Efficient hydrogen generation from formic acid using AgPd nanoparticles immobilized on carbon nitride-functionalized SBA-15

Article abstract of DOI:10.1039/c6ra06071d

Bimetallic AgPd nanoparticles were successfully immobilized on graphitic carbon nitride (g-C₃N₄) functionalized SBA-15 for the first time by a facile co-reduction method. These catalysts were applied in the decomposition of formic ac

Full text of DOI:10.1039/c6ra06071d

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Efficient hydrogen generation from formic acid
using AgPd nanoparticles immobilized on carbon
nitride-functionalized SBA-15†
Cite this: RSC Adv., 2016, 6, 46908
a
a
a
b
b
b
a
Lixin Xu, Bo Jin, Jian Zhang, Dang-guo Cheng, Fengqiu Chen, Yue An, Ping Cui
a
and Chao Wan*
3 4
Bimetallic AgPd nanoparticles were successfully immobilized on graphitic carbon nitride (g-C N )
functionalized SBA-15 for the first time by a facile co-reduction method. These catalysts were applied in
the decomposition of formic acid. The dehydrogenation of formic acid is dependent on the composition
of AgPd and the content of carbon nitride (CN). Among all of the AgPd/mCND/SBA-15 catalysts tested,
the Ag10Pd90/0.2CND/SBA-15 catalyst exhibits highly superior performance for the decomposition of
formic acid into high-quality hydrogen at 323 K with 100% hydrogen selectivity and a turnover frequency
Received 7th March 2016
Accepted 5th May 2016
DOI: 10.1039/c6ra06071d
ꢀ1
of 893 h , which is among the maximum values obtained at 323 K in this paper. The improved
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performance is a promising step towards the utilization of formic acid as a hydrogen storage material.
HCOOH (l) ¼ CO (g) + H
2
O (g) DG ¼ ꢀ14.9 kJ molꢀ
1
(2)
1
. Introduction
In recent years, the decomposition of FA has been investi-
Considering the current energy crisis, with the consumption of
fossil fuels and consequent environmental pollution increasing
continuously, it is highly desirable to search for renewable,
benign, and sustainable energy sources. Among a variety of
alternative energy sources, hydrogen, generating only water as
a byproduct, has been proposed as an environmentally attrac-
tive, clean, and efficient energy carrier for its extensive utiliza-
17
18
19,20
gated using various homogeneous Fe, Ir, and Ru
cata-
lysts, as well as a number of heterogeneous Pd and Au noble
10–12,21–24
metal catalysts.
Although some of these homogeneous
catalysts exhibit high activities and selectivities for the decom-
position of FA, their difficult recovery from the reaction mixture
25
impedes their practical application. Consequently, due to the
ease of carrying and separation, much effort has been concen-
trated on the development of metal nanoparticles (NPs) with
1,2
tion in proton exchange membrane fuel cells. However,
searching for efficient and safe hydrogen storage materials is
one of the most critical challenges that hinder the development
26–30
high activity and selectivity for the decomposition of FA.
To
3–6
date, most work on NPs for FA dehydrogenation has been
of hydrogen energy. Formic acid (FA, HCOOH), a natural
biomass accessible via CO reduction, has attracted much
attention due to its excellent stability, high energy density, and
31–33
focused on bimetallic and trimetallic composites.
The
2
performance of nanocatalysts is highly dependent on their
34–36
7–12
particle size, crystallinity, dispersion, support, etc.
non-toxicity.
FA can decompose through two principal
37
Zhang et al. reported a Schiff base (C]N) as an active group
with broaden applications in a great deal of homogeneous
processes, and metal–Schiff base complexes were also reported
to display catalytic activity in numerous reactions such as Heck
routes, dehydrogenation (eqn (1)) and dehydration (eqn (2)).
The former produces hydrogen (H ) and carbon dioxide (CO )
2
2
while the latter produces water (H O) and carbon monoxide
2
13–16
(CO), which is highly toxic to catalysts.
