Facile synthesis of amine-functionalized SBA-15-supported bimetallic Au-Pd nanoparticles as an efficient catalyst for hydrogen generation from formic acid

Article abstract of DOI:10.1039/C6RA26793A

In this study, a series of amine-functionalized SBA-15-supported bimetallic Au-Pd nanoparticles (Au-Pd/SBA-15-Amine) as catalysts are successfully synthesized by surface functionalization and co-reduction and characterized by inductively coupled plasma-atomic emission spectroscopy, XRD, XPS, and TEM. The Au-Pd/SBA-15-Amine catalysts thus obtained are tested for the dehydrogenation of formic acid (FA)-sodium formate (SF). Among the tested Au-Pd/SBA-15-Amine catalysts, as-synthesized Au₂Pd₈/SBA-15-Amine exhibits 100% H₂ selectivity and outstanding catalytic activity with an initial turnover frequency (TOF) of 1786 h^?1 at 323 K; this superior catalytic activity is attributed to synergy between Au-Pd and SBA-15-Amine and the promotion effect of SF. At SF concentrations of greater than 0.5 mol L^?1, SF can partially participate in dehydrogenation. The facile synthesis of the Au-Pd/SBA-15-Amine catalyst is imperative for accelerating the widespread application of FA-SF mixtures as a promising hydrogen carrier.

Full text of DOI:10.1039/C6RA26793A

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Facile synthesis of amine-functionalized SBA-15-
supported bimetallic Au–Pd nanoparticles as an
efficient catalyst for hydrogen generation from
formic acid†
Cite this: RSC Adv., 2017, 7, 4746
a
a
b
a
a
a
c
Lixin Xu, Fang Yao, Jili Luo, Chao Wan,* Mingfu Ye, Ping Cui* and Yue An
In this study, a series of amine-functionalized SBA-15-supported bimetallic Au–Pd nanoparticles (Au–Pd/
SBA-15-Amine) as catalysts are successfully synthesized by surface functionalization and co-reduction
and characterized by inductively coupled plasma-atomic emission spectroscopy, XRD, XPS, and TEM.
The Au–Pd/SBA-15-Amine catalysts thus obtained are tested for the dehydrogenation of formic acid
(
FA)–sodium formate (SF). Among the tested Au–Pd/SBA-15-Amine catalysts, as-synthesized Au
2 8
Pd /
SBA-15-Amine exhibits 100% H
2
selectivity and outstanding catalytic activity with an initial turnover
Received 14th November 2016
Accepted 27th December 2016
ꢀ1
frequency (TOF) of 1786 h at 323 K; this superior catalytic activity is attributed to synergy between Au–
ꢀ1
Pd and SBA-15-Amine and the promotion effect of SF. At SF concentrations of greater than 0.5 mol L
,
DOI: 10.1039/c6ra26793a
SF can partially participate in dehydrogenation. The facile synthesis of the Au–Pd/SBA-15-Amine catalyst
is imperative for accelerating the widespread application of FA–SF mixtures as a promising hydrogen carrier.
www.rsc.org/advances
easily handled and stored. Particularly, FA has attracted
increasing attention, attributed to the fact that as compared
Introduction
In the past decades, the search for sustainable, renewable with other substrates, it is less hazardous, and it can be recycled
24–27
energies has increased owing to the widespread utilization of by the hydrogenation of carbon dioxide (CO
2
).
