Fuel Processing Technology 264 (2024) 108133

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Fuel Processing Technology

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

Pd nanocatalyst supported on amine-functionalized mesoporous graphitic

carbon nitride for formic acid hydrogen generator in the polymer
electrolyte membrane fuel cell system
Tae Hoon Lee a, Seong Mo Yun b , Min Jae Kim b, Gibeom Kim c , Eun Sang Jung c ,
Taek Hyun Oh d,*
a
Hydrogen Fuel Cell System Lab, Hydrogen Fuel Cell Technology R&D Department, Future Powertrain Technologies Research Laboratory, Korea Automotive Technology
Institute, 86 Gongdan-ro 474beon-gil, Seongsan-gu, Changwon 51577, Republic of Korea
b
Department of Smart Manufacturing Engineering, Graduate School of Engineering, Changwon National University, 20 Changwondaehak-ro, Uichang-gu, Changwon
51140, Republic of Korea
c
Department of Bioenvironmental Energy, College of Life and Resources Science, Pusan National University, 1268-50 Samnangjin-ro, Miryang 50463, Republic of Korea
d
Department of Mechanical Engineering, College of Mechatronics, Changwon National University, 20 Changwondaehak-ro, Uichang-gu, Changwon 51140, Republic of
Korea

A R T I C L E I N F O A B S T R A C T

Keywords: Pd nanocatalyst supported on amine-functionalized mesoporous graphitic carbon nitride (Pd/NH2-mpg-C3N4)

Palladium nanocatalyst was investigated for dehydrogenation of formic acid. The catalyst was analyzed and tested to investigate the
Amine-functionalized mesoporous graphitic effect of amine functionalization on hydrogen generation from formic acid. Pd nanocatalyst was dispersed
carbon nitride
uniformly on NH2-mpg-C3N4 without agglomeration. The turnover frequency value of Pd/NH2-mpg-C3N4 was
Formic acid
Dehydrogenation
1870 h− 1, which was higher than that of Pd/mpg-C3N4 because of the amine functionalization. The Pd/NH2-mpg-
Hydrogen generator C3N4 was also tested to investigate the effect of various reaction conditions (formic acid concentration, sodium
Polymer electrolyte membrane fuel cell formate concentration, and reaction temperature) on hydrogen generation from formic acid. Formic acid con­
centration negatively affected the catalytic activity, whereas sodium formate concentration positively affected it.
Reaction temperature significantly affected the catalytic activity. The apparent activation energy of the Pd/NH2-
mpg-C3N4 catalyst was 60.7 kJ mol− 1, and a hydrogen generator with the catalyst exhibited high conversion
efficiency at an elevated temperature. Consequently, a hydrogen generator with Pd/NH2-mpg-C3N4 is suitable for
polymer electrolyte membrane fuel cell systems.

1. Introduction storage capacity and low cost [6–8]. However, benzene, toluene, and
naphthalene are difficult to handle because of their toxicity. In contrast,
Because of its many advantages, hydrogen is considered a sustain­ formic acid is a promising hydrogen storage material for PEMFCs
able energy source that may be used to replace fossil fuels in the future because of its relatively high hydrogen storage capacity (4.4 wt%) and
[1]. Hydrogen is an abundant source of energy because it can be low toxicity compared to other LOCHs [9].
generated from water [2]. It has a high energy density (120 MJ kg− 1) [3] Formic acid can be decomposed via two reaction pathways. Eq. (1)
and can be converted into electrical energy efficiently and simply using describes the dehydrogenation of formic acid, and Eq. (2) describes the
polymer electrolyte membrane fuel cells (PEMFCs). However, the low dehydration of formic acid. It is crucial to design catalysts that favor the
energy density of compressed gaseous hydrogen and the high cost of dehydrogenation pathway because the carbon monoxide generated from
liquid hydrogen have been considered technical challenges hindering formic acid dehydration can poison and degrade PEMFC catalysts [10].
commercialization of PEMFCs [4,5]. Therefore, catalysts with superior catalytic selectivity and activity are
Liquid organic hydrogen carriers (LOHCs) such as benzene, toluene, required for dehydrogenation of formic acid.
naphthalene, and formic acid have attracted attention as hydrogen
HCOOH→H2 + CO2 (1)
storage materials for PEMFCs because of their relatively high hydrogen