Therefore, it is highly
38
39
reactions, hydrogenation, and even the decomposition of
desirable to develop efficient and cost-effective catalysts for the
40
FA. In consequence, the functionalization of a Schiff base over
supported metal nanocatalysts presents a promising route for
(1) designing catalysts for the dehydrogenation of FA, although
heterogenization of a Schiff base over a support is challenging.
In the approach used in this study, polymeric carbon nitrides
decomposition of FA.
ꢀ
1
HCOOH (l) ¼ CO (g) + H (g) DG ¼ ꢀ35.0 kJ mol
2
2
(
CN) are employed to functionalize SBA-15 supports to stabilize
a
College of Chemistry and Chemical Engineering, Anhui University of Technology, 59 metal NPs. CN-modied SBA-15 was rst impregnated with
Hudong Road, Ma'anshan 243002, China. E-mail: wanchao1219@hotmail.com
b
a layer of CN using dicyandiamide as a precursor before being
used to support AgPd bimetallic NPs. These catalysts were then
applied in the decomposition of FA/sodium formate (SF). X-ray
diffraction (XRD), transmission electron microscopy (TEM), and
College of Chemical and Biological Engineering, Zhejiang University, 38 Zheda Road,
Hangzhou 310027, China
†
Electronic supplementary information (ESI) available. See DOI:
0.1039/c6ra06071d
1
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X-ray photoelectron spectroscopy (XPS) were used for structural
investigations. The generated gas was analyzed by a gas chro-
matograph connected to a thermal conductivity detector (TCD).
2. Experimental
2.1 Materials
Palladium(II) chloride (PdCl
2
, AR, Sinopharm Chemical Reagent
Co., Ltd.), silver nitrate (AgNO , AR, Sinopharm Chemical
3
Reagent Co., Ltd.), FA (98%, Aladdin Industrial Inc.), hydro-
chloric acid (HCl, 37%, Sinopharm Chemical Reagent Co., Ltd.),
tetraethyl orthosilicate (TEOS, Sinopharm Chemical Reagent
Co., Ltd., AR), Pluronic P123 triblock copolymer (EO20PO70EO20
av ¼ 5800, Sigma-Aldrich), ethanol (C OH, Sinopharm
Chemical Reagent Co., Ltd., AR) sodium borohydride (NaBH
6%, Sinopharm Chemical Reagent Co., Ltd.), dicyandiamide
C H N , 98%, Aladdin Industrial Inc.), potassium chloride
,
Scheme 1 Schematic illustration for the preparation of AgPd/mCND/
SBA-15.
M
2 5
H
4
,
9
(
(
into a 20 mL mixture solution of AgNO3 (0.04 mmol) and
2
4 4
K PdCl (0.36 mmol) at 298 K under stirring for 24 h to immo-
KCl, 99%, Sinopharm Chemical Reagent Co. Ltd.), and sodium
2
4
bilize the two metal precursors onto the support. Next, the ob-
tained mixture was reduced with fresh NaBH aqueous solution
formate (HCOONa, 99%, Sinopharm Chemical Reagent Co.
Ltd.) were employed as-purchased. Deionized water with
a conductance below 10 S cm was used in all synthesis and
washing processes.
4
ꢀ
6
ꢀ1
(2 mmol) under vigorous stirring. Finally, the Ag Pd /0.1CND/
10 90
SBA-15 catalyst was obtained by centrifugation, washed with
deionized water and ethanol, and dried at 333 K for 12 h. For
comparison, Ag10Pd90/0.2CND/SBA-15, Ag10Pd90/0.3CND/SBA-15,
Ag Pd /0.4CND/SBA-15, Ag/0.2CND/SBA-15, Pd/0.2CND/SBA-
2
.2 Preparation of CND/SBA-15 materials
1
0
90
SBA-15 was prepared using Pluronic P123 triblock copolymer as
a template according to the procedure reported by Zhao et al.