In general,
conventional fossil fuels, which has resulted in serious envi- the decomposition of FA occurs via dehydrogenation (1) and
1
,2
28–30
ronmental and energy problems. Hydrogen, which is the most dehydration (2):
abundant element in nature, has been recognized as a prom-
¼ ꢀ48.8 kJ molꢀ (1)
1
3
–5
2 2 298 K
HCOOH (l) / CO (g) + H (g); DG
ising and green energy source, attributed to its outstanding
ꢀ
1
energy density of as high as 142 MJ kg —nearly three times
greater than that of fossil fuels (55 MJ kg ). Furthermore,
with the use of hydrogen in a fuel cell, water is produced as the
HCOOH (l) / CO (g) + H
2
O (g); DG298 K ¼ ꢀ28.5 kJ molꢀ
1
ꢀ
1
6,7
(2)
8
only by-product. Despite these advantages, the economical,
Nevertheless, carbon monoxide (CO), which degrades cata-
lyst performance, can also be generated by reaction (2), which
should be strictly controlled. These two routes can be affected
by several factors, such as reaction temperature, selected cata-
lysts, as well as the pH of reaction mixture.
desirable to design and fabricate catalysts exhibiting excellent
performance for the dehydrogenation of FA.
It has been previously reported that, Pd-based bimetallic
nanoparticles (NPs), especially those combined with Au, Ni, Ag,
and Co, have been reported to demonstrate exhibit highly effi-
efficient, and safe production and storage of hydrogen remain
challenges for the current development of hydrogen energy.
In recent years, considerable efforts have been focused on
the development of novel materials that can store hydrogen and
31–33
Thus, it is highly
9–12
recycling liberation.
In this regard, several liquid materials,
1
3–15
16–19
such as hydrous hydrazine,
carbazole,
formic acid (FA),
N-ethyl-
20,21
22,23
and methanol,
have attracted considerable
attention as hydrogen storage materials; these materials can be
3
4–42
a
cient catalytic performance for the dehydrogenation of FA.
College of Chemistry and Chemical Engineering, Anhui University of Technology, 59
43
Hudong Road, Ma'anshan 243002, China. E-mail: wanchao1219@hotmail.com; Chen et al. have reported the reduction of mixed noble-metal
cokecp@outlook.com; Fax: +86 555 2311822; Tel: +86 555 2311807
precursors under ice-water bath conditions and successfully
synthesized Au–Pd alloy nanoparticles, which were well-
dispersed on carbon black using the reduction of mixed
noble-metal precursors under ice-water bath conditions, these
nanoparticles which exhibited a high activity and selectivity
b
PetroChina Huabei Oileld Company Gas Storage Management Service, 15 Battle
Road, Renqiu 062550, China
c
College of Chemical and Biological Engineering, Zhejiang University, 38 Zheda Road,
Hangzhou 310027, China
†
Electronic supplementary information (ESI) available. See DOI:
0.1039/c6ra26793a
ꢀ1
with an initial turnover frequency (TOF) as high as 635 h at
1
4746 | RSC Adv., 2017, 7, 4746–4752
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44
nearly 273 K. Jiang et al. have reported a facile and, green Synthesis of SBA-15-Amine
strategy for the synthesis of growing ultrane Au@Pd core–shell
First, 1.0 g of SBA-15 was dispersed into 50 g of anhydrous
toluene, followed by the addition of 13.7 mmol of 3-amino-
propyltriethoxysilane (APTES) under stirring. Second, the
resulting slurry was reuxed for 24 h at 353 K for graing the
mesoporous channel surfaces of SBA-15 with primary amine
groups. Next, aer ltration, the solid product was repeatedly
washed with toluene and ethanol and allowed to dry at 298 K.
Finally, APTES-graed SBA-15 was obtained, hereaer referred
nanoclusters, with exhibiting a good dispersity, grown on
nitrogen-doped mildly reduced graphene oxide (Au@Pd/N-
mrGO) without an additional reducing agent and any surfac-
tant. This catalyst exhibits 100% hydrogen selectivity and
superior catalytic performance for the decomposition of an FA
aqueous solution at 298 K without the introduction of any
45
additive at 298 K. Zahmakiran et al. have presented the use of
heterogeneous catalyst system consisting of amine-
a
52
to as SBA-15-Amine.