* Corresponding author.
E-mail address: [email protected] (T.H. Oh).

https://doi.org/10.1016/j.fuproc.2024.108133
Received 12 June 2024; Received in revised form 11 September 2024; Accepted 15 September 2024
Available online 24 September 2024
0378-3820/© 2024 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
T.H. Lee et al. Fuel Processing Technology 264 (2024) 108133

example, monometallic Pd catalysts [16–27], bimetallic catalysts (PdAg

[28–37], PdAu [37–43], PdCo [44], PdW [45]), and trimetallic catalysts
(PdAuCo [46,47], PdAuNi [48], PdCoNi [49]) have been investigated
for dehydrogenation of formic acid.
Furthermore, researchers have investigated amine-functionalized Pd
catalysts to improve catalytic activity. Gao et al. [50] investigated ul­
trafine CrPd nanoparticles supported on MIL-101-NH2 for dehydroge­
nation of formic acid. Cr0.4Pd0.6/MIL-101-NH2 had an excellent
turnover frequency (TOF) of 2009 h− 1 at 50 ◦ C. Bulut et al. [51]
developed Pd-MnOx/SiO2-NH2 with a TOF of 1300 h− 1 at 50 ◦ C.
Moreover, Zhao et al. [52] developed Pd/NH2-rGO with a TOF of 767
h− 1 at 25 ◦ C. Generally, the TOF value of amine-functionalized catalysts
has been higher than that of non-functionalized catalysts. Although
some researchers have investigated amine-functionalized Pd catalysts,
Fig. 1. Experimental setup for the hydrogen generation test.
Pd nanocatalyst supported on amine-functionalized mesoporous
graphitic carbon nitride (Pd/NH2-mpg-C3N4) has rarely been studied for
HCOOH→H2 O + CO (2) dehydrogenation of formic acid.
Thus, Pd/NH2-mpg-C3N4 was investigated for dehydrogenation of
Many researchers have developed heterogeneous catalysts with su­
formic acid in this study. The catalyst was characterized using various
perior catalytic selectivity and activity for dehydrogenation of formic
analytical methods, and the catalytic activity of the catalyst was eval­
acid. Catalysts based on noble metals such as gold [11–14], rhodium
uated and compared with those of other catalysts. Furthermore, the
[14], ruthenium [15], and palladium [16–49] have been studied
catalyst was tested under various reaction conditions (formic acid con­
extensively for this purpose. Among the catalysts, palladium-based
centration, sodium formate concentration, and reaction temperature) to
heterogeneous catalysts have attracted considerable attention because
investigate the effect of the reaction conditions on dehydrogenation of
of their superior catalytic selectivity and activity, which result from the
formic acid. Finally, a hydrogen generator with Pd/NH2-mpg-C3N4 for
low energy barrier for dehydrogenation of formic acid [27]. For
PEMFCs was validated by hydrogen generation test without any

Fig. 2. Experimental setup for the hydrogen generator test.

Scheme 1. Schematic illustration for the fabrication of Pd/mpg-C3N4 and Pd/NH2-mpg-C3N4.

