Facile synthesis of AgAuPd/graphene with high performance for hydrogen generation from formic acid

Article abstract of DOI:10.1039/c5ta03111g

AgAuPd nanoparticles with small particle size, good dispersity and high degree of crystallinity on graphene are synthesized by a facile co-reduction route. The resultant AgAuPd/graphene exhibits 100% H₂ selectivity, 100% conversion and excellent catalytic activity toward the hydrogen generation from decomposition of formic acid without any additive at room temperature.

Full text of DOI:10.1039/c5ta03111g

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Communication
Facile Synthesis of AgAuPd/Graphene with High Performance for
Hydrogen Generation from Formic Acid
Si-jia Li, Yun Ping, Jun-Min Yan,* Hong-Li Wang, Ming Wu and Qing Jiang
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
precursor.[13] AgAuPd/rGO is synthesized by coreduction of
AgAuPd nanoparticles with small particle size, good
50 GO and the metal precursors of Ag, Au and Pd, as illustrated
in Scheme 1. Typically, for preparation of
dispersity and high degree of crystallinity on graphene are
synthesized by a facile co-reduction route. The resultant
AgAuPd/graphene exhibit 100% H2 selectivity, 100%
Ag0.2Au0.4Pd0.4/rGO, 5.0 mL of aqueous solution containing
AgNO3 (0.02 mmol), Na2PdCl4 (0.04 mmol) and HAuCl4
(0.04 mmol) was added into the well dispersed GO aqueous
55 solution (32.5 mg, 45 mL), and then 40 mL of ethanol was
added into above solution. The PH of the solution was
adjusted to be 9-10 by adding KOH (1.0 M) aqueous solution.
The solution was refluxed in an water bath at 353 K for 3 h
with stirring. After 3 h, the obtained product is washed with
60 water for several times and re-dispersed in 10 mL of water for
the catalytic H2 generation from the FA aqueous solution at
298 K. Additionally, AgAuPd/rGO with different Ag:Au:Pd
molar ratio, the physical mixture of Ag0.2Au0.4Pd0.4 and rGO,
Pd/rGO and rGO were also synthesized through the same
65 method mentioned above for comparation. Since pure
graphene tends to aggregate due to its π - π stacking
interactions,[17a] various effors have been made to avoid the
aggration of graphene based catalysts, including electrostatic
stabilization, chemical functionalization and adhering metal
70 nanoparticles (NPs) on graphene sheets.[17a-c] The present co-
reduction method to prepare AgAuPd/rGO may has the
priority to suppress the aggration of rGO because the in situ
generated NPs can increase the interlayer spacing between
rGO sheets.[17d]
10 conversion and excellent catalytic activity toward the
hydrogen generation form decomposition of formic acid
without any additive at room temperature.
Hydrogen (H2) is capable of providing highly stable, efficient
and pollution-free power.[1] Its potential applications in
15 onboard automotive industry and stationary power generation
are promising.[2] However, H2 generation from renewable
sources and its secure storage remain as a big challenge in the
H2 energy based economy.[3] Formic acid (FA, HCOOH), as a
promising H2 storage material with nontoxicity, high energy
20 density, excellent stability, and possible regenerability by
hydrogenation of carbon dioxide (CO2), has attracted much
research interest.[4,5] H2 can be generated by catalytic
dehydrogenation of FA with the byproduct of CO2.[4] The
undesirable dehydration of FA to generate carbon monoxide
25 (CO) should be avoided.[4,6]
Recently, many homogeneous and heterogeneous catalysts
have been intensely investigated to increase the kinetic
property of the dehydrogenation of FA at the mild reaction
condition.[4,7]
For
example,
metal
complex-based
30 homogeneous catalysts have been reported to have high
performance for the formic acid decomposition at near-
ambient
temperatures.[4,8]
Generally,
heterogeneous
nanocatalysts have the superiorities on controlling, retrieving,
and recycling issues during or after reactions.[6,9] Therefore,
35 there is a strong desire to develop heterogeneous catalysts
with high activity and selectivity for the formic acid
decomposition under mild conditions.[9,10] The performance of
nanocatalyst is highly depended on its particle size, dispersion,
crystallinity, support and etc.[11, 12] Herein we report a facile,
40 eco-friendly, one-pot method for the synthesis of the reduced
graphene oxide (rGO) supported AgAuPd ultrafine nanoalloy
(~3 nm) with good dispersion and crystallinity (AgAuPd/rGO)
by simultaneous reduction using ethanol as the reduction
agent. The prepared AgAuPd/rGO exhibits the 100% H2
45 selectivity, and high activity toward H2 generation from FA
without any additive at 298 K.