functionalized SiO as a the carrier, which supported a phys-
2
ical mixture of a PdAu alloy and MnO NPs with an average
x
Synthesis of AuPd/SBA-15-Amine
diameter of 2.2 nm. This PdAu–MnO
for the decomposition of FA without an additive, in which good
performance was achieved with a TOF of up to 860 mol H (mol
. Furthermore, it was concluded that the support
x 2
/N-SiO catalyst was used
Bimetallic Au–Pd/SBA-15-Amine was prepared as follows. First,
1
g PdCl was added to 100 mL KCl (0.84 g, 2 equiv. with respect
2
2
ꢀ
1
ꢀ1
to PdCl ) at 298 K and completely dissolved to form potassium
2
catalyst)
h
tetrachloropalladinic acid (60 mM, K
stirring. Second, 1 g SBA-15-Amine was added to the metal
precursor solution containing both HAuCl (0.24 mmol) and the
PdCl (0.16 mmol) solution and stirred for 24 h for impreg-
nating the metal on SBA-15-Amine at 298 K. The resulting slurry
2 4
PdCl ) solution under
has been conrmed to play a decisive role in the dehydroge-
nation reaction.
The surface functionality of the support, such as the amine
groups, served as interaction sites for sustaining metallic
nanoclusters and co-catalytic species, which can act as depro-
tonation sites for FA molecules in the dehydrogenation of
4
K
2
4
was reduced with sodium borohydride (NaBH ) and stirred at
4
46–49
50
273 K for 4 h. Finally, the mixture was ltered and washed
several times, followed by drying the resulting solid at 373 K.
Hereaer, the solid catalyst thus obtained was denoted as
FA.
x
Jiang et al. have prepared a Au–Pd–MnO nano-
composite anchored on a bi-support (ZIF-8-rGO) consisting of
a zeolitic imidazolate framework (ZIF-8) and reduced graphene
oxide by a simple wet-chemical method; this catalyst exhibits
good catalytic activity for the generation of hydrogen from high-
concentration FA in the absence of additive at 298 K, the TOF
Au
and K
and the nominal total metal loading was 0.4 mmol. Au/SBA-15-
Amine, Pd/SBA-15-Amine, Au Pd /SBA-15-Amine, Au Pd /SBA-
6
Pd
4
/SBA-15-Amine. For comparison, the amounts of HAuCl
4
2
PdCl were varied with the desired Au–Pd atomic ratio,
4
ꢀ
1
ꢀ1
was as high as 382.1 mol H
2
(mol catalyst)
h
without
8
2
6
4
51
15-Amine, Au Pd /SBA-15-Amine, and Au Pd /SBA-15-Amine
4 6 2 8
were prepared in a similar manner.
additives. Asefa et al. have revealed a facile route for synthe-
sizing ultrasmall Pd NPs immobilized on amine-functionalized
SBA-15 (SBA-15-Amine/Pd), which exhibit high activity for the
dehydrogenation of FA with a high TOF of 293 h at ambient
temperature.
ꢀ
1
Hydrogen generation from FA/SF over AuPd/SBA-15-Amine
The production of hydrogen from an FA–SF solution was con-
ducted in a glass tube at a preset temperature (303–333 K) under
ambient atmosphere. Typically, 100 mg of a catalyst was placed
into a stirred glass tube, followed by the rapid injection of 2 mL
of an FA–SF mixture solution containing FA (3 mmol) and SF (1
mmol). A gas burette lled with water was connected to the
reaction vessel for measuring the volume of released gas. The
dehydrogenation performance of FA–SF over all catalysts was
conducted following the same procedure.
Herein, for the rst time, we report the synthesis of Au–Pd
NPs dispersed on SBA-15-Amine by the dehydrogenation of FA–
SF via co-reduction. Au–Pd/SBA-15-Amine exhibits excellent
activity and satisfactory stability for the production of hydrogen
from FA; it is markedly superior to the other catalysts reported
thus far.
