This is an open access article published under an ACS AuthorChoice License, which permits

copying and redistribution of the article or any adaptations for non-commercial purposes.

http://pubs.acs.org/journal/acsodf Article

Functionalized Graphitic Carbon Nitride Decorated with Palladium:

an Efficient Heterogeneous Catalyst for Hydrogenation Reactions
Using KHCO2 as a Mild and Noncorrosive Source of Hydrogen
Ashish Bahuguna* and Yoel Sasson
Cite This: ACS Omega 2020, 5, 12302−12312 Read Online

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Functionalization of the widely known graphitic carbon nitride

(GCN) material has been performed, and a novel heterogeneous catalyst is
reported by incorporating palladium over the surface of functionalized GCN. GCN
Downloaded via 192.114.91.213 on June 5, 2020 at 15:20:27 (UTC).

was functionalized using an optimized ratio of sulfuric acid, nitric acid, and
hydrogen peroxide. The developed catalyst was characterized by powder X-ray
diffraction, IR, scanning tunneling microscopy, tunneling electron microscopy, X-
ray photoelectron spectroscopy, Brunauer−Emmett−Teller, thermogravimetric
analysis, and solid-state CP-NMR. The developed material containing ≤1% Pd
exhibits superior catalytic activity in comparison to other carbon support materials
(such as 5% Pd/C) for various hydrogenation reactions under mild conditions.
Potassium formate has been chosen as the best hydrogen source among other alkali
metal formates. The developed catalyst was also able to catalyze a one-pot three-
step reaction for the synthesis of N-benzylaniline which is a precursor of various
antihistamine and anticholargenic drugs. Moreover, the catalyst could be recycled multiple times and consistent activity was
reported.

■ INTRODUCTION
Overdependence on conventional energy sources has con-
renewable ways of hydrogen production are water splitting,
biocatalyzed electrolysis, fermentative hydrogen production,
tributed to diminishing resources in near future. In addition, biomass gasification, and so forth.11−13 Although hydrogen is a
clean energy source, the safety issues pertaining to the storage
the use of conventional fossil fuels is continuously challenging
and transport limit its barrier-free usage. Chemical storage
the ecosystem and changing the global carbon cycle.1 Growing
methods have been found to be suitable alternatives to the
demand of the energy consumptions and climate change has
physical storage methods.14−16 The conventional chemical
envisioned the need of clean and sustainable energy.2 It has
hydrogen storage materials are amine-borane, metal hydrides,
become essential to mitigate the adverse effect of fossil fuels on
carbohydrates, formic acid, and so forth.17−19 Alkali metal
climate; thus, there is an urgent need of sustainable fuel to
formates, especially potassium formate (KHCO2), have
fulfill future energy requirements. Among other clean energy
emerged as a mild and noncorrosive hydrogen source in
vehicles, hydrogen is an emission-free fuel that generates water
comparison to formic acid at high concentrations.20−23 Alkali
and energy when burned in the presence of oxygen. Hence,
formates release H2 on decomposition in the presence of
hydrogen is considered as a clean energy vehicle and a
suitable catalysts and convert to bicarbonates, which can be
sustainable fuel for the next generation.3,4 Hydrogen and fuel
regenerated further to store hydrogen again (Figure 1). The
cells have the potential to overcome the issue of environmental released hydrogen can be used for various hydrogenation
pollution.5,6 It is used as a fuel in spacecrafts, electric vehicles, reactions under ambient conditions. Efforts on decomposition
fuel cells, and so forth.6−8 In general, it requires a large amount of alkali metal formates to release hydrogen gas have been
of primary energy for the industrial scale production of carried out using various metal-based homogeneous and
hydrogen. The most common industrial methods of hydrogen heterogeneous catalysts.24−26 In the case of heterogeneous
production include steam methane reforming and electrol-
ysis.9,10 However, the reforming method generates syngas
which contains carbon monoxide along with hydrogen. Received: March 5, 2020
Hydrogen has been traditionally used for various chemical Accepted: April 2, 2020
synthesis processes; however, the safety issues always remained Published: May 17, 2020
a concern. Although chemical sources of hydrogen have also
been in practice, these processes resulted in the issue of
pollution and were not considered sustainable. The clean and