1
5, Ag Pd /0.2CND/SBA-15, and Ag Pd /0.2CND/SBA-15 were
20 80 30 70
41
prepared by the same method (Scheme 1).
In a typical process, 2.0 g P123 was dissolved in 15.0 g water,
followed by the addition of 60.0 g 2 M HCl aqueous solution.
Next, 4.25 g TEOS was added into the mixture under stirring,
and further stirred at 313 K for 24 h. The milky liquid was
2
.4 Hydrogen generation from FA aqueous solution
2.4.1 Hydrogen release from FA/SF over AgPd/mCND/SBA-
transferred into an autoclave and hydrothermally treated at 373 15. Typically, as-prepared AgPd/mCND/SBA-15 (100 mg) was
K for 24 h. Aerwards, the white precipitate was ltered and placed into a two-necked round-bottomed ask with one neck
dried at 333 K overnight. The SBA-15 support was obtained by used for introducing a 2 mL mixture of FA (3 mmol) and SF (1
calcining at 823 K for 5 h to remove P123.
mmol), and the other for connection to a gas burette. The
Dicyandiamide (DCDA, 0.1 g) was dissolved in ethanol/water dehydrogenation reaction was initiated at the desired temper-
60/15 mL) by heating to 353 K and kept at this temperature for ature once the FA/SF mixture solution was injected into the two-
(
1
0 min to guarantee the complete dissolution of DCDA. The necked ask with magnetic stirring. The release of gas was
above-mentioned dicyandiamide solution was added to the measured by the gas burette. This reaction was performed at
previously dried SBA-15 (1 g) solid. Aer 6 h digestion, the 323 K under ambient atmosphere. The catalytic performance of
mixture was heated at 373 K until ethanol and water were all catalysts for the dehydrogenation of FA was investigated by
evaporated to form a white solid. Next, the resultant solid was the above procedure.
ꢀ1
ground in a mortar, heated at 2.5 K min up to 873 K under
2.4.2 NaOH trap test. In order to measure the composition
atmosphere (ow rate: 40 mL min ), and then treated for of H and CO in the gas mixture released during the AgPd/
The obtained sample was labeled as 0.1CND/ mCND/SBA-15-catalyzed decomposition of aqueous FA/SF
SBA-15. Based on the dicyandiamide content, the products solution, NaOH trap tests were conducted, according to
ꢀ
1
a N
a further 4 h.
2
2
2
42,43
35,36
were denoted as mCND/SBA-15, where m represents the mass of a previously reported procedure.
In a typical procedure, the
DCDA (m ¼ 0.2, 0.3, 0.4).
trap (10 M NaOH solution) was placed between the gas burette
and reactor. The gas produced from the dehydrogenation
reaction was measured by passing through the NaOH trap and
comparing to that generated in experiments without a trap.
2
.3 Synthesis of AgPd/mCND/SBA-15 catalysts
Potassium tetrachloropalladinic acid (0.06 M, K
was prepared by adding 1 g PdCl to 100 mL KCl (0.84 g)
2 4
PdCl ) solution
2
2.5 Characterization
aqueous solution at 298 K under stirring for complete
dissolution.