Experimental section
Materials
CO
2
trap
2 5
Anhydrous ethanol (C H OH, AR), potassium chloride (KCl,
AR), hydrochloric acid (HCl, AR), sodium formate (SF, HCOONa,
AR), formic acid (HCOOH, AR), toluene (C H , AR), and calcium
hydride (CaH
Reagent Co., Ltd. SBA-15 were obtained from Nanjing XFNANO
Materials Tech Co., Ltd. Chloroauric acid (HAuCl $4H O, AR)
and palladium chloride (PdCl , AR) were supplied from Nanjing
Chemical Reagent Co., Ltd. Deionized water was obtained by
For conrming the molar ratios of H
2
2
and CO in the gas
mixture obtained via the dehydrogenation of an aqueous FA–SF
solution over Au–Pd/SBA-15-Amine, the gas generated during
the reaction was passed through a NaOH trap (10 M NaOH
solution), and its volume was monitored using a gas burette.
7
8
2
, AR) were obtained from Sinopharm Chemical
4
2
2
Stability test
reverse osmosis, followed by ion exchange and ltration. For the recycling stability test, 2 mL of FA–SF was added into
Toluene was distilled over calcium hydride for removing a stirred glass tube aer completing the rst run of the dehy-
marginal amounts of water and stored in a vacuum glove box drogenation of FA–SF; these stability tests were repeatedly
under nitrogen. All other reagents were utilized as received conducted by the addition of fresh FA (3 mmol) to the reaction
without further purication.
ask.
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Calculation of turnover frequency (TOF)
on a Thermo Scientic Escalab 250Xi spectrometer equipped
with an Al Ka radiation source (1486.6 eV, 15 kV). All binding
energies were calibrated with the C 1s peak at 284.8 eV for
adventitious carbon. TEM images were obtained using an FEI
Tecnai F20 TEM with a working voltage of 200 kV. Detailed gas
for released from dehydrogenation were analyzed using a GC-
The initial TOF reported here is calculated by the total amount
2 2 a
of gas volume (H + CO ) when x reaches 20% from the
41
following equation:
P
atm
V
x
a
¼ 2
RTnFA
9
860 II (Shanghai Qiyang Information Technology Co., Ltd.)
with a TCD for CO and H and a ame ionization detector
FID)–methanator for CO (detection limit: ꢂ10 ppm for CO).
2
2
(
P
atm
V
TOF ¼ 2
RTnAgþPd
t
here, Patm is the atmospheric pressure (101 325 Pa), V is the Results and discussion
2 2
generated volume of (H + CO ) gas, R is the universal gas
3
ꢀ1 ꢀ1
As the pore walls of SBA-15 are covered with residual surface
silanols (^Si–OH), SBA-15 can be functionalized with organic
functional groups, which are benecial for anchoring metal
constant (8.3145 m Pa mol
298 K), nAg+Pd is the total mole number of Ag and Pd atoms in
the catalyst, and t is the initial time of the catalytic reaction
when x reaches 20%.
K ), T is the room temperature
(
52
ions to the SBA-15 surfaces. Hence, these surfaces are modi-
ed using APTES; this APTES-functionalized SBA-15 is referred
a

52
to as SBA-15-Amine. As shown in the scheme in Fig. 1, a series
Characterization
of Au–Pd/SBA-15-Amine catalysts are synthesized by a surfac-
The chemical composition of the catalysts was investigated tant-free co-reduction method. Specically, SBA-15-Amine is
using a Thermo iCAP6300 inductively coupled plasma-atomic rst added to a precursor solution containing HAuCl and
and stirred to impregnate Au and Pd into the SBA-
XRD) patterns were recorded on a Bruker D8-Advance XRD 15-Amine surface. Second, NaBH is added for reducing the
4
3
+
2+
emission spectroscopy (ICP-AES). Powder X-ray diffraction
2 4
K PdCl
(
4
instrument using a Cu Ka radiation source (l ¼ 0.154178 nm) metal precursor under ice-water bath conditions. Next, the
ꢁ
ꢀ1
with a velocity of 1 min . XPS measurements were conducted resultant solution is centrifuged and washed with copious
Fig. 1 Schematic illustration for the synthesis of the supported Au–Pd/SBA-15-Amine.
