Controlling catalytic dehydrogenation of formic acid over low-cost transition metal-substituted AuPd nanoparticles immobilized by functionalized metal-organic frameworks at room temperature

Article abstract of DOI:10.1039/c6ta05790j

A series of nonprecious transition metal (Fe, Co and Ni)-substituted AuPd nanoparticles (NPs) immobilized by porous metal-organic frameworks (MOFs) containing different functional groups were synthesized, and their catalytic performance for the dehydrogenation of formic acid (HCOOH, FA) was studied. In comparison with AuPdCo NPs immobilized by bare MIL-101 and MIL-101 functionalized by electron-accepting groups NO₂ and SO₃H, which had very low H₂ selectivity and activity, AuPdCo NPs immobilized by MIL-101 functionalized by electron-donating group NH₂ exhibited 100% H₂ selectivity and drastically high activity featuring a turnover frequency (TOF) value of 347 h^-1 at 298 K, comparable to the reported values of highly active heterogeneous noble-metal catalysts and homogeneous catalysts. The remarkably different and controllable activity and H₂ selectivity may be attributed to the different bonding modes between AuPdCo NPs and functionalized MOFs, which might lead to the different interaction pathways between the intermediates from the splitting of FA molecules and the metallic atoms on the catalyst surface.

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Controlling catalytic dehydrogenation of formic acid over low-cost
transition metal-substituted AuPd nanoparticles immobilized by
functionalized metal-organic frameworks at room temperature
Received 00th January 20xx,
Accepted 00th January 20xx
Jia Cheng, Xiaojun Gu,* Penglong Liu, Tianshu Wang and Haiquan Su*
DOI: 10.1039/x0xx00000x
A series of nonprecious transition metal (Fe, Co and Ni)-substituted AuPd nanoparticles (NPs) immobilized by porous
metal-organic frameworks (MOFs) containing different functional groups were synthesized, and their catalytic
performance on the dehydrogenation of formic acid (HCOOH, FA) was studied. In comparison with AuPdCo NPs
immobilized by bare MIL-101 and MIL-101 functionalized by electron-accepting groups NO2 and SO3H, which had very low
H2 selectivity and activity, AuPdCo NPs immobilized by MIL-101 functionalized by electron-donating group NH2 exhibited
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1
100 % of H2 selectivity and drastically high activity featuring turnover frequency (TOF) value of 347 h− at 298 K,
comparable to the reported values of the highly active heterogeneous noble-metal catalysts and homogeneous catalysts.
The remarkably different and controllable activity and H2 selectivity may be attributed to the different bonding modes
between AuPdCo NPs and functionalized MOFs, which might lead to the different interaction pathways between the
intermediates from the splitting of FA molecules and the metallic atoms on the catalyst surface.
catalysts only consist of noble metals such as Au and Pd, which
are the active species;[5] however, their scarcity in the earth
limits their practical applications. The partial substitution of
1. Introduction
The search for effective hydrogen storage materials and
methods for hydrogen generation in safe and efficient ways
remains one of the most challenging barriers in the
implementation of a fuel-cell-based hydrogen economy.[1]
Formic acid (HCOOH, FA), which has high energy density,
nontoxicity and excellent stability at room temperature and
can be obtained by biomass processing and artificial
photocatalytic CO2 reduction, has attracted tremendous
research interests for hydrogen storage and generation.[2]
Recently, noteworthy advances have been made in the field of
FA decomposition using various homogeneous catalysts in the
presence of organic amines as adducts, which can be
considered as proton scavengers to facilitate the cleavage of
noble metals by nonprecious metals such as Fe, Co and Ni in a
heterometallic catalyst may be an efficient method to solve
this problem. However, in many cases, this type of substitution
always leads to the decreasement in the catalytic
performance.[6] Though few catalysts containing noble metals
and nonprecious metals have been recently reported for the
FA decomposition,[6a] their activities still remain to be
enhanced at mild conditions, especially at room temperature.
In general, the properties of active metal nanoparticles (NPs)
in a supported catalyst can be adjusted through the interaction
between metal NPs and supports, which leads to the
modulation of activity and selectivity in a reaction.[7] To this
end, the rational design of supports functionalized by organic
O−H in FA molecule and then leads to the accelerated cleavage
of C
−
H in HCOO− and the final rate of hydrogen generation.[3] groups with electron donors or acceptors, which can be used
to tune the electronic state of active heterometallic NPs
For the practical applications such as convenient separation of
catalysts and fixed-bed flow-through operations, it is desirable
to develop highly efficient heterogenerous catalysts for the
decomposition of FA to generate H2 without CO poisoning the
catalysts in fuel cells.[4] So far, in spite of the tremendous
research efforts in the field of FA decomposition, almost all the
containing nonprecious metals, is the key issue to achieve the
high-performance hydrogen production from FA at room
temperature.