The detailed composition of the catalysts was measured by
Bimetallic AgPd/mCND/SBA-15 catalysts with various molar inductively coupled plasma-atomic emission spectroscopy (ICP-
ratios of Ag/Pd were synthesized. In brief, for the preparation of AES, Thermo iCAP6300) and elementary analysis (PerkinElmer
Ag10Pd90/0.1CND/SBA-15, 0.1CND/SBA-15 (200 mg) was placed EA2400 II). Powder XRD patterns were acquired on a Bruker D8-
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ꢁ
ꢀ1
Advance X-ray diffractometer with a velocity of 1 min using too little or too much Ag in the AgPd alloy can lead to a much
a Cu Ka radiation source (l ¼ 0.154178 nm). Surface area lower activity. Based on the above results, the Ag Pd /0.2CND/
1
0
90
measurements were conducted using nitrogen adsorption/ SBA-15 catalyst showed the best activity for the decomposition
desorption isotherms at 77 K aer dehydration under vacuum of FA/SF; the volume of released gas over 6.25 min reached 125
at 423 K for 8 h using a Micromeritics ASAP 2020 analyzer. XPS mL at 323 K. The Ag10Pd90/0.2CND/SBA-15 catalyst demon-
ꢀ
1
measurements were performed on a Thermo Scientic Escalab strates superior activity with a TOF value of 893 h at 323 K
50Xi with Al Ka radiation as the excitation source. TEM (Table 1), and 100% selectivity for hydrogen release from FA/SF.
2
experiments were conducted on an FEI Tecnai F20 transmission As shown in Fig. 2, the content of CN in Ag10Pd90/mCND/SBA-15
electron microscope operating at 200 kV. Detailed gas analyses has a great inuence on the dehydrogenation of FA/SF.
were conducted on a GC-9860 II (Shanghai Qiyang Information Compared with Ag Pd /SBA-15, TOF
over Ag Pd /
10 90
1
0
90
initial
Technology Co., Ltd.) with a TCD for CO and H , and a ame mCND/SBA-15 shows a volcano plot with respect to CN content.
2
2
ionization detector (FID)-Methanator for CO (detection limit: Ag Pd /0.2CND/SBA-15 was clearly the optimal catalyst for
1
0
90
ꢂ10 ppm for CO).
dehydrogenation in this study.
In order to conrm the composition of released gas, the gas
was passed through a 10 M NaOH solution trap, which can
3. Results and discussion
35,36,49,50
conrm complete absorption of CO
2
from the gas.
The
mCND/SBA-15 was prepared following a previously reported volume of gas reduced to half the original value aer passing
42,43
procedure.
As displayed in Scheme 1, monodisperse AgPd/ through the NaOH trap, as shown in Fig. S1,† implying that the
mCND/SBA-15 was synthesized by a one-step co-reduction
method in 1 h at 273 K, and AgNO , K PdCl , and mCND/SBA-
3
2
4
Table 1 Comparison performance of different catalysts for hydrogen
released from FA/SF
1
5 were added as the metal precursors, while NaBH was used
4
as the reducing agent. The composition of AgPd in AgPd/mCND/
SBA-15 was modied by changing the designed molar ratio of
E
a
ꢀ1
ꢀ1
Catalyst
T (K) TOF (h
)
(kJ mol
)
Reference
AgNO
3 2 4
and K PdCl , and measured using ICP-AES, as displayed
in Table S1.† Ag10Pd90/0.2CND/SBA-15, Ag20Pd80/0.2CND/SBA-
Ag10Pd90/0.2CND/SBA-15
Au/C
323
323
893
80
382
85
43.2
This work
15, Ag30Pd70/0.2CND/SBA-15, Ag/0.2CND/SBA-15, and Pd/
15
44
45
15
15
46
47
48
48
0.2CND/SBA-15 were prepared using metal precursors at Ag/ Monodisperse Ag42Pd58/C 323
22
20.5
Pd ratios of 1 : 9, 2 : 8, 3 : 7, 1 : 0, and 0 : 1, respectively. Ni18Ag24Pd58/C
323
323
Pd/C
30
Ag Pd /mCND/SBA-15 catalysts with different CN content were
1
0
90
Monodisperse Au41Pd59/C 323
230
113.5
106
125
144
28
also investigated. It should be noted that the dehydrogenation
activity of the AgPd/mCND/SBA-15 catalysts for FA/SF was
strongly dependent on Ag/Pd composition and CN content. As Ag@Pd
shown in Fig. 1 and Table S2,† the initial turnover frequency Ag/Pd alloy
PdAu/C–CeO
AuPd@ED-MIL-101
2
365
363
293
293
30.0
30
(TOFinitial) reached the optimal value at an Ag molar ratio of 0.1;
Fig. 1 Hydrogen generation from FA/SF with different of Ag/Pd Fig. 2 Hydrogen generation from FA/SF over Ag10Pd90/mCND/SBA-
content immobilized on 0.2CND/SBA-15 versus time at 323 K (nFA ¼ 3 15 with different of CN content versus time at 323 K (nFA ¼ 3 mmol,
mmol, nSF ¼ 1 mmol).
nSF ¼ 1 mmol).