Fig. 2 (A) Small-angle and (B) wide-angle XRD pattern of all as-prepared catalysts supported SBA-15-Amine with different molar ratio of Au/Pd.
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amounts of water. Finally, the solid thus obtained is dried in
a vacuum oven at 373 K for 10 h. The compositions of catalysts
3
+
2+
are modied by controlling the molar ratio of Au –Pd in the
precursor solution, as conrmed by ICP-AES. Table S1†
summarizes the ICP-AES results obtained for catalyst
compositions.
Fig. 2 shows the small- and wide-angle XRD patterns of Au/
SBA-15-Amine, Au
8
Pd
2
/SBA-15-Amine, Au
6 4
Pd /SBA-15-Amine,
Au Pd /SBA-15-Amine, Au
4
6
2
Pd /SBA-15-Amine, and Pd/SBA-15-
8
Amine. As shown in Fig. 2(A), three well-resolved diffraction
peaks are observed for all catalysts: a very strong peak at 2q ¼
ꢁ
ꢁ
ꢁ
1
.02 and two weak peaks at 2q ¼ 1.68 and 2q ¼ 1.95 , attrib-
uted to the (100), (110), and (200) planes, respectively; these
three peaks indicate that there is no evidence of any alteration
in the ordered two-dimensional hexagonal structure of Au–Pd/
Fig. 3 Time course plots for hydrogen generation from FA/SF over
52,53
SBA-15-Amine during catalyst synthesis.
As can be
Au–Pd/SBA-15-Amine with different molar ratio of AuPd (nFA
mmol, nSF ¼ 1 mmol).
¼
ꢁ
observed from Fig. 2(B), a broad diffraction peak at 2q ¼ 22.3 is
observed for all catalyst samples, which corresponds to the
presence of silica and can be assigned to the amorphous SBA-15
3
52,53
framework.
5-Amine are observed between those for bulk Au and Pd sup-
ported on SBA-15-Amine (JCPDS, 65-8601 and 65-2867), sug-
Furthermore, diffraction peaks for Au–Pd/SBA-
1
4
5,50,54,55
gesting the formation of Au–Pd alloy structure.
Fig. 3 and Table S2† show the performance of Au–Pd/SBA-15-
Amine at different molar ratios of Au–Pd for the dehydrogena-
tion of an FA–SF solution at 323 K. As shown, catalytic activity is
predominantly affected by the molar ratios of Au–Pd in Au–Pd/
SBA-15-Amine. Particularly, Au Pd /SBA-15-Amine exhibits the
2
8
best activity of all of the tested catalysts, where FA produces the
theoretical gas volume within only 2 min at 323 K. The corre-
ꢀ
1
sponding TOF is as high as 1786 h , which is signicantly
greater than most of the TOFs reported previously for other Au–
Pd catalysts used for the decomposition of FA (Table S3†). Alloy
formation between Au and Pd exerts a positive synergistic effect
on dehydrogenation, which is consistent with that reported in
Fig. 4 Hydrogen generation by decomposition of FA/SF with different
45,50,54,56
previous studies.
Moreover, as shown in Fig. S1–S3,† the
SF concentration catalyzed by Au
mmol).
2 8
Pd /SBA-15-Amine at 323 K (nFA ¼ 3
composition of the produced gas is identied by GC analysis
and a 10 NaOH solution trap. As shown in Fig. S1,† the gas
volume is reduced to half aer treatment with the NaOH trap,
Fig. 5 (A) Time course plots for hydrogen release by the dehydrogenation of FA/SF by Au
Plot of ln k vs. 1/T for Au Pd
/SBA-15-Amine (nFA ¼ 3 mmol, nSF ¼ 1 mmol).
