A review of g-C3N4 based catalysts for

direct methanol fuel cells Afdhal Yuda

& Anand Kumar
Visit to download the full and correct content document:
https://ebookmass.com/product/a-review-of-g-c3n4-based-catalysts-for-direct-methan
ol-fuel-cells-afdhal-yuda-anand-kumar/
 international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

ScienceDirect

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

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.
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
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.)

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
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
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
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

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
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
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
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

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
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
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
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
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
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

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
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.

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
- 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
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
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.
references
[1] Debe MK. Electrocatalyst approaches and challenges for
automotive fuel cells. Nature 2012. https://doi.org/10.1038/
nature11115.
[2] Matin MA, Kumar A, Bhosale RR, Saleh Saad MAH,
Almomani FA, Al-Marri MJ. PdZn nanoparticle
electrocatalysts synthesized by solution combustion for
methanol oxidation reaction in an alkaline medium. RSC
Adv 2017. https://doi.org/10.1039/c7ra07013f.
[3] Matin MA, Saad MAHS, Kumar A, Al-Marri MJ, Mansour SA.
Effect of fuel content on the electrocatalytic methanol
oxidation performance of Pt/ZnO nanoparticles synthesized
by solution combustion. Appl Surf Sci 2019. https://doi.org/
10.1016/j.apsusc.2019.06.213.
[4] Nazir R, Khalfani A, Abdelfattah O, Kumar A, Ali M, Saad S,
Ali S. Nanosheet synthesis of mixed Co3O4/CuO via
combustion method for methanol oxidation and carbon
dioxide reduction. 2020. https://doi.org/10.1021/
acs.langmuir.0c02554.
[5] Hoshi N, Kida K, Nakamura M, Nakada M, Osada K.
Structural effects of electrochemical oxidation of formic
acid on single crystal electrodes of palladium. J Phys Chem
B 2006. https://doi.org/10.1021/jp0608372.
[6] Cao J, Song L, Tang J, Xu J, Wang W, Chen Z. Enhanced
activity of Pd nanoparticles supported on Vulcan XC72R
carbon pretreated via a modified Hummers method for
formic acid electrooxidation. Appl Surf Sci 2013. https://
doi.org/10.1016/j.apsusc.2013.02.133.
[7] Huang H, Wang X. Pd nanoparticles supported on low-
defect graphene sheets: for use as high-performance
electrocatalysts for formic acid and methanol oxidation. J
Mater Chem 2012. https://doi.org/10.1039/c2jm33727d.
[8] Jin M, Zhang H, Xie Z, Xia Y. Palladium concave nanocubes
with high-index facets and their enhanced catalytic
properties. Angew Chem Int Ed 2011. https://doi.org/
10.1002/anie.201103002.
[9] Wang X, Yang J, Yin H, Song R, Tang Z. “raisin bun”-like
nanocomposites of palladium clusters and porphyrin for
superior formic acid oxidation. Adv Mater 2013. https://
doi.org/10.1002/adma.201205168.
[10] Nazir R, Kumar A, Saleh Saad MA, Ashok A. Synthesis of
hydroxide nanoparticles of Co/Cu on carbon nitride surface
via galvanic exchange method for electrocatalytic CO2
reduction into formate. Colloids Surfaces A Physicochem
Eng Asp 2020. https://doi.org/10.1016/j.colsurfa.2020.124835.
[11] Nazir R, Kumar A, Ali Saleh Saad M, Ali S. Development of
CuAg/Cu2O nanoparticles on carbon nitride surface for
methanol oxidation and selective conversion of carbon
 international journal of hydrogen energy xxx (xxxx) xxx
dioxide into formate. J Colloid Interface Sci 2020. https://
doi.org/10.1016/j.jcis.2020.06.033.
[12] Guo S, Dong S, Wang E. Constructing carbon nanotube/Pt
nanoparticle hybrids using an imidazolium-salt-based ionic
liquid as a linker. Adv Mater 2010. https://doi.org/10.1002/
adma.200903379.
[13] Antolini E, Passos RR, Ticianelli EA. Effects of the carbon
powder characteristics in the cathode gas diffusion layer on
the performance of polymer electrolyte fuel cells. J Power
Sources 2002. https://doi.org/10.1016/S0378-7753(02)00112-
X.
[14] Wang S, Manthiram A. Graphene ribbon-supported Pd
nanoparticles as highly durable, efficient electrocatalysts
for formic acid oxidation. Electrochim Acta 2013. https://
doi.org/10.1016/j.electacta.2012.10.125.
[15] De Miguel SR, Vilella JI, Jablonski EL, Scelza OA, Salinas-
Martinez de Lecea C, Linares-Solano A. Preparation of Pt
catalysts supported on activated carbon felts (ACF). Appl
Catal A Gen 2002. https://doi.org/10.1016/S0926-860X(02)
00112-6.
[16] Antolini E. Carbon supports for low-temperature fuel cell
catalysts. Appl Catal B Environ 2009. https://doi.org/10.1016/
j.apcatb.2008.09.030.
[17] Yuan X, Ding XL, Wang CY, Ma ZF. Use of polypyrrole in
catalysts for low temperature fuel cells. Energy Environ Sci
2013. https://doi.org/10.1039/c3ee23520c.
[18] Toupin M, Be
langer D. Thermal stability study of aryl
modified carbon black by in situ generated diazonium
salt. J Phys Chem C 2007. https://doi.org/10.1021/
jp066868e.
[19] Shao D, Jiang Z, Wang X. SDBS modified XC-72 carbon for
the removal of Pb(II) from aqueous solutions. Plasma
Process Polym 2010. https://doi.org/10.1002/
ppap.201000005.
[20] Paraknowitsch JP, Thomas A. Doping carbons beyond
nitrogen: an overview of advanced heteroatom doped
carbons with boron, sulphur and phosphorus for energy
applications. Energy Environ Sci 2013. https://doi.org/
10.1039/c3ee41444b.
[21] Liang HW, Wei W, Wu ZS, Feng X, Müllen K. Mesoporous
metal-nitrogen-doped carbon electrocatalysts for highly
efficient oxygen reduction reaction. J Am Chem Soc 2013.
https://doi.org/10.1021/ja407552k.
[22] Fu L, Tang K, Song K, Van Aken PA, Yu Y, Maier J. Nitrogen
doped porous carbon fibres as anode materials for sodium
ion batteries with excellent rate performance. Nanoscale
2014. https://doi.org/10.1039/c3nr05374a.
[23] Yang DS, Bhattacharjya D, Inamdar S, Park J, Yu JS.
Phosphorus-doped ordered mesoporous carbons with
different lengths as efficient metal-free electrocatalysts for
oxygen reduction reaction in alkaline media. J Am Chem
Soc 2012. https://doi.org/10.1021/ja306376s.
[24] Liang J, Jiao Y, Jaroniec M, Qiao SZ. Sulfur and nitrogen dual-
doped mesoporous graphene electrocatalyst for oxygen
reduction with synergistically enhanced performance.
Angew Chem Int Ed 2012. https://doi.org/10.1002/
anie.201206720.
[25] Yang S, Zhi L, Tang K, Feng X, Maier J, Müllen K. Efficient
synthesis of heteroatom (N or S)-doped graphene based on
ultrathin graphene oxide-porous silica sheets for oxygen
reduction reactions. Adv Funct Mater 2012. https://doi.org/
10.1002/adfm.201200186.
[26] Huang H, Zhu J, Zhang W, Tiwary CS, Zhang J, Zhang X,
Jiang Q, He H, Wu Y, Huang W, Ajayan PM, Yan Q.
Controllable codoping of nitrogen and sulfur in graphene
for highly efficient Li-oxygen batteries and direct methanol
fuel cells. Chem Mater 2016. https://doi.org/10.1021/
acs.chemmater.5b04654.
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
19
[27] Gong K, Du F, Xia Z, Durstock M, Dai L. Nitrogen-doped
carbon nanotube arrays with high electrocatalytic activity
for oxygen reduction. Science 2009;80. https://doi.org/
10.1126/science.1168049.
[28] Yang L, Jiang S, Zhao Y, Zhu L, Chen S, Wang X, Wu Q, Ma J,
Ma Y, Hu Z. Boron-doped carbon nanotubes as metal-free
electrocatalysts for the oxygen reduction reaction. Angew
Chem Int Ed 2011. https://doi.org/10.1002/anie.201101287.
[29] Patin~ o J, Lo

