High catalytic activity of a bimetallic AgPd alloy supported on UiO-66 derived porous carbon for transfer hydrogenation of nitroarenes using formic acid-formate as the hydrogen source

Article abstract of DOI:10.1039/c7nj00442g

Bimetallic AgPd nanoparticles anchored on metal-organic framework (UiO-66) derived N-doped porous carbon (NPC-UiO-66) was fabricated and used as a catalyst for the catalytic transfer hydrogenation of nitroarenes using formic acid-formate as the hydrogen source. The results demonstrated that the Ag₁Pd₉@NPC-UiO-66 composite exhibited extraordinary catalytic activity toward the hydrogenation of nitroarenes to anilines at room temperature. A series of substituted nitroarenes were successfully converted to the corresponding anilines in high yields under ambient conditions with other reducible groups remaining intact. The superior catalytic performance of the prepared catalyst can be attributed to the synergistic effect between the highly dispersed AgPd nanoparticles and the unique structure of the NPC-UiO-66 support, as well as the high adsorption ability of the catalyst for the nitroarenes.

Full text of DOI:10.1039/c7nj00442g

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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
rsc.li/njc

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High catalytic activity of bimetallic AgPd alloy supported
on UiOꢀ66 derived porous carbon for transfer hydrogenation
of nitroarenes using formic acidꢀformate as hydrogen source
Received 00th January 20xx,
Accepted 00th January 20xx
Saisai Cheng, Ningzhao Shang, Xin Zhou, Cheng Feng*, Shutao Gao, Chun Wang*, Zhi Wang
DOI: 10.1039/x0xx00000x
www.rsc.org/
College of Science, Hebei Agricultural University, Baoding 071001, China
Bimetallic AgPd nanoparticles anchored on metalꢀorganic framework (UiOꢀ66) derived Nꢀdoped porous
carbon (NPCꢀUiOꢀ66) was fabricated and used as the catalyst for the catalytic transfer hydrogenation of
nitroarenes using formic acidꢀformate as hydrogen source. The results demonstrated that Ag1Pd9@NPCꢀUiOꢀ
66 composite exhibited extraordinary catalytic activity toward the hydrogenation of nitroarenes to anilines at
room temperature. A series of substituted nitroarenes were successfully converted to the corresponding
anilines in high yields under ambient conditions with other reducible groups remaining intact. The superior
catalytic performance of the prepared catalyst can be attributed to the synergistic effect between the highly
dispersed AgPd nanoparticles and the unique structure of NPCꢀUiOꢀ66 support, as well as the high adsorption
ability of the catalyst for the nitroarenes.
approach for the preparation of aryl amines. Among the hydrogen
donor used in CTH, exploiting FA as a promising hydrogen source
1. Introduction
has received considerable interest due to its properties of nonꢀ
toxicity, high energy density, excellent stability. Moreover, FA is
one of the major byꢀproducts in biomass processing. So far, FA has
been used as hydrogen source in the catalytic transfer hydrogenation
of αꢀmethylbenzyl alcohol,10 fructose to γꢀvalerolactone,11 alkene12
and nitro compounds.13 For example, Beller et al.14 reported that
trinuclear Mo3S4 hydrides functionalized with diphosphane ligands
are efficient catalysts for the CTH of nitroarenes to the
Aromatic amines, especially with the functionalized groups, are
known as major feedstock, ubiquitous building blocks for the
manufacture
of
functional
polymers,
pharmaceuticals,
agrochemicals, dyes, fine chemicals, and more.1 The most
commonly employed method for the fabrication of aromatic anilines
is the reduction of corresponding nitroarenes. However, the
traditional noncatalytic reduction approach requires stoichiometric
reducing agents (such as Zn, Fe, Sn and metal sulfides) that produce
large amount of waste acids and residues, which result in serious
environmental pollution problems.2
o
corresponding anilines at 70 C using formic acid as the hydrogen
donor. Rajenahally et al.15 fabricated Fe2O3/NGr@Cꢀbased nanoꢀ
materials and used for the CTH of nitroarenes to anilines in the
presence of FA and triethylamine, the reaction was performed at 120
oC for 20−24 h. Cao et al.13 reported an approach for the targetꢀ
specific transformation of nitro compounds employing FA as the
hydrogen source. The reactions were catalyzed by supported Au
In contrast, the catalytic hydrogenation of nitro compounds with
the heterogeneous or homogeneous transitionꢀmetal catalysts is a
more efficient, highly selective and environmentalꢀfriendly process.3
Catalytic reduction with molecular hydrogen (H2) obviously
represents an attractive, more atomꢀeconomic alternative.4 However,
the reduction by H2 is generally performed at high temperature and
high pressure. Moreover, H2 is flammable, potentially dangerous and
requires special equipment for production, transportation and
storage. Recently, an alternative to reduction by H2, catalytic transfer
hydrogenation (CTH)5 of nitro compounds has attracted considerable
attention in which hydrogen is replaced by a hydrogen donor, such
as formic acid (FA),6 hydrazine,7 ammonia borane8 and sodium
borohydride.9 The catalytic transfer hydrogenation can be performed
under mild conditions (e.g. atmospheric pressure, room
temperature), which represents a more costꢀefficient and greener
o
catalyst at 60 C with toluene as the reaction solvent. Despite recent
progress, the reported catalytic systems still have one or more
shortcomings, such as toxic solvent, harsh reaction conditions and
high catalyst dosage are required. Therefore, exploring highly active
heterogeneous catalysts for reduction of nitroarenes is highly
desirable.