Compared to inorganic materials such as zeolites and Al2O3
with rigid framework structures,[8] porous metal-organic
frameworks (MOFs) have been recently attracted much
attention due to their high surface area, controllable
structures and easy functionalization through postsynthetic
modification or ligand design.[9] In the research on catalysis,
MOFs have been mostly used as supports that limit the
migration and aggregation of metal NPs using the confinement
effect of pores.[10] In fact, besides the pores of MOFs, their
functional groups also can immobilize metal NPs through
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strong interactions between these groups and metal NPs.[11] blockpoly(propylene glycol)-block-poly(ethylene glycol) (P123
,
More importantly, the functional groups featuring uniform Sigma-Aldrich), (3-aminopropyl)-triethoxysilane (APTES, Sigma-
sites in the well-defined crystalline structures of MOFs can Aldrich, 99%) and ethanol (C2H5OH, Tianjin FengChuan
help us explore the most possible activation ways of reaction Chemical Reagent Technologies Co., Ltd., >99.7%) were
molecules on the metal atoms on the surface of metal NPs, obtained. Deionized water was utilized in all experiments.
which affect the catalytic acvitity and selectivity. On the basis
2.2 Synthesis and catalytic study
of these facts, it can be envisioned that MOFs containing
All the catalysts were synthesized using an impregnation-
functional groups could be used to effectively immobilize
reduction process. Typically, for the synthesis of
heterometallic NPs containing nonprecious metals, which
Au0.28Pd0.47Co0.25/MIL-101-NH2, HAuCl4⋅4H2O (0.0115 g, 0.028
might lead to the high-performance selective activation of the
FA molecule for hydrogen generation at room temperature.
Herein, we reported a series of low-cost transition metal-
substituted AuPd NPs immobilized by functionalized MOFs,
which were used as catalysts for FA dehydrogenation. In order
to explore the effect of different functional groups on FA
dehydrogenation, MIL-101 functionalized by NH2, NO2 and
SO3H were selected to prepare heterometallic catalysts. As
expected that AuPdM (M = Fe, Co, Ni) NPs immobilized by
different types of MOFs exhibited remarkably different
activities and H2 selectivity at room temperature. Among these
catalysts with the low consumption of noble metals, AuPdCo
NPs immobilized by MIL-101-NH2 containing electron donors
exhibited 100 % of H2 selectivity and the exceedingly high
activity. Moreover, the possible activation pathways of FA
molecules over the catalysts containing different functional
groups were also discussed.
mmol), Na2PdCl4 (0.0138 g, 0.047 mmol) and Co(NO3)2·6H2O
(0.0073 g, 0.025 mmol) were dispersed in deionized H2O (4 mL).
Then, activated MIL-101-NH2 (0.04 g) was added into the
solution with stirring for 2 h. After that, the deionized H2O (2
mL) containing NaBH4 (0.06 g) was added into the above
mixture, which was vigorously stirred in Ar atmosphere for 2 h
to obtain the Au0.28Pd0.47Co0.25/MIL-101-NH2 as
a black
suspension for the catalytic reaction. For the synthesis of
Au0.28Pd0.47Fe0.25/MIL-101-NH2 and Au0.28Pd0.47Ni0.25/MIL-101-
NH2, the process was same as that for Au0.28Pd0.47Co0.25/MIL-
101-NH2 except for the utilization of Fe(NO3)2·6H2O and
Ni(NO3)2·6H2O as transition metal sources, respectively.