2 8
Pd /SBA-15-Amine at 303 K, 313 K, 323 K and 333 K. (B)
2
8
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ꢀ
1
conrming that dehydrogenation results in the generation of than 0.5 mol L , SF partially participates in dehydrogenation.
hydrogen and carbon dioxide, not CO, which is in agreement The dehydrogenation rate and efficiency of FA are concluded to
with GC analysis shown in Fig. S2 and S3.†
be enhanced with increasing SF concentration, and SF is
The SF concentration plays an important role in the involved in the decomposition reaction at a high SF concen-
ꢀ
1
enhancement of catalytic performance for the dehydrogenation tration (>0.5 mol L ).
4
5,49
of FA, as has been reported in previous studies.
using Au Pd /SBA-15-Amine without SF, only 66.7% of SF is Amine is conducted at various temperatures ranging from 303
decomposed into hydrogen in 9 min with a TOF of 207 h . On K to 333 K; an activation energy (E
the other hand, the catalytic performance for Au Pd /SBA-15- as shown in Fig. 5, which is in agreement with those reported
Amine is signicantly improved by the introduction of SF into previously.
the reaction system. With increasing SF concentration from 0 to SBA-15-Amine catalyst is investigated at 323 K. As can be
From Fig. 4,
2 8
The decomposition of FA–SF catalyzed by Au Pd /SBA-15-
2
8
ꢀ1
ꢀ1
a
) of 47.6 kJ mol is observed,
2
8
44,45,50,57,58
In addition, the reusability of the Au Pd /
2
8
ꢀ
1
0
.5 mol L (FA–SF molar ratio ¼ 3 : 1), FA from the FA–SF observed in Fig. 6, the catalyst exhibits excellent catalytic
solution completely reacts, resulting in the production of performance without a distinct decrease for dehydrogenation
a theoretical gas volume of 135 mL, while SF is not involved in activity aer ve runs.
dehydrogenation. Moreover, at SF concentrations of greater
The surface states of supported Au–Pd NPs are recorded by
XPS, and Fig. 7 shows the Au 4f and Pd 3d core level spectra for
Au/SBA-15-Amine, Pd/SBA-15-Amine, and Au Pd /SBA-15-
2 8
Amine. In the Au 4f spectrum (Fig. 7(A)), two strong peaks are
observed at 83.9 and 87.6 eV for Au/SBA-15-Amine, attributed to
0
metallic Au . The Au 4f spectrum for Au Pd /SBA-15-Amine is
2
8
divided into two peaks—83.5 and 87.1 eV. As compared with
that of Au/SBA-15-Amine, the binding energy for Au 4f is shied
to a lower value. From Fig. 7(B), two peaks are observed at 335.8
and 340.8 eV for Pd/SBA-15-Amine, attributed to 3d5/2 and 3d3/2
0
of Pd , respectively. The results obtained from the XPS signals
of Pd 3d for Au Pd /SBA-15-Amine exhibit a 3d peak at
5/2
2
8
336.1 eV and a 3d3/2 peak at 341.5 eV, corresponding to
a binding energy greater than that obtained for the Pd 3d of Pd/
55–57
SBA-15-Amine.
Thus, these changes in binding energy are
attributed to the occurrence of alloying in the supported Au–Pd
44,45,50,56–58
NPs,
which are in good agreement with XRD
characterization.
Fig. 6 Reusability test for the hydrogen generation from aqueous FA/
Fig. 8(a)–(d) show the typical TEM images of the as-synthesized
Au Pd /SBA-15-Amine catalysts. NPs are well dispersed with an
SF at 323 K in the presence of Au
mmol, nSF ¼ 1 mmol).
2
8
Pd /SBA-15-Amine catalyst (nFA
¼
2
8
3
2 8 2 8
Fig. 7 XPS spectra of (A) Au 4f of Au/SBA-15-Amine and Au Pd /SBA-15-Amine and (B) Pd 3d of Pd/SBA-15-Amine and Au Pd /SBA-15-Amine.
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(1608085QF156) and the Scientic Research Foundation of
Graduate School of Anhui University of Technology (2016012,
016017).
2
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2 8
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