The synergetic interaction between metal nanoparticles and
support plays an important role for the catalytic performance of a
heterogeneous catalyst.16 Recently, metalꢀorganic frameworks
(MOFs)17, 18 have attracted intense interest due to the advantage of
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high surface area, permanent nanoscale porosity, fascinating diverse formate were purchased from Huaxin Co., Ltd. (Baoding, China).
structures, topologies, and uniform structured cavities. MOFs have All materials were used as received without further purification.
been considered as ideal sacrificial templates to afford porous
20
carbons via facile pyrolysis.19,
MOFꢀderived porous carbons
2.2 Characterizations
possess great merits, such as high surface area, tailorable structure
and porosity. So far, MOFꢀderived porous carbon supported metal
Xꢀray photoelectron spectroscopy (XPS) spectra were acquired
nanoparticles catalysts have been used to catalyze Suzuki coupling with an ESCA Lab 250 (Thermo) spectrometer (Shanghai, China)
reaction,21 reduction of nitro compounds,22 catalytic hydrogen using a monochromatic Al Ka source (1486.6 eV). The Xꢀray
production reaction,23 oxygen reduction reaction24 and so on. diffraction (XRD) patterns of the samples were recorded with a
Nevertheless, the applications of MOFsꢀderived nanoporous carbons Rigaku D/max 2500 Xꢀray diffractometer (Dandong, China) using
as catalyst carriers are still in its infancy.
Cu Kα radiation (30 kV, 25 mA) in the range 2θ = 2°–80°. The size
and morphology of the nanoparticles were observed by scanning
electron microscopy (SEM) using a Hitachi S4800 field emission
electron microscope (Tokyo, Japan) operated at 30 kV and
transmission electron microscopy (TEM) using a JEOL model JEMꢀ
2011(HR) (Tokyo, Japan) at 200 kV. The Brunauer–Emmett–Teller
(BET) surface areas were determined from the N2 adsorption at 77 K
using VꢀSorb 2800P (Jinaipu, China). The metal content of the
materials was analyzed by a T.J.A. ICPꢀ9000 type inductively
coupled plasma atomic emission spectroscopy (ICPꢀAES)
instrument. Gas chromatography (GC) analyses were carried out on
an Agilent 7820A series gas chromatograph (Agilent Technologies,
CA, USA) equipped with a flame ionization detector (FID) and a
split/splitless injector. All the separations were performed on a HPꢀ5
capillary column (30 m × 0.32 mm i.d. × 0.25 ꢁm film thickness)
(Agilent J&W Scientific, CA, USA). An Agilent 7820A gas
chromatographyꢀ5977E mass spectrometry system (GCꢀMS) (Santa
Clara, CA, USA) was employed to identify all reaction products.
Scheme 1. Schematic illustration of the preparation process of the
AgPd@NPCꢀUiOꢀ66 catalyst.
UiOꢀ66 is a Zrꢀbased MOF with tunable pore size, high specific
surface area, high thermal and chemical stability,25 which have
found widely applications in different fields.26ꢀ28 UiOꢀ66 might be an
ideal precursor to fabricate porous carbons. To explore the
application potential of MOFꢀderived porous carbon and investigate
the effect of the porous structure on the dispersion of metal
nanoparticles, herein, Nꢀdoped porous carbon (NPCꢀUiOꢀ66) was
fabricated by oneꢀstep direct carbonization of UiOꢀ66 without using
any additional carbon and nitrogen precursors. AgPd nanoparticles
(NPs) were immobilized on NPCꢀUiOꢀ66 by an impregnation
method coupled with subsequent reduction with NaBH4 (Scheme 1).