For comparison of the effects of molar ratios of Au/Pd/Co
and different supports on catalytic hydrogen generation, other
twenty one trimetallic, bimetallic and monometallic catalysts,
Au0.28Pd0.47Co0.25/MIL-101-NO2,
Au0.28Pd0.47Co0.25/MIL-101-
SO3H, Au0.28Pd0.47Co0.25/MIL-101, Au0.28Pd0.47Co0.25/MOF-5-NH2,
Au0.28Pd0.47Co0.25/MOF-5,
Au0.28Pd0.47Co0.25/SBA-15-NH2,
Au0.19Pd0.56Co0.25/MIL-101-NH2,
Au0.47Pd0.28Co0.25/MIL-101-
Au0.28Pd0.47Co0.25/SBA-15,
Au0.375Pd0.375Co0.25/MIL-101-NH2,
2. Experimental
2.1 Chemicals
NH2, Au0.34Pd0.56Co0.1/MIL-101-NH2, Au0.32Pd0.53Co0.15/MIL-101-
NH2, Au0.26Pd0.44Co0.3/MIL-101-NH2, Au0.24Pd0.41Co0.35/MIL-101-
NH2, Au0.225Pd0.375Co0.4/MIL-101-NH2, Au0.75Co0.25/MIL-101-NH2,
Au0.38Pd0.62/MIL-101-NH2, Pd0.75Co0.25/MIL-101-NH2, Au/MIL-
101-NH2, Pd/MIL-101-NH2 and Co/MIL-101-NH2 were
synthesized using the similar process to that of
All chemicals were commercial and used without further
purification. Formic acid (HCOOH, Sigma-Aldrich, 99.0%),
sodium formate (HCOONa, SF, Sigma-Aldrich,
>99.0%),
tetrachloroauric acid (HAuCl4·4H2O, Sinopharm Chemical
Reagent Co., Ltd., Au >47.8%), palladium chloride (PdCl2,
Sinopharm Chemical Reagent Co., Ltd., Pd >59.0%), cobalt
nitrate hexahydrate (Co(NO3)2·6H2O, Sinopharm Chemical
Reagent Co., Ltd., ≥99.0%), iron nitrate hexahydrate
(Fe(NO3)2·6H2O, Sinopharm Chemical Reagent Co., Ltd.,
≥99.0%), nickel nitrate hexahydrate (Ni(NO3)2·6H2O,
Sinopharm Chemical Reagent Co., Ltd, ≥99.0%), sodium
borohydride (NaBH4, J&K Scientific Ltd., 98.0%), sodium
hydroxide (NaOH, Sinopharm Chemical Reagent Co.,
Ltd., >99.0%), hydrochloric acid (HCl, Beijing Chemical Plant,
AR), nitric acid (HNO3, Beijing Chemical Plant, AR), sulfuric acid
(H2SO4, Tianjin Chemical Reagent Factory, 95-98%), tin chloride
Au0.28Pd0.47Co0.25/MIL-101-NH2
Information).
(see
the
Supporting
For the catalytic study, the as-prepared catalyst was kept in
a two-necked round-bottom flask. One neck was connected to
a gas burette, and the other was connected to a pressure-
equalization funnel to introduce FA-SF aqueous solution. The
catalytic reaction began once the FA-SF solution was injected
into the flask. The evolution of gas was monitored using the
gas burette. The reaction was carried out at different
temperatures under ambient atmosphere.
2.3 Catalyst characterization
dihydrate (SnCl2⋅
AR), zinc nitrate hexahydrate (Zn(NO3)2
2H2O, Sinopharm Chemical Reagent Co., Ltd.,
6H2O, Sinopharm
Powder X-ray diffraction (PXRD) measurements were
performed on a Panalytical X-Pert X-ray diffract meter with a
Cu-Kα source. The surface area measurements were
performed by N2 adsorption/desorption at liquid N2
⋅
Chemical Reagent Co., Ltd., ≥99.0%), chromium nitrate
nonahydrate (Cr(NO3)3·9H2O, Sinopharm Chemical Reagent Co.,
Ltd., ≥99.0%), 2-aminoterephthalic acid (C8H7NO4, Sigma-
Aldrich, 99.0%), terephthalic acid (C8H6O4, Aladdin, 99+%),
N,N-diethylformamide (DEF, Tianjin Fengchuan Chemical
Reagent Technologies Co., Ltd., ≥ 99.5%), chloroform (CHCl3,
Aladdin, ≥ 99.5%), tetraethyl orthosilicate (TEOS, Sinopharm
Chemical Reagent Co., Ltd., ≥99%), poly(ethylene glycol)-
o
temperature (77 K) after dehydration under vacuum at 150 C
for 12 h using automatic volumetric adsorption equipment
(Autosorb-iQ2-MP). The X-ray photoelectron spectroscopy
(XPS) analyses were carried on an ESCALAB250 (Thermo VG
Corp.) equipped with an Al-Kα X-ray excitation source. The
2 | J. Name., 2012, 00, 1-3
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transmission electron microscopy (TEM, JEM-2010) equipped
with an energy dispersive X-ray spectroscopy (EDS) for
elemental analysis was applied for the morphologies and
composition of the as-synthesized samples. The IR spectra
were recorded on a Thermo Fisher Scientific's NEXUS-670
infrared spectrometer in the wavenumber range from 400 to
4000 cm−1. Detailed analyses for CO2, H2 and CO in the gas
generated from HCOOH were performed on Shimadzu GC-
2014 with thermal conductivity detector (TCD) and hydrogen
flame ionization detector (FID)-methanator (detection limit:
∼10 ppm). Inductively coupled plasma-atomic emission
spectroscopy (ICP-AES) measurement was performed on a
Thermo Jarrell Ash (TJA) Atomscan Advantage instrument.