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dehydrogenation reaction generates only carbon dioxide and
hydrogen without releasing CO. Furthermore, gas chromatog-
raphy (GC) analyses further conrmed the presence of CO and
2
absence of CO, as shown in Fig. S2 and S3.† Based on the above
results, the Ag10Pd90/0.2CND/SBA-15 catalyst exhibited excellent
H
2
selectivity for the decomposition of FA/SF.
The dehydrogenation reactions of FA/SF catalyzed by
Ag10Pd90/0.2CND/SBA-15 were conducted at a series of temper-
atures in the range of 323–353 K in order to obtain the activation
49–51
energy (E ) of this reaction.
The values of the rate constant k
a
at various temperatures can be acquired according to the slope
of the linear part of each plot in Fig. 3a. The Arrhenius plot of
ln k vs. 1/T for this catalyst is revealed in Fig. 3b, from which the
apparent activation energy could be calculated to be approxi-
ꢀ
1
mately 43.2 kJ mol (Table 1). As displayed in Fig. S4,† it can be
observed that the catalytic activity of catalyst decrease obviously
aer the fourth run. It can be revealed in Fig. S5† that the reason
for the decrease in their catalytic performance may be attrib-
Fig. 4 Small-angle XRD patterns of all samples: (a) Ag10Pd90/SBA-15;
uted to the increasing of the particle size, which is consistent (b) Ag10Pd90/0.1CND/SBA-15; (c) Ag10Pd90/0.2CND/SBA-15; (d)
36
Ag10Pd90/0.3CND/SBA-15; (e) Ag10Pd90/0.4CND/SBA-15.
with ths literature reported.
The small XRD angles of the Ag10Pd90/mCND/SBA-15 cata-
lysts with different CN content show similar diffraction peaks
assignable to SBA-15 (Fig. 4), suggesting that the porous
The morphology of Ag10Pd90/0.2CND/SBA-15 was further
structure of SBA-15 remains unchanged irrespective of the characterized by TEM (Fig. 6). The TEM images of Ag10Pd90
/
42,43
formation of CN, in accordance with previous results.
Fig. 5a shows the N2 adsorption/desorption isotherms of dispersed in 0.2CND/SBA-15. The nitrogen content of Ag10Pd90
Ag Pd /mCND/SBA-15. All samples demonstrate type IV 0.2CND/SBA-15 was 3.5 wt%. The mean diameter of AgPd NPs in
0.2CND/SBA-15 demonstrate that the AgPd NPs are well
/
1
0
90
isotherms with H1-type hysteresis loops attributing to ordered Ag10Pd90/0.2CND/SBA-15 was in the range of 4.5 ꢃ 0.5 nm
mesoporous structures, implying that the pore structure of (Fig. S6†), which is small enough for immobilization into the
SBA-15 is not damaged aer the generation of CN, in consistent mesoporous cavities of 0.2CND/SBA-15 (8 nm). As revealed in
with the XRD results shown in Fig. 4. As can be seen in Fig. 5b, Fig. 6b, the representative HRTEM image shows a d-spacing of
the Ag10Pd90/mCND/SBA-15 catalysts contain one type of pore 0.232 nm, which is between the (111) lattice spacing of face-
with small mesopores (the center of pore distribution from the centered cubic fcc Pd (0.22 nm) and (fcc) Ag (0.24 nm),
49–51
adsorption branch is 8 nm).
further conrming that AgPd is existed as an alloy structure.