pez-Salas N, Gutie

rrez MC, Carriazo D, Ferrer ML,
Del Monte F. Phosphorus-doped carbon-carbon nanotube
hierarchical monoliths as true three-dimensional
electrodes in supercapacitor cells. J Mater Chem A 2016.
https://doi.org/10.1039/c5ta09210h.
[30] Qu L, Liu Y, Baek JB, Dai L. Nitrogen-doped graphene as
efficient metal-free electrocatalyst for oxygen reduction in
fuel cells. ACS Nano 2010. https://doi.org/10.1021/
nn901850u.
[31] Sheng ZH, Gao HL, Bao WJ, Bin Wang F, Xia XH. Synthesis of
boron doped graphene for oxygen reduction reaction in fuel
cells. J Mater Chem 2012. https://doi.org/10.1039/
c1jm14694g.
[32] Dou C, Saito S, Matsuo K, Hisaki I, Yamaguchi S. A boron-
containing PAH as a substructure of boron-doped graphene.
Angew Chem Int Ed 2012. https://doi.org/10.1002/
anie.201206699.
[33] Zhang W, Huang H, Li F, Deng K, Wang X. Palladium
nanoparticles supported on graphitic carbon nitride-
modified reduced graphene oxide as highly efficient
catalysts for formic acid and methanol electrooxidation. J
Mater Chem A 2014. https://doi.org/10.1039/c4ta03326d.
[34] Fu Y, Zhu J, Hu C, Wu X, Wang X. Covalently coupled hybrid
of graphitic carbon nitride with reduced graphene oxide as
a superior performance lithium-ion battery anode.
Nanoscale 2014. https://doi.org/10.1039/c4nr03145h.
[35] Zhang W, Yao Q, Wu X, Fu Y, Deng K, Wang X. Intimately
coupled hybrid of graphitic carbon nitride nanoflakelets
with reduced graphene oxide for supporting Pd
nanoparticles: a stable nanocatalyst with high catalytic
activity towards formic acid and methanol electrooxidation.
Electrochim Acta 2016. https://doi.org/10.1016/
j.electacta.2016.03.169.
[36] Mabena LF, Sinha Ray S, Mhlanga SD, Coville NJ. Nitrogen-
doped carbon nanotubes as a metal catalyst support. Appl
Nanosci 2011. https://doi.org/10.1007/s13204-011-0013-4.
[37] Yang G, Li Y, Rana RK, Zhu JJ. Pt-Au/nitrogen-doped
graphene nanocomposites for enhanced electrochemical
activities. J Mater Chem A 2013. https://doi.org/10.1039/
c2ta00776b.
[38] Zhou Y, Neyerlin K, Olson TS, Pylypenko S, Bult J, Dinh HN,
Gennett T, Shao Z, O’Hayre R. Enhancement of Pt and Pt-
alloy fuel cell catalyst activity and durability via nitrogen-
modified carbon supports. Energy Environ Sci 2010. https://
doi.org/10.1039/c003710a.
[39] Sebastia
n D, Serov A, Matanovic I, Artyushkova K,
Atanassov P, Arico  AS, Baglio V. Insights on the
extraordinary tolerance to alcohols of Fe-N-C cathode
catalysts in highly performing direct alcohol fuel cells.
Nanomater Energy 2017. https://doi.org/10.1016/
j.nanoen.2017.02.039.
[40] Zheng Y, Liu J, Liang J, Jaroniec M, Qiao SZ. Graphitic carbon
nitride materials: controllable synthesis and applications in
fuel cells and photocatalysis. Energy Environ Sci 2012.
https://doi.org/10.1039/c2ee03479d.
[41] Wang Y, Wang X, Antonietti M. Polymeric graphitic carbon
nitride as a heterogeneous organocatalyst: from
photochemistry to multipurpose catalysis to sustainable
chemistry. Angew Chem Int Ed 2012. https://doi.org/
10.1002/anie.201101182.
20 international journal of hydrogen energy xxx (xxxx) xxx
[42] Zhang G, Lan ZA, Wang X. Conjugated polymers: catalysts
for photocatalytic hydrogen evolution. Angew. Chemie - Int.
Ed.; 2016. https://doi.org/10.1002/anie.201607375.
[43] Shalom M, Guttentag M, Fettkenhauer C, Inal S, Neher D,
Llobet A, Antonietti M. In situ formation of heterojunctions
in modified graphitic carbon nitride: synthesis and noble
metal free photocatalysis. Chem Mater 2014. https://doi.org/
10.1021/cm503258z.
[44] Zheng D, Cao XN, Wang X. Precise formation of a hollow
carbon nitride structure with a janus surface to promote
water splitting by photoredox catalysis. Angew Chem Int Ed
2016. https://doi.org/10.1002/anie.201606102.
[45] Martin DJ, Qiu K, Shevlin SA, Handoko AD, Chen X, Guo Z,
Tang J. Highly efficient photocatalytic H2 evolution from
water using visible light and structure-controlled graphitic
carbon nitride. Angew Chem Int Ed 2014. https://doi.org/
10.1002/anie.201403375.
[46] Zhang G, Lan ZA, Lin L, Lin S, Wang X. Overall water
splitting by Pt/g-C3N4 photocatalysts without using
sacrificial agents. Chem Sci 2016. https://doi.org/10.1039/
c5sc04572j.
[47] Zhang G, Zhang M, Ye X, Qiu X, Lin S, Wang X. Iodine
modified carbon nitride semiconductors as visible light
photocatalysts for hydrogen evolution. Adv Mater 2014.
https://doi.org/10.1002/adma.201303611.
[48] Cheng N, Tian J, Liu Q, Ge C, Qusti AH, Asiri AM, Al-
Youbi AO, Sun X. Au-nanoparticle-loaded graphitic carbon
nitride nanosheets: green photocatalytic synthesis and
application toward the degradation of organic pollutants.
ACS Appl Mater Interfaces 2013. https://doi.org/10.1021/
am401802r.
[49] Fu Y, Huang T, Jia B, Zhu J, Wang X. Reduction of
nitrophenols to aminophenols under concerted catalysis by
Au/g-C3N4 contact system. Appl Catal B Environ 2017.
https://doi.org/10.1016/j.apcatb.2016.09.051.
[50] Fu Y, Huang T, Zhang L, Zhu J, Wang X. Ag/g-C3N4 catalyst
with superior catalytic performance for the degradation of
dyes: a borohydride-generated superoxide radical approach.
Nanoscale 2015. https://doi.org/10.1039/c5nr03260a.
[51] Goettmann F, Thomas A, Antonietti M. Metal-free
activation of CO2 by mesoporous graphitic carbon nitride.
Angew Chem Int Ed 2007. https://doi.org/10.1002/
anie.200603478.
[52] Kuriki R, Sekizawa K, Ishitani O, Maeda K. Visible-light-
driven CO2 reduction with carbon nitride: enhancing the
activity of ruthenium catalysts. Angew Chem Int Ed 2015.
https://doi.org/10.1002/anie.201411170.
[53] Yang S, Feng X, Wang X, Müllen K. Graphene-based carbon
nitride nanosheets as efficient metal-free electrocatalysts
for oxygen reduction reactions. Angew Chem Int Ed 2011.
https://doi.org/10.1002/anie.201100170.
[54] Zhu M, Zhai C, Sun M, Hu Y, Yan B, Du Y. Ultrathin graphitic
C3N4 nanosheet as a promising visible-light-activated
support for boosting photoelectrocatalytic methanol
oxidation. Appl Catal B Environ 2017. https://doi.org/
10.1016/j.apcatb.2016.10.012.
[55] Yuda A, Ashok A, Kumar A. A comprehensive and critical
review on recent progress in anode catalyst for methanol
oxidation reaction. Catal Rev - Sci Eng 2020. https://doi.org/
10.1080/01614940.2020.1802811.
[56] Kroke E, Schwarz M. Novel group 14 nitrides. Coord Chem
Rev 2004. https://doi.org/10.1016/j.ccr.2004.02.001.
[57] Du HY, Wang CH, Hsu HC, Chang ST, Chen US, Yen SC,
Chen LC, Shih HC, Chen KH. Controlled platinum
nanoparticles uniformly dispersed on nitrogen-doped
carbon nanotubes for methanol oxidation. Diam Relat
Mater 2008. https://doi.org/10.1016/
j.diamond.2008.01.116.
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
[58] Shui J, Wang M, Du F, Dai L. N-doped carbon nanomaterials
are durable catalysts for oxygen reduction reaction in acidic
fuel cells. Sci Adv 2015. https://doi.org/10.1126/
sciadv.1400129.
[59] Di Noto V, Negro E, Vezzú K, Bertasi F, Nawn G. Origins,
developments, and perspectives of carbon nitride-based
electrocatalysts for application in low-temperature FCs.
Electrochem Soc Interface 2015. https://doi.org/10.1149/
2.F05152if.
[60] Gupta S, Tryk D, Bae I, Aldred W, Yeager E. Heat-treated
polyacrylonitrile-based catalysts for oxygen
electroreduction. J Appl Electrochem 1989. https://doi.org/
10.1007/BF01039385.
[61] Van Veen JAR, Van Baar JF, Kroese KJ. Effect of heat
treatment on the performance of carbon-supported
transition-metal chelates in the electrochemical reduction
of oxygen. J Chem Soc Faraday Trans 1 Phys Chem
Condens Phases 1981. https://doi.org/10.1039/
F19817702827.
[62] Pylypenko S, Borisevich A, More KL, Corpuz AR, Holme T,
Dameron AA, Olson TS, Dinh HN, Gennett T, O’Hayre R.
Nitrogen: unraveling the secret to stable carbon-supported
Pt-alloy electrocatalysts. Energy Environ Sci 2013. https://
doi.org/10.1039/c3ee40189h.
[63] Wang H, Maiyalagan T, Wang X. Review on recent progress
in nitrogen-doped graphene: synthesis, characterization,
and its potential applications. ACS Catal 2012. https://
doi.org/10.1021/cs200652y.
[64] Czerw R, Terrones M, Charlier JC, Blase X, Foley B,
Kamalakaran R, Grobert N, Terrones H, Tekleab D,
Ajayan PM, Blau W, Rühle M, Carroll DL. Identification of
electron donor states in N-doped carbon nanotubes. Nano
Lett 2001. https://doi.org/10.1021/nl015549q.
[65] Wood KN, O’Hayre R, Pylypenko S. Recent progress on
nitrogen/carbon structures designed for use in energy and
sustainability applications. Energy Environ Sci 2014. https://
doi.org/10.1039/c3ee44078h.
[66] Schwarzer A, Saplinova T, Kroke E. Tri-s-triazines (s-
heptazines)-From a “mystery molecule” to industrially
relevant carbon nitride materials. Coord Chem Rev 2013.
https://doi.org/10.1016/j.ccr.2012.12.006.
[67] Lotsch BV, Do € blinger M, Sehnert J, Seyfarth L, Senker J,
Oeckler O, Schnick W. Unmasking melon by a
complementary approach employing electron diffraction,
solid-state NMR spectroscopy, and theoretical calculations -
structural characterization of a carbon nitride polymer.
Chem - A Eur J 2007. https://doi.org/10.1002/
chem.200601759.
[68] Mansor N, Miller TS, Dedigama I, Jorge AB, Jia J, Bra
zdova
V,
Mattevi C, Gibbs C, Hodgson D, Shearing PR, Howard CA,
Cora  F, Shaffer M, Brett DJL, McMillan PF. Graphitic carbon
nitride as a catalyst support in fuel cells and electrolyzers.
Electrochim Acta 2016. https://doi.org/10.1016/
j.electacta.2016.11.008.
[69] Kouvetakis J, Bandari A, Todd M, Wilkens B, Cave N. Novel
synthetic routes to carbon-nitrogen thin films. Chem Mater
1994. https://doi.org/10.1021/cm00042a018.
[70] Todd M, Kouvetakis J, Groy TL, Chandrasekhar D, Smith DJ,
Deal PW. Novel synthetic routes to carbon nitride. Chem
Mater 1995. https://doi.org/10.1021/cm00055a023.
[71] Algara-Siller G, Severin N, Chong SY, Bjo € rkman T,
Palgrave RG, Laybourn A, Antonietti M, Khimyak YZ,
Krasheninnikov AV, Rabe JP, Kaiser U, Cooper AI, Thomas A,
Bojdys MJ. Triazine-based graphitic carbon nitride: a two-
dimensional semiconductor. Angew Chem Int Ed 2014.
https://doi.org/10.1002/anie.201402191.
[72] Tong Y, Chen P, Zhou T, Xu K, Chu W, Wu C, Xie Y. A
bifunctional hybrid electrocatalyst for oxygen reduction