3. Results and discussion
The heterometallic AuPdM NPs immobilized by functionalized
MOFs were synthesized by a facile impregnation-reduction
method (Fig. 1). The TEM images of Au0.28Pd0.47Co0.25/MIL-101-
NH2 showed that AuPdCo NPs were dispersed well and had an
Fig. 2 (a) TEM, (b) HRTEM and (c) HAADF-STEM images of
average size of 2.3
± 0.4 nm (Fig. 2a and S1). The high-
Au0.28Pd0.47Co0.25/MIL-101-NH2
and
the corresponding
resolution TEM (HRTEM) image revealed the crystalline nature
of the AuPdCo NPs and the lattice spacing was measured to be
0.230 nm (Fig. 2b), which was similar to that of the (111) plane
of face-centered cubic (fcc) Au (0.235 nm).[12] The elemental
mapping corresponded to a high-angel annular dark-field
scanning TEM (HAADF-STEM) image showed that the elements
of Au, Pd, Co, Cr, C, N and O were homogeneously distributed
in the randomly selected area (Fig. 2d-j), indicating the
formation of homogeneous AuPdCo alloy NPs dispersed on
MIL-101-NH2. The elemental mappings of AuPdFe/MIL-101-
NH2 also exhibited the formation of AuPdFe alloy NPs, which
were homogenerously dispersed on MIL-101-NH2 (Fig. S5). In
addition, the average sizes of AuPdFe and AuPdNi NPs in
Au0.28Pd0.47Fe0.25/MIL-101-NH2 and Au0.28Pd0.47Ni0.25/MIL-101-
elemental mappings for (d) Au, (e) Pd, (f) Co, (g) Cr, (h) N, (i) O
and (j) C.
The PXRD patterns demonstrated that the AuPdM NPs has
the fcc structure of metallic Au (Fig. S9). The coexistence of Au,
Pd and M elements in the pure fcc phase confirmed the
formation of a AuPdM alloy. Especailly, compared with fcc Au
(JCPDS file: 65-8601), the diffraction peaks of the present fcc
phase containing Au, Pd (JCPDS file: 65-2867) and Co (JCPDS
file: 15-0806) were slightly shifted to higher angles (Fig. S10),
which indicated a little decrease in the symmetry of the crystal
lattice of Au after the formation of trimetallic alloy.[6a] The
above results could also be explained that due to the relatively
small differences of the atomic radii of Au, Pd and Co, Pd and
Co atoms could be incorporated into the Au lattice to form an
fcc alloy structure in AuPdCo/MIL-101-NH2.[6a] The
investigation of IR spectra exhibited that there were the
NH2 were 5.2
± 0.5 and 4.2 ± 0.5 nm, respectively (Fig. S3 and
S6). All the EDS results also showed that the transition metals
Fe, Co and Ni were incorporated into the heterometallic NPs
(Fig. S2, S4 and S7). The molar ratios of Au:Pd:Co, Au:Pd:Fe and
Au:Pd:Ni in the three catalysts Au0.28Pd0.47Co0.25/MIL-101-NH2,
Au0.28Pd0.47Fe0.25/MIL-101-NH2 and Au0.28Pd0.47Ni0.25/MIL-101-
bending frequency band of N
stretching vibration of C
N at 1260 cm-1 in MIL-101-NH2, the
asymmetric and symmetry stretching vibrations of N O at
N at
−
H at 1588 cm-1 and the
−
−
−
1540 and 1354 cm-1 and the stretching vibration of C
NH2
were
determined
to
be
0.283:0.467:0.250,
1256 cm-1 in MIL-101-NO2 as well as the asymmetric and
symmetry stretching vibrations of O=S=O at 1229 and 1180
0.281:0.473:0.246 and 0.284:0.475:0.241 by ICP-AES,
respectively (Table S1).
cm-1 and stretching vibration of S O at 1080 cm-1 in MIL-101-
−
SO3H (Fig. S11). This indicated that the three functional groups
NH2, NO2 and SO3H were incorporated into MIL-101
framework structures.[13] The IR spectra also confirmed the
presence of functional groups in the catalysts (Fig. S12). The
XPS results showed that the binding energies for Pd 3d and Au
4f in Au0.28Pd0.47Co0.25/MIL-101-NH2 were both shifted to the
lower values compared with those in Pd/MIL-101-NH2 and
Au/MIL-101-NH2, while the binding energy for Co 2p in
Au0.28Pd0.47Co0.25/MIL-101-NH2 was shifted to higher value
relative to that in Co/MIL-101-NH2 (Fig. S13). These shifts
demonstrated that some electron cloud of Co deviated to Au
Fig. 1 Schematic illustration of the preparation and application
of AuPdM/MOF-R nanocatalysts for the dehydrogenation of FA.