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T.H. Lee et al. Fuel Processing Technology 264 (2024) 108133

Fig. 3. TEM images of catalyst supports and catalysts: (a) mpg-C3N4, (b) NH2-mpg-C3N4, (c) Pd/mpg-C3N4, and (d) Pd/NH2-mpg-C3N4.

additives. furnace at a rate of 200 mL min− 1 during the heat treatment process. The
resulting product was immersed in aqueous NH4HF2 solution (4 M),
2. Experimental after which the product was stirred at room temperature for 24 h to
remove silica particles. Finally, the mpg-C3N4 was filtered and washed
2.1. Chemicals with distilled water and ethanol. Then, it was stored at 40 ◦ C in a vac­
uum oven until catalyst evaluation.
The following chemicals were used in this study: cyanamide
(NH2CN, 99 %, Sigma-Aldrich, USA), Ludox HS-40 colloidal silica (SiO2, 2.2.2. Synthesis of Pd/mpg-C3N4
40 wt%, Sigma-Aldrich, USA), ammonium hydrogen difluoride The as-prepared mpg-C3N4 (0.5 g) was dispersed in distilled water
(NH4HF2, 95 %, Sigma-Aldrich, USA), distilled water (H2O, Samchun (150 mL). Then, Pd (II) nitrate dihydrate (0.063 g) was added to the
Chemical, Korea), ethanol (C2H5OH, 99.5 %, Samchun Chemical, mixture, which was stirred for 30 min. Subsequently, NaBH4 solution
Korea), Pd (II) nitrate dihydrate (Pd(NO3)2⋅2H2O, Sigma-Aldrich, USA), (30 mL) with a molar ratio of 16 (NaBH4):1 (catalyst precursor) was
sodium borohydride (NaBH4, 98.0 %, Samchun Chemical, Korea), (3- injected into the catalyst solution by syringe pump for 1 h. From the
Aminopropyl)triethoxysilane (APTES, H2N(CH2)3Si(OC2H5)3, 99 %, beginning of NaBH4 injection, the mixture including NaBH4 solution was
Sigma-Aldrich, USA), sodium citrate tribasic dehydrate (HOC(COONa) agitated with a magnetic stirrer for 2 h. The resulting product was
(CH2COONa)2•2H2O, ≥99.0 %, Sigma-Aldrich, USA), formic acid filtered and washed with distilled water and ethanol. Then, the Pd on
(HCOOH, >98.0 %, Junsei, Japan), silica gel (SiO2, Samchun Chemical, mpg-C3N4 (Pd/mpg-C3N4) was stored at 40 ◦ C in a vacuum oven until
Korea), and sodium formate (HCOONa, 98.0 %, Junsei, Japan). All of the catalyst evaluation.
chemicals were used without further purification.
2.2.3. Synthesis of NH2-mpg-C3N4
The as-prepared mpg-C3N4 (0.5 g) was dispersed in distilled water
2.2. Synthesis
(150 mL). Then, APTES (0.534 g) was added to the mixture, which was
stirred for 30 min. The resulting product was filtered and washed with
2.2.1. Synthesis of mpg-C3N4
distilled water and ethanol. Then, the amine-functionalized mpg-C3N4
The mesoporous graphitic carbon nitride (mpg-C3N4) was prepared
(NH2-mpg-C3N4) was stored at 40 ◦ C in a vacuum oven until catalyst
following the hard template method described in previous work [21].
evaluation.
Cyanamide (5 g) was added to the Ludox HS-40 colloidal silica (12.5 g),
and the mixture was stirred at 80 ◦ C for 6 h. After that, the white powder
2.2.4. Synthesis of Pd/NH2-mpg-C3N4
was heated in a furnace at a rate of 2.2 ◦ C min− 1 to 550 ◦ C and main­
The Pd on NH2-mpg-C3N4 (Pd/NH2-mpg-C3N4) was prepared
tained at 550 ◦ C for an additional 4 h. Nitrogen gas was supplied to the

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T.H. Lee et al. Fuel Processing Technology 264 (2024) 108133