2.3 Synthesis of NPC-UiO-66-T, NPC- Al-MOF-800, NPC-
MIL-125-800, and ZrO2
The UiOꢀ66(NH2) was prepared via a method as described29
To evaluate its catalytic performance, the AgPd@NPCꢀUiOꢀ66 was previously in a DMF–HCl mixed solvent with NH2ꢀBDC and ZrCl4
used as catalyst for the catalytic transfer hydrogenation of nitroꢀ as the organic linker and the metal source, respectively. In brief,
compound employing FA and ammonium formate (AF) as the NH2ꢀBDC (1.34 g, 7.5 mmol) was dissolved in 100 mL of DMF
hydrogen source. The results demonstrated that Ag1Pd9@NPCꢀUiOꢀ under ultrasonication for 10 min. Then the ZrCl4 (1.25 g, 5.4 mmol)
66 composite exhibited extraordinary catalytic activity and toward and 60 mL DMF:HCl (5:1, v/v) were added into the mixture and
the reduction of nitroarenes into anilines.
sonicated for 10 min. Subsequently, the solution was transferred to a
200 mL Teflonꢀlined stainless steel autoclave. The autoclave was
sealed and heated in an oven at 80 C overnight under autogenous
o
2. Experimental
pressure, and after cooling naturally, the sample was washed with
methanol to make sure that the occluded DMF molecules were
eliminated. The yellow UiOꢀ66(NH2) product was dried in a vacuum
2.1 Chemicals
o
at 80 C for 4 h. Then, the UiOꢀ66(NH2) was heated in a horizontal
2ꢀAminoꢀ1,4ꢀbenzenedicarboxylic
acid
(NH2ꢀBDC),
1,4ꢀ
o
o
o
tube furnace at different temperatures (700 C, 800 C and 900 C,
respectively) for 3 h under a flow of nitrogen gas. The resulting
product was denoted as NPCꢀUiOꢀ66ꢀT, where T represents the
carbonization temperature (700 oC, 800 oC and 900 oC).
benzenedicarboxylic acid (BDC), titanium isopropoxide (TOPT),
zirconium chloride (ZrCl4), zirconyl chloride octahydrate
(ZrOCl2·8H2O), aluminum chloride hexahydrate (AlCl3•6H2O),
palladium (II) chloride (PdCl2, AR), sodium borohydride (NaBH4,
96%) and all of the nitro compounds were obtained from Aladdin
Chemicals Co Ltd. (Shanghai, China). N,NꢀDimethylformamide
(DMF), toluence, methanol, ethyl acetate, hydrochloric acid (HCl,
37%), concentrated sulphuric acid (H2SO4, 98%), oleic acid (OA)
and ammonium hydroxide solution (NH4OH) were obtained from
Chengxin Chemical Reagents Company (Baoding, China). Silver
nitrate (AgNO3, AR), formic acid (HCOOH, 88%) and ammonium
UiOꢀ66 was prepared following a modified procedure as described
in literature.26 In a typical synthetic process, 106 mg of ZrCl4 and 68
mg of BDC were dissolved in 50 mL DMF and sealed in a stainless
steel vessel with Teflon liner. Then the solution was put into a
preheated oven at 120 oC. After 48 h, the oven was naturally cooled
to room temperature. The solid was filtered out, washed with DMF
and absolute ethanol and then dried in air at 90 oC. UiOꢀ66 was
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directly carbonized at 800 oC under a flow of nitrogen gas. The were used, respectively. AgPd nanoparticles catalyst was fabricated
obtained solid was named as CꢀUiOꢀ66ꢀ800. To preparation of the with the above procedure without the addition of NPCꢀUiOꢀ66ꢀT.
ZrꢀfreeꢀNPCꢀUiOꢀ66ꢀ800, 50 mg of NPCꢀUiOꢀ66ꢀ800 powder was
Table 1 Amount of Ag and Pd in AgPd@NPCꢀUiOꢀ66ꢀ800 catalysts.
dispersed in 20 mL of 50% H2SO4 and stirred at 80 oC for 6 h. Then
Ag
(wt%)
0.49
Pd
Ag–Pd initial
composition
1:9
Ag–Pd final
composition
1:8.96
the mixture was collected by centrifugation and washed with
distilled water until the pH reached 7. Finally, the ZrꢀfreeꢀNPCꢀUiOꢀ
66ꢀ800 was obtained by vacuum drying at 60 oC for 5 h.