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and Pd atoms in the AuPdCo alloy NPs. This conclusion can also catalysts under the similar conditions, i.e., AuPd-MnOx/ZIF-8-
1
be explained using the difference in the electronegativity of Co, rGO (382.1 at 298 K),[5h] Co0.30Au0.35Pd0.35/C (80− at 298 K),[6a]
1
1
Au and Pd: since the electronegativity of Co is less than that of Au/ZrO2 (252 h− at 298 K)[4b] and Pd/MSC-30 (750 h− at 298
Au and Pd,[14] the electron cloud in Co would deviate to Au and K)[5e] (Table S2). It should be noted that Au0.28Pd0.47Fe0.25/MIL-
Pd in the AuPdCo alloy NPs. Such electron cloud deviation in 101-NH2 and Au0.28Pd0.47Ni0.25/MIL-101-NH2 also had high
1
heterometallic NPs had the potential to endow themselves activities, featuring TOF values of 261 and 217 h− in 80 % of
with the high activity and selectivity in hydrogen generation FA conversion at 298 K, respectively. The gas chromatograph
from FA. Moreover, the Au and Pd species were in metallic (GC) analysis confirmed that no CO existed in the mixture of H2
state, while the low-cost transition metal species in the small and CO2 generated in FA decomposition over
sized trimetallic NPs in Au0.28Pd0.47Fe0.25/MIL-101-NH2, Au0.28Pd0.47Co0.25/MIL-101-NH2 and Au0.28Pd0.47Fe0.25/MIL-101-
Au0.28Pd0.47Ni0.25/MIL-101-NH2, Au0.28Pd0.47Co0.25/MIL-101-NO2 NH2 (Fig. 4a), which was crucial for fuel cell applications.
and Au0.28Pd0.47Co0.25/MIL-101-SO3H were in oxidation state Moreover, the GC analysis confirmed the equal molar amount
due to that metallic Fe, Co and Ni with low reduction of H2 and CO2 in the generated gas mixture (Fig. 4b). Moreover,
potentials were oxided in the air (Fig. S14-17). In comparison the molar ratio of FA/SF had an obvious effect on the
with MIL-101-NH2 with aperture sizes (2.9−3.4 nm), the performance of Au0.28Pd0.47Co0.25/MIL-101-NH2. Its activity
appreciable decrease in surface areas of catalysts indicated increased with increasing the concentration of SF in the FA-SF
that the cavities of the support framework were occupied by solution until the molar ratio of FA/SF reached 1:1, after which
AuPdM NPs and/or blocked by AuPdM NPs located at the further increase in the concentration of SF had only slight
surface (Fig. S18).
effect on FA dehydrogenation (Fig. S21). It needed to be
explained that though the decomposition of FA was
endothermic, the reaction temperature was controlled and
almost kept constantly at 298 K in the catalytic process (Fig.
S22). This ensured that the catalytic reaction was not
influenced by the change of the reaction temperature.
Fig. 3 Plots of time versus volume of the generated gas (H2 and
CO2)
Au0.28Pd0.47Co0.25/MIL-101-NH2, (b) Au0.28Pd0.47Fe0.25/MIL-101-
NH2 and (c) Au0.28Pd0.47Ni0.25/MIL-101-NH2 (nmetal nFA = 0.0125)
from
FA-SF
aqueous
solution
over
(a)
/
at 298 K. Inset: TOF values for FA dehydrogenation over the
above three catalysts.
Strikingly, the three catalysts Au0.28Pd0.47Co0.25/MIL-101-NH2,
Au0.28Pd0.47Fe0.25/MIL-101-NH2 and Au0.28Pd0.47Ni0.25/MIL-101-
NH2 exhibited complete and selective decomposition of FA
into H2 and CO2 with exceedingly high activities at 298 K (Fig.