75
Scheme 1 Schematic illustration for preparation of AgAuPd/rGO
The morphology of the as-prepared specimens,
Ag0.2Au0.4Pd0.4/rGO composite and Ag0.2Au0.4Pd0.4 NPs are
characterized by transmission electron microscopy (TEM). It
80 can be seen that the Ag0.2Au0.4Pd0.4 NPs supported on rGO are
well dispersed with an average particle size of about 3.0nm
(Fig. 1a and b), while the NPs without rGO are seriously
aggregated (Fig. 1d), suggesting that rGO lead to the good
dispersion of Ag0.2Au0.4Pd0.4 NPs on its surface. The high-
85 resolution TEM (HRTEM) image reveals the crystalline
Graphene oxide (GO) aqueous solution is firstly prepared
using the modified Hummers' method as the graphene
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DOI: 10.1039/C5TA03111G
Ag0.2Au0.4Pd0.4/rGO); (d) TEM images for free Ag0.2Au0.4Pd0.4 NPs; (e) XRD
pattern of Ag0.2Au0.4Pd0.4/rGO NPs; XPS spectra of C 1s in (f) GO and (g)
Ag0.2Au0.4Pd0.4/rGO; and XPS spectra of (h) Ag 3d for Ag/rGO and
25 Ag0.2Au0.4Pd0.4/rGO, (i) Au 4f for Au/rGO and Ag0.2Au0.4Pd0.4/rGO, (j) Pd 3d
for Pd/rGO and Ag0.2Au0.4Pd0.4/rGO.
nature of the Ag0.2Au0.4Pd0.4 NPs on rGO, and the lattice
spacing is measured to be 0.231 nm （Fig. 1c）, which is
between those of the (111) planes of face-centered cubic (fcc)
Au (0.235 nm, JCPDS file:65-8601), Ag (0.235 nm, JCPDS
file:65-2871) and Pd (0.224 nm, JCPDS file:65-2867).[14] And
this reveals the formation of AgAuPd trimetallic alloy
structure. Moreover, the X-ray diffraction (XRD) pattern of
Ag0.2Au0.4Pd0.4/rGO composite (Fig. 1e) shows that, besides
the peak of (002) plane of rGO,[14c] all diffraction peaks can
10 be assigned to (111), (200), (220) and (311) planes of a fcc
strcture located between fcc Ag, Au and Pd, which further
proves that the Ag0.2Au0.4Pd0.4 is formed as an alloy. The
accurate molar ratio of Ag:Au:Pd is determined to be
0.17:0.34:0.49 by inductively coupled plasma-atomic
15 emission spectrometry (ICP-AES), which is close to the
appointed value. Based on the above analyses, Ag0.2Au0.4Pd0.4
nanoalloy supported on rGO has been succesfully synthesized
by the present facile method.
5
X-ray photoelectron spectroscopy (XPS) measurements are
used to determine the compositions and chemical states of the
Ag0.2Au0.4Pd0.4/ rGO hybride. The result for C 1s of the as-
30 prepared GO (Fig. 1f) indicates that six different peaks
centered at 284.5, 284.8, 285.6, 286.7, 287.8 and 288.8 eV are
observed, corresponding to sp2C, C-C, sp3C, -C-O, -C=O and
–COO groups, respectively.[15,16] After reduction, the
intensities of all the C 1s peaks binding to oxygen obviously
35 decrease (Fig. 1g), revealing that most of the oxygen
containing species are removed and the majority of the
conjugated
C networks are restored. This confirms the
reduction of GO to rGO during the preparation of
Ag0.2Au0.4Pd0.4/rGO hybrid, which is consistent with the
40 Raman (Fig. S1) and ultraviolet visible (UV-Vis, Fig. S2)
specra. Additionally, the XPS results show that the binding
energy for Ag 3d in Ag0.2Au0.4Pd0.4/rGO is located at the
higher value relative to that in Ag/rGO (Fig. 1h); while
binding energies for Au 4f and Pd 3d in Ag0.2Au0.4Pd0.4/rGO
45 are shifted to the lower values compared with those in
Au/rGO and Pd/rGO, respectively. These shifts demonstrate
that some electrons are transferred from Ag to Au and Pd
atoms in the Ag0.2Au0.4Pd0.4/rGO alloy structure. Such
electron transfer in Ag0.2Au0.4Pd0.4/rGO has the potential to
50 endow itself with the high activity to H2 generation from FA
at 298 K.