Catalysts
(wt%)
4.39
Ag1Pd9@NPCꢀUiOꢀ66ꢀ800
Ag2Pd8@NPCꢀUiOꢀ66ꢀ800
Ag3Pd7@NPCꢀUiOꢀ66ꢀ800
NH2ꢀAlꢀMOF was prepared according to the reported procedure.30
AlCl3·6H2O (4.635 g, 19.2 mmol), NH2ꢀBDC (1.165 g, 6.45 mmol)
and methanol (61.75 mL) were transferred into a 100 mL Teflonꢀ
lined stainless steel autoclave. Then the autoclave was heated to 125
oC for 5 h under autogenous pressure. After cooling, the precipitate
was centrifuged and yellow microcrystalline solid was obtained. The
microcrystalline product was washed with deionized water three
0.93
1.39
3.91
3.37
2:8
3:7
2:8.41
3:7.27
2.5 Catalytic transfer hydrogenation of nitro compounds
Typically, to a mixture of nitro compound (1 mmol), catalyst (1
mol%), and 252 mg (4 mmol) ammonium formate in 5 mL
methanol , 172 ꢁL formic acid (4 mmol) was added and then the
reaction mixture was stirred at 25 oC for a certain time. The reaction
progress was monitored by thin layered chromatography. The yield
of the product was analyzed by GC. After completion of the
reaction, the recovered catalyst was separated by centrifugation and
repeatedly washed with methanol to remove the organic and
o
times and dried at 80 C under vacuum. The synthesis of NH2ꢀMILꢀ
125(Ti) crystals was accomplished using a solvothermal route.31 In a
typical synthesis, NH2ꢀBDC (1.12 g, 6.2 mmol) was dissolved in 60
mL DMF and methanol mixed solvent (VDMF/Vmethanol = 9:1). Then
TPOT (1.2 mL, 4.0 mmol) was added to the solution. After stirring
by ultrasonic concussion for 5 minutes, the mixture was transferred
to a 100 mL Teflonꢀlined steel autoclave and the autoclave was
o
o
placed in an oven at 150 C for 24 h under static conditions. After
inorganic part and dried in vacuum at 60 C overnight for another
cooling, the yellow solid product, NH2ꢀMILꢀ125(Ti), was washed
three times with DMF and twice with methanol. Then it was dried
overnight in a vacuum oven at 60 oC. NPCꢀ MILꢀ125ꢀ800 and NPCꢀ
AlꢀMOFꢀ800 was prepared according to the procedure for CꢀUiOꢀ
66ꢀ800 except that NH2ꢀMILꢀ125(Ti) and NH2ꢀAlꢀMOF was used.
ZrO2 powders were prepared by a conventional precipitation
consecutive reaction run. The product was extracted with ethyl
acetate (3×5 mL) and dried over anhydrous MgSO4 and then
evaporated under vacuum. The structure of the product was
confirmed by GCꢀMS.
3. Results and Discussion
method following the reported procedure.32 Briefly, 12.9
g
3.1 Characterization of the catalyst
ZrOCl2·8H2O was dissolved in 200 mL deionized water at room
temperature, and the pH was adjusted to about 9 by dropwise
addition of NH4OH (2.5 mol Lꢀ1) under stirring. After stirring for 8
h, the resultant hydrogel was washed with deionized water until free
of chloride ions. The precipitate was then dried at 110 C overnight
and calcined at 400 oC in air for 2 h.
o
2.4 Synthesis of supported AgPd catalysts
AgPd@NPCꢀUiOꢀ66ꢀT was prepared by the impregnation
method. Typically, 95 mg of NPCꢀUiOꢀ66ꢀT, 7.5 mL H2PdCl4
solution (1 mg mLꢀ1) and 0.8 mL AgNO3 solution (1 mg mLꢀ1) were
added into a 25 mL round bottomed flask and ultrasonicated for 5
min, then the solution was stirred for 6 h at room temperature.
Subsequently, 2 mL NaBH4 (0.66 mol Lꢀ1) solution was added
dropwise and vigorous stirred for 2 h. The product was collected by
centrifugation, washed with H2O until the pH reached 7, and dried at
60 oC in vacuum oven to yield Ag1Pd9@NPCꢀUiOꢀ66ꢀ800.
Ag2Pd8@NPCꢀUiOꢀ66ꢀ800, Ag3Pd7@NPCꢀUiOꢀ66ꢀ800, Ag@NPCꢀ
UiOꢀ66ꢀ800 and Pd@NPCꢀUiOꢀ66ꢀ800 catalysts were synthesized
with the above procedure except that the molar ratios of Ag and Pd
were 2:8, 3:7, 10:0 and 0:10, respectively. The content of Ag and Pd
in the composite was determined by ICPꢀAES (Table 1).
Fig 1. The nitrogen adsorptionꢀdesorption isotherms of NPCꢀUiOꢀ66,
Ag1Pd9@NPCꢀUiOꢀ66ꢀ800.
