3N4 using a hard
template of silica nanospheres and a precursor of cyanamide.
The final product’s characteristics were pores of 12 nm and
surface areas of between values of 86 and 439 m2 g1,
depending on the weight ratio of precursor to silica utilized.
Regarding the carbon to nitrogen atomic ratio a mean value of
0.71 was established and this is near to 0.75, which is the
theoretical value. Improvement of this approach was per-
formed by Jun and co-workers by implementing a hard tem-
plate of ordered mesoporous silica SBA-15 to generate an
ordered mesoporous graphitic carbon nitride [127]. The meso-
g-C3N4 produced were with 0.59 cm3 g1 pore volume, 4.89 nm
mean pore size, and 239 m2 g1 surface area. Park and
research team utilized the same precursor and performed a
facile technique to form nitrogen rich mesoporous g-C3N4
with various 2- and 3-dimensional structures through the
incipient wetness method in the absence of solvents [128].
Replicas with nitrogen to carbon ratio of 1.13 was synthesized
after carbonization for 3 h at 550  C. The 2- and 3-dimensional
mesoporous graphitic carbon nitrides were characterized by
big pore volumes of 0.50 and 0.67 cm3 g1 and high surface
areas of 361 and 343 m2 g1.
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7
The template of choice to synthesize meso-g-C3N4 could be
mesoporous silica or colloidal silica spheres. Using a template
of silica nanoparticles of 12 nm size, for example, could cause
the production of mesoporous g-C3N4 replica that possesses
12 nm spherical pores and 450 m2 g1 surface area organized
in an irregular manner [129]. With hard templates of colloidal
crystals of silica with bigger particles (20e80 nm), meso- or
macroporous graphitic carbon nitride could be successfully
fabricated [130]. Other than silica spheres, highly ordered
meso-g-C3N4 could be synthesized with 2-dimensional hex-
agonal SBA-15 and 3-dimensional cubic KIT-6 mesoporous
silica that can further act as a reactive template for producing
metal nitride of mesoporous form [72,104,126,131].
Chemical modification of carbon nitride
Modifying through chemical approach is an effective way of
altering the physicochemical properties of the precursors so
that their range of applications can be extended [132]. This
could be achieved by elemental doping of solid materials. It is
a strategy that is often applied to tailor the texture and surface
chemical characteristics, in addition to the electronic prop-
erties of materials such as TiO2 [133], carbon [134,135], and
silicon [136]. Applications of this heteroatom doping method
have previously been used to modify carbon nitride materials,
and studies on the doping effects with fluorine [88], boron
[110], sulfur [86], and other elements have also been reported.
Post-treatment modification
This technique, also known as post-functionalization, involves
introducing functional groups onto carbon nitrides’ surface. It
has been used in the past to modify fullerenes [137] and carbon
nanotubes [138] that enabled them to be suitable for different
applications. Due to the nitrogen-rich feature of carbon nitride
materials, direct protonation during counter ion addition is an
appropriate modification approach. In fact, it is possible to
reversibly protonate carbon nitride by dissolving in 37% hy-
drochloric acid at room temperature for 3 h [78]. XRD patterns
obtained after protonation have shown almost unchanged
characteristics (2 characteristic diffraction peaks at approxi-
mately 27 and 13 ) and this demonstrates that the original
carbon to nitrogen matrix has been preserved (Fig. 4aed).
Through protonation, the electronic bandgaps of carbon
nitride can be tuned to improve the ionic conductivity of the
material. The addition of protons also assisted in dispersing
the material in aqueous solutions that eased both character-
ization and processing. In addition, further modification of the
technique could be attained by a simple counter anion
exchange.
Cheng et al. performed the post-functionalization tech-
nique by doping carbon nitride with sulfur [86]. The resulting
material, g-C3N4-xSx, was attained by exposing pristine g-C3N4
to a gaseous hydrogen sulfide atmosphere at 450  C. Energy-
filtered TEM image showed a homogeneous sulfur doping
displaying a strong S contrast (Fig. 4e). Analysis with XPS and
XANES spectroscopy revealed the structural details of doping
with sulfur into the carbon-nitrogen framework and the re-
sults reported that C-S bonds generated in g-C3N4-sSx through
substitution of sulfur by lattice nitrogen (Fig. 4f). In a similar
way to protonation, doping with sulfur could also alter the
8 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 4 e (a) Images of as-prepared g-C3N4 and (b) regenerated g-C3N4 obtained using scanning electron microscope (with
200 nm scale bars). (c) The photocurrent-applied potential dependence at regenerated C3N4/ITO electrode in a solution of KCl
of 0.1 M concentration in the presence of visible light (inset image is the photocurrent biased at ¡0.2 V). (d) The plots of
Nyquist impedance (as scatter) of g-C3N4-HþCl¡ and g-C3N4 and simulation (as lines). The range of frequency is from a value
of 106 to 103 Hz, and the perturbation signal is of the value of 100 mV. The inset image shows the dotted area in large
magnification and the equivalent circuit mold. The value of the calculated resistances (Rb) pre- and post-protonation were
approximately 28 and 1.5 MU, respectively. (e) Images of energy-filtered transmission electron microscopy of carbon,
nitrogen, and sulfur in C3N4 (top row) and C3N4-xSx (bottom row). (f) The model of atomic structure of a perfect g-C3N4 sheet
that comprises of melem units, and 2 melem units with a substitutional N atom at various periodic sites by S atom. Carbon,
nitrogen, and sulfur in sites 1 and 2 are displayed by spheres in yellow, red, green, and blue colour [78,86]. (For
interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

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 international journal of hydrogen energy xxx (xxxx) xxx
morphology and surface area of graphitic carbon nitride to
make it suitable for catalytic applications.
Modified carbon nitride in-situ synthesis strategy
Through this method additive is added in situ before the for-
mation of lattice, and heteroatoms of boron, fluorine or others
are introduced into the matrix. An example that implements
this technique is the fabrication of mesoporous carbon nitride
polymers that contains fluorine and boron [139]. The method
involves ionic liquids with an anion of BF 4 from a range of
various ionic liquids. BF 4 anion is introduced in the C-N
condensation process during organic precursor (e.g., dicyan-
diamide) self-condensation. 1-butyl-3-methyl-imidazolium
hexafluorophosphate, or BmimPF6, is an ionic liquid that was
used in another study as a mild source of phosphorous to dope
carbon nitride. The improvement achieved through phos-
phorous doping offered better photocurrent production by a
factor of up to 5 in addition to enhanced electrical conduc-
tivity that reached four orders of magnitude. This method
utilizing ionic liquid could be further modified to include other
types of heteroatoms by replacing the ionic liquids’ cation or
anion into materials based on carbon and nitrogen for other
specific applications.
Another experiment demonstrated the doping of carbon
nitride materials with fluorine and boron separately involved
co-monomers of ammonium fluoride and aminoborane. Fluo-
rination was performed on the newly thermally induced
condensation of dicyandiamide [88]. Analysis using solid-state
MAS NMR spectroscopy and X-ray photoelectron spectroscopy
showed fluorine atoms being introduced into the matrix of
carbon nitride as C-F bonds that caused the sp2 carbon to
convert partially to sp3 carbon in the matrix of carbon nitride
that may produce a lower plane order of the materials. Relative
to g-C3N4 that has not been modified, XRD revealed that after
fluorination has occurred the graphitic stacking is much
weakened. Carbon atoms replacement in the system with
boron produces aminoborane-modified g-C3N4 that forms a
planar layered configuration in a similar manner to melon. The
planar heterocyclic macrocycle arrangement still exists in the
material, while the boron sites present on the surface might
behave as sites of strong Lewis acid, that therefore comple-
ments the basic sites of nitrogen in bifunctional catalysis [110].
Information of the structure due to boron inclusion into the
carbon to nitrogen matrix were achieved through XPS and 11B
solid-state MAS NMR analysis. The 11B NMR spectrum dis-
played two peaks that designates two distinct positions in the
structure (for bay boron and corner boron).
Other modification techniques include nitrogen precursor
(e.g., dicyandiamide) copolymerization with other organic
additives (e.g., barbituric acid (BA)) [87]. When compared to
the inorganic modification approaches, the carbon nitride
obtained from the organic copolymerization-based method
displayed significant optical absorption red shift from a value
of 470 nm to 750 nm with escalating amount of BA. This would
enable photochemical application of wavelengths that could
lead to a maximum solar photon flux.
It is also possible to dissolve metal salts into the cavities of
nitrogen in the matrix of graphitic carbon nitride. Such
strategy was reported by Kawaguchi et al. in 1995 to fabricate
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9
metal-modified carbon nitride [80]. The team reported that the
proposed carbon nitride structure consists of a hole being
bounded by three radicals of amino in a unit cell. The hole
mentioned was expected to permit the introduction of specific
species of chemicals that could be metal atoms. When the
powder of [(C3N3)2(NH)3]n was heated with metal chloride (e.g.,
ZnCl2 or AlCl3) for an hour at 500  C a yellowish material was
produced. The final product had an IR spectrum that was akin
to that of the initial carbon nitride material, which further
proved the conservation of the original framework. Even
though the widening and weakening of (002) diffraction was
detected in the final material, its position remained un-
changed and this indicated a graphitic stacking arrangement
like that of the host material. The nitrogen “pots” contained
large quantities of metal that could be partially included (up to
59 wt%). Furthermore, the XRD patterns showed no metal (Zn
or Al) or metal salt (ZnCl2 or AlCl3) diffraction that signified the
homogeneous incorporation of the metal in the host material
matrix. Besides, only minute quantities of counter ions were
found in the matrix and this indicates that the CN framework
must have taken up the negative charges.
Similarly, the iron ions inclusion into the matrix of carbon
nitride have also been observed without damaging the host’s
graphitic system [140]. Optical absorption spectra studies and
XRD patterns suggested that iron insertion into the carbon
nitride matrix could strongly alter the material’s electronic
properties and generate systems with novel capabilities.
Types of electrocatalyst that uses g-C3N4 for MOR
Electrocatalysts of graphitic carbon nitride with non-metals
Graphitic carbon nitride itself is a stoichiometric material
which consists sites of Lewis acid and base (terminal and
bridging group of NH- and lone pairs of nitrogen in rings of
triazine/heptazine, respectively) that could potentially act as
platinum anchoring sites and CO adsorption sites. Its first
known application as a support material for a catalyst was
performed by Yu and co-workers in 2007 for use in DMFC [141].
From their study, it was observed that an electrocatalyst of
PtRu being supported by graphitic carbon nitride could
demonstrate 78e83% greater power density than when
Vulcan XC-72 was used as the support.
A research study performed by Meenu et al. implemented g-
C3N4 to develop, for the first time, morphologically engineered
metal-free g-C3N4 for the oxidation of methanol (Fig. 5) [142]. g-
C3N4 of 2-dimensional nanosheets, 1-dimensional nanorods,
and 0-dimensional quantum dots were successfully synthe-
sized from bulk by a process that involved thermo-chemical
etching. The team studied the behaviour of the different g-
C3N4 materials for MOR in basic medium using cyclic voltam-
metry (CV) and found that the material in quantum dots form
showed greater methanol oxidation activity in comparison to
the other types of graphitic carbon nitride developed. This is
because of the existence of abundant edges in nano-
morphology and maximum active site atomic percentages of
pyridinic nitrogen. However, the quantum dots g-C3N4 itself
has unstable electrocatalytic activity as it exhibited a marked
10 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 5 e (a) CV results obtained for CNQD and CNQD-PANI in a solution of NaOH with 0.5 M concentration (with 50 mV/s scan
speed). (b) Cyclic voltammogram traces of methanol oxidation reaction of glassy carbon electrode modified with CNQD and
CNQD-PANI in a solution of methanol and NaOH, each with a concentration of 0.5 M. (c) Curves of CV of 1st (lined in black)
and 150th (lined in red) cycle in a solution of methanol and NaOH, each with a concentration of 0.5 M. (d) Curves of cyclic
voltammogram of methanol oxidation reaction of CNQD-PANI in different concentrations of methanol solutions [142]. (For
interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