3). Particularly, Au0.28Pd0.47Co0.25/MIL-101-NH2 had a much
better activity than Au0.28Pd0.47Fe0.25/MIL-101-NH2 and
Au0.28Pd0.47Ni0.25/MIL-101-NH2. 445 mL of gas generated in a
FA-SF system. No gas was detected from the hydrolysis of SF at
298
K
(Fig. S20), which further confirmed that
promoted complete
Au0.28Pd0.47Co0.25/MIL-101-NH2
Fig. 4 GC spectra obtained using (a) FID-Methanator for the
mixture of CO and CO2 with 100 ppm of CO and the evolved
gas and (b) TCD for the evolved gas from FA-SF aqueous
decomposition of FA into H2 and CO2. The turnover frequency
(TOF) value over Au0.28Pd0.47Co0.25/MIL-101-NH2 was measured
1
to be 347 h− in 80 % of FA conversion at 298 K, which was
solution
over
Au0.28Pd0.47Co0.25/MIL-101-NH2
and
among the highest reported so far and comparable to the
values acquired from the heterogeneous noble-metal-based
Au0.28Pd0.47Fe0.25/MIL-101-NH2 (nmetal
/nFA = 0.0125) at 298 K.
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had much higher activity than Au0.28Pd0.47Co0.25/MOF-5 (Fig.
S25). The TEM investigation showed that the average sizes of
AuPdCo
NPs
in
Au0.28Pd0.47Co0.25/MOF-5-NH2
0.5 and 7.4
and
Au0.28Pd0.47Co0.25/MOF-5 were 3.6
±
±
0.5 nm,
respectively (Fig. S26 and S28). The EDS and ICP-AES results
indicated that the Co species was incorporated into the
heterometallic
NPs
in
Au0.28Pd0.47Co0.25/MIL-101-NO2,
Au0.28Pd0.47Co0.25/MIL-101-SO3H, Au0.28Pd0.47Co0.25/MOF-5-NH2
and Au0.28Pd0.47Co0.25/MOF-5 (Fig. S23, S24, S27 and S29, Table
S1). In order to check whether the NH2 group in all the
supports was crucial for FA dehydrogenation, we selected
inorganic SiO2 SBA-15 and NH2-functionalized SBA-15 (SBA-15-
NH2) as supports to immobilize AuPdCo NPs and examined
their catalytic properties. The results showed that
Au0.28Pd0.47Co0.25/SBA-15 almost had no activity and
Au0.28Pd0.47Co0.25/SBA-15-NH2 had low activity and 95 % of H2
selectivity for decomposition of FA into H2 (Fig. S30). The
above results confirmed that the NH2 group in all the supports
indeed drastically enhanced the performance in the
decomposition of FA into H2 and MIL-101-NH2 was the optimal
supports for active heterometallic NPs containing nonprecious
metals.
Fig. 5 TEM images of the catalysts and the corresponding size
distribution of AuPdCo NPs: (a, b) Au0.28Pd0.47Co0.25/MIL-101; (c,
d) Au0.28Pd0.47Co0.25/MIL-101-NO2; (e, f) Au0.28Pd0.47Co0.25/MIL-
101-SO3H.
There is different interaction between active metal NPs and
supports with different functional groups.[15] From this
viewponit, NO2 and SO3H-functionalized MIL-101 (MIL-101-
NO2 and MIL-101-SO3H) and bare MIL-101 were also used as
supports to immobilize AuPdCo NPs. The TEM investigation
showed that the average sizes of AuPdCo NPs in
Au0.28Pd0.47Co0.25/MIL-101, Au0.28Pd0.47Co0.25/MIL-101-NO2 and
Au0.28Pd0.47Co0.25/MIL-101-SO3H were 3.6 ± 0.5, 2.6 ± 0.3 and
5.3 ± 0.5 nm, respectively (Fig. 5), which were larger than
Fig. 6 Plot of time versus volume of the generated gas (H2 and
those of AuPdCo NPs in Au0.28Pd0.47Co0.25/MIL-101-NH2. This
could be explained that electron-donating group NH2 in the
support could effectively immobilize the free metal ions
through coordination or electrostatic interactions and then
induce the formation of highly dispersed and small sized metal
NPs on the surface of NH2-functionalized support.[16] The
catalytic results showed exhibited drastically lower activities
and H2 selectivity than Au0.28Pd0.47Co0.25/MIL-101-NH2 (Fig. 6).