The porosity of the NPCꢀUiOꢀ66 and AgPdꢀNPCꢀUiOꢀ66ꢀ800
was determined employing N2 adsorption/desorption analysis at 77
K (Fig 1). The series of characterizations N2 adsorption studies
revealed that NPCꢀUiOꢀ66 contained micropore, mesopore and a
small amount of macropore. The surface areas and pore volumes of
NPCꢀUiOꢀ66 is related to the carbonization temperature, which are
210 m2 gꢀ1 and 0.27 m3 gꢀ1 for NPCꢀUiOꢀ66ꢀ700, 417 m2 gꢀ1 and 0.43
m3 gꢀ1 for NPCꢀUiOꢀ66ꢀ800, 371 m2 gꢀ1 and 0.39 m3 gꢀ1 for NPCꢀ
UiOꢀ66ꢀ900, respectively. As shown in Fig 1, the Ag1Pd9ꢀNPCꢀUiOꢀ
66ꢀ800 also showed similar characteristic with NPCꢀUiOꢀ66. The
BET surface area and pore volume of the Ag1Pd9@NPCꢀUiOꢀ66ꢀ
Ag1Pd9@CꢀUiOꢀ66ꢀ800,
Ag1Pd9@ZrꢀfreeꢀNPCꢀUiOꢀ66ꢀ800,
Ag1Pd9@NPCꢀMILꢀ125ꢀ800 and Ag1Pd9@NPCꢀAlꢀMOFꢀ800 were
prepared with the above procedure except that CꢀUiOꢀ66ꢀ800, Zrꢀ
freeꢀNPCꢀUiOꢀ66ꢀ800, NPCꢀMILꢀ125ꢀ800 and NPCꢀAlꢀMOFꢀ800
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800 is 356 m2 gꢀ1 and 0.38 m3 gꢀ1. The slightly decrease in the BET dominant, which were attributed to Pd0 and indicate that metallic Pd
surface area suggests the occupation of AgPd NPs inside the was formed as the major phase on the support. While in Fig 4C, the
nanoporous channel of the NPCꢀUiOꢀ66. As shown in the TEM 3d3/2 peaks of Ag0 appear at 373.4 and 374.9, the 3d5/2 peak of Ag0
image (Fig 2) of Ag1Pd9@NPCꢀUiOꢀ66ꢀ800, fine Pd NPs are appear at 367.9 eV, respectively, with no obvious peak of Ag+ was
uniformly distributed throughout the porous carbon (Fig 2A). The observed, indicating the coꢀexistence of both metals. Besides, XPS
highꢀresolution TEM image displays clear lattice fringe, suggesting results showed that both Ag and Pd are in the reduced states.
the good crystallinity. Besides, the lattice spacing is measured to be Compared to the monometallic Pd@NPCꢀUiOꢀ66ꢀ800 and
0.23 nm, which is between the (111) plane of faceꢀcentered cubic Ag@NPCꢀUiOꢀ66ꢀ800 samples, the 3d peaks for Ag(0) and Pd(0) in
(fcc) Pd (0.224 nm)33 and fcc Ag (0.235 nm)34, suggesting that AgPd Ag1Pd9@NPCꢀUiOꢀ66ꢀ800 shift to lower binding energies by ∼0.8
is formed as an alloy structure, which is also supported by STEMꢀ and∼0.5 eV, respectively (Fig S4). Such observed shifts for both Pd
EDS lineꢀscan of Ag1Pd9@NPCꢀUiOꢀ66ꢀ800 (Fig S1) and the XRD 3d and Ag 3d may be attributed to the flow of electron from Ag to
results. Fig 3 shows the XRD patterns of the asꢀsynthesized Pd (gaining electrons from Ag), indicative of the presence of an
materials. The wellꢀdefined diffraction peak of Ag1Pd9, Ag2Pd8 and interaction between Ag and Pd and the formation of AgPd alloy
Ag3Pd7 NPs is between the peaks of Ag (2θ = 38.03°) and Pd (2θ = NPs, which is in good agreement with previous reports.36 The
40.10°) NPs, further indicating that AgPd is formed as an alloy. The formation of AgPd alloy NPs is reasonable because the two soluble
+
diffraction lines at 2θ=28.4°, 31.5°, 50.6°, 60.3° were attributed to metal salts have close reduction potentials (E°Ag
= +0.80 eV vs
/Ag
2+
the monoclinic phase of the ZrO2 support (mꢀZrO2), the tetragonal SHE; E°Pd
= +0.915 eV vs SHE, SHE: standard hydrogen
/Pd
ZrO2 (tꢀZrO2) was observed at 2θ = 30.17°, 34.3°, which is in good electrode). Besides, the line scan results unambiguously
agreement with the standard cards (JCPDS PDF no. 37ꢀ1484 and demonstrated that AgꢀPd was formed as an alloy structure (Fig S1).
JCPDS PDF no. 49ꢀ1642 respectively).35 The results indicated the Two Zr 3p3/2 and Zr 3p1/2 peaks were identified at approximately
existence of both monoclinic and tetragonal mixed phase ZrO2 in the 332.5 and 346.5 eV (Fig 4A), respectively, and these two binding
support.
energies in particular indicated the presence of ZrO2. In Fig 4B, the
characteristic peaks for oxidation state of Zr can be clearly seen at
182.2 and 184.5 eV assigned to Zr 3d5/2 and Zr 3d3/2, respectively,
revealing that ZrO2 was present in the catalyst. The surface nitrogen
content estimated from the XPS data was ~2 wt. %. The N1s XPS
spectrum (Fig 4D) could be fitted well to peak positioned at binding
energy of 400.0 eV.