reduction in the first cycle from 13 A g1 to 10.8 A g1 in the
hundredth cycle. Such phenomenon could be because of the
slow catalyst dissolution in basic solution and material’s poor
electrical conductivity. The problem was subjugated when the
0-dimensional g-C3N4 was supported on conducting polyani-
line (CNQD-PANI). The resulting material did not only display
better methanol oxidation electrocatalytic activity than the Pt/
C commercially available, but also better carbon monoxide
resistivity. The nanocomposite was able to display high current
density in the first cycle with a value of 28.4 A g1 and managed
to maintain up to 92% of the value even after 1000 electro-
catalytic cycles. The reason for this development could be
assigned to the electrostatic interaction that exists between
conducting polyaniline (PANI) and 0-dimensional g-C3N4,
which could further enhance the methanol adsorption and
electrical conductivity of CNQD-PANI and oxidation of adsor-
bed CO to minimize CO poisoning.
g-C3N4 as a support for metal nanoparticles
Containing noble metals
Platinum: With regards to noble metals, platinum is a popular
catalyst material for use in methanol oxidation reaction
[143e146]. The electrooxidation produces CO-based by-prod-
ucts that reduces the electrocatalyst’s performance. The issue
of CO poisoning and slow oxidation kinetics are the main
disadvantages faced with using platinum catalyst. Further-
more, platinum is also an expensive material that makes it
economically unsuitable for fuel cells commercialization.
Hence, proper utilization of platinum is necessary for their
implementation in fuel cells. Platinum nanoparticles of few
nanometers dimension and narrow size distribution could
offer appropriate use of noble metals by enhancing the elec-
trocatalytic activity. A number of research teams reported
that the size and shape of platinum nanoparticles could in-
fluence the rate of electrooxidation [147]. There is also the
problem of long-term durability of anode platinum catalysts
being supported by carbon for methanol oxidation. The car-
bon support that is often used could also be effortlessly elec-
trochemically oxidized to CO2 during fuel cell operation,
which could result in structural degradation of the support.
Platinum nanoparticles could, in addition, be electrically dis-
engaged from the supporting material. Platinum nano-
particles’ migration, aggregation, and Ostwald ripening [148]
could degrade the electrochemical characteristics. There are
two strategies often implemented to upgrade the durability
and catalytic activity of platinum electrocatalysts. The first is
by synthesizing a platinum alloy with other metals and the
second is by utilizing good support materials.
The design and fabrication of a catalyst comprising of Ag-
Pt bimetal was performed by Liu and co-workers that dis-
played enhanced performance towards methanol oxidation
by minimizing CO chemisorption affinity [149]. The inclusion
of ruthenium into electrocatalyst containing platinum could
assist in the oxidation of carbon monoxide being produced
during methanol electrooxidation. In this way the issue of

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 international journal of hydrogen energy xxx (xxxx) xxx
carbon monoxide poisoning could be avoided during the
oxidation of methanol [150]. However, the issue being faced
with utilizing bimetallic catalyst is in its synthesis because
maintaining specific ratio of two metals is vital in addition to
its shape to acquire the desired effective catalytic
performance.
A 2-dimensional support material known as graphene has
been determined to be a suitable material to act as a support
for nanoparticle dispersion due its physical and chemical
properties [151] that include high electrical conductivity, sur-
face area, and thermal stability [152e154]. Nonetheless, gra-
phene also has its limitation for electrocatalytic purposes
such as high hydrophobicity and low polarity. Graphene ag-
gregation in aqueous solution and the challenge in achieving
metal NPs uniform loading on graphene surface limits further
enhancement in the electrocatalytic activities [155]. Further-
more, the use of acidic media can lead to carbon support
corrosion that generally takes place at the interface with the
novel metal NPs that further degrade supported catalysts’
performance. To upgrade both the stability and dispersion of
the NPs on the surface of graphene, sheets of graphene need
to be functionalized. This strategy helps enhance the solubi-
lity and the NPs dispersion ability on the graphene surface.
Graphene attachment with surfactant molecules or polymer,
and graphene oxidation to generate graphene oxide (GO)
reduce graphene aggregation and improve metal NPs disper-
sion resulting in an enhancement of the electrocatalytic ac-
tivities [156,157].
On the other hand, graphene doping with heteroatom (e.g.,
nitrogen, boron, etc.) can be performed to alter graphene’s
characteristics. Doping with nitrogen, for instance, can
improve the electrocatalytic activity in addition to better
durability because of the strong interaction that exists be-
tween the catalyst and the support [158,159]. A carbon-based
material of g-C3N4, similar in structure with graphene, could
also be utilized as a support because of the existence of sites of
Lewis acid/base into the moiety [160e166]. Metal/semi-
conductor NPs being supported by g-C3N4 have been proven
to be an effective composite for organo-catalysis [167], photo-
catalysis [168], biosensors [169], and electrochemical applica-
tions [170]. Recently, various research studies have also been
performed to synthesize monometallic platinum catalysts
that are supported by porous graphene composites [171e173]
and by nitrogen-doped graphene [159] to electrochemically
oxidize methanol.
Sadhukhan et al. utilized g-C3N4 to produce a composite of
Pt/CNx by involving sodium borohydride reduction that
involve ultrasound technique (Fig. 6) [174]. The resulting
composite of Pt/CNx possessed a large electrochemical surface
area (ECSA) due to better platinum nanoparticles distribution
on sheets of CNx. Analysis using XPS and FT-IR performed by
the team have reported the existence of great interactions
between the metal and support material in the composite. To
observe the electrocatalytic performance of the materials on
methanol oxidation the team performed the experiments in
an aqueous H2SO4 solution of 1 M concentration consisting of
1 M methanol using cyclic voltammogram (CV). Comparison
was also made with a Pt/C modified glassy carbon (GC) elec-
trode using CV at a scan rate of 50 mV/s in an acidic solution.
The CV curves generated by both the samples displayed two
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11
peaks (in the forward scan and the backward scan). The for-
ward scan peak is the peak characterizing methanol oxidation
while the peak in the backward scan indicates the efficiency to
remove carbonaceous species. The Pt/CNx (310 mA/mgPt) dis-
played a forward peak current density that was 2.7 times
greater than that of Pt/C catalyst that displayed 114 mA/mgPt.
The onset potentials of Pt/CNx and Pt/C towards methanol
oxidation are 0.193 V and 0.28 V, respectively. The low onset
potential and the high mass activity signify that Pt/CNx is a
superior catalyst for MOR relative to commercial Pt/C. The
forward to the backward current density ratio (If/Ib), an indi-
cator of the catalyst’s poison resistance towards carbona-
ceous species, was also determined. The team found out that
the If to Ib ratio of Pt/CNx was 2.68 and this is greater than Pt/C
commercially available (If/Ib ¼ 1.9) by 1.41 times. This shows
that MOR taking place on the Pt/CNx catalyst surface is much
easier in the forward scan to form smaller quantities of
carbonaceous components. In addition, the Pt/CNx catalyst
could demonstrate an excellent long-term stability. This
ability was analysed through chronoamperometric (CA) ex-
periments at a constant 0.7 V potential in a similar solution
saturated with nitrogen. During the study, Pt/CNx continu-
ously displayed greater current density than that of Pt/C
during the whole scan duration. When 5000 s of amperometric
scan had passed, the current density of Pt/CNx (57.3 mA/mgPt)
was 17 times larger than the value obtained for Pt/C (3.3 mA/
mgPt).
Mansor et al. developed three distinct materials of
graphitic carbon nitride in the form of polymeric carbon
nitride (gCNM), poly(triazine) imide carbon nitride (PTI/
LiþCl), and boron-doped graphitic carbon nitride (B-gCNM)
[175]. When the research group performed the accelerated
corrosion experiment, all the developed materials were
observed to be electrochemically stable in comparison to
conventional carbon black (CB) with boron-doped graphitic
carbon nitride displaying the superior stability. Analysis of
performance was also conducted with platinum nanoparticles
deposition on each material and it was determined that Pt/
PTI-LiþCl electrocatalyst exhibited greater durability with
ECSA loss of only 19% relative to 36% obtained for Pt/Vulcan
after 2000 scans.
Huang and co-workers developed an efficient technique to
produce platinum-decorated 3-dimensional architectures
constructed from graphitic carbon nitride nanosheets and
graphene (Pt/G-CN) as an anode electrocatalysts for the
oxidation of MeOH [173]. The final product possessed large,
accessible, multi-size pores that could enable reactants to be
swiftly transferred to the electroactive sites and favourable
conditions to preserve the catalyst’s electrical conductivity. In
comparison to Pt-Vulcan XC-72 and Pt-graphene hybrids (Pt/C
and Pt/G, respectively), the 3-dimensional Pt/G-CN electro-
catalyst could demonstrate better properties such as good
activity, satisfactory stability, and unusual poisoning species
tolerance during MOR. The research team also varied the G/CN
ratios of the electrocatalyst’s architecture and investigation of
its activity using CV in H2SO4 solution of 1 M concentration
showed that Pt/G3-(CN)7 possess the greatest electrochemi-
cally active surface area value of 69 m2 g1. When compared to
Pt/C, Pt/G, and Pt/CN, they displayed lower ECSA values of less
than 40.8 m2 g1. Methanol oxidation measurements
12 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 6 e (a) CV of MOR of the catalysts Pt/C and Pt/CNx in a solution of MeOH and H2SO4, each with a concentration of 1 M (at
50 mV/s scan rate). (b) Pt/CNx and Pt/C catalysts onset potentials being compared for MOR. (c) Mass activity and specific
activity comparison between the catalysts of Pt/C and Pt/CNx at a potential of 0.65 V in forward scan for MOR. (d) Pt/CNx
cyclic voltammogram curves in a solution of methanol and H2SO4, each with a concentration of 1 M, at various scan rates
(from 10 mV/s to 200 mV/s). (e) A plot of forward peak current densities against scan rates square root. (f) Curves obtained
from chronoamperometry analysis of the catalysts Pt/C and Pt/CNx for MOR in a solution of methanol and H2SO4, each with
a concentration of 1 M (at 0.7 V constant potential). (g) The variation of forward peak current density with number cycle for
MOR of the Pt/C and Pt/CNx catalysts in a solution of methanol and H2SO4, each with a concentration of 1 M [174].