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsomega.0c00996

12302 ACS Omega 2020, 5, 12302−12312
ACS Omega http://pubs.acs.org/journal/acsodf
Figure 1. Schematic representation of the formate−bicarbonate cycle.
catalysts, metals are generally supported over various materials
such as activated carbon, graphene, graphene oxide, graphitic
carbon nitride (GCN), and so forth.27−29 These supports
provide dispersion of active catalysts onto the surfaces and also
add to the stability.
Nanomaterial catalysts form a bridge between homogeneous
and heterogeneous catalysts, therefore playing an important
role in green chemistry and sustainability.30,31 Several efforts
on developing the solid supports for metal nanoparticles have
been carried out and led to exploration of various carbon-based
supports for catalytic applications. GCN is one of the recently
emerged carbon materials used for various applications such as
photocatalysis (because of a low band gap of 2.7 eV),
heterogeneous organocatalysis (because of the presence of
Lewis and Brønsted basic sites), and support material for
various metals owing to stability and adsorption capabil-
ity.32−35 A review article by Gong et al. critically describes the
applications of GCN as a potential catalyst or catalyst support
for various reactions in detail.36 Functionalization of GCN for
various applications is also an interesting area to explore, and
continuous efforts are being made in this direction. Sulfonic
acid functionalization of graphitic carbon nitride (sg-CN) has
been successfully carried out by Varma et al.37,38 Wang’s group
modified GCN by grafting the organic moiety onto it and used
it for C−H bond activation reaction.39 Lithium ion-function-
alized GCN has been used for high-capacity hydrogen storage
by Jena et al.40 Jiang’s group synthesized polyethylamine-
functionalized GCN and claimed it as an effective material for
Scheme 1. Schematic Diagram for the Synthesis of GCN, OGCN, and Pd-OGCN
12303
Article
CO2 capture.41 Krishnan et al. developed functionalized GCN
as a catalyst for Knoevenagel condensation, biomass
conversion, and synthesis of functionalized indoles.42−45
Markus Antonietti’s group developed Pd-GCN-catalyzed
selective hydrogenation of phenol and its derivatives.46
Wang’s group also used Pd over the mesoporous GCN surface
and for the hydrogenation of quinolone and phenol and
semihydrogenation of phenylacetylene.47−49 The same group
also explored the effect of the alkaline metal in selective
hydrogenation of phenol.50 Recently, our group has developed
a Ru-gC3N4 catalyst to perform photocatalytic transfer
hydrogenation of aldehydes and ketones.51 We also ventured
a Pd-gC3N4 catalytic system for in situ hydrogenation of
alkenes and nitro functionalities in the presence of magnesium
and water.52
To continue our efforts toward sustainable chemistry,
herein, we report oxidative functionalization of GCN using
sulfuric acid, nitric acid, and hydrogen peroxide mixture. The
functionalized GCN (to be used OGCN hereafter) has been
used as a support for Pd metal to fabricate a nanocomposite
(Pd-OGCN) where the oxidized carbon nitride backbone is
decorated with palladium. The synthesized nanocomposite has
been found to be an efficient heterogeneous catalyst for in situ
hydrogenation of nitro, imine, and alkene functionalities. The
Pd-OGCN nanocomposite exhibited better catalytic activity
than its counterpart Pd-GCN material. The reason for good
catalytic performance can be contemplated because of
oxidative surface modification of GCN to OGCN. The
extensive functionalization of the GCN surface has been
supported by solid-state CP-NMR data also. We assume that
the functionalized surface holds the Pd metal strongly and also
helps the reactants to interact with the catalytic surface more
efficiently. Alkali metal formates are noncorrosive sources of
hydrogen gas. Hence, potassium formate has been used as a
mild and noncorrosive source of hydrogen in this study. A
typical formate−bicarbonate cycle for release and storage of
hydrogen gas has been presented in Figure 1. Formates after
releasing H2 in the reaction get converted to bicarbonates. The
https://dx.doi.org/10.1021/acsomega.0c00996
ACS Omega 2020, 5, 12302−12312
ACS Omega http://pubs.acs.org/journal/acsodf
generated bicarbonates can be recycled to formates by
reducing them with hydrogen gas under controlled pressure.
Hence, the catalytic cycle proposes the sustainability of the
protocol where potassium formate has been used as a
noncorrosive source of hydrogen for various hydrogenation
reactions.
■ RESULTS AND DISCUSSION
Synthesis of GCN, oxidized graphitic carbon nitride (OGCN),
and the Pd-OGCN nanocomposite is presented in Scheme 1.
The obtained materials such as GCN, OGCN, and Pd-OGCN
have been characterized by various macroscopic, microscopic,
and spectral techniques.
The powder X-ray diffraction (PXRD) patterns of GCN,
OGCN, and Pd-OGCN are shown in Figure 2. The calcination
Figure 2. PXRD patterns of GCN, OGCN, and the Pd-OGCN
nanocomposite.
of urea at 550 °C for 3 h resulted in two distinguished peaks at
12.9 and 27.4° because of two different diffraction planes. The
intense peak at 27.4° corresponds to the (002) diffraction
plane and confirms the π−π stacking and interplaner d-spacing
of the aromatic systems, while the weak diffraction peak at 12.9
corresponding to the (100) plane resulted because of
interplaner separation. When GCN was oxidized to OGCN,
the peak corresponding to the (002) plane was shifted to a
slightly lower value of 27.1°, which confirms the change in d-
spacing after functionalization of GCN to OGCN. In addition,
the 12.9° peak (present in GCN) was also found to shift
toward a lower value (12.2°) with a sharp increase in intensity
of the peak in the case of OGCN. The sharp and intense peak
at 12.2° resembles the pattern of a similar peak in graphene
oxide, and this assumption could be correlated with the
transformation of GCN to OGCN because of oxidation of the
surface. The PXRD patterns of the Pd-OGCN composite show
peaks corresponding to the OGCN material but the peak for
Pd was not visible because of low loading of the metal and
confirmed the successful synthesis of the material. The peak at
27.2° slightly shifts (from 27.1 in OGCN) because of metal
incorporation but appears same as in OGCN which predicts no
change in interplaner spacing after composite fabrication of Pd
with OGCN.
The synthesis of OGCN from GCN and Pd-loaded Pd-
OGCN was further characterized by Fourier-transform infrared
spectroscopy (Figure 3). In the IR spectrum of GCN, the
broad absorption band in the range of 3100−3300 cm−1
indicates the existence of N−H stretching vibrations, while
the absorption bands in the ranges 1380−1400 and 1600−
12304
Article
Figure 3. IR spectra of GCN, OGCN, and Pd-OGCN nanocomposite
materials.
1630 cm−1 correspond to the C−N and CN stretching
vibrations of the aromatic triazine ring system, respectively.
In the IR spectrum of OGCN, there was a distinctive change
in the absorption bands in the ranges of 3000−3300 and
1600−1620 cm−1. The strong absorption band at 1601 cm−1
was observed in OGCN, which confirms the change in CN
stretching modes of GCN after functionalization. Furthermore,
the intensity of the band in the range 3000−3300 cm−1 was
also enhanced after functionalization of GCN to OGCN,
which confirms the OH stretching vibrations of carboxylic or
hydroxyl groups in addition to N−H vibrations. In the case of
Pd-OGCN, the IR absorption bands are similar to OGCN,
which confirms the retention of chemical functionalities after
Pd-OGCN composite synthesis.
To find out more information of surface functionalization,
we characterized GCN and OGCN by solid-state CP-NMR
(Figure 4). For the bare GCN, only two peaks are observed at
δ 164.0 and δ 155.89, respectively. The peak at δ 164
corresponds to the carbon in the aromatic system attached to
the amine group outside of the ring (i.e., C−NH2). Moreover,
the peak at δ 155.89 corresponds to the carbon atom attached
to bridging nitrogen atoms of heptazine units. In the case of
OGCN, the solid-state 13C NMR signal splits into multiple
peaks which confirm the extensive surface functionalization of
GCN. An increase in the number of signal also suggests the
possibility of functionalization both on edges and the interior
of the heptazine ring system.
Microscopic analyses of GCN, OGCN, and Pd-OGCN were
carried out using scanning tunneling microscopy (SEM), as
shown in Figure 5. It is clearly visible from the SEM images
that GCN consists of wrinkled flower morphology (Figure
5a,b) and OGCN consists of porous bud morphology (Figure
5c,d). However, the morphology in the case of Pd-OGCN has
changed into rod-shaped structures (Figure 5e,f) along with
some porous bud morphology intact. Further morphological
analysis was carried out using tunneling electron microscopy
(TEM), and images are presented in Figure 6. TEM analysis of
GCN (Figure 6a) shows wrinkled morphology similar to SEM
analysis. The morphology of OGCN also confirmed the porous
nature of the material shown (Figure 6b,c).In the case of Pd-
OGCN, the Pd nanoparticles are uniformly distributed onto
the OGCN surface (Figure 6d−f). The presence of Pd
nanoparticles has also been confirmed by the high-resolution
TEM image of Pd-OGCN (Figure 6f), and the average size of
the nanoparticle has been found to be from 2.5 to 4.5 nm.
https://dx.doi.org/10.1021/acsomega.0c00996
ACS Omega 2020, 5, 12302−12312
ACS Omega http://pubs.acs.org/journal/acsodf Article