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
Ag Au Pd /rGO
0.2 0.4 0.4
Raw
Fit
(f)
(e)
Au(JCPDS:65-8601)
Pd(JCPDS:65-2867)
Ag(JCPDS:65-2871)
sp2C
C-C
sp3
C
-C-O
-C=O
-COO-
280
282
284
286
288
290
292
294
10
20
30
40
50
60
70
80
90
Binding Enegy / eV
2θ / degree
0
20
40
60
80
100
120
AgAuPd/rGO
Raw
(g)
(h)
Fit
Time / min
sp2C
C-C
sp3C
-C-O
Fig. 2 Gas generation by the decomposition of FA (1 M, 5 mL) vs. time in
the presence of (a) Ag0.2Au0.4Pd0.4/rGO hybrid, (b) the physical mixture of
55 Ag0.2Au0.4Pd0.4 and rGO, (c) Ag0.33Au0.67/rGO, (d) Ag0.33Pd0.67/rGO, (e)
Au0.5Pd0.5/rGO, (f) Ag/rGO, (g) Au/rGO, (h) Pd/rGO, (i) rGO at 298K
under ambient atmosphere. (nmetal/nFA = 0.02)
-C=O
-COO-
Ag/rGO
280
282
284
286
288
290
292
364 366 368 370 372 374 376 378 380
Binding Energy / eV
Fig. 2 shows the catalytic activities of Ag0.2Au0.4Pd0.4/rGO
hybrid, the physical mixture of Ag0.2Au0.4Pd0.4 and rGO, bi-
Binding Energy / eV
AgAuPd/rGO
AgAuPd/rGO
(j)
(i)
60 metallic
(Ag0.33Au0.67/rGO,
Ag0.33Pd0.67/rGO
and
Au0.5Pd0.5/rGO), mono-metallic (Ag/rGO, Au/rGO and
Pd/rGO) counterparts and rGO for H2 generation from FA
Au/rGO
Pd/rGO
decomposition at 298
K
under ambient atmosphere.
Obviously, the as-prepared Ag0.2Au0.4Pd0.4/rGO hybrid
65 exhibits the highest activity, with which 245 mL of gas can be
released within 77.5 min without any additive at 298 K,
corresponding to a conversion of 100%. Furthermore, the
initial TOF over the Ag0.2Au0.4Pd0.4/rGO composite is
80
82
84
86
88
90
333
336
339
Binding Energy / eV
342
345
348
351
Binding Energy / eV
20 Fig. 1 TEM images with the (a) low, (b) middle, (c) high resolutions for
Ag0.2Au0.4Pd0.4/rGO (Fig. 2b inset: the corresponding SAED pattern for
2
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DOI: 10.1039/C5TA03111G
measured to be 73.6 mol H2 mol catalyst-1 h-1 at 298 K during
the first 20 min, which is faster than most of the additive free 60 show the similar eletronic states with no obvious peak shift
the XPS spectra of Ag, Au, and Pd in the three specimens
heterogeneous catalysts ever reported at the room temperature.
(Fig. S11). The catalytic activities of the there specimens for
hydrogen generation from FA at 298 K are presented in Fig.
S10 for comparasion. It can be seen that, within 90 min, only
150 mL of gas can be generated over Ag0.2Au0.4Pd0.4/rGO
10h, 21, 23b, 23c, 24, 25]
(Table S1)[6,
In contrast, the physical
mixture (Ag0.2Au0.4Pd0.4 and rGO) shows much lower activity,
with which 110 mL of gas is obtained within 120 min. Over
5
bimetallic Ag0.33Pd0.67/rGO and Au0.5Pd0.5/rGO catalysts, 124 65 reduced by NaBH4 at 353 K, and no gas was obtained with
and 120 mL gas can be released within 120 min, respectively,
while Ag0.33Au0.67/rGO has no activity. With monometallic
10 Pd/rGO, only 47 mL of gas can be generated within 120 min,
whereas Au/rGO and Ag/rGO shows no activity. In addition,
catalyst reduced by NaBH4 at 298 K. Therefore, it can be
conclued that the small particle size, good dispersity and high
degree of crystallinity due to the present synthetic method
result
in
the
excellent
catalytic
performace
of
no gas is generated from FA in the case of only rGO, 70 Ag0.2Au0.4Pd0.4/rGO.