2.4. Catalyst evaluation

Dehydrogenation of formic acid was performed to evaluate the cat­

alytic activity. Fig. 1 shows the experimental setup used for the
hydrogen generation test. First, the as-prepared catalyst (30 mg) was
added to distilled water in a 25 mL two-necked round-bottom flask. The
mixture was stirred and maintained at 55.1 ± 1.4 ◦ C using a hot plate.
Once the reaction temperature was achieved, formic acid was injected
into the flask. The mass of formic acid solution (formic acid + distilled
water) was 2.5 g. The volume of gas generated from dehydrogenation of
formic acid was measured using a volume flow meter.
The catalytic activity was evaluated quantitatively using the TOF,
which is expressed in Eq. (3):
Patm Vgas 1
TOF = × (3)
2RTnPd t

where Patm is the atmospheric pressure, Vgas is the volume of gas

generated when the conversion rate reaches 20 %, R is the universal gas
constant, T is the ambient temperature, npd is the number of moles of Pd
in the catalyst, and t is the reaction time when the conversion rate
reaches 20 %.

2.5. Hydrogen generator test

The experimental setup for the hydrogen generator test was similar
to that used in a previous study [54]. Fig. 2 shows the experimental
setup for the hydrogen generator test. First, the as-prepared catalyst (6
g) was added to distilled water in a 500 mL round-bottom flask. The
mixture was stirred and maintained at 55.7 ± 0.8 ◦ C using a hot plate.
Once the reaction temperature was attained, formic acid in the syringe
was injected into the flask by a syringe pump. The impurities and
moisture in the generated gas were removed by water and silica gel,
respectively. The volume of gas generated by the dehydrogenation of
formic acid was measured using a volumetric flow meter. The temper­
atures of the mixture and the gas were measured using K-type
thermocouples.
Fig. 4. Microstructure of catalyst supports and catalysts: (a) catalyst supports The conversion efficiency was used to evaluate the performance of
and (b) catalysts. the hydrogen generator quantitatively. Eq. (4) represents the conversion
efficiency:
following previous work [53]. The as-prepared mpg-C3N4 (0.5 g) was Total amount of generated gas (L)
dispersed in distilled water (150 mL). Then, sodium citrate (0.940 g) and Conversion efficiency (%) = × 100
Theoretical amount of gas (L)
APTES (0.534 g) were added to the mixture, which was stirred for 30
(4)
min. After stirring, Pd (II) nitrate dihydrate (0.063 g) was added to the
mixture, which was stirred for an additional 30 min. Subsequently,
3. Results and discussion
NaBH4 solution (30 mL) with a molar ratio of 16 (NaBH4):1 (catalyst
precursor) was injected into the catalyst solution by syringe pump for 1
3.1. Catalyst characterization
h. From the beginning of NaBH4 injection, the mixture including NaBH4
solution was agitated with a magnetic stirrer for 2 h. The resulting
The mpg-C3N4, NH2-mpg-C3N4, Pd/mpg-C3N4, and Pd/NH2-mpg-
product was filtered and washed with distilled water and ethanol. Then,
C3N4 were prepared to investigate the characteristics of the catalysts
the Pd/NH2-mpg-C3N4 was stored at 40 ◦ C in a vacuum oven until
supports and catalysts for dehydrogenation of formic acid, as shown in
catalyst evaluation.
Scheme 1. Figs. 3(a) and (b) show the morphology of the catalyst sup­
ports. The mpg-C3N4 and NH2-mpg-C3N4 have large numbers of pores,
2.3. Catalyst characterization which is a similar morphological characteristic. Figs. 3(c) and (d) show
the morphology of the catalysts. Pd/mpg-C3N4 has aggregated Pd par­
The morphology of catalyst supports and catalysts was investigated ticles (4.5 ± 2.4 nm) as shown in the red circles in Fig. 3(c). However,
by transmission electron microscopy (TEM, JEM-2100F, Jeol, Japan). Pd/NH2-mpg-C3N4 has relatively well-dispersed Pd particles (3.2 ± 2.2
The microstructure of catalyst supports and catalysts was characterized nm), as shown in Fig. 3(d). The relatively uniform distribution was due
by X-ray diffraction (XRD, X'Pert PRO MPD, Malvern Panalytical, UK), to the influence of sodium citrate and APTES, a result similar to the
and their chemical state was analyzed by X-ray photoelectron spec­ result of a previous study [53]. Thus, the amine did not affect the
troscopy (XPS, AXIS SUPRA+, Kratos Analytical, UK). The surface area morphological characteristic of the catalysts supports but did affect the
of catalyst supports and catalysts was determined by the Bru­ Pd particle distribution of the catalysts.
nauer–Emmett–Teller (BET, BELSORP-max II, Microtrac MRB, USA) Fig. 4(a) shows the microstructure of the catalyst supports, which
method. The Pd amount of catalysts was analyzed by inductively had two diffraction peaks at 12.8◦ and 27.8◦ , corresponding to the (100)
coupled plasma optical emission spectroscopy (ICP-OES, 720, Agilent, and (002) planes of g-C3N4, respectively. Fig. 4(b) shows the micro­
USA). structure of the catalysts. The catalysts had an additional two diffraction