Figure 4. Solid-state 13C NMR of (a) GCN and (b) OGCN materials.

Figure 5. SEM images of GCN (a,b), OGCN (c,d), and Pd-OGCN (e,f) nanocomposite materials.

Figure 6. TEM images of GCN (a), OGCN (b,c), and Pd-OGCN (d−f) nanocomposite materials.

Furthermore, the elemental composition of the constituent
element present in OGCN and Pd has also been determined
using energy-dispersive spectroscopy analysis, as presented in
Figures S1 and S2 (refer the Supporting Information).
Elemental mapping of the Pd-OGCN material, as shown in
Figure S3, confirms the presence and distribution of carbon,
nitrogen, oxygen, and palladium in the composite material.
The amount of Pd in the material was found to be
approximately ≤1% in the EDAX data. The EDAX data were
12305
also supported by X-ray photoelectron spectroscopy (XPS)
analysis, which also confirmed the amount of Pd to be 0.98%
which is almost similar to EDAX data.
To analyze the surface area of the catalytic materials,
Brunauer−Emmett−Teller (BET) analysis was performed and
data have been presented in Figure 7. By comparing the
adsorption−desorption isotherms of all the partner materials, it
can be observed that OGCN has higher adsorption−
desorption capability in comparison to GCN. The reason for
https://dx.doi.org/10.1021/acsomega.0c00996
ACS Omega 2020, 5, 12302−12312
ACS Omega http://pubs.acs.org/journal/acsodf
Figure 7. Adsorption−desorption isotherms and pore area analysis of materials.
Figure 8. XPS data of different elements in OGCN (a−d) and Pd-OGCN (e−h) materials.
the higher surface area of OGCN could be functionalization of
the GCN surface. The surface areas of GCN and OGCN were
found to be 13.124 and 34.148 m2/g, respectively, which
clearly supports the abovementioned statement (refer Figure
S4). The surface area of Pd-OGCN was found to be 33.691
m2/g, which is almost similar to the surface area of the OGCN
material. Moreover, the pore radius and pore volume of GCN,
OGCN, and Pd-OGCN were calculated to be 21.4, 16.9, and
16.9 Å and 0.013, 0.33, and 0.27 cc/g, respectively. Values of
both the pore radius and pore volume correspond to the
surface areas of the materials.
The XPS technique was employed to know the electronic
state of the elements present in the precursor and catalytic
materials (Figure 8). XPS analyses were performed on bare
OGCN and Pd-OGCN materials to see the incorporation and
change in electronic environment of elements onto the surface
of OGCN after Pd incorporation. Survey spectra (refer Figure
S5) of OGCN and Pd-OGCN show the presence of all the
constituent elements present in the material. Atomic
composition of elements in the materials has been provided
in Table S1. Deconvoluted spectra of constituent elements
have been compiled and presented in Figure 6. In the case of
OGCN, the deconvoluted spectra of C 1s show two
characteristic peaks at 288.5 and 289.1 eV owing to N−C
N and C−N−C components of the material, respectively. The
other peaks at 284.9 and 286.3 eV correspond to the C−C and
12306
Article
C−O bond systems, respectively, in the material which
confirms the oxidation of GCN to form the OGCN material.
The deconvoluted spectra of N 1s show peaks at 399.1 and
400.5 eV representing the CN−C and N(C)3 types of
arrangement of nitrogen atoms in the material, respectively. In
addition, the low intensity peaks at 404.9 and 406.6 eV
correspond to N−O and NO types of arrangements,
respectively. The peaks at 531.6 and 532.2 eV in the spectra
of O 1s correspond to C−O and CO types of linkage,
respectively, in the material contemplating the introduction of
oxygen functionality (in the form of carboxyl or hydroxyl
group) over the surface GCN material. This statement could
also be verified by increased oxygen content (10.12%) in the
material. Moreover, the presence of two distinct peaks at 165.8
and 169.6 in the deconvoluted spectra of S 2p confirms the
presence of −SO2 functionality in the material which could
arise because of H2SO4 of the oxidizing mixture (i.e., HNO3,
H2SO4, and H2O2) used for the synthesis of OGCN.
The peak positions of elements in Pd-OGCN have been
found in the range of 285−290 eV. Deconvoluted C 1s spectra
show an intense peak at 288.2 which corresponds to C−N
bonds. This peak has observed a shift of 0.3 eV from its peak
position in OGCN, which confirmed the change in electronic
environment because of the incorporation of Pd metal onto the
surface. Another low intensity peak at 288.9 eV corresponds to
a typical C−H bond which could be generated because of
https://dx.doi.org/10.1021/acsomega.0c00996
ACS Omega 2020, 5, 12302−12312
ACS Omega http://pubs.acs.org/journal/acsodf Article