conducted in H2SO4 and methanol solution of 1 M and 2 M
concentration, respectively, showed that the forward anodic
peak current density of the catalysts of Pt/G-CN declines in the
following pattern: Pt/G3-(CN)7 (15.7 mA cm2) > Pt/G5-(CN)5
(12.2 mA cm2) > Pt/G7-(CN)3 (10.8 mA cm2) > Pt/G1-(CN)9
(1.3 mA cm2). An interesting discovery reported by the group
was that when the content of nanosheets of g-C3N4 increase
from 30% to 90%, the catalyst poison resistance improved. The
If/Ib ratio of Pt/G3-(CN)7 is 1.82 and 1.3 times greater than the
ratio obtained for Pt/C and Pt/G catalysts, respectively. In
addition, Pt/G3-(CN)7 has a mass activity value of
612.8 mA mg1 and its resistivity towards poisoning species
are better than those of the recently discovered nano-
structures that are based on platinum that include Pt/gra-
phene [176,177], Pt/CNTs [178], Pt/N-doped carbons [159,179],
Pt/porous carbons [180], and Pt-based bimetallic catalysts
[37,181].
Zhang et al. previously published their work on the
development of 3-dimensioal hierarchically porous carbon
nanocomposites that consisted of g-C3N4 that was chemically
combined with rGO through C-N covalent bonds to support Pt
NPs (3D Pt-g-C3N4-rGO) [182]. The synthesized nanocomposite
possessed high nitrogen content, large surface area, fine
electrical conductivity, and interconnected porous networks.
Towards MOR, the catalyst could display high activity, good
poison resistivity, and excellent stability in the long run. It
also possessed high value of electrochemically active specific
surface area of 80.3 m2 g1 that is far greater than other recent
state-of-the-art platinum-based electrocatalysts. The
enhanced features could be due to the existence of good
conductivity and large specific surface area of g-C3N4-rGO,
superlative structural stability as a result of covalent in-
teractions that exist between rGO and graphitic carbon
nitride, as well as the large triple-phase boundaries generated
by the Pt NPs that are finely distributed.
Zhu and research team prepared a support for ultrasmall
platinum nanoclusters in the form of ultrathin 2-dimensional
g-C3N4 nanosheet [54]. The platinum nanoclusters had a mean
size of approximately 3.2 nm. In addition to demonstrating
better electrocatalytic ability towards MOR relative to bare Pt
NPs, during the irradiation of visible light higher MOR per-
formance was discovered relative to traditional ambient
electrocatalytic oxidation. The reason could be due to the
synergistic influences of both photo- and electro-catalytic
oxidation of MeOH along with efficient transfer of interfacial
charge in Pt/g-C3N4. Linear sweep voltammetric (LSV) behav-
iours of Pt/g-C3N4 and pure platinum NPs were performed
under light and dark illumination in a solution of CH3OH and
KOH, each having a concentration of 1 M. The Pt/g-C3N4
electrode when illuminated by light showed a value of onset

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 international journal of hydrogen energy xxx (xxxx) xxx
potential that was more negative than in the absence of light.
In addition, Pt/g-C3N4 electrode displayed a value
132 mA mg1 as the current density under visible light irra-
diation and this is approximately 2.4 and 3.1 times higher than
the value obtained for Pt/g-C3N4 without light irradiation
(56 mA mg1) and of pure platinum NPs electrode
(42.3 mA mg1), respectively.
Li et al. supported an alloy of platinum and ruthenium
(PtRu) on a g-C3N4 nanosheet covered Vulcan XC-72 carbon
black (C@g-C3N4 NS) to produce an electrocatalyst that is
synthesized through a microwave-assisted polyol process
(MAPP) [183]. An excellent activity was observed during elec-
trochemical measurements of PtRu/C@g-C3N4 NS because of
even distribution and minute size of NPs of PtRu, and greater
stability owing to robust interaction between the composite
support and the PtRu NPs. Analysis using X-ray diffraction
(XRD), X-ray photoelectron spectroscopy (XPS), and trans-
mission electron microscopy (TEM) determined that the shell
of the bulk graphitic carbon nitride on the exterior of the
produced bulk graphitic carbon nitride coated Vulcan XC-72
carbon black (C@bulk g-C3N4) in fact exfoliated to g-C3N4 of
layered nanosheets and resulted in a composite material of
Vulcan XC-72 coated with nanosheets of g-C3N4. Furthermore,
the mass catalytic activity of synthesized catalyst significantly
improved by 2.1 times greater than the mass catalytic activity
observed for PtRu/C catalyst produced by similar method.
Accelerated potential cycling tests (APCTs) showed that the
catalyst can display 14% greater stability in addition to higher
poison resistivity when compared to the as-synthesized PtRu/
C. The enhancement in performance observed could be due to
a few reasons. The first one could be due to the support’s
upgraded electron conductivity by generating C@g-C3N4 NS
core-shell structure. Secondly, there is also the presence of
excellent mechanical resistance and stability of the nano-
sheets of g-C3N4 in oxidative and acidic conditions. Thirdly, a
stronger interaction is present between the metal and support
(SMSI) that exists between the composite support and the
metal nanoparticles.
Li and team also implemented a p-p stacking technique to
synthesize a support for ultrafine PtRu nanoparticles in the
form of graphene/ultrathin g-C3N4 nanosheet composite ma-
terial for methanol electrooxidation [160]. Graphitic carbon
nitride electrical conductivity is due to the electron-hole
puddle that developed on the sheet interfaces between gra-
phene and g-C3N4. Due to the remarkable textural properties
that include large surface area, layered structure, high nitro-
gen content, homogeneous ultrafine PtRu NPs dispersion, and
the strong interaction between the nanosheet of g-C3N4 and
metal nanoparticles, the final material could perform well as
an electrocatalyst. The enhanced properties include greater
stability, better poison tolerance, and excellent electro-
catalytic activity. The existence of 25% g-C3N4 content in the
mixed support enabled the catalyst (PtRu/G75-(CN)25) to
perform with best activity and stability. The forward peak
current densities of 0.91 A mg1 Pt was determined for this
catalyst, which is 1.4 times greater than the value achieved by
PtRu/rGO. Increasing the content of g-C3N4 would lead to
graphitic carbon nitride nanosheet agglomeration on the rGO
surface that could reduce the catalytic activity because of poor
conductivity of electron. However, increasing the g-C3N4 NS
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13
content from 0% to 30% caused the catalysts’ poison resis-
tance ability to become much better. Hence, PtRu/G70-(CN)30
has higher If/Ib ration (4.06) than that of PtRu/G75-(CN)25 (2.34).
Such phenomenon could be due to the marginal nitrogen
composition in the supports that would activate a huge
quantity of neighbouring atoms of carbon and further speed
up the generation of OH by H2O dissociation. Therefore, pro-
motion of the oxidative removal of the intermediate poisoning
species that were absorbed takes place.
Wang et al. deposited a traditional electrocatalyst of Pt
and Au on a 2-dimensional visible-light-activated nano-
sheets of graphitic carbon nitride through a facile one-pot
hydrothermal technique [184]. Altering the quantities of
gold and platinum allowed the construction of 3-
dimensional platinum island-on-gold architectures on
graphitic carbon nitride nanosheets surface (Pt-Au/CN). The
performance of the resulting Pt-Au/CN composite towards
MOR was analysed by the research team. In comparison to a
graphitic carbon nitride-supported platinum (Pt/CN) modi-
fied electrode, the prepared catalyst could demonstrate an
enhanced electrocatalytic activity for MOR by 13.8 times.
Visible light illumination also continuously enhanced the
current density and stability of the composite. Factors that
contribute to the improved stability and electrocatalytic ac-
tivity include the bimetallic electronic effects of platinum
and gold, 3-dimensional Pt islands-on-Au architectures, 2-
dimensional support nanosheet of graphitic carbon nitride,
and the synergistic influence of electro- and photo-catalytic
processes.
Palladium: Many researchers have studied the inclusion of
palladium as a noble metal to substitute platinum to produce
non-Pt based anode catalysts. For example Qian et al. reported
the development of high-performance Pd/g-C3N4/carbon black
for the electrooxidation of both MeOH and formic acid [185].
The production was achieved by a facile 2-step technique that
involved g-C3N4 coating on the carbon black surface by heating
treatment at low temperature followed by uniform deposition
of palladium NPs through wet chemistry approach. Promoted
by the individual components’ synergistic influences, the
resulting catalyst could exhibit excellent forward peak current
densities of the value 1720 mA mg1Pd for MOR in alkaline so-
lutions. This performance is significantly better than that
shown by the commercial Pd-C catalyst.
In another study performed by Fang and co-workers, g-
C3N4 and rGO was combined to fabricate a hybrid support to
anchor ultrafine Pd NPs through a simple technique involving
a one-step electrodeposition [186]. Characterization study of
the morphology and structure by implementing XRD, scan-
ning/transmission electron microscopy (SEM/TEM), XPS, and
Raman spectroscopy confirmed the uniform dispersion of Pd
NPs on g-C3N4@rGO support with particles of 5.87 nm mean
size, originating from the N in graphitic carbon nitride that
contribute to the electron transport highway on the reduced
graphene oxide nanosheet layer surface. In addition, reports
from electrochemical experiments indicated that the syn-
thesized catalyst displayed a high efficiency of electrocatalytic
activity for MOR with a value of current density of
0.131 mA cm2.
Zhang and team developed a covalently coupled g-C3N4
and rGO hybrid to load Pd NPs using an in situ chemical
14 international journal of hydrogen energy xxx (xxxx) xxx
synthesis technique [33]. Pd NPs with a 3.83 nm mean diam-
eter were deposited evenly on the g-C3N4-rGO surface. When
compared to catalysts of commercial Pd-activated carbon (Pd-
AC) and Pd-rGO, the nanocomposite of ternary Pd-g-C3N4-rGO
possesses great electrocatalytic characteristics for the oxida-
tion of both formic acid and MeOH. These remarkable prop-
erties include notably high forward peak current densities,
large electrochemically active surface area (ECSA), and fine
long-term stability. Reasons for the improved activity could be
due to the specific properties of the catalyst’s special nano-
structure and the synergistic influence of the individual spe-
cies. These include the large specific surface area of the
mesoporous structure, finer rGO conductivity, well-dispersed
Pd NPs due to the influence of planar groups introduced by
g-C3N4, and satisfactory stability of the structure due to the
covalent interactions that exists between rGO and graphitic
carbon nitride.
Zhang et al. also developed a novel support material rich
in nitrogen, consisting of rGO and g-C3N4 in the form of
nanoflakelets (CNNF) to load Pd NPs [35]. The CNNF was
formed by splitting decomposition of the polymer of graphitic
carbon nitride on reduced graphene oxide at higher temper-
ature values. The CNNF produced was also intimately com-
bined with the reduced graphene oxide nanosheets. It was
observed that the CNNF could help in offering edge sites that
are more exposed and species containing active nitrogen for
the great distribution of palladium NPs. It was also deter-
mined that the nanoparticles of palladium had a mean
diameter of the value 3.92 nm that were evenly distributed on
sheets of CNNF-G. DFT computations reported that the CNNF
could trap the palladium adatom, and therefore behave as a
nucleation site for palladium at which atoms of palladium
are more likely to gather to generate palladium clusters. The
excellent properties possessed by the final Pd-CNNF-G
nanocatalyst were satisfactory for both MOR and formic
acid oxidation and they include large ECSA values
(91.2 m2 g1), fine stability and durability, and remarkably
high forward peak current densities. These properties
enabled Pd-CNNF-G nanocatalyst to surpass Pd-graphene,
commercial palladium catalyst supported by activated car-
bon or Pd-carbon nanotubes. Pd-CNNF-G had the ability to
display a peak current density as great as 1770 mA mg1 for
MOR in NaOH and methanol solution, each with a concen-
tration of 1 M. This value is much greater than the value
found for Pd-g-C3N4-rGO (1550 mA mg1), Pd-rGO
(835 mA mg1), Pd-CNT (725 mA mg1), Pd-AC
(535 mA mg1), Pd-g-C3N4 (67 mA mg1). In addition, the
recorded value is even greater than those recently reported
for nanostructures based on palladium that include Pd-SnO2/
MWNTs (778.8 mA mg1) [187], Pd/graphene hydrogel on a
foam of nickel (788 mA mg1) [188], Pd1Ag1 nanoparticles/
graphene (630 mA mg1) [189], Pd-Cu bimetallic nano-
particles/graphene (392.6 mA mg1) [190], Pd1Pt3/nano-
platelets of graphite (385.22 mA mg1) [191], Pd/CuO-TiO2
(381 mA mg1) [192], Pd-Ni-P NPs/carbon black
(~360 mA mg1) [193], and porous Pt-Pd nanospheres/gra-
phene (180 mA mg1) [194].
Eswaran and team previously reported a simple one-step
approach of producing a new g-C3N4/polyaniline/palladium
NPs (g-C3N4/PANI/PdNPs) based nanohybrid composite altered
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screen-printed electrode (SPE) to achieve efficient MOR [195].
The structure of the nanohybrid was attained by a single-step
simultaneous electro-deposition technique that involved an
electrolyte solution of aniline, palladium chloride, and nano-
sheets of graphitic carbon nitride. The final product also
featured needle-shaped polyaniline and spherical nano-
particles of palladium being positioned between nanomatrix
of g-C3N4. Analysis of the as-prepared composite altered SPE
using CV and CA have shown that a great electro-oxidation
and excellent catalytic performance for MOR could be
exhibited by the material in comparison to commercial 10% Pd
deposited carbon black and other type of catalysts previously
studied.
Qian et al. have, in the past, utilized bimetallic NPs of Pt-Pd
to fabricate a composite catalyst with g-C3N4 modified carbon
black through a facile 2-step approach [196]. An extraordi-
narily fine catalytic activity as well as stability in the long-
term could be demonstrated by the resulting materials for
oxidizing MeOH, C2H5OH, glycerol and ethylene glycol in basic
solutions. The enhanced properties could be due to the planar
amino group of graphitic carbon nitride promoting a template
effect for the distributed decoration of platinum-palladium
nanoparticles, with complementary roles of platinum (site
for dehydrogenation) and palladium (site for removal of CO-
like species). Other factors could include the presence of car-
bon black having large specific surface area to promote a fast
diffusion of electrolyte, quick elimination of carbonaceous
species, and the support’s structural stability established on
the covalent link that exists between CB and g-C3N4 for pre-
serving the catalytic system durability. The group studied the
behaviour of the as-prepared catalyst towards MOR in alkaline
medium using CV. It was determined that Pt-Pd-gCN-CB dis-
played the greatest value of anodic peak current density of
4420 mA mg1metal. This value is then followed by the result-
ing current densities in the following order: Pt-Pd-CB (2017 mA
mg1metal) > Pt-gCN-CB (2000 mA mg1Pt) > Pd-gCN-CB
(955 mA mg1Pd). The value obtained for Pt-Pd-gCN-CB is even
remarkably higher than the value attained for Pt/C commer-
cially available (1410 mA mg1Pt) [197], Pt-Pd/graphene
(636 mA mg1metal) [198], Pt@Pd/RGO (588 mA mg1metal)
[199], and commercial Pd/C (459 mA mg1Pd) [185].
Containing non-noble metals
Junlan Lv and co-workers utilized a low-cost transition metal
of iron and g-C3N4 to fabricate a novel type of anode catalyst
[200]. Iron was chosen because the d-orbital of its atoms is
likely to obtain or lose electrons, and the resulting catalyst
could possess strong redox properties. Catalysts containing
iron have also been shown to have great performance towards
methanol decomposition and oxidation [201,202]. Adsorption
results have also reported that methanol molecules could get
adsorbed on the iron atoms through the O atoms, that they
could easily dissociate into H and CH3O, and then C-H bond
could be gradually broken to generate the final products.
Using g-C3N4 as a catalyst substrate that possesses six-fold
cavities has higher potential of capturing metal atoms. The
energy required for O-H bond cleavage in methanol is 0.99 eV,
which signifies that the reaction could proceed easily.
Furthermore, the adsorption energy of CO2 (3.44 eV) is
smaller in value than that of CO (4.65 eV), suitable for
 international journal of hydrogen energy xxx (xxxx) xxx 15