 international journal of hydrogen energy xxx (xxxx) xxx
and evolution: cobalt oxide nanoparticles strongly coupled
to B,N-decorated graphene. Angew Chem Int Ed 2017.
https://doi.org/10.1002/anie.201702430.
[73] Cao DH, Stoumpos CC, Farha OK, Hupp JT, Kanatzidis MG.
2D homologous perovskites as light-absorbing materials for
solar cell applications. J Am Chem Soc 2015. https://doi.org/
10.1021/jacs.5b03796.
[74] Chong SY, Jones JTA, Khimyak YZ, Cooper AI, Thomas A,
Antonietti M, Bojdys MJ. Tuning of gallery heights in a
crystalline 2D carbon nitride network. J Mater Chem A 2013.
https://doi.org/10.1039/c2ta01068b.
[75] Zhang Z, Leinenweber K, Bauer M, Garvie LAJ, McMillan PF,
Wolf GH. High-pressure bulk synthesis of crystalline
C6N9H3$HCl: a novel C3N4 graphitic derivative. J Am Chem
Soc 2001. https://doi.org/10.1021/ja0103849.
[76] Gludovatz B, Hohenwarter A, Catoor D, Chang EH,
George EP, Ritchie RO. A fracture-resistant high-entropy
alloy for cryogenic applications. Science 2014;80. https://
doi.org/10.1126/science.1254581.
[77] Gillan EG. Synthesis of nitrogen-rich carbon nitride
networks from an energetic molecular azide precursor.
Chem Mater 2000. https://doi.org/10.1021/cm000570y.
[78] Zhang Y, Thomas A, Antonietti M, Wang X. Activation of
carbon nitride solids by protonation: morphology changes,
enhanced ionic conductivity, and photoconduction
experiments. J Am Chem Soc 2009. https://doi.org/10.1021/
ja808329f.
[79] Miller DR, Wang J, Gillan EG. Rapid, facile synthesis of
nitrogen-rich carbon nitride powders. J Mater Chem 2002.
https://doi.org/10.1039/b109700h.
[80] Kawaguchi M, Nozaki K. Synthesis, structure, and
characteristics of the new host material [(C3N3)2(NH)3]n.
Chem Mater 1995. https://doi.org/10.1021/cm00050a005.
[81] Deifallah M, McMillan PF, Cora  F. Electronic and structural
properties of two-dimensional carbon nitride graphenes. J
Phys Chem C 2008. https://doi.org/10.1021/jp711483t.
[82] Thomas A, Fischer A, Goettmann F, Antonietti M, Müller JO,
Schlo€ gl R, Carlsson JM. Graphitic carbon nitride materials:
variation of structure and morphology and their use as
metal-free catalysts. J Mater Chem 2008. https://doi.org/
10.1039/b800274f.
[83] Wang X, Maeda K, Thomas A, Takanabe K, Xin G,
Carlsson JM, Domen K, Antonietti M. A metal-free
polymeric photocatalyst for hydrogen production from
water under visible light. Nat Mater 2009. https://doi.org/
10.1038/nmat2317.
[84] Wang J, Miller DR, Gillan EG. Photoluminescent carbon
nitride films grown by vapor transport of carbon nitride
powders. Chem Commun 2002. https://doi.org/10.1039/
b207041c.
[85] Yan SC, Li ZS, Zou ZG. Photodegradation performance of g-
C3N4 fabricated by directly heating melamine. Langmuir
2009. https://doi.org/10.1021/la900923z.
[86] Liu G, Niu P, Sun C, Smith SC, Chen Z, Lu GQ, Cheng HM.
Unique electronic structure induced high photoreactivity of
sulfur-doped graphitic C3N4. J Am Chem Soc 2010. https://
doi.org/10.1021/ja103798k.
[87] Zhang J, Chen X, Takanabe K, Maeda K, Domen K, Epping JD,
Fu X, Antonieta M, Wang X. Synthesis of a carbon nitride
structure for visible-light catalysis by copolymerization.
Angew Chem Int Ed 2010. https://doi.org/10.1002/
anie.200903886.
[88] Wang Y, Di Y, Antonietti M, Li H, Chen X, Wang X. Excellent
visible-light photocatalysis of fluorinated polymeric carbon
nitride solids. Chem Mater 2010. https://doi.org/10.1021/
cm1019102.
[89] Liu T, Liu Q, Asiri AM, Luo Y, Sun X. An amorphous CoSe
film behaves as an active and stable full water-splitting
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
21
electrocatalyst under strongly alkaline conditions. Chem
Commun 2015. https://doi.org/10.1039/c5cc06892d.
[90] Zhang M, Nakayama Y, Harada S. Photoluminescence of
hydrogenated amorphous carbon nitride films after
ultraviolet light irradiation and thermal annealing. J Appl
Phys 1999. https://doi.org/10.1063/1.371468.
[91] Wang X, Maeda K, Chen X, Takanabe K, Domen K, Hou Y,
Fu X, Antonietti M. Polymer semiconductors for artificial
photosynthesis: hydrogen evolution by mesoporous
graphitic carbon nitride with visible light. J Am Chem Soc
2009. https://doi.org/10.1021/ja809307s.
[92] Zhang Y, Mori T, Ye J. Polymeric carbon nitrides:
semiconducting properties and emerging applications in
photocatalysis and photoelectrochemical energy
conversion. Sci Adv Mater 2012. https://doi.org/10.1166/
sam.2012.1283.
[93] Wang X, Blechert S, Antonietti M. Polymeric graphitic
carbon nitride for heterogeneous photocatalysis. ACS Catal
2012. https://doi.org/10.1021/cs300240x.
[94] Li XH, Antonietti M. Metal nanoparticles at mesoporous N-
doped carbons and carbon nitrides: functional
motteSchottky heterojunctions for catalysis. Chem Soc Rev
2013. https://doi.org/10.1039/c3cs60067j.
[95] Cao S, Low J, Yu J, Jaroniec M. Polymeric photocatalysts
based on graphitic carbon nitride. Adv Mater 2015. https://
doi.org/10.1002/adma.201500033.
[96] Zhai C, Zhu M, Bin D, Wang H, Du Y, Wang C, Yang P.
Visible-light-assisted electrocatalytic oxidation of methanol
using reduced graphene oxide modified Pt nanoflowers-
TiO2 nanotube arrays. ACS Appl Mater Interfaces 2014.
https://doi.org/10.1021/am504263e.
[97] Mojumder N, Sarker S, Abbas SA, Tian Z, Subramanian V.
Photoassisted enhancement of the electrocatalytic oxidation
of formic acid on platinized TiO2 nanotubes. ACS Appl Mater
Interfaces 2014. https://doi.org/10.1021/am406040v.
[98] Wang T, Tang J, Wu S, Fan X, He J. Preparation of ordered
mesoporous WO3-TiO2 films and their performance as
functional Pt supports for synergistic photo-
electrocatalytic methanol oxidation. J Power Sources 2014.
https://doi.org/10.1016/j.jpowsour.2013.09.109.
[99] Su CY, Hsueh YC, Kei CC, Lin CT, Perng TP. Fabrication of
high-activity hybrid pt@zno catalyst on carbon cloth by
atomic layer deposition for photoassisted electro-oxidation
of methanol. J Phys Chem C 2013. https://doi.org/10.1021/
jp400830y.
[100] Yue R, Zhang Q, Wang C, Du Y, Yang P, Xu J. Graphene-
poly(5-aminoindole) composite film as Pt catalyst
supportfor methanol electrooxidation in alkaline medium.
Electrochim Acta 2013. https://doi.org/10.1016/
j.electacta.2013.06.021.
[101] Wang C, Wang H, Zhai C, Ren F, Zhu M, Yang P, Du Y. Three-
dimensional Au0.5/reduced graphene oxide/Au0.5/reduced
graphene oxide/carbon fiber electrode and its high catalytic
performance toward ethanol electrooxidation in alkaline
media. J Mater Chem A 2015. https://doi.org/10.1039/
c4ta05193a.
[102] Zhai C, Zhu M, Pang F, Bin D, Lu C, Goh MC, Yang P, Du Y.
High efficiency photoelectrocatalytic methanol oxidation
on CdS quantum dots sensitized Pt electrode. ACS Appl
Mater Interfaces 2016. https://doi.org/10.1021/
acsami.5b10234.
[103] Polarz S, Antonietti M. Porous materials via nanocasting
procedures: innovative materials and learning about soft-
matter organization. Chem Commun 2002. https://doi.org/
10.1039/b205708p.
[104] Groenewolt M, Antonietti M. Synthesis of g-C3N4
nanoparticles in mesoporous silica host matrices. Adv
Mater 2005. https://doi.org/10.1002/adma.200401756.
22 international journal of hydrogen energy xxx (xxxx) xxx
[105] Liang C, Hong K, Guiochon GA, Mays JW, Dai S. Synthesis of
a large-scale highly ordered porous carbon film by self-
assembly of block copolymers. Angew Chem Int Ed 2004.
https://doi.org/10.1002/anie.200461051.
[106] Thomas A, Goettmann F, Antonietti M. Hard templates for
soft materials: creating nanostructured organic material.
Chem Mater 2008. https://doi.org/10.1021/cm702126j.
[107] Antonietti M. Surfactants for novel templating applications.
Curr Opin Colloid Interface Sci 2001. https://doi.org/10.1016/
S1359-0294(01)00089-9.
[108] Chen D, Li Z, Wan Y, Tu X, Shi Y, Chen Z, Shen W, Yu C,
Tu B, Zhao D. Anionic surfactant induced mesophase
transformation to synthesize highly ordered large-pore
mesoporous silica structures. J Mater Chem 2006. https://
doi.org/10.1039/b517975k.
[109] Liang C, Li Z, Dai S. Mesoporous carbon materials: synthesis
and modification. Angew Chem Int Ed 2008. https://doi.org/
10.1002/anie.200702046.
[110] Wang Y, Li H, Yao J, Wang X, Antonietti M. Synthesis of
boron doped polymeric carbon nitride solids and their
use as metal-free catalysts for aliphatic C-H bond
oxidation. Chem Sci 2011. https://doi.org/10.1039/
c0sc00475h.
[111] Xu Y, Xu H, Wang L, Yan J, Li H, Song Y, Huang L, Cai G.
The CNT modified white C3N4 composite photocatalyst
with enhanced visible-light response photoactivity. J
Chem Soc Dalton Trans 2013. https://doi.org/10.1039/
c3dt32871f.
[112] Corma A. From microporous to mesoporous molecular
sieve materials and their use in catalysis. Chem Rev 1997.
https://doi.org/10.1021/cr960406n.
[113] Davis ME. Ordered porous materials for emerging
applications. Nature 2002. https://doi.org/10.1038/
nature00785.
[114] Taguchi A, Schüth F. Ordered mesoporous materials in
catalysis. Microporous Mesoporous Mater 2005. https://
doi.org/10.1016/j.micromeso.2004.06.030.
[115] Wan Y, Zhao D. On the controllable soft-templating
approach to mesoporous silicates. Chem Rev 2007. https://
doi.org/10.1021/cr068020s.
[116] Hartmann M. Ordered mesoporous materials for
bioadsorption and biocatalysis. Chem Mater 2005. https://
doi.org/10.1021/cm0485658.
[117] Ying JY, Mehnert CP, Wong MS. Synthesis and applications
of supramolecular-templated mesoporous materials.
Angew Chem Int Ed 1999. https://doi.org/10.1002/(sici)1521-
3773(19990115)38:1/2<56::aid-anie56>3.0.co;2-e.
[118] Wang Y, Wang X, Antonietti M, Zhang Y. Facile one-pot
synthesis of nanoporous carbon nitride solids by using soft
templates. ChemSusChem 2010. https://doi.org/10.1002/
cssc.200900284.
[119] Shen W, Ren L, Zhou H, Zhang S, Fan W. Facile one-pot
synthesis of bimodal mesoporous carbon nitride and its
function as a lipase immobilization support. J Mater Chem
2011. https://doi.org/10.1039/c0jm03666h.
[120] Vinu A. Two-dimensional hexagonally-ordered
mesoporous carbon nitrides with tunable pore diameter,
surface area and nitrogen content. Adv Funct Mater 2008.
https://doi.org/10.1002/adfm.200700783.
[121] Vinu A, Ariga K, Mori T, Nakanishi T, Hishita S, Golberg D,