reduction of COOH groups of the OGCN during Pd-OGCN that the remaining amount is pure carbon and metal % in the
synthesis. The low intensity peaks at 286.2 eV also observed a material.
slight shift (0.1 eV) from their original position in OGCN,
confirming the change in C−O bond energy after the
formation of the composite with the Pd metal. The
■ CATALYTIC ACTIVITY STUDIES
Hydrogenation of Chemical Functionalities. The Pd-
deconvoluted N 1s spectra of Pd-OGCN witnessed only two OGCN catalyst has been utilized for the formate decom-
prominent peaks at 398.8 and 400.2 eV, respectively, position cum in situ hydrogenation of chemical functionalities
corresponding to CN−C and N(C)3 types of bonding. such as nitro to amines, alkenes to alkanes, imine to amine, and
These peak positions also observed a significant shift (0.3 eV) so forth under mild reaction conditions. To verify the potential
from their original positions in OGCN spectra (i.e., 399.1 and of our developed catalyst for the conversion of nitro
400.5 eV). It was interesting to note that the peak for S 2p functionality to amines, a model reaction of hydrogenation
could not be observed in the case of Pd-OGCN unlike OGCN, of nitrobenzene to aniline was studied (Table 1). Various
where it is approximately 0.53%. This could be due to the
removal of the sulfonic group by the action of KHCO2, which Table 1. Optimization of Reaction Conditions for
was used as a reducing agent in the Pd-OGCN synthesis. The Hydrogenation of the Nitro Group
deconvoluted spectra of O 1s in Pd-OGCN also witnessed a
shift in the peak positions (531.6−531.3 and 532.2−532.7),
which also confirms the change in electronic environment of
oxygen atoms because of the incorporation of Pd metal onto
OGCN. The Pd 3d spectra confirm the presence of Pd metal
on the surface of OGCN, and the loading of the metal was S. no. catalyst optimization metal % temp. time (h) % yield
found to be approximately 0.98 wt %. Peak positions of Pd in
1 gC3N4 (GCN) NA RT 24 0
Pd-OGCN have been found at 335.5 and 340.8 eV,
2 OGCN NA RT 24 0
respectively, and representing Pd 5/2 and Pd 3/2 in the zero
3 Pd-GCN 2 RT 6 81
oxidation state on the material surface. Deconvoluted spectra
4 Pd-GCN 2 60 °C 2 92
of Pd-OGCN also confirmed the presence of some amount of
5 Pd-OGCN 1 RT 6 97
Pd(II) in the material contemplating the bonding of Pd with
6 Pd-OGCN 1 50 °C 2 95
hydroxyl or carbonyl functionalities present on the material
7 Pd-OGCN 1 60 °C 1 96
surface.
8 Pd-OGCN 1 70 °C 1 94
The thermogravimetric analysis (TGA) of GCN, OGCN,
9 Pd-OGCN 0.5 RT 6 58
and PGCN materials has been presented in Figure 9. GCN
10 Pd-OGCN 2 RT 3 98
11 Pd-OGCN 5 RT 1 98
11 Pd/C 5 RT 6 80
12 Pd/C 5 60 °C 2 88
13 Pd/charcoal 5 RT 6 73
14 Pd/charcoal 5 60 °C 2 85