Fig. 7 e Curves obtained from CV analysis of glassy carbon electrodes modified with (a) Ni/CN, (b) (Ni-Cu)/CN, and Cu/CN in a
solution of 1 M sodium hydroxide and different concentrations of methanol (at 50 mV/s potential scan rate). (d) Curves
attained from CV study of glassy carbon electrode modified with catalysts of Cu/CN (in black), Cu-Ni/CN (in red), and Ni/CN
(in blue) in a solution of 1 M sodium hydroxide and 3 M MeOH (at 50 mV/s scan rate). Inset image displays the magnified
version of the CV curves to show the onset of MOR. (e) A plot of current densities against time for a glassy carbon electrode
modified with films of Ni/CN (in blue), Ni-Cu/CN (in red), and Cu/CN (in black) catalysts in a solution of 1 M sodium hydroxide
and 3 M MeOH (at E ¼ 0.5 V vs Ag/AgCl). (f) A graph of current densities of electrodes modified with Ni/CN, Ni-Cu/CN, and Cu/
CN in the presence and absence of visible light [203]. (For interpretation of the references to colour in this figure legend, the
reader is referred to the Web version of this article.)

minimizing the toxicity of CO to iron and enhancing the

efficiency.
Pieta et al. synthesized nanostructures of Cu, Ni, and Cu-Ni
that were homogeneously embedded on ultrathin 2-
dimensional g-C3N4 (Fig. 7) [203]. The research team drop-
casted the novel hierarchical hetero-structures on glassy
carbon anodes. The behaviour of the novel electrocatalyst
toward MOR was also examined under basic conditions.
Nanosized nickel particles, finely dispersed on g-C3N4, were
very active towards MOR and exhibited a value of 0.35 V as the
onset potential and a charge transfer resistance of 0.12 kU.
The modified glassy carbon electrode stability was also stud-
ied using CA and a consistent current density of around
36 A g1 (12 A cm2) was attained during the duration of the
entire experiment (up to 160 min) when 4 wt% of nickel oxide
was loaded on the electrode. In addition, illumination by UV
light with wavelength of ~400 nm assisted in enhancing the
current density of all the catalysts studied. It was determined
that 4 wt% Ni/CN catalyst exhibited the highest current den-
sity value of 127 A g1 (22 A cm2). The inclusion of copper into
the hybrid material helped reduce the activity losses due to
Cuþ undergoing irreversible reduction/oxidation to Cu0 and
Cu2þ, segregation of copper oxide, and affecting the process of
electron transfer that lead to increased redox potential.
Table 1 presents a list of selected C3N4 based electrocatalysts
along with key experimental observations for a quick
reference.
Key challenges and future prospects
With the many studies performed on electrocatalysts consist-
ing of graphitic carbon nitride, significant progress could be
observed in this field. However, further systematic examina-
tions are required as the studies are still in the early stages.
Implementing rational design of complex heterostructures
could enable the simultaneous achievement of efficient carrier
formation, separation, transfer, and utilization in addition to
efficient optical absorption that is fundamental to the devel-
opment of new generation of excellent performing photo-
catalysts. Challenges still exist in the development of such
complex structure that needs to be considered as follows:
- It is necessary to understand the basics of charge transport
process taking place in photocatalysts with multi-
heterostructure to optimize the charge cascading process
to ensure the maximum usage of photogenerated charge
carriers to achieve the satisfactory reduction-oxidation
chemistry. Although electron-hole separation and trans-
portation in a 2-component heterostructure can easily be
understood, the understanding becomes much more
complex in multi-component heterostructures to control
charge transport, especially in the scale of nanometers.
The photocatalysts interface properties determine the
resulting efficiency of the photocatalyst. Furthermore, it is

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16 international journal of hydrogen energy xxx (xxxx) xxx