A
B
B
A
Fig 2. TEM pattern (A) and HRTEM pattern (B) of Ag1Pd9@NPCꢀ
UiOꢀ66ꢀ800.
C
D
Fig 4. The XPS images of Pd (A), Zr (B), Ag (C) and N (D) of
Ag1Pd9@NPCꢀUiOꢀ66ꢀ800.
Fig 3. The XRD pattern of NPCꢀUiOꢀ66, AgPd@NPCꢀUiOꢀ66ꢀT
and ZrO2.
3.2 The catalytic hydrogenation of nitroarenes
Xꢀray photoelectron spectroscopy analysis (Fig 4, Fig S2) and
energyꢀdispersive Xꢀray spectroscopy (EDX) (Fig S3) confirmed the
coꢀexistence of Ag, Pd, Zr, C, N and O in the Ag1Pd9@NPCꢀUiOꢀ
66ꢀ800 catalyst. The Pd XPS spectra (Fig 4A) demonstrated that the
Pd3d spectral peaks at binding energy 335.1 and 341.1 eV were
At the start of our work, the reduction of nitrobenzene was
investigated as a benchmark system to development an optimal
catalytic system, various reaction parameters such as the type of
catalysts, hydrogen sources, solvent, catalyst dosage were
optimized. We started our study with CTH of nitrobenzene in
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methanol catalyzed by Ag1Pd9@NPCꢀUiOꢀ66ꢀ800 (1 mol%) at 25 nitroarenes.15 To further investigate whether the support has a
oC with different hydrogen sources. Only 15% aniline was obtained dramatic effect on the catalytic activity of Ag1Pd9@NPCꢀUiOꢀ66ꢀ
after 12 h when we employed FA as the hydrogen source (Table S1, 800 hybrid, the catalytic activity of the AgPd NPs is also examined
entry 1). In contrast to the protocols reported previously,37 the (Table 2, entries 9). It shows much lower catalytic activity than that
addition of formate in the catalytic system can significantly enhance of the Ag1Pd9@NPCꢀUiOꢀ66ꢀ800 hybrid under analogous
the reaction efficiency. Among the hydrogen donor investigated, the conditions.
excellent result was achieved when 1:1 (molar ratio) FA/AF was
employed (Table S1, entries 2ꢀ6). Aniline was obtained in a high Table
2
Reduction of nitrobenzene to aniline under various
yield of 99% with excellent selectivity at 25 C for 20 min. Relative conditions. [a]
long reaction time was required when 1:1 FA/HCOONa, or
FA/HCOOK were used as the hydrogen source. In the blank
experiment, no reaction occurred in the absence of catalyst, using
o
Catalyst
NO2
NH2
FA, HCOONH4
1a
2a
NPCꢀUiOꢀ66ꢀ800 or ZrO2 as the catalyst at room temperature
(Table 2, entries 1ꢀ3), suggesting that integrated AgPd NPs play a
decisive role in catalyzing the CTH reaction.
A further noteworthy finding in the present work is that apart
from the AgPd NPs, the component of the underlying support also
plays an essential role in determining the catalytic performance of
the final materials. For comparison, the hydrogenation of
Time
(min)
Conversion
(%)
Selectivity
(%)
Entry
Cat
ꢀ
Solvents
1
2
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
Water
6 h
ꢀ
ꢀ
NPCꢀUiOꢀ66ꢀ800
ZrO2
30 h
6 h
20
ꢀ
ꢀ
3
ꢀ
ꢀ
nitrobenzene
over
Ag1Pd9@ZrꢀfreeꢀNPCꢀUiOꢀ66ꢀ800
was
Ag1Pd9@NPCꢀ
UiOꢀ66ꢀ800
investigated (Table 2, entry 5). Triple reaction time is required in the
absence of ZrO2. Compared with Ag1Pd9@ZrꢀfreeꢀNPCꢀUiOꢀ66ꢀ
800, Ag1Pd9@NPCꢀUiOꢀ66ꢀ800 exhibited much higher activity
revealing that ZrO2 also play very important role for the CTH of
nitroarenes. Previous researches have demonstrated that nitro groups
4
>99
>99
52
>99
>99
83
Ag1Pd9@Zrꢀfreeꢀ
NPCꢀUiOꢀ66ꢀ800
5
60
Ag1Pd9@NPCꢀ
AlꢀMOF
6
60
39
can be easily adsorbed on the basic or reducible supports.38,
Ag1Pd9@NPCꢀ
MILꢀ125
7
60
>99
>99
>99
ꢀ
97
Zirconia is weakly basic and possesses redox functions, which may
forebode a strong interaction between ZrO2 surface and nitro
groups.40
Ag1Pd9@CꢀUiOꢀ
66ꢀ800
8
40
98
To further examine the effect of metal oxide on the catalytic
activity of the catalyst, Ag1Pd9@NPCꢀAlꢀMOF and Ag1Pd9@NPCꢀ
MILꢀ125, in which containing Al2O3 and TiO2 respectively, were
prepared and their catalytic activity was evaluated at the identical
reaction conditions (Table 2, entries 6, 7). The conversions of
nitrobenzene were 52% and 99% at 60 min for the Ag1Pd9@NPCꢀ
AlꢀMOF and Ag1Pd9@NPCꢀMILꢀ125 catalysts, respectively. These
results indicated that both the noble metal and the nature of the
support played important roles in the CTH of nitroarenes. The
previous study has demonstrated that the zirconia support can
substantially facilitate crucial FA deprotonation,41 thus achieve FA
dehydrogenation efficiently. We can say it specifically that the
combination of AgPd NPs and NPCꢀUiOꢀ66 containing ZrO2 is
found to be crucial to give an exceptionally active catalyst capable of
facilitating the CTH of nitro compounds under ambient conditions.