reaction parameters were optimized to see the best reaction

Figure 9. TGA of GCN, OGCN, and Pd-OGCN materials.
shows slight initial weight loss below 120 °C because of the
loss of water molecules in the form of moisture. After that,
GCN remains stable until 540 °C and then starts decreasing its
weight and decomposes to almost below 5 wt % at 750 °C. In
the case of OGCN, the material observes approximately 15%
loss in weight until 300 °C and decreases sharply after that and
complete decomposition occurs at 750 °C. It can be clearly
seen from the TGA graph that OGCN attains stability after
making a composite with Pd. The stability of the Pd-OGCN
nanocomposite remains intermediate ranging between the
stability of GCN and OGCN materials. It is visible that Pd-
OGCN also loses an initial weight of 15% because of the loss
of adsorbed moisture/water molecules until 150 °C. After that,
it remains relatively stable up to 400 °C and loses only 15−
20% weight. Thereafter, it decomposes quickly nearby 450 °C
and loses approximately 97% weight until 600 °C, suggesting
12307
conditions for the developed protocol. The developed Pd-
OGCN nanocomposite catalyst showed the best activity
among various other carbon support-based catalysts used for
hydrogenation of the nitro group to amines (Table 1, S. nos.
1−12). It was interesting to note that Pd-OGCN with ≤1 wt %
Pd showed excellent activity in comparison to similar carbon
support-based catalysts such as Pd−C3N4 and Pd/C (i.e.,
charcoal or activated carbon) catalysts with higher metal
contents. Pd-OGCN catalysts with 1% Pd showed better
catalytic activity in comparison to Pd-GCN (2% Pd) and Pd/C
(5% Pd) catalysts under similar reaction conditions.
Various aromatic nitro compounds could be hydrogenated
using this protocol (Table 2, S. nos. 1−8), and excellent yields
of the products were obtained. A majority of substituted
nitrobenzenes were hydrogenated to the corresponding
substituted anilines in good yields. It was interesting to note
that bromo-substituted nitrobenzene led to dehalogenation in
addition to hydrogenation, while 4-fluoronitrobenzene resulted
in 4-fluoroaniline (Table 2, S. nos. 2 and 3). This could be
correlated to the bond strength of the carbon halogen bond in
different halonitrobenzenes. In addition to 4-methoxy and 4-
methyl nitrobenzenes, this protocol has been found suitable for
hydrogenation of 2-hydroxy and 2-amino nitrobenzene
moieties also (Table 2, S. nos. 7 and 8).
https://dx.doi.org/10.1021/acsomega.0c00996
ACS Omega 2020, 5, 12302−12312
ACS Omega http://pubs.acs.org/journal/acsodf
Table 2. Substrate Scope for Hydrogenation of Nitro Functionality by KHCO2 in the Presence of the Pd-OGCN Catalyst at
Room Temperature
The Pd-OGCN catalyst also showed excellent activity for
hydrogenation of imine and alkenes (Scheme 2). The reactions
were very quick (i.e., 2−4 h reaction time) unlike hydro-
genation of nitrobenzene and were performed under ambient
conditions.
Scheme 2. Pd-OGCN-Catalyzed Hydrogenation of Alkene
and Imine under Ambient Conditions
Various alkenes were hydrogenated by the Pd-OGCN
catalyst using in situ-generated hydrogen to form the
corresponding alkanes (Table 3, S. nos. 1−5). Good yields
of ethyl benzene and 1,2 diphenylethane or bibenzyl were
reported (Table 3, S. nos. 1−3) from the hydrogenation of
styrene and stilbene, respectively. Both cis and trans stilbene
were found to be hydrogenated to bibenzyl. Although
allylbenzene could not be hydrogenated to the corresponding
alkane under similar conditions, all other conjugated alkenes
12308
Article
were hydrogenated to the corresponding alkanes. In addition,
the developed protocol could also be extended for the
hydrogenation of imines to amines (Table 3, S. nos. 6−10)
in a very short reaction time with excellent yields.
After getting insights from the hydrogenation of nitro-
benzene and imines, we designed a model one-pot reaction for
the hydrogenation of nitrobenzene to N-benzylaniline via an
imine intermediate (Scheme 3). In brief, nitrobenzene was
reduced to aniline in the first step followed by in situ reaction
with benzaldehyde to form an imine. The in situ-formed imine
intermediate in the same reaction mixture was reduced to N-
benzylaniline. Hence, the Pd-OGCN catalyst was successfully
utilized for a three-step reaction in one pot. The above-
obtained N-benzylaniline or its derivatives can be used as a
precursor to several drug molecules such as antazole,
chloropyramine, tripelennamine, and so forth which are potent
antihismaines in nature.
Finally, recyclability study (Figure 10) was carried out for
the activity of the Pd-OGCN catalyst and there was no
significant loss of activity even after multiple cycles.
Recyclability study has been conducted on an optimized
model reaction discussed above using 100 mg of the catalyst
and 4 mmol of nitrobenzene. Moreover, it can be seen clearly
that the catalyst is quite efficient even after multiple cycles and
no loss of activity was observed. The apparent loss in the
catalyst amount was observed during centrifugation, washing,
https://dx.doi.org/10.1021/acsomega.0c00996
ACS Omega 2020, 5, 12302−12312
ACS Omega http://pubs.acs.org/journal/acsodf Article

Table 3. Pd-OGCN-Catalyzed Hydrogenation of Alkene and Imine and by KHCO2 at Room Temperature