Table 1 e List of various electrocatalysts containing graphitic carbon nitride and their electrocatalytic properties toward
methanol oxidation reaction.
Catalysts Method Mass/Specific activity/ If/Ib Medium Reference
Current density
CNQD-PANI Thermo-chemical etching 28.4 A g1 (mass spec. peak - 3.58 0.5 M MeOH þ 0.5 M NaOH [142]
forward)
Stellated Pt NPs þ Ag core One-pot approach 72 mA cm2 (peak current 1.125 1 M MeOH þ 0.1 M HClO4 [149]
density e forward)
Pt-CNx Ultrasound mediated 310 mA mg1 Pt (mass activity 2.68 1 M MeOH þ 1 M H2SO4 [174]
sodium borohydride e forward scan)
reduction of H2PtCl6 (CNx
nanosheets present)
Pt/gCNM Thermolysis and 3.21 mA cm2ECSA e 1 M MeOH þ 0.1 M HClO4 [175]
condensation reactions,
ethylene glycol reduction
Pt/PTI-LiþCl e 174 mA cm2ECSA e 1 M MeOH þ 0.1 M HClO4 [175]
Pt/B-gCNM e 209 mA cm2ECSA e 1 M MeOH þ 0.1 M HClO4 [175]
Pt/G3-(CN)7 Modified Hummers method, 15.7 mA cm2 (peak current 1.64 2 M MeOH þ 1 M H2SO4 [173]
liquid-phase exfoliation density e forward)
3D Pt-g-C3N4-rGO e 705 mA mg1 (peak current 1.47 1 M MeOH þ 0.5 M H2SO4 [182]
density e forward)
Pt/g-C3N4 nanosheets Simple reflux method 158.9 mA mg1 (in e 1 M MeOH þ 1 M KOH [54]
darkness),
520.4 mA mg1 (visible light
irradiation)
PtRu/C@g-C3N4 NS Microwave-assisted polyol 1.14 A mg1
Pt (peak current 1.73 0.5 M MeOH þ 0.5 M H2SO4 [183]
process density e forward)
PtRu/G75-(CN)25 Microwave-assisted polyol 0.91 A mg1
Pt (peak current 2.34 0.5 M MeOH þ 0.5 M H2SO4 [160]
process density e forward)
Pt10-Au1/CN One-pot hydrothermal 1.52 mA cm2 (in darkness), e 1 M MeOH þ 1 M KOH [184]
approach 2.58 mA cm2 (visible light
irradiation) (peak current
density e forward)
Pd/g-C3N4/carbon black-30 Facile ultrasonic process, 1.66 mA cm2 Pd (peak current e 1 M MeOH þ 1 M NaOH [185]
wet chemistry method density e forward)
Pd/g-C3N4@rGO One-step electrodeposition 0.131 A cm2 (peak current e 1 M MeOH þ 1 M KOH [186]
technique density e forward)
Ternary Pd-g-C3N4-rGO-2 In situ chemical synthesis 1550 mA mg1 (peak current e 1 M MeOH þ 1 M NaOH [33]
nanocomposite method, modified density e forward)
Hummers’ method
Pd-CNNF-G Modified Hummers’ method 1770 mA mg1 (peak current e 1 M MeOH þ 1 M NaOH [35]
density e forward)
ASPE-g-C3N4/PANI/PdNPs e 3.42 mA cm2 (peak current 2.736 1 M MeOH þ 0.5 M KOH [195]
density e forward)
Pt-Pd-gCN-CB Surfactant-free soft 4420 mA mg1 metal (peak e 1 M MeOH þ 1 M NaOH [196]
chemistry process current density e forward)
Ni/CN One-pot hydrothermal 57 A g1 (in darkness), e 3 M MeOH þ 1 M NaOH [203]
synthesis 127 A g1 (visible light
irradiation)

critical to have a good understanding of the nanoscale in-
terfaces of charge generation, separation, and trans-
portation. Studies performed so far have mostly focused on
the photocatalytic system’s overall apparent efficiency. In
order to further advance in the field, detailed study on the
mechanism of charge transfer should be performed for
photocatalysts that consists three or more components.
- A less addressed property of g-C3N4-based nanocomposites
is the stability, which could become the main obstacle in
the development of photocatalysts. Even if a photocatalyst
with very high efficiency is developed its application could
be limited if its lifetime is short. In many cases, a photo-
catalyst’s chemical corrosion and/or photo-degradation
cannot be prevented. So far, satisfactory stability has
only been achieved by few photocatalysts which was
possible through very sophisticated synthesis techniques.
One of the focus of future research could be to develop a
stable photocatalyst possessing great efficiency at a rela-
tively cheaper cost that could be suitable for practical ap-
plications and commercialization.
- It is still necessary to understand the mechanisms involved
in the photocatalytic enhancement by semiconductor
composites based on graphitic carbon nitride. In addition,
it is important to come up with a uniform technique to
evaluate the photocatalytic performance as currently there
are multiple assessment methods available.

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 international journal of hydrogen energy xxx (xxxx) xxx
- Efforts should be made to explore the enhancement in
properties from the combination of g-C3N4 and novel
photocatalysts. Good understanding of the photocatalytic
mechanism of the combination in addition to rapid novel
nanomaterials development could help overcome the
bottleneck that arises from global energy and environ-
mental issues.
Conclusions and outlook
Many research studies have utilized g-C3N4 in various forms
and as supports to design and construct suitable electro-
catalysts for methanol oxidation reaction. Graphitic carbon
nitride inclusion as a support component has been proven to
improve the properties, and hence the performance of the
final material owing to its ideal 2-dimensional structure,
remarkable chemical and thermal stability.
Based on the studies that have used g-C3N4 as an additional
electrocatalyst material for MOR there are several fabrication
techniques that could be followed to ensure that a satisfactory
performance is achieved during methanol oxidation process.
Incorporating mesoporous structures and modifying the spe-
cific surface area could assist in obtaining appropriate physi-
cochemical properties suitable for better photo/electro-
catalytic performance. Such improvements are achievable
by performing nanocasting, or mesoporous silica matrices
duplication. Mesoporous features on graphitic carbon nitride
allows the enhancement of semiconductor properties and
introduces more pore walls of crystalline form suitable for
enhancing mass transfer. Utilizing soft templates of some
ionic liquids or surfactants for meso-g-C3N4 synthesis (via
self-polymerization reaction of dicyandiamide) is an option to
achieve various forms of pore structures as well as specific
surface area. With the hard-templating method that involve
using primary nanopores present in the silica template, a
stable replica structure could be fabricated. Utilization of
ethylenediamine precursors, carbon tetrachloride and a hard-
template of SBA-15 in nanocasting method produces an or-
dered meso-CN. The ratio of C to N of the final material could
also be adjusted from a value of 4.5 to 3.5 by escalating the
weight ratio of ethylenediamine to CCl4 from a value of 0.3 to
0.9. The hard template that could also be utilized to synthesize
a meso-carbon nitride NPs with relatively greater C to N
atomic ratio of 2.3 is the mesoporous silica IBN-4. This could
be a result of the enlarged pore size of the template helping
with the ethylenediamine impregnation. Implementing a
precursor of cyanamide and a hard template of silica nano-
spheres can help develop mesoporous graphitic carbon nitride
with an average atomic ratio of C to N of 0.71, near to the
theoretical value of 0.75.
Modification of carbon nitride by elemental doping of solid
materials can help in adjusting the physicochemical proper-
ties. With this strategy, one can change the texture, surface
chemical characteristics, and the electronic properties of
carbon-based materials. Direct protonation method during
counter-ion addition is a suitable modification technique as
the characteristics of the carbon nitride could be maintained
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17
(original C/N matrix is unchanged). Furthermore, protonation
can tune the electronic bandgaps to enhance the ionic con-
ductivity of the material. Protonation could also help in
achieving fine dispersion of the materials that can then make
characterization and processing simpler. Sulfur doping has
emerged as an alternative to protonation that could also
modify the surface area and morphology of g-C3N4 allowing it
to be used in catalytic processes.
Involving an ionic liquid of 1-butyl-3-methyl-imidazolium
hexafluorophosphate (BmimPF6) as a mild phosphorous
source for carbon nitride doping could help obtain enhanced
generation of photocurrent by a factor that could reach a value
of five. Improved electrical conductivity could also be ach-
ieved up to four orders of magnitude.
Related to the possibility of dissolving metal salts into g-
C3N4 matrix’s nitrogen cavities, the incorporation of iron ions
into the carbon nitride matrix could help avoid damaging the
host graphitic structure. In addition, iron introduction could
strongly modify the final product’s electronic properties.
Graphitic carbon nitride of 0-dimensional quantum dots
could show better performance towards MOR in comparison
to those with 1-dimensional nanorods or 2-dimensional
nanosheets structure. Factors that contribute to the
enhancement include maximum active site atomic per-
centages of pyridinic N and abundant edges in nano
morphology. Further improvement of the carbon-based
materials property could be attained by supporting it on
conducting polyaniline. In this way, better catalytic perfor-
mance in the form of better electrical conductivity and CO
poisoning resistivity could be observed in the resulting
combination for MOR because of the electrostatic interaction
between the two components.
Using Pt by itself as an electrocatalyst is a challenge as it
has slow oxidation kinetics and it is prone to poisoning by CO
species produced during the methanol oxidation reactions. In
addition, anode platinum catalysts also have an issue of
maintaining stability in the long run. Nanoparticles of plat-
inum could migrate, aggregate, and undergo Ostwald
ripening leading to poor electrochemical performance. Ap-
proaches such as alloying of platinum with other metals and
supporting platinum on good support materials with high
conductivity, durability and suitable pore structure could
lead to enhanced mass transfer to the active sites. For
instance, preparing a Pt/CNx composite can help achieve
large electrochemical surface area as Pt NPs are widely
dispersed on CNx sheets. As a result, low onset potentials,
high mass activity, better poison tolerance towards carbo-
naceous species, and reliable long-term stability could be
demonstrated by Pt/CNx in comparison to commercially
available Pt/C. Synthesizing g-C3N4 materials in the form of
poly(triazine) imide carbon nitride (PTI/LiþCl) and using it to
support platinum can enhance the durability by maintaining
81% of the ECSA during MOR. Supporting Pt on g-C3N4 nano-
sheets and graphene could help build large pores of different
sizes to promote the reactants transportation to the electro-
active sites as well as suitable environment for maintaining
good electrical conductivity. In addition, Pt/G3-(CN)7 dis-
played the highest forward anodic peak current density
18 international journal of hydrogen energy xxx (xxxx) xxx
relative to other Pt/G-CN electrocatalyst with different G/CN
ratios for MOR. Increasing the g-C3N4 nanosheets content to
90% also improved the catalyst ability to resist poisoning
species.
Alloying platinum with ruthenium and supporting them
on a Vulcan XC-72 carbon black coated with graphitic carbon
nitride nanosheet could help establish an even dispersion of
small nanoparticles of PtRu and fabricate a catalyst that is
highly stable as a result of a strong link that is present be-
tween the composite support and the bimetallic nano-
particles. Alloying Pt with gold, on the other hand, and
depositing the two metals on the graphitic carbon nitride
nanosheets surface could demonstrate greater activity rela-
tive to Pt/CN. Illuminating the electrocatalyst with visible light
further improved both the current density and stability of the
composite. Replacing platinum with palladium and support-
ing the metal on reduced graphene oxide and graphitic carbon
nitride hybrid support enabled the achievement of remark-
ably high value of forward peak current densities, large ECSA,
and stable MOR performance for long duration. The factors
that contribute to the satisfactory properties are because of
the existence of good rGO conductivity, mesoporous structure
with high value of specific surface area, fine palladium NPs
dispersion, and great stability because of the covalent links
that are present between reduced graphene oxide and
graphitic carbon nitride. Forming bimetallic nanoparticles of
platinum and palladium and fabricating carbon black modi-
fied with g-C3N4 could also help in developing extraordinary
catalysts with long-term stability and satisfactory activity.
The improvement is the result of a combination of the tem-
plate effect, complementary roles of platinum and palladium,
high specific surface area of carbon black, and the covalent
interaction between g-C3N4 and carbon black. The template
effect is promoted by the graphitic carbon nitride planar
amino group resulting in highly dispersed decoration of
nanoparticles of Pt-Pd.
Regarding the use of non-noble metals, supporting iron on
g-C3N4 allows the metal atoms to be easily captured by the
carbon-based support. The result is an electrocatalyst that
could efficiently break the O-H bond in CH3OH showing a great
potential for non-noble metal MOR catalysis. The combination
also minimized the adsorption energy of CO2 to less than that
for CO that further signifies the ability to reduce CO toxicity to
iron.
Even though significant advancements have been estab-
lished related to the utilization of g-C3N4 with an array of
materials based on the properties and improvements
mentioned above, further investigations are still necessary to
design complex structures achieving a satisfactory perfor-
mance for methanol oxidation reaction. It is important to
undertake detailed mechanism analysis of the charge transfer
process and the reaction pathways taken to progress further
in the field. As a better understanding of the reaction mech-
anism and molecular level interactions at the catalyst surface
are developed, it would be possible to envision the develop-
ment of a suitable catalyst in the future that is active and
stable for MOR reaction leading to large scale commercial
applications.
Please cite this article as: Yuda A, Kumar A, A review of g-C3N4 based catalysts for direct methanol fuel cells, International Journal of
Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.01.080
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
The author(s) would like to acknowledge the support from
Qatar University internal grant QUCG-CENG-19/20-7.
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Another random document with
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 Turning to the volume of Orations and Addresses, the reader finds
himself in another world. Bryant’s memorial orations are among the
best of their kind, stately, uplifting, and at times even majestic. They
belong to a type of composition which lies midway between oratory and
literature and unites certain characteristics of each. Written primarily to
be heard, and adapted to public utterance, they are also meant to be
read. They must stand the test of the ear and then that of the eye. The
listener must find his account in them as they come from the lips of the
orator, and he who afterward turns at leisure the pages of the printed
report must be satisfied. Bryant’s speeches are markedly ‘literary;’ and
though oratorical they are wholly free from bombast. Poet though he
was, he built no cloud-capped towers of rhetoric.
Coming now to his verse, we find that his poetic flights, though
lofty, were neither frequent nor long continued. Apparently he was
incapable of writing much or often. This seems true even after
allowance is made for his busy and exacting life as a journalist. For
years together he composed but a few lines in each year.
His theory fitted his own limitations. Bryant maintained that there is
no such thing as a long poem, that what are commonly called long
poems are in reality a succession of short poems united by poetical
links. The paradox grows out of the vagueness attaching to the words
‘length’ and ‘poem.’ Exactly what a poem is, we shall never know. That
is a shadowy line which divides poetry from verse. And there is no term
so unmeaning as length. When does a poem begin to be long—is it
when the poet has achieved a hundred verses or a thousand, when he
has written six cantos or twelve?
To say, as Bryant is reported to have said, that ‘a long poem is no
more conceivable than a long ecstasy,’ is to make all poetry dependent
on an ecstatic condition. And it reduces all poetic temperaments to the
same level. Why may not poetry be an outcome of ‘the true enthusiasm
that burns long’?
Bryant showed skill in handling a variety of metrical forms; it is
unsafe to say that he excelled only in blank verse. With declared
partisanship for the short poem, he nevertheless did not cultivate the
sonnet. Up to the time he was fifty-eight years of age he had written but
twelve, and for some of these he apologized, saying, ‘they are rather
poems in fourteen lines than sonnets.’
 Comparing the length of his life with the slenderness of his poetical
product, we are tempted to bring against this eminent man the charge
of wilful unproductiveness. This reluctance, or inertia, or whatever it
may be called, has helped to give the impression of a lack of
spontaneity. We are aware of the effort through the very exactness with
which the thing has been done. Bryant resembled certain pianists who
plead as excuse for not playing, a lack of recent practice. When after
repeated urgings one of the reluctant brotherhood ‘consents to favor
us,’ he plays with precision enough but rarely with abandon. The
conscious and over-solicitous artist shows in every note.
If much writing has its drawbacks, it also has its value. And the poet
who sings frequently cannot offer as a reason for not performing, the
excuse that his lyre has not been out of the case for weeks, and that in
all probability a string is broken.