Bando Y. Preparation and characterization of well-ordered
hexagonal mesoporous carbon nitride. Adv Mater 2005.
https://doi.org/10.1002/adma.200401643.
[122] Vinu A, Srinivasu P, Sawant DP, Mori T, Ariga K, Chang JS,
Jhung SH, Balasubramanian VV, Hwang YK. Three-
dimensional cage type mesoporous CN-based hybrid
material with very high surface area and pore volume.
Chem Mater 2007. https://doi.org/10.1021/cm070657k.
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
[123] Jin X, Balasubramanian VV, Selvan ST, Sawant DP,
Chari MA, Lu GQ, Vinu A. Highly ordered mesoporous
carbon nitride nanoparticles with high nitrogen content: a
metal-free basic catalyst. Angew Chem Int Ed 2009. https://
doi.org/10.1002/anie.200903674.
[124] Shi Y, Wan Y, Zhao D. Ordered mesoporous non-oxide
materials. Chem Soc Rev 2011. https://doi.org/10.1039/
c0cs00186d.
[125] Huynh MHV, Hiskey MA, Archuleta JG, Roemer EL.
Preparation of nitrogen-rich nanolayered, nanoclustered,
and nanodendritic carbon nitrides. Angew Chem Int Ed
2005. https://doi.org/10.1002/anie.200461758.
[126] Huynh MHV, Hiskey MA, Archuleta JG, Roemer EL, Gilardi R.
3,6-Di(azido)-1,2,4,5-tetrazine: a precursor for the
preparation of carbon nanospheres and nitrogen-rich
carbon nitrides. Angew Chem Int Ed 2004. https://doi.org/
10.1002/anie.200460708.
[127] Jun YS, Hong WH, Antonietti M, Thomas A. Mesoporous, 2D
hexagonal carbon nitride and titanium nitride/carbon
composites. Adv Mater 2009. https://doi.org/10.1002/
adma.200803500.
[128] Park SS, Chu SW, Xue C, Zhao D, Ha CS. Facile synthesis of
mesoporous carbon nitrides using the incipient wetness
method and the application as hydrogen adsorbent. J Mater
Chem 2011. https://doi.org/10.1039/c1jm10849b.
[129] Goettmann F, Fischer A, Antonietti M, Thomas A. Chemical
synthesis of mesoporous carbon nitrides using hard
templates and their use as a metal-free catalyst for Friedel-
Crafts reaction of benzene. Angew Chem Int Ed 2006.
https://doi.org/10.1002/anie.200600412.
[130] Fukasawa Y, Takanabe K, Shimojima A, Antonietti M,
Domen K, Okubo T. Synthesis of ordered porous graphitic-
C3N4 and regularly arranged Ta3N5 nanoparticles by using
self-assembled silica nanospheres as a primary template.
Chem - An Asian J 2011. https://doi.org/10.1002/
asia.201000523.
[131] Zheng D, Pang C, Liu Y, Wang X. Shell-engineering of hollow
g-C3N4 nanospheres via copolymerization for
photocatalytic hydrogen evolution. Chem Commun 2015.
https://doi.org/10.1039/c5cc03143e.
[132] Panchakarla LS, Govindaraj A, Rao CNR. Boron- and
nitrogen-doped carbon nanotubes and graphene. Inorg
Chim Acta 2010. https://doi.org/10.1016/j.ica.2010.07.057.
[133] Wang Q, Chen C, Ma W, Zhu H, Zhao J. Pivotal role of
fluorine in tuning band structure and visible-light
photocatalytic activity of nitrogen-doped TiO2. Chem - A
Eur J 2009. https://doi.org/10.1002/chem.200900221.
[134] Wang X, Li X, Zhang L, Yoon Y, Weber PK, Wang H, Guo J,
Dai H. N-doping of graphene through electrothermal
reactions with ammonia. Science 2009;80. https://doi.org/
10.1126/science.1170335.
[135] Zhao L, Baccile N, Gross S, Zhang Y, Wei W, Sun Y,
Antonietti M, Titirici MM. Sustainable nitrogen-doped
carbonaceous materials from biomass derivatives. Carbon
N Y 2010. https://doi.org/10.1016/j.carbon.2010.06.040.
[136] Fukata N. Impurity doping in silicon nanowires. Adv Mater
2009. https://doi.org/10.1002/adma.200900376.
[137] Ouyang T, Loh KP, Qi D, Wee ATS, Nesladek M. Chemical
bonding of fullerene and fluorinated fullerene on bare and
hydrogenated diamond. ChemPhysChem 2008. https://
doi.org/10.1002/cphc.200800054.
[138] Karousis N, Tagmatarchis N, Tasis D. Current progress on
the chemical modification of carbon nanotubes. Chem Rev
2010. https://doi.org/10.1021/cr100018g.
[139] Wang Y, Zhang J, Wang X, Antonietti M, Li H. Boron- and
fluorine-containing mesoporous carbon nitride polymers:
metal-free catalysts for cyclohexane oxidation. Angew
Chem Int Ed 2010. https://doi.org/10.1002/anie.201000120.
 international journal of hydrogen energy xxx (xxxx) xxx
[140] Wang X, Chen X, Thomas A, Fu X, Antonietti M. Metal-
containing carbon nitride compounds: a new functional
organic-metal hybrid material. Adv Mater 2009. https://
doi.org/10.1002/adma.200802627.
[141] Kim M, Hwang S, Yu JS. Novel ordered nanoporous graphitic
C3N4 as a support for Pt-Ru anode catalyst in direct
methanol fuel cell. J Mater Chem 2007. https://doi.org/
10.1039/b702213a.
[142] Chandrasekharan Meenu P, Datta SP, Singh SA,
Dinda S, Chakraborty C, Roy S. Polyaniline supported
g-C3N4 quantum dots surpass benchmark Pt/C:
development of morphologically engineered g-C3N4
catalysts towards “metal-free” methanol electro-
oxidation. J Power Sources 2020. https://doi.org/10.1016/
j.jpowsour.2020.228150.
[143] Yang Z, Luo F. Pt nanoparticles deposited on dihydroxy-
polybenzimidazole wrapped carbon nanotubes shows a
remarkable durability in methanol electro-oxidation. Int J
Hydrogen Energy 2017. https://doi.org/10.1016/
j.ijhydene.2016.10.148.
[144] Zhang JJ, Sui XL, Zhao L, Zhang LM, Gu DM, Wang ZB. Hybrid
of molybdenum trioxide and carbon as high performance
platinum catalyst support for methanol electrooxidation.
Int J Hydrogen Energy 2017. https://doi.org/10.1016/
j.ijhydene.2016.10.086.
[145] Zhu Z, Bukowski B, Deskins NA, Zhou HS. Bamboo shaped
carbon nanotube supported platinum electrocatalyst
synthesized by high power ultrasonic-assisted
impregnation method for methanol electrooxidation and
related density functional theory calculations. Int J
Hydrogen Energy 2015. https://doi.org/10.1016/
j.ijhydene.2014.12.039.
[146] Cao J, Yin X, Wang L, Guo M, Xu J, Chen Z. Enhanced
electrocatalytic activity of platinum nanoparticles
supported on nitrogen-modified mesoporous carbons for
methanol electrooxidation. Int J Hydrogen Energy 2015.
https://doi.org/10.1016/j.ijhydene.2015.01.014.
[147] Li Y, Jiang Y, Chen M, Liao H, Huang R, Zhou Z, Tian N,
Chen S, Sun S. Electrochemically shape-controlled
synthesis of trapezohedral platinum nanocrystals with high
electrocatalytic activity. Chem Commun 2012. https://
doi.org/10.1039/c2cc34322c.
[148] Shao-Horn Y, Sheng WC, Chen S, Ferreira PJ, Holby EF,
Morgan D. Instability of supported platinum nanoparticles
in low-temperature fuel cells. Top Catal 2007. https://
doi.org/10.1007/s11244-007-9000-0.
[149] Liu H, Ye F, Yao Q, Cao H, Xie J, Lee JY, Yang J. Stellated Ag-
Pt bimetallic nanoparticles: an effective platform for
catalytic activity tuning. Sci Rep 2014. https://doi.org/
10.1038/srep03969.
[150] Salgado JRC, Fernandes JCS, Botelho Do Rego AM,
Ferraria AM, Duarte RG, Ferreira MGS. Pt-Ru nanoparticles
supported on functionalized carbon as electrocatalysts for
the methanol oxidation. Electrochim Acta 2011. https://
doi.org/10.1016/j.electacta.2011.07.039.
[151] Geim AK. Graphene: status and prospects. Science 2009;80.
https://doi.org/10.1126/science.1158877.
[152] Guo S, Dong S, Wang E. Three-dimensional Pt-on-Pd
bimetallic nanodendrites supported on graphene
nanosheet: facile synthesis and used as an advanced
nanoelectrocatalyst for methanol oxidation. ACS Nano
2010. https://doi.org/10.1021/nn9014483.
[153] Shang N, Papakonstantinou P, Wang P, Silva SRP. Platinum
integrated graphene for methanol fuel cells. J Phys Chem C
2010. https://doi.org/10.1021/jp105470s.
[154] Karimi Shervedani R, Amini A, Moetamedi Sedeh N.
Preparation of graphene/Nile blue nanostructure on glassy
carbon electrode: decoration with platinum nanoparticles
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
23
and application for electro-oxidation of methanol. Int J
Hydrogen Energy 2016. https://doi.org/10.1016/
j.ijhydene.2016.06.142.
[155] Xu C, Wang X, Zhu J. Graphene - metal particle
nanocomposites. J Phys Chem C 2008. https://doi.org/
10.1021/jp807989b.
[156] Wang H, Xia B, Yan Y, Li N, Wang JY, Wang X. Water-soluble
polymer exfoliated graphene: as catalyst support and
sensor. J Phys Chem B 2013. https://doi.org/10.1021/
jp401418z.
[157] Chen X, Wu G, Chen J, Chen X, Xie Z, Wang X. Synthesis of
“clean” and well-dispersive pd nanoparticles with excellent
electrocatalytic property on graphene oxide. J Am Chem Soc
2011. https://doi.org/10.1021/ja110313d.
[158] Huang H, Ye G, Yang S, Fei H, Tiwary CS, Gong Y, Vajtai R,
Tour JM, Wang X, Ajayan PM. Nanosized Pt anchored onto
3D nitrogen-doped graphene nanoribbons towards efficient
methanol electrooxidation. J Mater Chem A 2015. https://
doi.org/10.1039/c5ta05372b.
[159] Xiong B, Zhou Y, Zhao Y, Wang J, Chen X, O’Hayre R, Shao Z.
The use of nitrogen-doped graphene supporting Pt
nanoparticles as a catalyst for methanol electrocatalytic
oxidation. Carbon N Y 2013. https://doi.org/10.1016/
j.carbon.2012.09.019.
[160] Li CZ, Wang ZB, Sui XL, Zhang LM, Gu DM. Ultrathin
graphitic carbon nitride nanosheets and graphene
composite material as high-performance PtRu catalyst
support for methanol electro-oxidation. Carbon N Y 2015.
https://doi.org/10.1016/j.carbon.2015.05.034.
[161] Negro E, Polizzi S, Vezzù K, Toniolo L, Cavinato G, Di Noto V.
Interplay between morphology and electrochemical
performance of “core-shell” electrocatalysts for oxygen
reduction reaction based on a PtNix carbon nitride “shell”
and a pyrolyzed polyketone nanoball “core. Int J Hydrogen
Energy 2014. https://doi.org/10.1016/j.ijhydene.2013.08.053.
[162] Di Noto V, Negro E, Polizzi S, Vezzù K, Toniolo L, Cavinato G.
Synthesis, studies and fuel cell performance of “core-shell”
electrocatalysts for oxygen reduction reaction based on a
PtNix carbon nitride “shell” and a pyrolyzed polyketone
nanoball “core. In: Int. J. Hydrogen Energy; 2014. https://
doi.org/10.1016/j.ijhydene.2013.08.054.
[163] Di Noto V, Negro E. A new Pt-Rh carbon nitride
electrocatalyst for the oxygen reduction reaction in polymer
electrolyte membrane fuel cells: synthesis, characterization
and single-cell performance. J Power Sources 2010. https://
doi.org/10.1016/j.jpowsour.2009.08.005.
[164] Negro E, Vezzù K, Bertasi F, Schiavuta P, Toniolo L, Polizzi S,
Di Noto V. Interplay between nitrogen concentration,
structure, morphology, and electrochemical performance of
PdCoNi “core-shell” carbon nitride electrocatalysts for the