Scheme 3. Pd-OGCN-Catalyzed One-Pot Synthesis of N-

Benzylaniline from Nitrobenzene and Benzaldehyde

and recollection from centrifugation tubes after the drying

process. The ICP-OES data reconfirmed that there is negligible
leaching (0.0004% or 4 ppm) of the metal after five cycles. Figure 10. Recyclability data of the Pd-OGCN nanocomposite for a
Furthermore, the TGA and PXRD data of the recycled catalyst model hydrogenation reaction.
also support that there was no apparent change in material
after the recycling process and has been presented in Figure S6.
Moreover, EDAX spectra of recycled Pd-OGCN (Figure S7)
12309 https://dx.doi.org/10.1021/acsomega.0c00996
ACS Omega 2020, 5, 12302−12312
ACS Omega http://pubs.acs.org/journal/acsodf
also support the stability of the material, which showed no
significant change after recycling and quantification.
■
CONCLUSIONS
In conclusion, we state that the developed Pd-OGCN catalyst
has been found to act as an efficient catalyst which leads to
decomposition of formates to release hydrogen and results in
hydrogenation of various chemical functionalities. The activity
of this catalyst for the hydrogenation of nitro, imine, and
aromatic olefins confirmed its wide substrate scope and
applicability. The Pd-OGCN catalyst has potential to catalyze
various other in situ hydrogenation reactions also. Further
studies on application of Pd-OGCN for various chemical
transformations are currently ongoing in our laboratory.
■ EXPERIMENTAL SECTION
GCN Synthesis. Graphitic carbon nitride was synthesized
from urea by a conventional method.53 In brief, 10 g of urea
was placed in an alumina crucible and heated up to 550 °C in a
furnace for 3 h. After 3 h, the furnace was allowed to cool
down to room temperature (RT), and the obtained product
(0.45 g) could be used without further purification.
Functionalized Graphitic Carbon Nitride (OGCN)
Synthesis. GCN was functionalized with an optimized ratio
of sulfuric acid, nitric acid, and hydrogen peroxide using a
reported method with some modifications.54 On account of
significant modifications in the synthesis strategy, the material
prepared by this method shows novel patterns in powder X-
ray. In brief, 1 g of GCN was taken in a 250 mL conical flask,
and 20 mL of 1:1 mixture of sulfuric acid and nitric acid was
added to it. The mixture was then stirred for 1 h at RT
followed by dropwise addition of 6 mL of H2O2 (30% w/w in
H2O). The addition of H2O2 witnessed brown color fumes
until the addition completed under stirring at RT. After the
complete addition of H2O2, the mixture was allowed to stir at
RT for another 30 min or until the solution becomes colorless.
Finally, 150 mL of deionized water was added to the
abovementioned mixture which led to the precipitation of a
white color material. The mixture was centrifuged and washed
thoroughly multiple times alternatively with water and acetone.
The material was dried in an oven at 70 °C overnight and
weighed 745 mg in yield.
Palladium-Decorated Functionalized Graphitic Car-
bon Nitride (Pd-OGCN) Synthesis. In a round-bottomed
flask, 1 g of OGCN was taken, and 220 mL of deionized water
was added to it. The mixture was stirred for 4−6 h at RT
followed by the addition of 12 mL of aqueous KHCO2 solution
(2 M) and different amounts (i.e., 11.1, 22.2, 44.5, and 89 mg)
of PdCl2 dissolved in 20 mL of H2O. The abovementioned
mixture was further stirred at RT for 24 h. After 24 h, the
mixture was centrifuged and washed thoroughly with ethanol
and deionized water. Finally, the obtained gray-colored
material was kept for drying in an oven at 70 °C overnight
to yield 700−720 mg of the nanocomposite material. These
materials were given the names Pd-OGCN (11), Pd-OGCN
(22), Pd-OGCN (44), and Pd-OGCN (89), depending upon
the amount (in mg) of PdCl2 used.
Hydrogenation of Chemical Functionalities. In a sealed
reaction tube, 1.0 mmol of the substrate (i.e., nitro, alkene, or
imine) was placed and dissolved in 5 mL of ethanol. To this,
25 mg of the Pd-OGCN catalyst and 300 mg of KHCO2 were
added, and the reactants were stirred at RT-60 °C until the
12310
Article
completion of reaction monitored by thin layer chromatog-
raphy. After completion of the reaction, all the products were
extracted with dichloromethane or ethyl acetate and the
catalyst was washed multiple times with water and ethanol
followed by heating at 70 °C overnight to use in the next cycle.
One-Pot Synthesis of N-Benzylaniline. In a sealed reaction
tube, 1.1 mmol of nitrobenzene and 1.0 mmol of benzaldehyde
were dissolved in 10 mL of ethanol. To this, 40 mg of the Pd-
OGCN catalyst and 500 mg of KHCO2 were added, and the
reactants were stirred for 3 h at RT. After 3 h, 4 mL of
dichloromethane (DCM) was added to the reaction mixture
and stirred at RT for another 2−3 h until reaction completes.
The progress of reaction was monitored by thin layered
chromatography. After completion of the reaction, the catalyst
was filtered off and the product was extracted with DCM or
ethyl acetate and dried using a rotary evaporator. The product
was confirmed by 1H and 13C NMR spectroscopy.
Note: The abovementioned reaction forms a viscous gel
kind of mixture after the reduction of nitrobenzene to aniline.
This gel matrix seizes the stirring of the magnetic stir bar and
interferes in the reaction to proceed further. Hence, DCM was
added to the abovementioned reaction after 3 h.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsomega.0c00996.
Instrumentation details; EDAX data; elemental map-
ping; BET parameters; XPS survey spectra and
associated atomic composition table; and PXRD, TGA,
and TEM data of the recycled catalyst (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Ashish Bahuguna − Casali Center of Applied Chemistry,
Institute of Chemistry, The Hebrew University of Jerusalem,
Jerusalem 91904, Israel; orcid.org/0000-0001-5542-1708;
Email: ashish.bahuguna@mail.huji.ac.il
Author
Yoel Sasson − Casali Center of Applied Chemistry, Institute of
Chemistry, The Hebrew University of Jerusalem, Jerusalem
91904, Israel
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.0c00996
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
Authors acknowledge the Casali Center of Applied Chemistry
and Nano Center of The Hebrew University for the
instrumentation facilities.
■
REFERENCES
(1) Höök, M.; Tang, X. Depletion of fossil fuels and anthropogenic
climate changeA review. Energy Policy 2013, 52, 797−809.
(2) Bilgen, S. Structure and environmental impact of global energy
consumption. Renewable and Sustainable Energy Reviews 2014, 38,
890−902.
(3) Singh, S.; Jain, S.; Venkateswaran, P.; Tiwari, A. K.; Nouni, M.
R.; Pandey, J. K.; Goel, S. Hydrogen: A sustainable fuel for future of
https://dx.doi.org/10.1021/acsomega.0c00996
ACS Omega 2020, 5, 12302−12312
ACS Omega http://pubs.acs.org/journal/acsodf
the transport sector. Renewable and Sustainable Energy Reviews 2015,
51, 623−633.
(4) Momirlan, M.; Veziroglu, T. The properties of hydrogen as fuel
tomorrow in sustainable energy system for a cleaner planet. Int. J.
Hydrogen Energy 2005, 30, 795−802.
(5) Andrews, J.; Shabani, B. The role of hydrogen in a global
sustainable energy strategy. Wiley Interdiscip. Rev.: Energy Environ.
2014, 3, 474−489.
(6) Edwards, P. P.; Kuznetsov, V. L.; David, W. I. F.; Brandon, N. P.