Fig. 3 (a) Time course plots for gas produced by the dehydrogenation of FA/SF by Ag10Pd90/0.2CND/SBA-15 at different temperatures. (b)
Arrhenius plot of ln k vs. 1/T over Ag10Pd90/0.2CND/SBA-15 according to the data of (a) (nFA ¼ 3 mmol, nSF ¼ 1 mmol).
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Fig. 5 Nitrogen adsorption–desorption isotherms (A) and pore size distributions (B) of all samples: (a) Ag10Pd90/SBA-15; (b) Ag10Pd90/0.1CND/
SBA-15; (c) Ag10Pd90/0.2CND/SBA-15; (d) Ag10Pd90/0.3CND/SBA-15; (e) Ag10Pd90/0.4CND/SBA-15.
Fig. 6 (a and b) TEM images of Ag10Pd90/0.2CND/SBA-15 with different magnification.
Fig. S7† display the related element mapping of Si, O, C, N, Ag 0.2CND/SBA-15. Fig. 7 shows high-resolution XPS spectra of Ag
and Pd of Ag10Pd90/0.2CND/SBA-15 and the high-angle annular (3d), Pd (3d), C (1s), and N (1s) observed in Ag10Pd90/0.2CND/
dark eld scanning TEM (HAADF-STEM), respectively. It can be SBA-15. The XPS results (Fig. 7) of Ag10Pd90/0.2CND/SBA-15
0
observed that the elements of C, N, Ag and Pd have a similar reveal the presence of metallic Ag , with Ag 3d5/2 at 367.5 eV
0
distribution map. The results proved the hypothesis that we and Ag 3d3/2 at 373.5 eV, as well as metallic Pd , with Pd 3d5/2 at
3
4,35,49–51
designed above about the preparation for the catalyst. In addi- 335.3 eV and Pd 3d3/2 at 340.6 eV.
These binding energy
ꢁ
ꢁ
tion, the XRD patterns at 38.03 and 40.10 in Fig. S8† can be shis of the core electrons reveal that some electrons are
ascribed to Ag/0.2CND/SBA-15 and Pd/0.2CND/SBA-15, respec- changed, conrming the alloy structure of Ag Pd NPs in
1
0
90
tively. The XRD patterns of Ag Pd /0.2CND/SBA-15, Ag Pd / Ag Pd /0.2CND/SBA-15, in accordance with previous
1
0
90
20
80
10
90
4
9–51
0
.2CND/SBA-15 and Ag30Pd70/0.2CND/SBA-15 show a series of reports.
The C 1s spectrum can be deconvoluted into two
2
diffraction peaks that located between the diffraction patterns peaks at 286.3 and 284.7 eV, ascribed to the sp C atoms bonded
of pure Pd and Ag with a face-centered cubic structure, also to N inside the aromatic structure and adventitious carbon
50,51
suggesting the formation of AgPd alloy nanoparticles.
impurities, respectively. Two peaks are observed in the N 1s
XPS was conducted to investigate the chemical composition spectrum of Ag10Pd90/0.2CND/SBA-15 at 399.8 and 398.1 eV,
2
and elucidate the elemental chemical states of Ag Pd / which can be attributed to pyrrolic or pyridonic N (C–N) and sp -
1
0
90
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Fig. 7 XPS spectra of Ag10Pd90/0.2CND/SBA-15.
hybridized nitrogen atoms involved in pyridinic N (C]N–C),
Notes and references
respectively. These assignments are consistent with the re-
52
ported data for CN. More importantly, the presence of a Schiff
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heterogeneous catalyst using AgPd alloy NPs deposited on g-
C N -functionalized SBA-15, and applied it to the dehydrogena-
3
4
tion of FA/SF. We also investigated the synergistic effect of AgPd/
mCND/SBA-15 for the dehydrogenation of FA for the rst time.
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6
ꢀ1
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9
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