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T.H. Lee et al. Fuel Processing Technology 264 (2024) 108133

Fig. 5. XPS spectra of catalyst supports and catalysts: (a–b) full spectrum, (c–d) Si 2p, and (e) Pd 3d.

peaks at 39.5◦ and 45.6◦ , corresponding to the (111) and (200) planes of
Table 1 Pd, respectively. The diffraction peaks at 39.5◦ and 45.6◦ were much
Specific surface area of catalyst supports and catalysts.
lower than the diffraction peak at 27.8◦ because the amount of loaded
Catalyst supports and catalysts Specific surface area (m2 g− 1) Pd was smaller than that of carbon. The microstructures of the catalyst
mpg-C3N4 174.4 supports and catalysts were similar to those of previous research
NH2-mpg-C3N4 92.0 [55,56].
Pd/mpg-C3N4 185.4 Fig. 5 shows the chemical states and electronic effects of the catalyst
Pd/NH2-mpg-C3N4 134.3
supports (mpg-C3N4 and NH2-mpg-C3N4) and catalysts (Pd/mpg-C3N4
and Pd/NH2-mpg-C3N4). NH2-mpg-C3N4 and Pd/NH2-mpg-C3N4
exhibited peaks corresponding to Si 2s and Si 2p originated from the
Table 2 amine-functionalization, whereas mpg-C3N4 and Pd/mpg-C3N4 did not
Weight percentage of Pd loaded on catalyst support.
exhibit these peaks in full spectrum [53]. As shown in Figs. 5(c) and (d),
Catalysts Manufacture (wt%) Analysis (wt%) NH2-mpg-C3N4 and Pd/NH2-mpg-C3N4 exhibited the Si 2p3/2 peak at
Pd/mpg-C3N4 4.8 4.0 99.8 eV. The result confirms that the amine was well functionalized on
Pd/NH2-mpg-C3N4 4.8 4.0 mpg-C3N4 [53]. Fig. 5(e) presents the Pd 3d peaks of the catalysts. The

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T.H. Lee et al. Fuel Processing Technology 264 (2024) 108133

occurred because small Pd particles were relatively well dispersed on

NH2-mpg-C3N4 owing to sodium citrate and APTES, as shown in Fig. 3
(d).
Table 2 presents the weight percentage of Pd loaded on the catalyst
support. Because the catalyst was manufactured to a mass ratio of 1 (Pd):
20 (catalyst support), the intended weight percentage of Pd loaded on
catalyst support was 4.8 wt%. However, the measured weight percent­
age of Pd loaded on the catalyst support was 4.0 wt%. Thus, Pd was
relatively well reduced on the catalyst support by a reducing agent.