Hydrogen and fuel cells: towards a sustainable energy future. Energy
Policy 2008, 36, 4356−4362.
(7) Verhelst, S. Recent progress in the use of hydrogen as a fuel for
internal combustion engines. Int. J. Hydrogen Energy 2014, 39, 1071−
1085.
(8) Ramachandran, R.; Menon, R. K. An overview of industrial uses
of hydrogen. Int. J. Hydrogen Energy 1998, 23, 593−598.
(9) Sharma, S.; Ghoshal, S. K. Hydrogen the future transportation
fuel: from production to applications. Renewable Sustainable Energy
Rev. 2015, 43, 1151−1158.
(10) Kothari, R.; Buddhi, D.; Sawhney, R. L. Comparison of
environmental and economic aspects of various hydrogen production
methods. Renewable and Sustainable Energy Reviews 2008, 12, 553−
563.
(11) Bičaḱ ová, O.; Straka, P. Production of hydrogen from
renewable resources and its effectiveness. Int. J. Hydrogen Energy
2012, 37, 11563−11578.
(12) Turner, J.; Sverdrup, G.; Mann, M. K.; Maness, P.-C.; Kroposki,
B.; Ghirardi, M.; Evans, R. J.; Blake, D. Renewable hydrogen
production. Int. J. Energy Res. 2008, 32, 379−407.
(13) Wang, J.; Wan, W. Factors influencing fermentative hydrogen
production: a review. Int. J. Hydrogen Energy 2009, 34, 799−811.
(14) Niaz, S.; Manzoor, T.; Pandith, A. H. Hydrogen storage:
Materials, methods and perspectives. Renewable and Sustainable Energy
Reviews 2015, 50, 457−469.
(15) Dalebrook, A. F.; Gan, W.; Grasemann, M.; Moret, S.;
Laurenczy, G. Hydrogen storage: beyond conventional methods.
Chem. Commun. 2013, 49, 8735−8751.
(16) Eberle, U.; Felderhoff, M.; Schüth, F. Chemical and physical
solutions for hydrogen storage. Angew. Chem., Int. Ed. 2009, 48,
6608−6630.
(17) Umegaki, T.; Yan, J.-M.; Zhang, X.-B.; Shioyama, H.; Kuriyama,
N.; Xu, Q. Boron-and nitrogen-based chemical hydrogen storage
materials. Int. J. Hydrogen Energy 2009, 34, 2303−2311.
(18) Lan, R.; Irvine, J. T. S.; Tao, S. Ammonia and related chemicals
as potential indirect hydrogen storage materials. Int. J. Hydrogen
Energy 2012, 37, 1482−1494.
(19) Yadav, M.; Xu, Q. Liquid-phase chemical hydrogen storage
materials. Energy Environ. Sci. 2012, 5, 9698−9725.
(20) Papp, G.; Csorba, J.; Laurenczy, G.; Joó, F. A charge/discharge
device for chemical hydrogen storage and generation. Angew. Chem.,
Int. Ed. 2011, 50, 10433−10435.
(21) Wang, X.; Qi, G.-W.; Tan, C.-H.; Li, Y.-P.; Guo, J.; Pang, X.-J.;
Zhang, S.-Y. Pd/C nanocatalyst with high turnover frequency for
hydrogen generation from the formic acid−formate mixtures. Int. J.
Hydrogen Energy 2014, 39, 837−843.
(22) Loges, B.; Boddien, A.; Gärtner, F.; Junge, H.; Beller, M.
Catalytic generation of hydrogen from formic acid and its derivatives:
useful hydrogen storage materials. Top. Catal. 2010, 53, 902−914.
(23) Zaidman, B.; Wiener, H.; Sasson, Y. Formate salts as chemical
carriers in hydrogen storage and transportation. Int. J. Hydrogen
Energy 1986, 11, 341−347.
(24) Wang, Z.-L.; Yan, J.-M.; Wang, H.-L.; Ping, Y.; Jiang, Q. Pd/C
synthesized with citric acid: an efficient catalyst for hydrogen
generation from formic acid/sodium formate. Sci. Rep. 2012, 2, 598.
(25) Wiener, H.; Sasson, Y.; Blum, J. Palladium-catalyzed
decomposition of aqueous alkali metal formate solutions. J. Mol.
Catal. 1986, 35, 277−284.
(26) Treigerman, Z.; Sasson, Y. Generation and Quantification of
Formate Ion Produced from Aqueous Sodium Bicarbonate in the
12311
Article
Presence of Homogeneous Ruthenium Catalyst. ACS Omega 2018, 3,
12797−12801.
(27) Bahuguna, A.; Kumar, A.; Krishnan, V. Carbon-Support-Based
Heterogeneous Nanocatalysts: Synthesis and Applications in Organic
Reactions. Asian J. Org. Chem. 2019, 8, 1263−1305.
(28) White, R. J.; Luque, R.; Budarin, V. L.; Clark, J. H.; Macquarrie,
D. J. Supported metal nanoparticles on porous materials. Methods
and applications. Chem. Soc. Rev. 2009, 38, 481−494.
(29) Li, X.-H.; Antonietti, M. Metal nanoparticles at mesoporous N-
doped carbons and carbon nitrides: functional Mott−Schottky
heterojunctions for catalysis. Chem. Soc. Rev. 2013, 42, 6593−6604.
(30) Polshettiwar, V.; Varma, R. S. Green chemistry by nano-
catalysis. Green Chem. 2010, 12, 743−754.
(31) Polshettiwar, V.; Basset, J.-M.; Astruc, D. Editorial: Nano-
science Makes Catalysis Greener. ChemSusChem 2012, 5, 6−8.
(32) 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, 51, 68−89.
(33) Zheng, Y.; Lin, L.; Wang, B.; Wang, X. Graphitic carbon nitride
polymers toward sustainable photoredox catalysis. Angew. Chem., Int.
Ed. 2015, 54, 12868−12884.
(34) Wang, X.; Blechert, S.; Antonietti, M. Polymeric graphitic
carbon nitride for heterogeneous photocatalysis. ACS Catal. 2012, 2,
1596−1606.
(35) Cao, S.; Low, J.; Yu, J.; Jaroniec, M. Polymeric photocatalysts
based on graphitic carbon nitride. Adv. Mater. 2015, 27, 2150−2176.
(36) Gong, Y.; Li, M.; Li, H.; Wang, Y. Graphitic carbon nitride
polymers: promising catalysts or catalyst supports for heterogeneous
oxidation and hydrogenation. Green Chem. 2015, 17, 715−736.
(37) Baig, R. B. N.; Verma, S.; Nadagouda, M. N.; Varma, R. S.
Room temperature synthesis of biodiesel using sulfonated graphitic
carbon nitride. Sci. Rep. 2016, 6, 39387.
(38) Verma, S.; Baig, R. B. N.; Nadagouda, M. N.; Len, C.; Varma,
R. S. Sustainable pathway to furanics from biomass via heterogeneous
organo-catalysis. Green Chem. 2017, 19, 164−168.
(39) Zhang, P.; Li, H.; Wang, Y. Post-functionalization of graphitic
carbon nitrides by grafting organic molecules: toward C−H bond
oxidation using atmospheric oxygen. Chem. Commun. 2014, 50,
6312−6315.
(40) Wu, M.; Wang, Q.; Sun, Q.; Jena, P. Functionalized graphitic
carbon nitride for efficient energy storage. J. Phys. Chem. C 2013, 117,
6055−6059.
(41) Peng, H.-L.; Zhong, F.-Y.; Zhang, J.-B.; Zhang, J.-Y.; Wu, P.-K.;
Huang, K.; Fan, J.-P.; Jiang, L.-L. Graphitic carbon nitride
functionalized with polyethylenimine for highly effective capture of
carbon dioxide. Ind. Eng. Chem. Res. 2018, 57, 11031−11038.
(42) Bahuguna, A.; Kumar, A.; Chhabra, T.; Kumar, A.; Krishnan, V.
Potassium-Functionalized Graphitic Carbon Nitride Supported on
Reduced Graphene Oxide as a Sustainable Catalyst for Knoevenagel
Condensation. ACS Appl. Nano Mater. 2018, 1, 6711−6723.
(43) Bahuguna, A.; Kumar, A.; Kumar, S.; Chhabra, T.; Krishnan, V.
2D-2D nanocomposite of MoS2-graphitic carbon nitride as multi-
functional catalyst for sustainable synthesis of C3-functionalized
indoles. ChemCatChem 2018, 10, 3121−3132.
(44) Bahuguna, A.; Choudhary, P.; Chhabra, T.; Krishnan, V.
Ammonia-Doped Polyaniline−Graphitic Carbon Nitride Nanocom-
posite as a Heterogeneous Green Catalyst for Synthesis of Indole-
Substituted 4 H-Chromenes. ACS Omega 2018, 3, 12163−12178.
(45) Chhabra, T.; Bahuguna, A.; Dhankhar, S. S.; Nagaraja, C. M.;
Krishnan, V. Sulfonated graphitic carbon nitride as a highly selective
and efficient heterogeneous catalyst for the conversion of biomass-
derived saccharides to 5-hydroxymethylfurfural in green solvents.
Green Chem. 2019, 21, 6012−6026.
(46) Wang, Y.; Yao, J.; Li, H.; Su, D.; Antonietti, M. Highly selective
hydrogenation of phenol and derivatives over a Pd@ carbon nitride
catalyst in aqueous media. J. Am. Chem. Soc. 2011, 133, 2362−2365.
https://dx.doi.org/10.1021/acsomega.0c00996
ACS Omega 2020, 5, 12302−12312
ACS Omega http://pubs.acs.org/journal/acsodf Article