oxygen reduction reaction. ChemElectroChem 2014. https://
doi.org/10.1002/celc.201402041.
[165] Negro E, Di Noto V. Polymer electrolyte fuel cells based on
bimetallic carbon nitride electrocatalysts. J Power Sources
2008. https://doi.org/10.1016/j.jpowsour.2007.08.029.
[166] Bhowmik T, Kundu MK, Barman S. Highly efficient
electrocatalytic oxidation of formic acid on palladium
nanoparticles-graphitic carbon nitride composite. Int J
Hydrogen Energy 2017. https://doi.org/10.1016/
j.ijhydene.2016.11.095.
[167] Polshettiwar V, Varma RS. Green chemistry by nano-
catalysis. Green Chem 2010. https://doi.org/10.1039/
b921171c.
[168] Bhowmik T, Kundu MK, Barman S. Ultra small gold
nanoparticles-graphitic carbon nitride composite: an
efficient catalyst for ultrafast reduction of 4-nitrophenol
and removal of organic dyes from water. RSC Adv 2015.
https://doi.org/10.1039/c5ra04913j.
24 international journal of hydrogen energy xxx (xxxx) xxx
[169] Kundu MK, Sadhukhan M, Barman S. Ordered assemblies of
silver nanoparticles on carbon nitride sheets and their
application in the non-enzymatic sensing of hydrogen
peroxide and glucose. J Mater Chem B 2015. https://doi.org/
10.1039/c4tb01740d.
[170] Kundu MK, Bhowmik T, Barman S. Gold aerogel supported
on graphitic carbon nitride: an efficient electrocatalyst for
oxygen reduction reaction and hydrogen evolution
reaction. J Mater Chem A 2015. https://doi.org/10.1039/
c5ta06740e.
[171] Qiu H, Dong X, Sana B, Peng T, Paramelle D, Chen P, Lim S.
Ferritin-templated synthesis and self-assembly of Pt
nanoparticles on a monolithic porous graphene network for
electrocatalysis in fuel cells. ACS Appl Mater Interfaces
2013. https://doi.org/10.1021/am3022366.
[172] Qin Y, Chao L, Yuan J, Liu Y, Chu F, Kong Y, Tao Y, Liu M.
Ultrafine Pt nanoparticle-decorated robust 3D N-doped
porous graphene as an enhanced electrocatalyst for
methanol oxidation. Chem Commun 2016. https://doi.org/
10.1039/c5cc07482g.
[173] Huang H, Yang S, Vajtai R, Wang X, Ajayan PM. Pt-decorated
3D architectures built from graphene and graphitic carbon
nitride nanosheets as efficient methanol oxidation catalysts.
Adv Mater 2014. https://doi.org/10.1002/adma.201401877.
[174] Sadhukhan M, Kundu MK, Bhowmik T, Barman S. Highly
dispersed platinum nanoparticles on graphitic carbon
nitride: a highly active and durable electrocatalyst for
oxidation of methanol, formic acid and formaldehyde. Int J
Hydrogen Energy 2017. https://doi.org/10.1016/
j.ijhydene.2017.03.097.
[175] Mansor N, Jorge AB, Cora  F, Gibbs C, Jervis R, McMillan PF,
Wang X, Brett DJL. Graphitic carbon nitride supported
catalysts for polymer electrolyte fuel cells. J Phys Chem C
2014. https://doi.org/10.1021/jp412501j.
[176] Huang H, Chen H, Sun D, Wang X. Graphene nanoplate-Pt
composite as a high performance electrocatalyst for direct
methanol fuel cells. J Power Sources 2012. https://doi.org/
10.1016/j.jpowsour.2012.01.023.
[177] Li Y, Tang L, Li J. Preparation and electrochemical
performance for methanol oxidation of pt/graphene
nanocomposites. Electrochem Commun 2009. https://
doi.org/10.1016/j.elecom.2009.02.009.
[178] Chu H, Shen Y, Lin L, Qin X, Feng G, Lin Z, Wang J, Liu H,
Li Y. Ionic-liquid-assisted preparation of carbon nanotube-
supported uniform noble metal nanoparticles and their
enhanced catalytic performance. Adv Funct Mater 2010.
https://doi.org/10.1002/adfm.201001240.
[179] Su F, Tian Z, Poh CK, Wang Z, Lim SH, Liu Z, Lin J. Pt
nanoparticles supported on nitrogen-doped porous carbon
nanospheres as an electrocatalyst for fuel cells. Chem
Mater 2010. https://doi.org/10.1021/cm901542w.
[180] Jiang H, Zhao T, Li C, Ma J. Functional mesoporous carbon
nanotubes and their integration in situ with metal
nanocrystals for enhanced electrochemical performances.
Chem Commun 2011. https://doi.org/10.1039/c1cc12942b.
[181] Wang L, Nemoto Y, Yamauchi Y. Direct synthesis of
spatially-controlled Pt-on-Pd bimetallic nanodendrites with
superior electrocatalytic Activity. J Am Chem Soc 2011.
https://doi.org/10.1021/ja202655j.
[182] Zhang W, Fu Y, Wang J, Wang X. 3D hierarchically porous
graphitic carbon nitride modified graphene-Pt hybrid as
efficient methanol oxidation catalysts. Adv Mater Interfaces
2017. https://doi.org/10.1002/admi.201601219.
[183] Li CZ, Wang ZB, Sui XL, Zhang LM, Gu DM, Gu S. Graphitic
carbon nitride nanosheet coated carbon black as a high-
performance PtRu catalyst support material for methanol
electrooxidation. J Mater Chem A 2014. https://doi.org/
10.1039/c4ta04594g.
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
[184] Wang X, Sun M, Guo Y, Hu J, Zhu M. Three dimensional Pt
island-on-Au architectures coupled with graphite carbon
nitride nanosheets for effective photo-accelerated
methanol electro-oxidation. J Colloid Interface Sci 2019.
https://doi.org/10.1016/j.jcis.2019.09.085.
[185] Qian H, Huang H, Wang X. Design and synthesis of
palladium/graphitic carbon nitride/carbon black hybrids as
high-performance catalysts for formic acid and methanol
electrooxidation. J Power Sources 2015. https://doi.org/
10.1016/j.jpowsour.2014.10.109.
[186] Fang D, Yang L, Yang G, Yi G, Feng Y, Shao P, Shi H, Yu K,
You D, Luo X. Electrodeposited graphene hybridized
graphitic carbon nitride anchoring ultrafine palladium
nanoparticles for remarkable methanol electrooxidation.
Int J Hydrogen Energy 2020. https://doi.org/10.1016/
j.ijhydene.2020.05.273.
[187] Ren Y, Zhang S, Li H. Electro-oxidation of methanol on
SnO2-promoted Pd/MWCNTs catalysts in alkaline solution.
Int J Hydrogen Energy 2014. https://doi.org/10.1016/
j.ijhydene.2013.10.012.
[188] Tsang CHA, Hui KN, Hui KS, Ren L. Deposition of Pd/
graphene aerogel on nickel foam as a binder-free
electrode for direct electro-oxidation of methanol and
ethanol. J Mater Chem A 2014. https://doi.org/10.1039/
c4ta03138e.
[189] Li L, Chen M, Huang G, Yang N, Zhang L, Wang H, Liu Y,
Wang W, Gao J. A green method to prepare Pd-Ag
nanoparticles supported on reduced graphene oxide and
their electrochemical catalysis of methanol and ethanol
oxidation. J Power Sources 2014. https://doi.org/10.1016/
j.jpowsour.2014.04.021.
[190] Dong Q, Zhao Y, Han X, Wang Y, Liu M, Li Y. Pd/Cu
bimetallic nanoparticles supported on graphene
nanosheets: facile synthesis and application as novel
electrocatalyst for ethanol oxidation in alkaline media. Int J
Hydrogen Energy 2014. https://doi.org/10.1016/
j.ijhydene.2014.06.139.
[191] Zhang G, Huang C, Qin R, Shao Z, An D, Zhang W, Wang Y.
Uniform Pd-Pt alloy nanoparticles supported on graphite
nanoplatelets with high electrocatalytic activity towards
methanol oxidation. J Mater Chem A 2015. https://doi.org/
10.1039/c4ta06076h.
[192] Xu W, Zhu S, Li Z, Cui Z, Yang X. Evolution of palladium/
copper oxide-titanium dioxide nanostructures by
dealloying and their catalytic performance for methanol
electro-oxidation. J Power Sources 2015. https://doi.org/
10.1016/j.jpowsour.2014.10.147.
[193] Zhao M, Abe K, Yamaura SI, Yamamoto Y, Asao N.
Fabrication of Pd-Ni-P metallic glass nanoparticles and their
application as highly durable catalysts in methanol electro-
oxidation. Chem Mater 2014. https://doi.org/10.1021/
cm403185h.
[194] Li SS, Lv JJ, Hu YY, Zheng JN, Chen JR, Wang AJ, Feng JJ.
Facile synthesis of porous Pt-Pd nanospheres supported on
reduced graphene oxide nanosheets for enhanced
methanol electrooxidation. J Power Sources 2014. https://
doi.org/10.1016/j.jpowsour.2013.08.088.
[195] Eswaran M, Dhanusuraman R, Tsai PC, Ponnusamy VK.
One-step preparation of graphitic carbon nitride/
Polyaniline/Palladium nanoparticles based nanohybrid
composite modified electrode for efficient methanol
electro-oxidation. Fuel 2019. https://doi.org/10.1016/
j.fuel.2019.04.040.
[196] Qian H, Chen S, Fu Y, Wang X. Platinum-palladium
bimetallic nanoparticles on graphitic carbon nitride
modified carbon black: a highly electroactive and durable
catalyst for electrooxidation of alcohols. J Power Sources
2015. https://doi.org/10.1016/j.jpowsour.2015.09.051.
 international journal of hydrogen energy xxx (xxxx) xxx
[197] Yuan W, Cheng Y, Shen PK, Li CM, Jiang SP. Significance of
wall number on the carbon nanotube support-promoted
electrocatalytic activity of Pt NPs towards methanol/formic
acid oxidation reactions in direct alcohol fuel cells. J Mater
Chem A 2015. https://doi.org/10.1039/c4ta04613g.
[198] Zhang Y, Chang G, Shu H, Oyama M, Liu X, He Y. Synthesis
of Pt-Pd bimetallic nanoparticles anchored on graphene for
highly active methanol electro-oxidation. J Power Sources
2014. https://doi.org/10.1016/j.jpowsour.2014.03.127.
[199] Feng JX, Zhang QL, Wang AJ, Wei J, Chen JR, Feng JJ.
Caffeine-assisted facile synthesis of platinum@palladium
core-shell nanoparticles supported on reduced graphene
oxide with enhanced electrocatalytic activity for methanol
oxidation. Electrochim Acta 2014. https://doi.org/10.1016/
j.electacta.2014.07.152.
[200] Lv J, Feng W, Yang S, Liu H, Huang X. Methanol dissociation
and oxidation on single Fe atom supported on graphitic
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
25
carbon nitride. Appl Organomet Chem 2019. https://doi.org/
10.1002/aoc.4930.
[201] Yanagisawa S, Tsuneda T, Hirao K, Matsuzaki Y. Theoretical
investigation of adsorption of organic molecules onto
Fe(110) surface. J Mol Struct THEOCHEM 2005. https://
doi.org/10.1016/j.theochem.2004.10.043.
[202] Zhou H, Tamura H, Takami S, Kubo M, Zhanpeisov N,
Miyamoto A. Adsorption properties of CH3OH on Al (111) and Fe
(100) surfaces: a periodic first-principles investigation,
Japanese J. Appl. Physics, Part 1 Regul. Pap Short Notes Rev Pap
2000. https://doi.org/10.1143/jjap.39.4275.
[203] Pieta IS, Rathi A, Pieta P, Nowakowski R, Hołdynski M,
Pisarek M, Kaminska A, Gawande MB, Zboril R.
Electrocatalytic methanol oxidation over Cu, Ni and
bimetallic Cu-Ni nanoparticles supported on graphitic
carbon nitride. Appl Catal B Environ 2019. https://doi.org/
10.1016/j.apcatb.2018.10.072.
Another random document with
no related content on Scribd:
 Hannes painoi kiiltävän sormuksen tytön nimettömään. Tytön
täytyi painaa päänsä piiloon pojan olkapäähän.