IV
THE POET
The fine stanzas entitled ‘The Poet’ contain Bryant’s theory of his art.
The framing of a deathless poem is not the pastime of a drowsy
summer’s day.

No smooth array of phrase,

Artfully sought and ordered though it be,
Which the cold rhymer lays
Upon his page with languid industry,
Can wake the listless pulse to livelier speed,
Or fill with sudden tears the eyes that read.
 The secret wouldst thou know
To touch the heart or fire the blood at will?
Let thine own eyes o’erflow;
Let thy lips quiver with the passionate thrill;
Seize the great thought, ere yet its power be past,
And bind, in words, the fleet emotion fast.

* * * * *

Yet let no empty gust

Of passion find an utterance in thy lay,
A blast that whirls the dust
Along the howling street and dies away;
But feelings of calm power and mighty sweep,
Like currents journeying through the windless deep.

This is flat contradiction of the idea that entirely self-conscious and

self-controlled art can avail to move the reader. Bryant pleads for
deepest feeling in exercise of the poetic function; it is more than
important, it is indispensable. Of that striking poem ‘The Tides,’ he said
‘it was written with a certain awe upon me which made me hope that
there might be something in it.’ The poem proved to be one of Bryant’s
noblest conceptions. Yet a lady of ‘judgment’ told one of Bryant’s
friends, who of course told him, that she did not think there was much
in it.
Nature appeals to Bryant in her broad and massive aspects. ‘The
Prairies’ is an illustration. Gazing on the ‘encircling vastness’ for the
first time, the heart swells and the eye dilates in an effort to
comprehend it:—

Lo! they stretch,

In airy undulations, far away,
As if the ocean, in his gentlest swell,
Stood still, with all his rounded billows fixed,
And motionless forever.
 As the poet looks abroad over the vast and glowing fields, there
sweeps by him a vision of the races that have peopled these solitudes
and perished to make room for races to come. It is magnificent even if it
is not scientific. In the sense it gives of the spaciousness of the prairies
with the myriad sounds of life projected on the great elemental silence,
it is a true American poem.
‘A Hymn of the Sea’ is another illustration of that largeness of view
characteristic of Bryant. Each thought is lofty and far-reaching. The
cloud that rises from the ‘realm of rain’ shadows whole countries, the
tornado wrecks a fleet, whirling the vast hulks ‘like chaff upon the
waves:’—

These restless surges eat away the shores

Of earth’s old continents; the fertile plain
Welters in shallows, headlands crumble down,
And the tide drifts the sea-sand in the streets
Of the drowned city.

He conveys the idea not only of spaciousness but of endless

duration in the lines describing the coral worm laying his ‘mighty reefs,’
toiling from ‘age to age’ until

His bulwarks overtop the brine, and check

The long wave rolling from the southern pole
To break upon Japan.

Certain lines in ‘A Forest Hymn’ are also remarkable for the sense
they give of vast reaches of time, stretching not forward but backward
into eternity:—
 These lofty trees
Wave not less proudly that their ancestors
Moulder beneath them. Oh, there is not lost
One of earth’s charms: upon her bosom yet,
After the flight of untold centuries,
The freshness of her far beginning lies
And yet shall lie.

The ‘Song of the Stars,’ though not one of Bryant’s happiest

poems,—the hypercritical reader feeling that the ‘orbs of beauty’ and
‘spheres of flame’ might have made a more appropriate metrical choice
for their song,—shows none the less the poet’s strength in dealing with
nature in the large. The lines ‘To a Waterfowl’ are magical in part by
virtue of the impression they make of immense distance. With the
poet’s penetrating vision we can see the solitary way through the rosy
depths, the pathless coast, and the one bit of life in
The desert and illimitable air.
Bryant’s mind readily lifts itself from the minute to the massive, as
in the poem ‘Summer Wind,’ a fine example of the crescendo effects he
knew so well how to produce. In a few lines he gives the sensation of
heat, closeness, exhaustion, and pictures the plants drooping in a
stillness broken only by the ‘faint and interrupted murmur of the bee.’
His thought then sweeps upward to the wooded hills towering in
scorching heat and dazzling light, and then still higher to the bright
clouds,

Motionless pillars of the brazen heaven—

Their bases on the mountains—their white tops
Shining in the far ether....

The poet never wearies of this majestic pageantry of the natural

world. In ‘The Firmament,’ in ‘The Hurricane’ (imitated from Heredia), in
‘Monument Mountain,’ his chief thought is to translate the reader to his
own lofty vantage-ground.
 But Nature is not merely a spectacle, it has a power to heal and
invigorate. Life loses its pettiness when one leaves the city and seeks
the forest. The holy men who hid themselves ‘deep in the woody
wilderness’ perhaps did not well—

But let me often to these solitudes

Retire, and in thy presence reassure
My feeble virtue. Here its enemies,
The passions, at thy plainer footsteps shrink
And tremble and are still.

The poet finds inspiration not alone in the terror of the storm, the
majesty of the forest, the gray waste of ocean, the mystery of the night
of stars, but in the humbler things, the rivulet by which he played as a
child, the violet growing on its bank, the hum of bees, the notes of
hang-bird and wren, the gossip of swallows, and the gay chirp of the
ground squirrel. ‘The Yellow Violet’ and the lines ‘To the Fringed
Gentian’ spring from this love of the unobtrusive charms of Nature.
Less familiar than these, but a faultless example of Bryant’s art, is ‘The
Painted Cup:’—

... tell me not

That these bright chalices were tinted thus
To hold the dew for fairies, when they meet
On moonlight evenings in the hazel bowers,
And dance till they are thirsty.

The poet will not call up ‘faded fancies of an ‘elder world.’ If the
fresh savannahs must be peopled with creatures of imagination, it may
be done without borrowing European elves:—
 Let then the gentle Manitou of flowers,
Lingering among the bloomy waste he loves,
Though all his swarthy worshippers are gone—
Slender and small, his rounded cheek all brown
And ruddy with the sunshine; let him come
On summer mornings, when the blossoms wake,
And part with little hands the spiky grass,
And touching, with his cherry lips, the edge
Of these bright beakers, drain the gathered dew.

Bryant wrote poems of freedom. The earlier of these, ‘The Song of

the Greek Amazon,’ the ‘Massacre at Scio,’ the ‘Greek Partisan,’ and
‘Italy,’ voice his sympathy with the oppressed nations of the Old World,
the ‘struggling multitude of states,’ that ‘writhe in shackles.’
Among his later poems on the same theme, ‘Earth,’ ‘The Winds,’
‘The Antiquity of Freedom,’ and ‘The Battle Field’ are representative.
The first three with their many stately lines show how spontaneously his
thought, even when nature is not the subject, grows out of the
contemplation of nature and then returns to such contemplation as to a
resting place. ‘The Battle Field,’ the expression of a noble faith in the
outcome of ‘a friendless warfare,’ contains the most inspiring of his
quatrains, as it is one of the best contributions made by an American
poet to the stock of quotable English verse:—

Truth, crushed to earth, shall rise again;

The eternal years of God are hers;
But Error, wounded, writhes with pain,
And dies among his worshippers.

His patriotic poems are few in number, but Bryant’s reticence must
be taken into account. Coming from him, the verses mean more than if
they came from another. Two of the best are ‘Oh Mother of a mighty
Race’ and ‘Not Yet.’ The second of these, written in July, 1861, has a
finely imaginative stanza in which are pictured the dead monarchies of
the past eager to welcome another broken and ruined land among their
number:—

Not yet the hour is nigh when they

Who deep in Eld’s dim twilight sit,
Earth’s ancient kings, shall rise and say,
“Proud country, welcome to the pit!
So soon art thou like us brought low!”
No, sullen group of shadows, No!