It should be noted that though the average size of AuPdCo NPs
in Au0.28Pd0.47Co0.25/MIL-101-NO2 was slightly larger than that
in Au0.28Pd0.47Co0.25/MIL-101-NH2, Au0.28Pd0.47Co0.25/MIL-101-
NO2 exhibited the very low activity and H2 selectivity. From the
above comparison, it could be seen that the NH2 group in the
MOF support was crucial for FA dehydrogenation. In addition,
the different functional groups resulted in the different surface
areas of catalyst supports MIL-101-NH2, MIL-101-NO2 and MIL-
101-SO3H (Fig. S19), which might be another factor influencing
the resulting catalytic performance. In order to further confirm
this conclusion, we chose bare MOF-5 and NH2-functionalized
MOF-5 (MOF-5-NH2) as supports to prepare AuPdCo catalyts.
The catalytic results showed that Au0.28Pd0.47Co0.25/MOF-5-NH2
CO2)
Au0.28Pd0.47Co0.25/MIL-101-NH2, (b) Au0.28Pd0.47Co0.25/MIL-101-
NO2, (c) Au0.28Pd0.47Co0.25/MIL-101-SO3H and (d)
Au0.28Pd0.47Co0.25/MIL-101 (nmetal nFA = 0.0125) at 298 K. Inset:
from
FA-SF
aqueous
solution
over
(a)
/
H2 selectivity for FA dehydrogenation over the above four
catalysts.
For the FA decomposition, the activity and H2 selectivity of
catalysts was strongly related with the activation of FA
molecule, which depends on structural and electronic aspects
of active metal NPs.[2f,4b,5g] As illustrated in Fig. 7, in the FA
decomposition over AuPdCo/MIL-101-NH2, the electron-
donating group NH2 was bonded to Co with relatively low
electron density in the AuPdCo NPs and then a complex
H2N
scavenger, was conducive to the cleavage of the O
the FA molecule, resulting in the formation of a species
H2NH+
Co. At the same time, due to the big steric hindrance of
Co center, the OOCH− group from FA was bonded to Pd in the
AuPdCo NPs,[2f] which leaded to the formation of
−
Co formed. After that, this complex, as
a
proton
−
H bond in
−
a
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ARTICLE
Journal Name
coordination
intermediate
H2NH+ OOCH−. Au0.28Pd0.47Co0.25/MIL-101-NH2 were enhanced obviously. Both
−CoAuPd−
Subsequently, this coordination intermediate could undergo Au0.28Pd0.47Co0.25/MIL-101-NH2 and Au0.38Pd0.62/MIL-101-NH2
hydride elimination to produce CO2 and a metal hydride had the similar activities, indicating that the non-noble metal
H2NH+
−
CoAuPd
desorption of H− and H+ in H2NH+
−
H−. Finally, the H2 generation through the doping did not lower the catalytic activity of active noble-
CoAuPd
H− happened. In metal species in spite of the fact that their amounts decreased
−
−
the contrast, in the FA decomposition over AuPdCo/MIL-101- in the heterometallic catalyst. These phenomena indicated
NO2, the OOCH− group from FA and the electron-accepting that the synergistic interaction among different metals played
group NO2 were bonded to Co and Pd in the AuPdCo NPs, an important role in the enhanced performance of
respectively, resulting in two coordination intermediates heterometallic nanocatalysts containing nonprecious metals.
OOCH−
the bonding strength of Co
from the catalysis involving AuPdCo/MIL-101-NO2 was higher
than that of Pd
OOCH−, Co H+ and Pd H− resulted from the
−
CoAuPd
−
(H++NO2) and H−
−
CoAuPd
−
(H++NO2). Since
−
OOCH−, Co
−
H− and Pd
−
H+ resulted
−
−
−
catalysis involving AuPdCo/MIL-101-NH2, the desorption of
CO2 and H2 from the surface of AuPdCo/MIL-101-NO2 was
difficult, leading to the very low activity and H2 selectivity of
AuPdCo/MIL-101-NO2. From the above assumption and logical
reasoning, the rate-determining step (RDS) in the catalytic
pathway of AuPdCo/MIL-101-NH2 containing basic groups was
the step 3 involving H2 formation, while the RDS in the
catalytic pathway of base-free AuPdCo/MIL-101-NO2 was the
step 2 involving CO2 release.[3c]
Fig. 8 Plot of time versus volume of the generated gas (H2 and
CO2) from FA-SF aque ous solution over (a) AuxPdyCo0.25/MIL-
101-NH2 (x+y+0.25 = 1.0) and (b) AumPdnCok/MIL-101-NH2
Fig. 7 Possible activation pathways of the FA molecule in the
reaction using the catalysts containing different functional
groups.
(m+n+k = 1.0, m/n
≈ 0.6) (nmetal/nFA = 0.0125) at 298 K.