suggesting that rGO serve as a support for the growth of
Ag0.2Au0.4Pd0.4/rGO NPs, rather than catalysts for this
15 reaction. Therefore, the enhanced catalytic performance of
Ag0.2Au0.4Pd0.4/rGO may be attributed to its special
In summary, Ag0.2Au0.4Pd0.4 NPs decorated on rGO with
small particle size, good dispersity and high degree of
crystallinity are successfully synthesized by co-reduction of
GO and the metal precursors using ethanol as the reduction
composition and surface electronic state in the alloy tructure 75 agent at 353 K. The resultant Ag0.2Au0.4Pd0.4/rGO composite
as well as the small particle size and well dispersion due to
the support of rGO. The generated gas over
20 Ag0.2Au0.4Pd0.4/rGO is identified by mass spectrometry (MS,
Fig. S3) and gas chromatography (GC, Fig. S4) to be H2 and
shows 100% conversion, 100% H2 selectivity, and excellent
activity for dehydrogeneration of FA in aqueous solution
without any additive at room temperature. This improvement
in the catalytic performance of the Ag0.2Au0.4Pd0.4/rGO
CO2 with the H2: CO2 molar ration of 1.0: 1.0, and no CO has 80 composite may strongly encourage the practical application of
been detected (Fig. S5, detection limit for CO: 10 ppm). This
indicates the as-synthesized Ag0.2Au0.4Pd0.4/rGO catalyst can
25 catalyze FA aqueous solution decomposition into CO-free H2,
which is very important for fuel cell applications. To further
determine the effect of the metal composition in system of
AgAuPd/rGO on the catalytic performance, the molar ration
of Ag: Au: Pd has been varied by several values. Setting the
30 molar content of Ag as a constant of 0.2, Ag0.2Au0.8-xPdx/rGO
system (x=0, 0.2, 0.4, 0.6, 0.8) reaches its highest activity
when the molar ratio of Au:Pd is 1:1, namely, x is 0.4 (Figure
S6). And then, setting the molar ratio of Au:Pd as 1:1, Ag1-
2yAuyPdy/rGO (y= 0.5, 0.4, 0.3, 0.25, 0.2, and 0) shows the
35 best performace when the Ag molar content is 0.2, namely, y
is 0.4 (Figure S7). As a result, once the ratio of Ag: Au: Pd is
changed from 0.2: 0.4: 0.4, the resultant AgAuPd/rGO shows
the decreased catalytic performance, and can not lead to the
full conversion of FA within 120 min.
FA as a promising H2 storage material.
Acknoeledgements
This work was supported in part by theNational Natural
Science Foundation of China (51471075, 51401084 and
85 51101070); National Key Basic Research, Development
Program(2010CB631001).
Notes and references
Key Laboratory of Automobile Materials Ministry of Education,
Department of Materials Science and Engineering Jilin University,
90 Changchun 130022, China; E-mail: junminyan@jlu.edu.cn
† Electronic Supplementary Information (ESI) available: experimental
procedures; Raman, UV-Vis, XPS, TEM, MS and GC, XRD data; TOF
and conversion data; and the results of H2 generation from FA. See DOI:
10.1039/b000000x/
95
40
In order to demonstrate the advantages of ethanol as the
reducing agent, we use similar method to synthesize
Ag0.2Au0.4Pd0.4/rGO NPs with NaBH4 as the reducing agent,
and the reducing temperature is 353 K and 298 K respectively.
As shown in Fig. S8, the NPs reducing at 353 K have a larger
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Journal of Materials Chemistry A
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DOI: 10.1039/C5TA03111G
Table of Contents Entry
Well dispersed and ultrafine AgAuPd nanoalloy supported on rGO shows excellent catalytic performance toward
hydrogen generation from formic acid decomposition.