To the same year belong the spirited verses ‘Our Country’s Call:’—

Strike to defend the gentlest sway

That Time in all his course has seen.

* * * * *

Few, few were they whose swords of old

Won the fair land in which we dwell;
But we are many, we who hold
The grim resolve to guard it well.
Strike, for that broad and goodly land,
Blow after blow, till men shall see
That Might and Right move hand in hand,
And glorious must their triumph be!

Such was the temper of men who had looked with philosophic
composure and curiosity on the movements of the sometimes well-nigh
frenzied abolitionists. The blow at the integrity of the nation fired their
cool patriotism to white heat.
What lightness of touch Bryant had is shown in that exquisite lyric
‘The Stream of Life.’ He could be conventional, as in the love poem
where he celebrates ‘the gentle season’ when ‘nymphs relent,’ and very
sensibly advises the young lady ’ere her bloom is past, to secure her
lover.’ He was not strong in wit or humor. The verses ‘To a Mosquito’
might have been read with good effect to a party of well-fed clubmen
after dinner, but finding them in the same volume with ‘A Forest Hymn’
gives one an uncomfortable surprise, like finding a pun in Lowell’s
Cathedral. That Bryant could write agreeable narrative verse, ‘The
Children of the Snow’ and ‘Sella’ bear witness. That he is at his best in
meditative poems, lofty characterizations of Nature, grand visions of
Life and Death, is proved by hundreds of felicitous verses which have
become an inalienable part of our young literature.
He never really excelled the work of his youth. Bryant will always
be known as the author of ‘Thanatopsis.’ This great vision of Death is
his stateliest poem and his best, the most felicitous of phrase and the
loftiest in imagery. Written by a stoic, magnificently stoical in tone, it
offers but a stoic’s comfort after all. Perhaps this is a secret of its
popularity, on the theory that while professed pagans are few the
instinct towards paganism still exists, and most among those who say
least about it.

V
LATEST POETICAL WORK
THE ILIAD AND THE ODYSSEY

The collected edition of Bryant’s poems of 1854 contains a handful of

translations, twelve from the Spanish, four from the German, one each
from the French, the Provençal, the Portuguese, and the Greek. In
1864 a translation of the fifth book of the Odyssey was printed in the
volume entitled Thirty Poems. The praise which it called out gave
Bryant the impulse to further experiments of the same sort; and after
the death of his wife (in 1866), when the necessity was upon him of
forgetting his grief so far as possible in some engrossing work, he
undertook a version of the Iliad and the Odyssey entire.
He gave himself methodically to the task, translating about forty
lines a day. Later he increased the daily stint to seventy-five lines. He
chose blank verse because ‘the use of rhyme in a translation is a
constant temptation to petty infidelities.’
Bryant retained the misleading Latin forms of proper names.
Worsley says: ‘Not even Mr. Gladstone’s example can now make Juno,
Mercury, and Venus admissible in Homeric story.’ But Worsley
confessed his own inability to write Phoibos, Apollôn, and Kirké.
Bryant’s argument for his course looks specious: ‘I was translating from
Greek into English, and I therefore translated the names of the gods, as
well as the other parts of the poem.’ Probably he had an affection for
the old nomenclature, a sentiment like Macaulay’s, who ‘never could
reconcile himself to seeing the friends of his boyhood figure as Kleon,
6
and Alkibiadês, and Poseidôn, and Odysseus.’
An enthusiastic admirer of Bryant declares that in the opinion of
‘competent critics’ his versions of Homer ‘will hold their own with the
translations of Pope, Chapman, Newman, or the late Earl Derby.’ Much
depends on the question of what a ‘competent critic’ is, and which one
of several competent critics is to be taken as final authority. Competent
critics, who, by the way, seldom agree, have a habit of agreeing on
anything sooner than the merits of a version of Homer. And when one
remembers the fearful attack made by Matthew Arnold on Newman
(‘Any vivacities of expression which may have given him pain I
sincerely regret’)—he may well hesitate to take as a compliment the
statement that Bryant will ‘hold his own’ with Newman.
The question of the higher merit of the poem rests with the experts
at last. Pessimists all, they are discouragingly hostile to metrical
versions of the Iliad. Yet the most uncompromising of them would
hardly deny a lay reader the privilege of enjoying Homer, in so far as
possible, through the medium of Bryant’s blank verse. They might even
be persuaded to admit that this version has a peculiar adaptability to
the needs of the public; that the clarity and beauty of the English, the
dignified ease of the measure, the sustained energy and vigor of the
performance as a whole, fit Bryant’s Homer in a high degree to the use
for which it was intended. The argument from popularity, that always
unsafe and often vicious argument, has a measure of force here.
Granting that Homer in any honest translation is better than no Homer
at all, may not the uncompromising scholars be called on to rejoice that
this more than honest, nay, this admirable translation of the Iliad has
sold to the extent of many thousands of copies? Where there are so
many buyers, there must be readers not a few.

* * * * *
Bryant was one of those unusual men who have two distinct
callings. Much surprise has been expressed at his apparent ability to
carry on his functions of journalist and poet without clash. But is it true,
or more than superficially true, that he did so carry them on? To be
sure, he wrote his editorial articles at the newspaper office and his
verses elsewhere, but this is a mere mechanical distinction. A man of
Bryant’s depth of conviction and passionate temperament does not
throw off care when he boards a suburban train for his country home.
The history of Bryant’s inner life has not been written, perhaps
cannot be. This is not to imply that his character was enigmatic and
mysterious, but merely to emphasize the fact of his extraordinary
reserve. More than most self-contained men he kept his own counsel.
Such a history would show how deep his experience of the world had
ploughed into him, and it might explain in a degree the remote and
stoical character of his verse.
Bryant’s poetical work as a whole has an impassive quality often
described as coldness. Partly due to his genius and accentuated by the
excessive retouching to which he subjected his verse, it grew in still
larger measure out of his determination not to impart to his verse any of
the feverishness of spirit consequent upon a life of political warfare.
The poet held himself wonderfully in check, as a man of iron will allows
no mark of the strong passion under which he labors to show in his
face. Bryant was rarely betrayed into so much of personal feeling as
flashed out in that bitter stanza of ‘The Future Life:’—

For me the sordid cares in which I dwell,

Shrink and consume my heart, as heat the scroll;
And wrath has left its scar—that fire of hell
Has left its scar upon my soul.

While the detachment was not complete, Bryant undoubtedly kept

his poetic apart from his secular life in a way to command admiration.
This he accomplished by extraordinary self-restraint. As a part of the
varied and long-continued discipline to which he subjected himself, the
self-restraint made for character. The question, however, arises
whether the poetry did not, in certain ways, suffer under the very
discipline by which the character developed.

FOOTNOTES:
1
Bryant’s contributions were the stories entitled ‘Medfield’ and
‘The Skeleton’s Cave.’ As originally planned the book was to
have been called The Sextad, but Verplanck, who would have
made the sixth author, withdrew.
2
John Bigelow.
3
W. C. Bronson.
4
Bryant’s apology to the public for his course, together with
Leggett’s statement as an eye-witness, will be found in the
‘Evening Post’ of Thursday, April 21, 1831. Neither the guarded
account of the episode in Godwin’s Bryant, nor the brief notice in
Haswell’s Reminiscences of an Octogenarian is quite accurate.
5
As in an ironical leader commending journalists who refuse to say
that a man ‘was drowned,’ a dangerous innovation, and, ‘to
preserve the purity of their mother tongue,’ stick to time-honored
metaphors and say that the man ‘found a watery
grave.’—‘Evening Post,’ August 17, 1831.
6
G. O. Trevelyan.
 III
James Fenimore Cooper

REFERENCES:

W. C. Bryant: A Discourse on the Life, Character,

and Genius of James Fenimore Cooper, 1852.
T. R. Lounsbury: James Fenimore Cooper,
‘American Men of Letters,’ fourth edition, 1884.
W. B. Shubrick Clymer: James Fenimore Cooper,
‘Beacon Biographies,’ 1900.