3.2. Catalytic activity of the Pd/NH2-mpg-C3N4

The catalytic activities of mpg-C3N4, NH2-mpg-C3N4, Pd/mpg-C3N4,

Pd/NH2-mpg-C3N4, and Pd/C were evaluated to compare the catalytic
activity of Pd/NH2-mpg-C3N4 with those of others. The hydrogen gen­
eration test was conducted at 55.0 ± 0.8 ◦ C.
Fig. 6(a) presents the volume of gas (CO2 + H2) generated from the
dehydrogenation of formic acid without any additive. As shown in Fig. 6
(a), Pd/mpg-C3N4, Pd/NH2-mpg-C3N4, and Pd/C showed catalytic ac­
tivity for dehydrogenation of formic acid. However, the catalyst sup­
ports (mpg-C3N4 and NH2-mpg-C3N4) were inactive for
dehydrogenation of formic acid. Thus, Pd played an important role in
the dehydrogenation.
Fig. 6(b) shows TOF values of the catalysts. The TOF values were as
follows: Pd/NH2-mpg-C3N4 (1870 h− 1) > Pd/mpg-C3N4 (513 h− 1) > Pd/
C (91 h− 1). Pd/NH2-mpg-C3N4 had higher catalytic activity than Pd/
mpg-C3N4 and Pd/C for dehydrogenation of formic acid. This is a result
of the synergistic interaction between the Pd and amine-functionalized
catalyst support, which results in the uniform distribution of Pd parti­
cles [43]. Table 3 shows a comparison of the TOF values among the
various catalysts. In comparison with the amine-functionalized cata­
lysts, the TOF value of Pd/NH2-mpg-C3N4 was slightly lower than that of
Cr0.4Pd0.6/MIL-101-NH2 but higher than that of Pd-MnOx/SiO2-NH2
[50,51]. The TOF value of Pd/NH2-mpg-C3N4 was much higher than
those of the non-functionalized catalysts (Pd/AC, Ag42Pd58/C,
Fig. 6. Catalytic activity of catalyst supports and catalysts (formic acid solu­
Au41Pd59/C, and Co5Pd5/CTF-600). It was comparable to that of
tion: 2.5 wt% HCOOH +97.5 wt% H2O; reaction temperature: 55.0 ± 0.8 ◦ C):
Co5Pd5/CTF-600, which was obtained from dehydrogenation of formic
(a) volume of generated gas (CO2 + H2) and (b) TOF.
acid with additive [44].
Pd/NH2-mpg-C3N4 had the highest catalytic activity for dehydroge­
peaks were shifted to lower binding energy by amine-functionalization,
nation of formic acid among the as-prepared catalysts, which was
a result similar to the result of a previous study [57].
attributable to its ultrafine and well-dispersed Pd particles. In a com­
Table 1 presents the specific surface areas of the catalyst supports
parison of the TOF value of Pd/NH2-mpg-C3N4 with those of other cat­
and catalysts. The specific surface area of NH2-mpg-C3N4 (92.0 m2 g− 1)
alysts (Table 3), Pd/NH2-mpg-C3N4 had a relatively higher catalytic
was smaller than that of mpg-C3N4 (174.4 m2 g− 1). This difference
activity in dehydrogenation of formic acid without additive. Conse­
occurred because pores of the catalyst support were blocked by amine.
quently, Pd/NH2-mpg-C3N4 could be considered one of the excellent
The specific surface area of Pd/mpg-C3N4 was 185.4 m2 g− 1, which was
catalysts for dehydrogenation of formic acid.
slightly larger than that of mpg-C3N4 (174.4 m2 g− 1). This difference
occurred because the small Pd particles were supported on the catalyst
support, which was similar to the result of a previous study [58]. The 3.3. Effect of formic acid concentration
specific surface area of Pd/NH2-mpg-C3N4 was 134.3 m2 g− 1, which was
much larger than that of NH2-mpg-C3N4 (92.0 m2 g− 1). This difference The formic acid concentration is an important parameter in
hydrogen generation systems because it affects their energy density. As

Table 3
Comparison of catalytic activity among various catalysts.
Catalysts HCOOH concentration Additive Temperature (◦ C) TOF (h− 1) Apparent Reference
activation
energy
(kJ mol− 1)