Runsaat suortuvat hivelivät pojan kasvoja ja tytön käsi hieman

epävarmana kiertyi hänen kaulaansa. Tyttö värähteli siinä hänen
sylissään. Miten sillä olikin raikkaan pehmeät huulet.

— Mutta minulla ei ole… virkkoi tyttö hiljaa katsellen sormustaan.

— Minullapas on.

Ja Hannes otti toisen samanlaisen esille.

— Anna kun minä panen sen sinun sormeesi, pyysi tyttö

hätäisesti.

He katselivat vain vaieten toisiaan.

— Ja sitten elonkorjuun jälkeen on meidän häämme, sanoi

Hannes. Vai tahtoisitko ehkä myöhemmin.

— Milloin sinä vain tahdot.

*****

Hannes seisoi ikkunassa ja katseli ulos. Liisa oli jo mennyt

nukkumaan.
Oo, miten ruumiissa tuntui pidätetty voima pursuvan.

Olisi ihanata antaa se perinnöksi tulevalle polvelle. Pieni

herttainen Liisa oli koskematon kuin tuomen kukka salolla. Hänkin
antaisi terveen sukuelämän perinnöksi lapsilleen.
XVII.

Keskikesän henki liikkui kartanolla, täyteläisessä ruispellossa ja

pienen puutarhan kukkaismaassa. Hakalassa oli piha niitetty ja
kuivuva heinä tuoksui voimakkaasti.

Pieni poika koetti astuksia heinäluokojen yli, mutta tupsahti

suulleen heiniin ja kirkaisi ilosta. Äiti istui tuvan portaan alimmalla
astuimella ja katseli hymyillen pienokaisensa puuhia.

— Missä äidin poju!

Pienokainen tallusteli ja kutsun kuultuaan lähti juoksemaan. Jalka

tarttui heiniin ja nenä sattui kovaan hiekkaan. Äyväyväy!

Isä koppasi pojan syliinsä ja antoi äidille.

Se oli heidän ensimäinen lapsensa, onnen ja raikkaan ilon

täyskypsä hedelmä.

Liisasta oli tullut herttainen, hyvä emäntä. Täyteläisenä, iloa

ympärilleen jakavana liikkui hän askareissaan aamusta iltaan. Yksi
piirre hänessä oli vain ilmaantunut, joka oli outoa Hannekselle. Liisa
oli alkanut salaa seurailla miehensä liikkeitä, peläten häntä
palvelijoihinsa.

Tämän oli Hannes huomannut ja pitänyt sitä ensin leikkinä ja

ainakin pienenä mustasukkaisuutena. Vaikka eihän oikea rakkaus
tällaiselle tilaa antanut kuin joko kehittymättömien tai sitten
ajattelemattomien ihmisten keskuudessa.

Vaikka Liisa oli kansan lapsi niinkuin hänkin, ei hän olisi ollut
taipuvainen mitään tällaista uskomaan.

Mutta näytti sittenkin siltä, että olisi uskottava.

Toinenkin seikka oli ehken synnyttänyt Liisassa harha-ajatuksia.

Hannes oli viime aikoina ja heti avioliittoon mentyään alkanut lueksia
kaikkina joutohetkinään. Hän seuraili etupäässä avioliittoa ja
sukukysymystä käsittelevää kirjallisuutta. Ja tämä kirjallisuus oli
saanut hänet vakuutetuksi, että avioliitossakin oli ainakin henkisesti
edullista elää säännöllisesti ja kohtuullisen pidättyvästi.

Liisa oli voimakas luonne ja pohjaltaan melkoisen tulinen. Kun

Hannes aikoi panna käytäntöön saamiaan vaikutelmia heidän
yhteiselämässään ja puhui tästä Liisalle, arveli tämä kiivaasti:

— Sinä et siis rakasta minua.

Hannes koetti selittää, ettei raakuus ole rakkautta ja jos he kovin

pian kuluttaisivat tulensa, tulisi heidän keski-ikänsä varmasti
kylmäksi.

Liisa ei vain tuntunut tätä käsittävän. Se vahvisti hänen orastavia

epäluulojaan.
 Mutta Hannes ei voinut aavistaa, että tässä oli myöskin
sukuperintö kysymyksessä. Liisan äiti oli ollut luulosairas ja hänen
äitinsä samoin. Liisan isoäiti oli lopettanut elämänsä väkivaltaisesti
sairautensa takia ja Liisan äiti sairasti sukuvikaa synkkyyteen
saakka, tehden miehensäkin elämän synkäksi ja ilottomaksi.

Mistäpä Hannes tätä osasi aavistaakaan. Sen vähemmän hän voi

sitä ottaa vakavasti, kun se oli vasta selvennyt hänelle. Eihän Liisa
vielä ollut koskaan mitään sanonut. Silmissä vain oli ollut
epäluuloinen välähdys.

Mutta pian oli taistelu alkava tästäkin sukuperinnöstä, joka heidän

onneansa uhkasi.
XVIII.

Kesäinen iltapäivä. Helteisenä paahtoi aurinko ja Hakalahti talon alla

lepäsi rantojaan kuvastellen.

Hannes katseli järvelle pihamaan laidassa aitaan nojaten. Pitäisipä

käydä laskemassa verkot. Ei ollut aamullisella uimakäynnillään
muistanutkaan. Nyt sieltä saisi suuria särkiä ja ahvenia. Saattoivatpa
hauetkin paistatella kaislikossa.

— Käyn laskemassa verkot, tulkoon Mari toveriksi, sanoi Hannes

vaimolleen, joka kulki hänen ohitseen.

Hannes astui jo muutaman askelen rantatielle.

— Mari ei tule nyt verkonlaskuun, kuuli hän vaimonsa kylmästi

sanovan.

Hannes kääntyi.

— Ja miks'ei? Joutaahan se…

— Kyllä sen puolesta, mutta muuten. Enköhän minäkin kelpaisi

joskus toveriksi?
 Nyt oli Liisan äänessä jo pistävä sointi. Hannes hätkähti. Joko
taaskin. Tuliko se tästäpuolin jokapäivä tuo Liisan luulonpuuska?
Sillä muutakaan se ei saattanut olla. Liisa oli eilenkin väittänyt: —
Sinä et välitä minusta enää, muuten ottaisit joskus mukaasi
työpaikoille.

— Tule sitten pian, luikkasi Hannes mennessään Liisalle. Rantaan

oli vain muutama kivenheitto ja Hannes kiirehti jo verkkoja
puikkaroimaan. Tottapahan sieltä Liisa tulisi.

Hannes sai jo verkot veneeseen ja istui kivelle odottamaan. Miksei

se jo tule? Ahvenet hyppivät niin että ruohikko meni yhtenä
pohkeena. Olisi pitänytkin mennä nuotalle.

Hannes käveli pihaan hakemaan Liisaa. Liisa oli porstuakamarissa

nyyhkimässä.

— Mitä on tapahtunut?

Hannes istui nolona sängynlaidalla. Tähän saakka hän oli tuntenut

vain onnea kotielämässä, nyt tuntui kuin joku olisi haparoinut ilkeillä
niljaisilla sormillaan hänen kohtalonsa lankoja: pitää sinun saada
tuntea hieman toistakin puolta.

Tuntui kuin kukkaset kamarin ikkunalla olisivat surkastuneet ja

päivä ulkona lakannut paistamasta.

Ei, jotain tässä olisi tehtävä. Liisan tunteista ja mielialasta olisi

päästävä selvyyteen.