The catalytic performance was optimized by tuning the
molar ratios of different metal components. The results
showed that when the molar ratio of Co/(Au+Pd+Co) was 2.5,
increasing the content of Pd leaded to the increase in activity
(Fig. 8a). When the molar ratio of Au/Pd was kept constantly,
decreasing the content of Co leaded to the increase in activity
(Fig. 8b). However, when the molar ratio of Co/(Au+Pd+Co)
was below 2.5, the activities of catalysts had no significant
enhancement. Therefore, from the viewpoints of both keeping
the high activity and reducing the amounts of noble metals,
2.5 of Co/(Au+Pd+Co) seemed to be the optimal value for the
high-performance catalysis. However, the H2 selectivity of all
these catalysts was kept at 100%. In addition, monometallic
and bimetallic catalysts were also synthesized for catalysis. The
results showed that without Pd addition, Au/MIL-101-NH2,
Co/MIL-101-NH2 and AuCo/MIL-101-NH2 had no activities (Fig.
9). However, with Pd addition, the activities of Pd/MIL-101-
NH2, Co0.25Pd0.75/MIL-101-NH2, Au0.38Pd0.62/MIL-101-NH2 and
Fig. 9 Plot of time versus volume of the generated gas (H2 and
CO2) from FA-SF aqueous solution over (a) Au0.38Pd0.62/MIL-
101-NH2, (b) Au0.28Pd0.47Co0.25/MIL-101-NH2, (c) Pd/MIL-101-
NH2, (d) Pd0.75Co0.25/MIL-101-NH2, (e) Au/MIL-101-NH2, (f)
Co/MIL-101-NH2 and (g) Au0.75Co0.25/MIL-101-NH2 (nmetal/nFA =
0.0125).
6 | J. Name., 2012, 00, 1-3
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Journal Name
ARTICLE
The temperature played an important role in the
dehydrogenation of FA.[1f] It could be clearly seen that the
hydrogen evolution rate using Au0.28Pd0.47Co0.25/MIL-101-NH2
as catalyst greatly depended on the reaction temperature (Fig.
10a). The the obtained activation energy (Ea) of this process
reached 32.45 kJ mol−1, which was comparable to the values
acquired from the reported highly active noble-metal catalysts
(Fig. 10b).[4,5]
4. Conclusions
In summary, porous MOFs containing different functional
groups were selected as supports to synthesize a series of
transition metal-substituted AuPd NPs, where AuPdCo NPs
immobilized by MIL-101 functionalized by electron-donating
group NH2 exhibited 100 % of H2 selectivity and drastically high
activity. The remarkably different activity and H2 selectivity of
catalysts containing different functional groups may be due to
the different interaction pathways between the intermediates
from the splitting of FA molecules and metal atoms on the
catalyst surface. The present approach for improving the
selectivity for target product and the activity of heterometallic
catalysts containing nonprecious metals using the distinct
interaction between active metal NPs and functionalized MOFs
may open up a new avenue for the development of high-
performance and low-cost nanocatalysts in various fields
including sustainable energy production and chemical
synthesis.
For the stability test, the catalyst Au0.28Pd0.47Co0.25/MIL-101-
NH2 was recycled by adding the same amount of FA into the
reactor after the completion of the first run. It was found that
the activity and H2 selectivity remained no significant change
(Fig. S31), which may be due to no significant increase in the
size of AuPdCo NPs during the catalytic process (Fig. S32).
These results also testified that the rate in H2 generation
decreased after 80 % of FA conversion (turnover number (TON)
of 64) was caused by the reducing concentration of FA during
the reaction process. In order to check whether
Au0.28Pd0.47Co0.25/MIL-101-NH2 retained the activity for a long
period of time, the multi-cycles of catalysis were carried out.
The results showed that the activity of catalyst significantly
decreased after nine cycles (980 min) (Fig. S34), possibly due
to that there were aggregations of AuPdCo NPs (Fig. S35) and
the acidic catalytic environment of FA-SF aqueous solution
weakened the interaction force between AuPdCo NPs and MIL-
101-NH2.
Acknowledgements
The authors gratefully acknowledge the financial support from
the Program for New Century Excellent Talents in University of
the Ministry of Education of China (grant no. NCET-13-0846),
the National Natural Science Foundation of China (grant no.
21101089), the Inner Mongolia Natural Science Foundation
(grant no. 2011JQ01) and the Program for Young Talents of
Science and Technology in Universities of Inner Mongolia
Autonomous Region (grant no. NJYT-13-A01).
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Through tuning the functionalized groups in MIL-101, the low-cost catalyst containing
NH2 exhibited remarkably high activity in dehydrogenation of HCOOH.