Pd/NH2-mpg-C3N4 2.5 wt% X 55 1870 60.7 This work

Pd/mpg-C3N4 1.0 M X 55 324 29.1 [21]
Co5Pd5/CTF-600 2.5 M O 50 2129 35.9 [44]
Cr0.4Pd0.6/MIL-101-NH2 1M X 50 2009 43.5 [50]
Pd-MnOx/SiO2-NH2 1.1 vol% X 50 1300 61.9 [51]
Pd/AC 1M X 55 1100 56.2 [59]
Ag42Pd58/C 1M X 50 382 22.0 [60]
Au41Pd59/C 1M X 50 230 28.0 [61]

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T.H. Lee et al. Fuel Processing Technology 264 (2024) 108133

Fig. 8. Effect of sodium formate concentration on dehydrogenation of formic

Fig. 7. Effect of formic acid concentration on dehydrogenation of formic acid acid (catalyst: Pd/NH2-mpg-C3N4; formic acid solution: 2.5 wt% HCOOH + x wt
(catalyst: Pd/NH2-mpg-C3N4; formic acid solution: x wt% HCOOH + (100 – x) % HCOONa + (97.5 – x) wt% H2O; reaction temperature: 55.1 ± 1.2 ◦ C): (a)
wt% H2O; reaction temperature: 55.1 ± 1.4 ◦ C): (a) volume of generated gas volume of generated gas (CO2 + H2) and (b) TOF.
(CO2 + H2) and (b) TOF.
effect on the dehydrogenation of formic acid. The heterogeneous cata­
the formic acid concentration increases, the system mass decreases. lyst could not decompose high-concentration formic acid efficiently.
Therefore, the formic acid concentration was varied from 2.5 to 15 wt%
to investigate the effect of formic acid concentration on the dehydro­
3.4. Effect of sodium formate concentration
genation of formic acid with Pd/NH2-mpg-C3N4. The hydrogen gener­
ation test was conducted at 55.1 ± 1.4 ◦ C.
Additives such as sodium formate help decompose formic acid
Fig. 7(a) shows the effect of the formic acid concentration on the
[63,64]. Thus, the sodium formate concentration was varied from 0 to 5
volume of gas (CO2 + H2) generated from the dehydrogenation of formic
wt% to investigate the effect of sodium formate concentration on the
acid. As the formic acid concentration increased from 2.5 to 15 wt%, the
dehydrogenation of formic acid with Pd/NH2-mpg-C3N4. The hydrogen
dehydrogenation kinetics decreased. As shown in Fig. 7(b), the TOF
generation test was conducted at 55.1 ± 1.2 ◦ C.
value decreased from 1870 to 343 h− 1 as the formic acid concentration
Fig. 8(a) presents the effect of the sodium formate concentration on
increased from 2.5 to 10 wt%. When the formic acid concentration was
the volume of gas (CO2 + H2) generated from dehydrogenation of formic
15 wt%, the conversion rate of the gas generated from the dehydroge­
acid. As the sodium formate concentration increased from 0 to 5 wt%,
nation of formic acid was lower than 20 %. Consequently, the TOF could
the dehydrogenation kinetics also increased. As shown in Fig. 8(b), the
not be calculated. This result was similar to the trend of the previous
TOF value increased from 1870 to 2297 h− 1 as the sodium formate
study by Zhang et al. who used C-Ag42Pd58 catalyst for dehydrogenation
concentration increased from 0 to 5 wt%. This result was similar to the
of formic acid at various formic acid concentrations [60]. As the formic
results of previous study, which also showed that the TOF value
acid concentration increased from 1 to 2 M, the TOF value decreased
increased with an increase in sodium formate concentration [63,64].
from 380 to 330 h− 1. Grad et al. also found a similar result, which was
The sodium formate accelerates the dehydrogenation of formic acid,
slow dehydrogenation kinetic at high formic acid concentration [62].
increasing the initial concentration of formate anions [59].
The catalysts for dehydrogenation of formic acid were deactivated under
An increase in the sodium formate concentration had a positive effect
high concentration conditions, due to poisoning of the catalyst [59].
on the dehydrogenation of formic acid. However, the use of sodium
Thus, an increase in the formic acid concentration had a negative
formate for dehydrogenation of formic acid decreases the energy density

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T.H. Lee et al. Fuel Processing Technology 264 (2024) 108133

Fig. 10. Performance evaluation of the hydrogen generator with Pd/NH2-

mpg-C3N4.