Miten tässä oikein aloittaisi?

 — Liisa, oma hyvä toverini, selitä minulle surusi syyt. Sinä olet jo
usein sanonut, että minä en pitäisi sinusta. Olen sen käsittänyt
pieneksi tuskitteluksi tytöltäni siitä, että en haluaisi uhrata
lakkaamatta elämän voimaa syystä, että siten vanhuus tulee ennen
keski-ikää. Mutta äsken sinä sanoit sellaista, jota en sinun
sanomanasi ymmärrä. Jos kävisi päinsä, pitäisin sinut aina
mukanani. Mutta vaikka et olekaan aina luonani ja mukanani,
ajattelen minä sinua silti melkein aina, ehkä liiankin paljon. Pitäisihän
minun jakaa ajatuksiani niin kovin moneen muuhunkin asiaan, mutta
sinäpä niistä aina viet suurimman osan. Mitä varten siis tällaista…
minä en ymmärrä… Sinä kannat meidän toista lastamme ja sinun
pitäisi olla rauhallinen. Ethän luule, että muista pitäisin kuin sinusta?

Hannes oli puhunut viihdytellen kuin lapselle.

Liisa kietasi kätensä hänen kaulaansa.

— Minä taidan olla paha välistä sinulle… anna anteeksi typerälle

vaimollesi, mutta minä tosiaankin pelkään, että sinä välittäisit muista
etkä minusta.

— Voi sitä omaa pientä hupakkoani. Et saa enää milloinkaan

ajatella niin… Tule pian rantaan.

— Vietkös minut joskus mukanasi metsäänkin?

Liisa seisoi siinä sinisissä silmissään vielä kyynelten jälkiä, hiukset

auenneina, valkoiset käsivarret paljaina.

Miten somalle hän näyttikään siristäessään vielä silmiään ja

poskille hymykuoppien kuin väkivalloin ilmestyessä.

Hannes koppasi hänet syliinsä.

 — Johan toki vienkin oman tyttöni. Pistän taskuuni kuin omenan.
Mennään pian verkonlaskuun.

Varjot olivat taas hävinneet. Mutta Hannes oli varma siitä, että
ne ilmestyisivät uudelleen. Hän olisi tahtonut vielä puhua asiasta
Liisalle, muttei kehdannut tällä kertaa. Saisipahan toiste sanoa, että
Liisa tällä tavoin särki pala palalta kodin onnea ja rauhallisuutta.

Liisa oli virkeä ja iloinen. Kun verkot oli saatu lasketuksi, ehdotti
hän, että jäätäisi uimaan. Lahden vastaisella rannalla pulisi lapsia ja
aikuisia vedessä mekastaen ja hoilaten.

Oli hiestävää ja Hannes riisuutui nopeasti pulahtaen järveen.

Pohja oli matalalla ja Hannes ohjaili venhettä Liisaa odotellen.

— Miten sinä oletkin kaunis, Liisa. En koskaan olisi sitä osannut

ajatella. Tuntuu kuin ihmeeltä että sinä olet vaimoni.

— Miten niin?

— Minähän rikoin niin paljon nuoruudessani, enkä olisi ollut

oikeutettu sellaiseen kuin sinä… Miten ihmeen tavalla sitä voikin.
Nuorukaisena en olisi voinut tällä tavoin katsella alastomuutta. Nyt
se on minulle pyhää, niin kuin kuuntelisin kaunista musiikkia.

— Kaikki eivät voi niin katsella.

— Eivät voikaan, mutta heillehän on lapsesta pitäen opetettu että

ihmisen ruumis on syntipesä ja että alastomuus on jotain hyvin
häpeällistä ja saastaista, ja se on johtanut ja johtaa yhä edelleen
nuorisoa väärään. Uskopas tyttö, kerran tulee vielä aika, jolloin
alastomuutta katsellaan vain kauneuden kannalta, pidetään sitä
pyhänä.
 — Mutta silloin ei saa ihmisillä olla rumia ajatuksia.

— Ei saakaan. Ihmiskunnan täytyy tulla uudeksi ja se tulee siksi

vielä kerran.

— Miten luulet sen siksi tulevan?

— Kasvatuksen kautta. Luonto ja työ karkaisee ja muuttaa huonon

hyväksi. Minä en olisi ennen näin voinut sinua siinä katsella.

— Enhän minä olisi ollut sinun katseltavanasikaan, nauroi Liisa

vettä pärskytellen.

— Kun näin vähänkin alastomuutta, värisin himosta.

— Miten opit sitten toisin katselemaan?

— Minä opin sen siellä tehtaassa. No, älä naura! Tämä on vakava
asia.
Väkivasarain jyskeessä minä aloin kasvattaa itseäni uudeksi
ihmiseksi.
Työ ja luonto minua paransi.

— Sinä puhut niin kauniisti.

— Jos sen kaikki oppisivat samalla tavalla, niin miten voimakas ja

raitis nuoriso meille kasvaisikaan.

He meloivat rantaan. Liisa istui venheen kokassa kuin veden neito.

Ihmeellinen mies tuo Hannes, mietti hän. On täynnä aina niin
ihmeellisiä ajatuksia ja puhuu niin kauniisti. Sanoo työn opettaneen
itseään kaikessa. Olisiko todellakin työ semmoinen koulu, jossa niin
paljon oppii. Kun minä vain voisin kaikessa pysyä hänen rinnallaan.
Pitääköhän hän todellakin minusta enemmän kuin kenestäkään
muusta? Olenhan minä tosin kaunis, ajatteli hän lopuksi katsellen
itseään. Ettei hän vain rakastuisi milloinkaan johonkin toiseen. Taitaa
olla typerää ajatella sellaista.

Liisa oli mennyt pihaan ja Hannes jäänyt pellolle, jossa

rakennettiin uutta riihtä. Miehet hikoilivat helteessä. Pihka hikosi
veistetyistä petäjistä ja tuoksui voimakkaasti. Miehet istuivat
levähtämään hirsikasalle. Heillä näytti olevan jotain erikoista
mielessä, se selveni liikkeistä, joilla piippuja rassailtiin ja täytettiin.

Kohta aloittikin yksi miehistä.

— Ei tässä pysy leivissä… lisäpalkkaa on saatava. Johan minä

sen sanoin jo alussa…

Hannes odotti.

— Ja kyllähän tämä isäntä maksaakin… jatkoi toinen. Sopuisa

mies…

Vai viitattiin siihen. Hän oli tosin rakennuttanut mökkeihin, joiden

asukkaita nämä olivat, uudet tilavat asunnot ja perkkauttanut
palstoja. Siihen ei olisi tarvinnut vedota. Siitä ei näyttänyt paljonkaan
hyötyä koituneen, ainakaan muutamien suhteen.

— Onhan isännällä varoja, jos maksaa kohtupalkatkin, jurahti

kolmas imien piippuaan.

Hannesta hieman sapetti miesten kyyräily. Tämä ei ollut sitä

suoraa, rehellistä työainesta, jollaiseksi hän oli kerran kuvitellut talon
alustalaiset kasvattavansa. Mutta olihan se ymmärrettävääkin. Vihaa
ja kiukkua oli kylvettykin tämän polven työväen vereen. Kuinkapa
moni tahtoi ja kehtasi rakkaudella rakentaa hyvää sopua.

— Miksi ette sanoneet aikanaan, että palkka on pieni? Ja onhan

teillä leipä talosta itsellenne ja perheellenne, eikä sitä grammoilla
mitata. Paljonko teidän pitäisi saada?

Miehet sanoivat summan.

— Tällä kertaa minä sen maksan, mutta periaatettani vastaan.

Minä tahtoisin kasvattaa teistä kunnon työmiehiä ja siksi…

— Kasvattaa, kivahti vanhin mies joukosta, Mutkan Tuomas,

keskeyttäen
Hanneksen puheen… Mikä sinä olet, poikaloppi, vanhojen
kasvattajaksi!

— Voi p—le! kivahti toinenkin. Siitä on paisunut aika pohto. Vie

sun…

Mies mutisi puoliääneen toisille, mutta Hannes kuuli sen hyvin.

— Te käsitätte väärin. Minä rakennutin teille uudet asunnot ja

paransin olojanne…

— No, siitä ei kannata ylpeillä, keskeytti tulistunut Tuomas. Jos se

on isännälle niin suuri asia, niin ottaa vain pois mökin. Niinhän ne
suurporvarit tekevät aina.

Hannes tulistui.

— Enkö minä lähtenyt tästä talosta tyhjempänä kuin yksikään

teistä ja eikö ole työllä ansaittua kaikki mitä olen saanut? Minä olen
antanut teille osan työllä kokoomastani ja toivonut, että voisimme
työskennellä yhdessä kuin veljet. Teidän pitäisi hävetä!

Miehet olivat käyneet noloiksi. Hannes taisi olla oikeassa.

Työllähän hän oli saanut riippumattoman aseman. Taisi tulla suotta
kuvailluksi.

Ei puhuttu enää sanaakaan ja Hannes lähti pihaan alakuloisena.

Huonoja hedelmiä kantoivat hänen hyvät työnsä. Eivät osanneet

arvostella asioita paikalleen. Se oli tavallaan yhteiskunnankin syy,
joka oli antanut työväen kasvaa sosialistiagitaattorien varassa. Koko
työväenliike maassa oli saanut asettua väärälle pohjalle. Seuraukset
siitä varmasti pian tulisivat näkyviin.

Kun nyt jo täälläkin, hänen hiljaisessa ympäristössään, hymähti

Hannes.
Ei voinut kieltää, että tuntui kuin joten kuten ilkeältä.

Olihan hyväkin, että sattui aina jotain, joka ei ollut myötäsukaista.

Siten ei päässyt pensistymään eikä raukeamaan yhtämittaiseen
onneensa.
XIX.

Talon koko työväki oli lähdössä takamaalle kaskenkaatoon.

Heinänkorjuu oli saatu lopetetuksi ja kun peltotöiltä jäi kaskenkaato
juhannuksen jälkeen, oli se nyt suoritettava.

Varusteltiin eväskontteja ja piimäleilejä ja kaksi talon nuorta

palvelijatarta, Mari ja Maikki, odotteli jo vesurit kädessä pihamaalla.

Liisa tuli portaille.

— Minutko te aiotte kotiin jättää? sanoi hän palvelijoille.

— Niin, emännän tietysti, virkkoivat ja nauraa tirskuttelivat omille

vähäpätöisille asioilleen.

Se nauru kirpaisi Liisan mieltä, joka oli taas kipeytynyt. Heillä on

varmasti jotain mielessä. Olisikohan Hannes sanonut, ettei emäntää
oteta mukaan? Olisihan siellä piikojen mukava kiemailla
Hannekselle, kun hänen tarkka silmänsä ei olisi vartioimassa.

Hannes tuli pirtistä täysinäinen eväskontti selässä.