To illustrate the role of nitrogen in the catalyst, the hydrogenation of
nitrobenzene over nitrogenꢀfree Ag1Pd9@CꢀUiOꢀ66ꢀ800 catalyst
was investigated (Table 2, entry 8). Compared with Ag1Pd9@NPCꢀ
UiOꢀ66ꢀ800, Ag1Pd9@CꢀUiOꢀ66ꢀ800 exhibited lower catalytic
activity and comparable selectivity. After 40 min reaction, the
conversions of nitrobenzene were 99%. The result can be ascribed to
that nitrogen doped support can affected the dispersion of metal
nanoparticles, which can improve the catalytic activity for the
transfer hydrogenation of nitrobenzene. This has been demonstrated
by the previous reports.15, 42 Bulusheva et al.42 recently proposed that
single isolated Pd atoms supported on Nꢀdoped carbon is an efficient
catalyst for dehydrogenation from FA. Nꢀdoped grapheneꢀFe2O3
exhibited high catalytic performance for the hydrogenation of
9[b]
10
11
12
13
14
15
16
17
18
19
20[c]
21[d]
22[e]
AgPd
75
>99
ꢀ
Ag@NPCꢀUiOꢀ
66ꢀ800
6 h
6 h
60
Pd@NPCꢀUiOꢀ
66ꢀ800
15
>99
>99
>99
>99
>99
95
Ag2Pd8@NPCꢀ
UiOꢀ66ꢀ800
>99
>99
45
Ag3Pd7@NPCꢀ
UiOꢀ66ꢀ800
2.5 h
2 h
2 h
2 h
70
Ag1Pd9@NPCꢀ
UiOꢀ66ꢀ800
Ag1Pd9@NPCꢀ
UiOꢀ66ꢀ800
DMF
98
Ag1Pd9@NPCꢀ
UiOꢀ66ꢀ800
Toluene
>99
>99
>99
46
Ag1Pd9@NPCꢀ
UiOꢀ66ꢀ700
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
>99
>99
99
Ag1Pd9@NPCꢀ
UiOꢀ66ꢀ900
30
Pd@C
24 h
3 h
20 h
20
Ag1Pd9@NPCꢀ
UiOꢀ66ꢀ800
>99
96
>99
>99
99
Ag1Pd9@NPCꢀ
UiOꢀ66ꢀ800
Ag1Pd9@NPCꢀ
UiOꢀ66ꢀ800
96
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ARTICLE
Journal Name
[a] nitrobenzene (1 mmol), FA (4 mmol), HCOONH4 (4 mmol),
catalyst (1 mol% metal), solvent (5 mL); GC analysis using nꢀdecane
as an internal standard. [b] 1 mol% metal. [c] 0.5 mol% metal. [d]
0.1 mol% metal. [e] 10 mmol nitrobenzene.
The effect of reaction solvent on the CTH reaction was also
investigated. Using toluene, water and DMF as the solvent, the
desired product was obtained in moderate or good conversions after
2 h reaction (Table 2, entries 14ꢀ16). We were pleased to find that
the reaction occurred efficiently to afford the corresponding product
after 20 min in 99% conversion and selectivity with methanol as the
solvent (Table 2, entry 4). The effect of the dosage of catalyst was
also investigated. When the Ag1Pd9@NPCꢀUiOꢀ66ꢀ800 catalyst
dosage was reduced from 1 mol% to 0.5 and 0.1 mol%, the reaction
time needed 3 h and 20 h, respectively, to achieve complete
conversion (Table 2, entries 20, 21). It is worth noting that the
transfer hydrogenation of nitrobenzene catalyzed by Ag1Pd9@NPCꢀ
UiOꢀ66ꢀ800 was performed in the air and it did not require
conducting under nitrogen atmosphere. Therefore, the protocol of the
catalytic transfer hydrogenation of nitro compounds is facile.