3.5. Effect of reaction temperature

The reaction temperature was varied from 25 to 55 ◦ C to investigate

the effect of reaction temperature on the dehydrogenation of formic acid
with Pd/NH2-mpg-C3N4. The hydrogen generation test was conducted at
25.1 ± 0.2, 35.2 ± 0.5, 45.4 ± 0.3, and 54.5 ± 0.3 ◦ C, respectively.
Fig. 9(a) presents the effect of the reaction temperature on the vol­
ume of gas (CO2 + H2) generated from dehydrogenation of formic acid.
As reaction temperature increased from 25 to 55 ◦ C, dehydrogenation
kinetics also increased. As shown in Fig. 9(b), the TOF value increased
from 216 to 1870 h− 1 as the reaction temperature increased from 25 to
55 ◦ C.
Fig. 9(c) presents the Arrhenius plot obtained from the experimental
data. The apparent activation energy of the catalyst was determined
using Eq. (5). In the equation, k is the reaction rate constant, A is the pre-
exponential factor, Ea is the apparent activation energy, R is the gas
constant, and T is the reaction temperature. The apparent activation
energy of the catalyst was 60.7 kJ mol− 1, which was higher than that of
Pd/mpg-C3N4 (29.1 kJ mol− 1) [21]. The apparent activation energy of
the catalyst increased after the amine-functionalization [53]. In addi­
tion, it was higher than those of other catalysts, as shown in Table 3.
Ea 1
lnk = lnA − × (5)
R T
The degree of change in the reaction rate of Pd/NH2-mpg-C3N4 was
larger than those of other catalysts. Therefore, Pd/NH2-mpg-C3N4 is
more suitable for a hydrogen generator operated at a relatively high
temperature.

3.6. Performance evaluation of the hydrogen generator

The hydrogen generator with Pd/NH2-mpg-C3N4 was tested to

evaluate its performance. The hydrogen generation test was conducted
at 55.7 ± 0.8 ◦ C.
Fig. 10 shows the gas generation rate and reaction temperature. The
average gas generation rate was 240.4 mL min− 1, and average gas
Fig. 9. Effect of reaction temperature on dehydrogenation of formic acid
(catalyst: Pd/NH2-mpg-C3N4; formic acid solution: 2.5 wt% HCOOH +97.5 wt% temperature was 24.1 ◦ C. Because the amount of formic acid solution
H2O; reaction temperature: 25.1 ± 0.2, 35.2 ± 0.5, 45.4 ± 0.3, or 54.5 ± used for 60 min was 13.7 mL, formic acid solution was supplied to the
0.3 ◦ C): (a) volume of generated gas (CO2 + H2), (b) TOF, and (c) Arrhe­ hydrogen generator at a rate of 0.23 mL min− 1 by the syringe pump. The
nius plot. conversion efficiency determined by Eq. (4) was 87.5 %.
The hydrogen generator with Pd/NH2-mpg-C3N4 could effectively
of the hydrogen generation system because sodium formate is a reaction generate hydrogen from formic acid solution at 55 ◦ C. Thus, the
promoter rather than an energy source. Consequently, a suitable value of hydrogen generator can be used for a PEMFC system.
sodium formate concentration should be determined based on the
dehydrogenation of formic acid and the energy density of the hydrogen 4. Conclusions
generation system.
In this study, Pd/NH2-mpg-C3N4 was investigated for use in a formic
acid hydrogen generator in a PEMFC system. Among the as-prepared
catalysts, Pd/NH2-mpg-C3N4 exhibited superior catalytic activity, with
a TOF value of 1870 h− 1. Pd/NH2-mpg-C3N4 was tested under various

8
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No data was used for the research described in the article.
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