— Minä lähden kaskeen. Mari saa jäädä kotiin, sanoi Liisa hänelle.
En minä suostu aina jäämään…
 — Mutta eihän se käy… talo jäisi moneksi päiväksi vieraaseen
varaan, esteli Hannes. Ja muutenkin tulisi hankalaksi sinulle.
Voinhan minä käydä kotona joka yö.

Mutta Liisa ei tahtonut kuulla puhuttavankaan kotiin jäämisestä.

Hän neuvoi jo töitä Marille.

Miehet olivat jo kujasilla menossa ja tytöt olivat loitonneet

pihamaan toiselle puolelle.

— Jos minä jään, niin Mari jää myöskin, sinkosi Liisa tiukasti.
Sinne kuhertelemaan…

— Mitä, mitä sinä sanot, kivahti Hannes. Kuhertelemaan… minäkö

piikojen kanssa…

— Kaipa minun pitää niin uskoa, kun sinä et milloinkaan laskisi

minua mukaan.

Minä en nyt tiedä mitä ajatella, sanoi Hannes synkästi.

Tapahtukoon siis sinun tahtosi tällä kertaa, jatkoi hän kylmästi. Mari
saa jäädä sinun kanssasi.

Hannes lähti astumaan miesten jälkeen.

Liisa jäi portaille.

— Nyt minä tiedän, minkälainen sinä olet, huusi hän Hanneksen

jälkeen, mutta tämä ei enää kääntynyt.

Hannes polki kuin vihoissaan kumahtelevaa kangaspolkua. Kaunis

sopu, joka oli kestänyt useita päiviä, oli taaskin särkynyt. Liisa oli
heittänyt hänelle solvaavia sanoja. Liisa, hänen oma vaimonsa.
 Mikä oli oikein vaikuttamassa Liisan luulomieltä? Hän ei
kertaakaan ollut aiheuttanut sitä millään muotoa. Talon naispalvelijat
tiesivät velvollisuutensa ja puhuivat vain välttämättömistä asioista
hänen kanssaan. Hän oli kyllä ystävällinen heille, mutta sitähän hän
oli kaikille, jotka kunnollisesti suorittivat tehtävänsä. Maikki oli
hiljainen ja erillään pysyvä kaikista, Mari oli kyllä iloinen hälläkkä,
mutta mitään ei ollut sattunut hänenkään kanssaan, joka
vähimmässäkään määrässä olisi aiheuttanut Liisan naurettavaa
epäluuloa.

Mistä se sitten johtui?

Selvyyttä tähän ei saanut miettimälläkään. Liisa oli hellä ja hyvä

hänelle. Joskus vain purkautui esiin tällaista, joka sanomattomasti
painoi häntä. Jos hän olisi vähemmän välittänyt Liisasta, ei hänen
mielenpurkauksensa olisi tuntunut niin tuskallisilta.

Merkillistä, mietti Hannes. Minä sain murskatuksi sukukiroukseni,

tulin kuin onnen potkusta saaneeksi kotikonnun itselleni. Kaikki
menestyy. Pellot lupaavat runsaita satoja ja kaikki on kuin
voittokulkua, mutta kaikista kallein ja rakkain on menossa murskaksi
minulta.

Ennemmin muuta vastoinkäymistä kuin tätä. Ennemmin joku

karjasta kuolleeksi aholle, viljapelloista joku lohko raesateen
ruhjottavaksi, ennemmin mitä tahansa, kuin oma vaimo epäilemään
olemattomista.

Tie kulki kiemurrellen Hakalan takamaahongikon läpi. Vahvat

petäjät ojentelivat suorana runkojaan korkeuteen. Oli kuin ihmeen
kaupalla jäänyt ukolta tämä lohko myymättä.
 Hänen edellään kulkeva vanha Tuomas virkkoi puita katsellen:

— On siinä aika älliköitä… Saat sinä Hannes niistä tuhansia

monioita.

Hannes käveli allapäin. Suuri omaisuus ei antanut onnea. Hän oli

tottunut aina vain luottamaan työhön. Hän olisi luovuttanut kernaasti
tämän metsäpalstansa, jos olisi sillä saanut korjatuksi sen mitä oli
vinossa. Taisi olla köyhä mökin mies, sellainen kuin tuo Tuomas
tuossa, kaikista onnellisin. Terve ruumis ja hyvä työhalu. Ei huolta
suurista tuloista eikä menoista. Oma turve antoi ja hankkimalla sai
lisää.

Olisi pitänyt kysyä Tuomaalta, oliko hän täysin tyytyväinen ja

onnellinen. Tuomas olisi varmaan merkitsevästi hymähtänyt. Heidän
taannoisen riitansa jälkeen oli Tuomaasta tullut mitä mukavin mies.
Teki aina työnsä hyvin eikä pyrkinyt napisemaan. Ehkä hän oli
tyytyväinen elämäänsä.

Toiset olivat menneet edellä ja Hannes pysähtyi Tuomaan kanssa

lepäämään.

— Sanohan Tuomas, olisitko mieluummin talon- kuin

mökinmiehenä? kysyi
Hannes.

Tuomas vilkaisi kysyjään ja mietittyään virkkoi

— Enpä tahtoisi talonmieheksi. On niin vapaata olla

mökinmiehenä. Mitä varten sitä kysyt?

— Muuten vain. Olin halukas tietämään, oletko tyytyväinen

elämääsi.
 — Mikäpäs siinä… kun vain olisi terveyttä, että jaksaisi tehdä
työtä.

Se oli mökinmiehen elämänfilosofiaa. Tyyntä ja tervettä. Jaksaisi

tehdä työtä, olisi terveyttä… Ei olisi kai tuokaan tuossa vaihtanut
mökkiään ja pientä perkkiötään mihinkään maailmassa.

Kaskimaa oli päivärinteessä. Ei tuulen henkäyskään vilvoittanut

hikisiä raatajia. Puut kaatuivat parahdellen ja ennen päivällistä oli jo
iso aukio kaadettuna. Kun oli lämmintä ja aurinkoa, niin oli iloa
myöskin. Rupatellen ja naureksien syötiin tuoksuvassa
koivurykelmässä.

Hannes ei voinut tällä kertaa ottaa juttuihin osaa. Liisa oli jäänyt
sinne alakuloisena, ehken vihaisenakin. Oli saattanut itkeäkin. Taisi
tulla liian jyrkästi hänelle sanotuksi. Vaikka sanoihan hänkin. Olisi
kumminkin mukaan saanut tulla ja niinhän hän oli jo aikonutkin,
mutta kun katkerat, solvaavat sanansa sanoi, niin tuli niinkuin
äkäpäissä lähdetyksi.

Kuinkahan tässä vielä viimein käy? Eikö millään saa Liisaa

vakuutetuksi, että luulonsa ovat aiheettomia?

Miehet kuorsailivat ruokauntaan lehdesvuoteillaan ja naiset

taittelivat vastoja. Hannes istui erillään muista koivun rungolla
ajatuksiin vaipuneena.

Käki lensi koivuun, joka oli sille kasken keskellä lepopuuksi jätetty,
ja alkoi kukkua. Miehet heräsivät siihen ja lähtivät työhönsä.

— Hyvää halmeonnea kukkuu, sanoi joku miehistä.

— Onnen vuosiapa se minulle helkyttää, tiesi iloinen Mari.

 Hannes nousi ja sanoi miehille kotiin lähtevänsä ja aamulla
tulevansa takaisin.

Ei jaksanut olla, vaikka vasta illalla oli luvannut kotiutua. Liisa voisi
siellä taas tuhertaa kauniit silmänsä punaisiksi.

— Kovinpa pian sille tuli eukkoaan ikävä, jurahti joku mies

Hanneksen mentyä.
XX.

Liisa seisoi vielä hetkisen portailla Hanneksen mentyä. Sitten hän

kuin juosten meni kamariinsa ja alkoi nyyhkiä. Pikku Pentti nukkui
kehdossaan sinikellokimppu pääaluksella. Hannes oli ennen
lähtöään jättänyt sen siihen. Ikkuna oli auki ja tuulenhenkäykset
toivat sisään ruispellon tuoksua. Pelto kartanon alla lainehti
lupaavana.

Liisa koetti rauhoittua, mutta ei voinut. Miksi Hannes ei ottanut

häntä mukaansa, vaikka hän pyysi? Miksi hän on joskus niin kovin
jyrkkä päätöksissään? Ja onko sittenkin niin, että hän saattoi välittää
muistakin, ei vain yksin hänestä.

Liisa koetti miettiä ja päästä selvyyteen.

Jos Hannes ei olisi kertonut hänelle nuoruudestaan, ei hän ehkä

olisi mitään epäillytkään. Hannes syytti nuoruudenhairioistaan
sukuperintöä, mutta oliko hän sen jo kokonaan voittanut? Hän kyllä
vakuutti niin, mutta saattoihan siltikin… Ja Mari on viehättävä tyttö,
ehkä kauniimpi kuin minä, jatkoi Liisa tuskallisia ajatuksiaan.

Voisiko Hannes pitää kahdesta yhtaikaa?

 Tuntui pahalta ajatella sitä ja että ehkä luuloillaan loukkasi
syyttömästi miestään, joka oli aina hyvä hänelle, vaikka joskus oli
tinkimätön päätöksissään.

Liisa ajatteli äitiään, joka hänen mielestään oli saanut kärsiä

samanlaisesta… Isä oli ollut uskoton hänelle, niin äiti oli ainakin
sanonut. — Uskottomalle miehelle ei voi mitään, oli äiti aina
päätellyt, ja hänen vanhempiensa elämä oli ollut alituista riitaa,
aamusta iltaan.

Sellaiseksiko heidänkin kaunis elämänsä oli muuttuva? Tuntui

tuskalliselta ajatella sitä.

Liisa oli tuntenut syvää kiitollisuutta miestään kohtaan aina.

Kaikesta huolimatta Hannes olisi saanut ison talon isäntänä
vaimokseen kenet vain olisi ottanut. Hän, köyhä mökin tyttö, oli tullut
hänen valitukseen. Eikä Hannes ollut vielä kertaakaan sanonut
moitteen sanaa mistään. Ja oli aina vakuuttanut rakastavansa vain
häntä ja houkutellut kuin pientä lasta silloin, kun hänelle sattui omat
omituiset mielenpurkauksensa.

Hannes oli kovin hyvä. Hän saattoikin olla lapsellisen typerä

luulotellessaan kaikkea sellaista.

Liisa oli rauhoittunut ja katseli nukkuvaa lasta. Isän

hellyydenosoitus, sinikellokimppu pieluksella, liikutti häntä. Tuntui
niinkuin joku näkymätön olisi sanonut: Niin, hän on hyvä, mutta
miten sinun laitasi on? Ansaitsetko sinä rehellisen ja uskollisen
miehen hyvyyttä? — Olenhan minä hyvä ja hellä hänelle ja hoidan
hyvin tehtäväni. — Se ei riitä, jyrisi tuntematon. Sinun on jätettävä
turhat ajatuksesi, kasvatettava itseäsi niinkuin hänkin. Sinun on