(47) Gong, Y.; Zhang, P.; Xu, X.; Li, Y.; Li, H.; Wang, Y. A novel
catalyst Pd@ ompg-C3N4 for highly chemoselective hydrogenation of
quinoline under mild conditions. J. Catal. 2013, 297, 272−280.
(48) Deng, D.; Yang, Y.; Gong, Y.; Li, Y.; Xu, X.; Wang, Y. Palladium
nanoparticles supported on mpg-C 3 N 4 as active catalyst for
semihydrogenation of phenylacetylene under mild conditions. Green
Chem. 2013, 15, 2525−2531.
(49) Li, Y.; Xu, X.; Zhang, P.; Gong, Y.; Li, H.; Wang, Y. Highly
selective Pd@ mpg-C 3 N 4 catalyst for phenol hydrogenation in
aqueous phase. RSC Adv. 2013, 3, 10973−10982.
(50) Chen, Y.; Kong, X.; Mao, S.; Wang, Z.; Gong, Y.; Wang, Y.
Study of the role of alkaline sodium additive in selective hydro-
genation of phenol. Chin. J. Catal. 2019, 40, 1516−1524.
(51) Sharma, P.; Sasson, Y. A photoactive catalyst Ru−gC 3 N 4 for
hydrogen transfer reaction of aldehydes and ketones. Green Chem.
2017, 19, 844−852.
(52) Sharma, P.; Sasson, Y. Sustainable visible light assisted in situ
hydrogenation via a magnesium−water system catalyzed by a Pd-gC 3
N 4 photocatalyst. Green Chem. 2019, 21, 261−268.
(53) Liu, J.; Zhang, T.; Wang, Z.; Dawson, G.; Chen, W. Simple
pyrolysis of urea into graphitic carbon nitride with recyclable
adsorption and photocatalytic activity. J. Mater. Chem. 2011, 21,
14398−14401.
(54) Kumar, R.; Barakat, M.; Alseroury, F. Oxidized gC 3 N 4/
polyaniline nanofiber composite for the selective removal of
hexavalent chromium. Sci. Rep. 2017, 7, 12850.

12312 https://dx.doi.org/10.1021/acsomega.0c00996
ACS Omega 2020, 5, 12302−12312