I
HIS LIFE

James Cooper was the eleventh of the twelve children of William and
Elizabeth (Fenimore) Cooper, of Burlington, New Jersey. He was born
in that picturesque town by the Delaware on September 15, 1789. The
name James, given him in honor of his grandfather, had also been
borne by his first American ancestor, who is said to have come from
Stratford-on-Avon, in 1679. In fulfilment of a promise to his mother
(whose family had become extinct in the male line), the novelist, in
1826, changed his name to Fenimore-Cooper.
At the close of the Revolutionary War, William Cooper acquired
large tracts of land on Otsego Lake in New York, settled there in 1790,
founded the village still known as Cooperstown, and built for himself a
stately home to which he gave the name of Otsego Hall. He was the
first judge of the county and a member of Congress, a man of strong
7
character and agreeable address.
Cooper’s boyhood was passed amid picturesque natural
surroundings, on the edge of civilization, the scene of The Deerslayer
and The Pioneers. He attended the village school, prepared for college
with the rector of St. Peter’s Church, Albany, entered Yale in the
second term of the Freshman year (Class of 1806), and was dismissed
in the Junior year for some boyish escapade the nature of which is
unexplained.
It was decided that he should enter the navy. There was then no
training school, and boys took the first lessons in seamanship in the
merchant marine. Cooper spent a year before the mast in the ‘Sterling,’
sailing from New York to London, thence to Gibraltar, back to London,
and from London to Philadelphia. His experiences are set forth in the
early chapters of Ned Myers. The ‘Sterling’ lost two of her best hands
by impressment as soon as she reached English waters. Cooper’s
indignation at these outrages afterwards found voice through the lips of
Ithuel Bolt in the story entitled Wing-and-Wing.
He was commissioned midshipman on January 1, 1808, and
served awhile on the ‘Vesuvius.’ In the following winter he was one of
the party sent to Oswego to build a brig for the defence of the lake, and
became acquainted with the regions described in The Pathfinder. In the
summer of 1809 he had charge of the gun-boats on Lake Champlain,
and in the autumn was ordered to the sloop of war ‘Wasp.’
He left the service on his betrothal with Miss Susan DeLancey of
Mamaroneck, New York, whom he married on January 1, 1811. For a
few years he lived the life of a landed proprietor, dividing his time
between Cooperstown, Scarsdale, and Mamaroneck. The dulness of a
novel he was reading aloud to his wife provoked him to say that he
could write a better one himself. Challenged to prove it, he produced
Precaution (1820), a story of English life, following conventional lines. It
was apprentice work. The effort of composition taught Cooper that he
could write, but not that he could write well. He had no conceit of the
book, and refused it a place in his collected writings.
 In 1821 The Spy, a Tale of the Neutral Ground, was published; its
unqualified good fortune made Cooper a professed man of letters.
From that time on until his death, twenty-nine years later, he produced
books with uninterrupted regularity.
The Spy was followed by The Pioneers, or the Sources of the
Susquehanna, 1823; The Pilot, a Tale of the Sea, 1824; Lionel Lincoln,
or the Leaguer of Boston, 1825; The Last of the Mohicans, a Narrative
of 1757, 1826. But one of this group of four can be pronounced a
failure and two have had a success almost phenomenal in the history of
letters.
Cooper shared the American passion for seeing foreign lands. The
proceeds of authorship enabled him to carry out a plan he had formed
of spending some time abroad. With his family and servants (a party of
ten in all), he set sail from New York on June 1, 1826. He proposed to
be gone five years. He overstayed that time by two years and five
months. From May, 1826, to about January, 1829, he held the ‘nominal
position’ of American consul at Lyons. His journeyings were made in a
leisurely way after the fashion of the time. Eighteen months were spent
in Paris and the vicinity, four months in London, and a few weeks in
Holland, Belgium, and Switzerland. The winter of 1828–29 was passed
in Florence, and was followed by a voyage to Naples. After spending
some months at Sorrento and Naples, he settled in Rome for the winter
of 1829–30. Thence to Venice, Munich, Dresden, and finally back to
Paris.
He published while abroad The Prairie, 1827; The Red Rover,
1828; Notions of the Americans, Picked up by a Travelling Bachelor,
1828; The Wept of Wish-ton-Wish, 1829; The Water-Witch, or the
Skimmer of the Seas, 1830; The Bravo, 1831; The Heidenmauer, or the
Benedictines, 1832; The Headsman, or the Abbaye des Vignerons,
1833.
In November, 1833, Cooper returned to America. That and several
ensuing winters were passed in New York, the summers in
Cooperstown. Later he made Otsego Hall his permanent home.
He soon became embroiled in quarrels with the press. While in
Paris his defence of Lafayette’s position in what is known as the
‘Expenses Controversy’ had provoked from his native land criticism
which Cooper resented. He angered a part of the inhabitants of
Cooperstown by making clear to them that Three Mile Point (a wooded
tract on the lake, long used by the villagers as a picnic ground) was not
theirs, as they maintained, but a part of the Cooper estate. With no
thought of robbing them of their pleasure park, he insisted on their
understanding that they enjoyed its use by favor and not by right.
For this the country papers assailed him. Combative by nature,
Cooper brought suits for libel and recovered damages. The novel
spectacle of an author baiting the newspapers ‘caused remark.’ The
city press joined in the attack, the ‘Courier and Enquirer,’ the ‘New York
Tribune,’ the ‘Albany Evening Journal,’ edited by Thurlow Weed, who
once said apropos of his skill in stirring up litigation: ‘There is
something in my manner of writing that makes the galled jades wince.’
Verdicts were given in Cooper’s favor. More libels followed, more suits
were brought, more damages recovered. A cry arose that the liberty of
the press was endangered. Cooper did not think so. He was a bulldog;
when he had once fastened his teeth in a Whig editor, nothing could
make him let go. He continued his prosecutions until he made his
detractors respect him. It took about six years to do it. Bryant has
described with grim humor the novelist’s warfare with that leviathan the
Press: ‘He put a hook into the nose of this huge monster,’ said Bryant
8
admiringly.
This warfare disturbed Cooper’s peace of mind, but in no wise
interrupted his literary activity. The following list records by no means
all that he wrote after 1834, but will suffice to show his right copious
and often happy industry. Besides ten volumes of travels, Cooper
published: A Letter to his Countrymen, 1834; The Monikins, 1835; The
American Democrat, 1838; Homeward Bound, or the Chase, 1838;
Home as Found, 1838; The History of the Navy of the United States of
America, 1839; The Pathfinder, or the Inland Sea, 1840; Mercedes of
Castile, or the Voyage to Cathay, 1840; The Deerslayer, or the First
War Path, 1841; The Two Admirals, 1842; The Wing-and-Wing, or Le
Feu-Follet, 1842; Wyandotté, or the Hutted Knoll, 1843; Ned Meyers, or
a Life before the Mast, 1843; Afloat and Ashore, or the Adventures of
Miles Wallingford, 1844; Miles Wallingford (the second part of Afloat
and Ashore), 1844; Satanstoe, or the Littlepage Manuscripts, 1845;
The Chainbearer, or the Littlepage Manuscripts, 1846; Lives of
Distinguished American Naval Officers, 1846; The Redskins, or Indian
and Injin, 1846; The Crater, or Vulcan’s Peak, 1847; Jack Tier, or the
Florida Reefs, 1848; The Oak Openings, or the Bee Hunter, 1848; The
Sea Lions, or the Lost Sealers, 1849; The Ways of the Hour, 1850.
9
The Spy was dramatized and played successfully. Dramatizations
were also made of The Pilot, The Red Rover, The Water-Witch, The
Pioneers (‘The Wigwam, or Templeton Manor’), and The Wept of Wish-
ton-Wish (‘Miantonomah and Narrahmattah’). An original comedy,
10
‘Upside Down, or Philosophy in Petticoats,’ was withdrawn after four
performances. No satisfactory account exists of Cooper’s earnings by
literature. It is believed that in the later years he was obliged to write, if
not for the necessities of life, at least for the comforts and luxuries.
The hostility provoked by his energetic criticisms subsided in time.
There was even a project on foot in New York to pay him the
compliment of a public dinner as a proof of returning confidence. His
untimely illness put to one side the question of honors of this poor sort.
Cooper died at Otsego Hall on September 14, 1851.

II
HIS CHARACTER
Cooper was a democrat in theory but not in practice. The rude
‘feudalism’ in which his boyhood was passed fostered the aristocratic
sentiment. A residence abroad, in the obsequious atmosphere with
which the serving classes invest any one who has the appearance of
wealth, aggravated it. No one could have been more heartily ‘American’
than Cooper; but he made distinctions and his countrymen abhorred
the distinctions.
Pride of this not unreasonable sort may go hand in hand with
genuine modesty. Cooper was more unpretentious than his enemies
were willing to allow. With a reputation that would have opened many
doors he made no capital of it; he had no mind ‘to thrust himself on all
societies.’
 He was never slow to make use of the inalienable American
privilege of speaking one’s mind. In 1835 the theory of the entire
perfection of the American character was seldom challenged, at least
by a native writer. That Cooper should entertain doubts on the subject
was thought monstrous. It was resented in him the more because of his
manner. Opinions quite as radical might have been uttered wittily and
the end accomplished. Cooper had little wit. His touch was heavy and
he was in dead earnest. He lacked neither courage, nor honesty, nor
highmindedness, nor generosity, nor yet judgment (if his temper was
unruffled), but he was entirely wanting in tact, and largely wanting in
geniality of the useful, if superficial, sort, which lessens the wear and
tear of human intercourse.
A philosopher divides famous men into two classes: those who are
admired in their own homes (as well as in the world), and those who
are admired anywhere but at home. Cooper belonged to the first class
rather than the second. This proud, irascible, contentious, dogmatic
man of letters enjoyed the unswerving loyalty and deep affection of
every member of his family. And from this his biographer argues an
essential sweetness of nature.
Cooper somewhere says: ‘Men are as much indebted to a
fortuitous concurrence of circumstances for the characters they sustain
in this world, as to their personal qualities.’ It was his ill-luck to have the
accidents of his character often mistaken for the character itself.

III
THE WRITER
Cooper’s English at best, though fluent and spirited, is without grace;
at worst it is clumsy and intractable. This writer of world-wide fame is
singularly wanting in literary finish. He is not careless but colorless, not
slovenly but neutral. He succeeds almost without the aid of what is
commonly called ‘style.’ He is read for what he has to say, not for the
way in which he says it. There are surprises in store for the reader, but
they are not to be found in the perfect word, the happy phrase, or the
balance of a sentence, but always in the unexpected turn of an
adventure, in a well-planned episode abounding in incident, in the
release of mental tension following the happy issue out of danger. As
was said of another copious writer, ‘he weaves a loose web;’ one might
add that it is often of coarse fibre. In few writers of eminence is form so
subservient to contents. The defect was due to haste, to the natural
and lordly contempt of a spontaneous story-teller for the niceties of
rhetoric.

IV
ROMANCES OF THE AMERICAN REVOLUTION
THE SPY, LIONEL LINCOLN

Life in that unhappy strip of country known during the Revolution as

‘the neutral ground,’ Westchester County, New York, is the subject of
The Spy. Here frequent and bloody encounters took place between
skirmishers from the opposing armies. Marauding bands, ostensibly
‘loyal’ or ‘patriotic,’ though often composed of banditti, made life a
misery and a terror to peaceably inclined householders. Cooper wrote
from first-hand traditions. The family of his wife had been loyalists, and
the most famous of Westchester County raiders was a DeLancey.
The chief character is Harvey Birch, the Spy. Professing to be in
the employ of the British, he is the most trusted of Washington’s secret
agents. His devotion to his chief is a passion, almost a religion. Mean of
appearance, niggardly in his mode of life, he is capable of the last
degree of personal sacrifice. His patriotism is of the most exalted kind,
since it can have no proportionate reward. He must live (perchance die)
detested by the people for whom he risks his life daily. Cooper makes
us deeply interested in this uncouth being, who, persecuted to the point
of despair, and even brought to the gallows, finds always a way of
escape. Birch gambled with his life in stake. It was a desperate throw
when he destroyed the bit of paper signed by Washington.
 The romantic hero of the story is Peyton Dunwoodie, a youth
whose ‘dark and sparkling glance’ played havoc with the hearts of
impressionable ladies. But Peyton was true, and loved but one. More to
the modern taste are the humors of Lawton and Sitgreaves, of
Sergeant Hollister and Betty Flanagan. ‘Mr. Harper’ is impressive, and
the mystery of his character well sustained. The ladies of ‘The Locusts’
have the quaint charm inseparable from other-day manners and
costume. To be sure one of them, who seems likely to die of love, is
mercifully killed by a random bullet, and another becomes a maniac.
Novel-readers wanted a deal for their money in 1821. But Frances
Wharton is a likable little creature, though her talk does not in the least
resemble that of Miss Clara Middleton.
As an Irish bishop said of Gulliver’s Travels, the book contains
improbabilities. The device of a masque which converts young Henry
Wharton into the counterfeit presentment of an old gray-headed negro
is far-fetched. The Spy was not intended to be a realistic novel.
Cooper projected another story on the background of the
Revolution. Lionel Lincoln, for all the work put on it, was not a success.
It had merits among which the merit of spontaneity is not conspicuous.
Had the failure been less apparent, the novelist might have been
tempted to continue the ‘Legends of the Thirteen Republics.’

V
THE LEATHER-STOCKING TALES AND OTHER
INDIAN STORIES
A French critic once remarked that nothing was so like a chanson de
geste as another chanson de geste. Readers have deplored the fact
that nothing was so like a Leather-Stocking tale as another Leather-
Stocking tale. But The Pioneers, the first of the series in order of
composition, bears little resemblance to the others, and as a picture of
life in a New York village at the end of the Eighteenth Century has a
historical value. The narrative is firm in texture. The characters are
thirty in number, and every man in his humor. The Judge, Cousin