Moreover, the newly developed methodology is also effective for the
large scale reaction with consistent product conversion (Table 2,
entry 22).
An array of different catalysts, i.e., Ag@NPCꢀUiOꢀ66ꢀ800,
Pd@NPCꢀUiOꢀ66ꢀ800 and AgPd@NPCꢀUiOꢀ66ꢀ800 with different
molar ratio of Ag and Pd were screened for the transfer
hydrogenation reaction to determine the effect of the metal
composition on the catalytic performance. No product was obtained
in the absence of catalyst (Table 2, entry 1) indicating that the
catalyst was necessary for the CTH reaction. Using NPCꢀUiOꢀ66ꢀ
800 and Ag@NPCꢀUiOꢀ66ꢀ800 as catalyst (Table 2, entries 2, 10),
no conversion of nitrobenzene was observed after 6 h. In addition,
low nitrobenzene conversion of 15% was produced after 6 h in the
presence of Pd@NPCꢀUiOꢀ66ꢀ800 catalyst. To our surprise,
bimetallic AgPd NPs catalyst, Ag1Pd9@NPCꢀUiOꢀ66ꢀ800, exhibited
excellent catalytic activity for the CTH of nitrobenzene. 99% of
conversion and 99% of selectivity were achieved after 20 min
o
reaction at 25 C. Thus, it can be safely concluded that AgPd NPs
In order to evaluate the efficiency of the Ag1Pd9@NPCꢀUiOꢀ66ꢀ
800 for the transfer hydrogenation of nitrobenzene, the present
catalytic system was compared with other reported catalysts in terms
of the reaction temperature, reaction time and turnover frequency
(TOF) (Table S2). The data in Table S2 indicated that the asꢀ
prepared Ag1Pd9@NPCꢀUiOꢀ66ꢀ800 can efficiently catalyze the
CTH reaction at mild conditions with high TOF.
were the catalytic active sites for the CTH of nitrobenzene and the
cooperative effect between Ag and Pd plays a crucial role for
realizing the highly catalytic performance of the catalyst. To further
examine the effect of the ratio of Ag and Pd on the catalytic activity,
Ag2Pd8@NPCꢀUiOꢀ66ꢀ800 and Ag3Pd7@NPCꢀUiOꢀ66ꢀ800 were
fabricated. The results indicated that the catalytic activity decreased
with increasing the ratio of Ag in AgPd@NPCꢀUiOꢀ66ꢀ800 (Table
2, entries 12, 13), the reaction time needed 60 min and 2.5 h,
respectively, to achieve 99% conversion.
The catalytic stability is also a very important criterion to evaluate
the catalysts. A series of recycling experiments were conducted for
the transfer hydrogenation of nitrobenzene under the same reaction
condition to evidence the robustness and recyclability of the catalyst.
The Ag1Pd9@NPCꢀUiOꢀ66ꢀ800 can be easily recovered by
centrifugation and reused up to five cycles. It can be seen that the
activity and selectivity of Ag1Pd9@NPCꢀUiOꢀ66ꢀ800 were well
retained during five consecutive runs (Table S3), which
demonstrated its recyclability. From the TEM image of the recycled
catalyst, we can see that the AgPd NPs remain a high level of
dispersion and crystallinity, which revealed the good stability of the
catalyst (Fig S5). In addition, XRD results indicated that no obvious
diffraction peak change can be observed between fresh and recycled
catalyst (Fig 5A). The XPS spectra of the used catalyst (Fig S6)
demonstrated that the existential states of Ag and Pd have not
obvious difference with that of the fresh catalyst. In order to further
confirm that the reduction of nitrobenzene is a real heterogeneous
process, a filtration test was carried out after 10 min of the reaction.
No further conversion was observed even after 2 h of reaction under
identical conditions (Fig 5B). In addition, ICPꢀAES analysis
indicated that no metal could be detected in the liquid solution. Since
nitrogen is powerfully electronegative and usually has a lone pair of
electrons, the nitrogen functionalities on the surface might act as
Lewis base sites and are expected to be more effective in retaining
metal NPs.43 According to the above results, it can be safely
concluded that the Ag1Pd9@NPCꢀUiOꢀ66ꢀ800 catalyst was robust,
recyclable and has great application potential in the catalytic
reduction of nitro compounds.
A
B
Fig 5. XRD pattern of Ag1Pd9@NPCꢀUiOꢀ66ꢀ800 and ZrO2 (A) and
the filtration test for the reduction of nitrobenzene over
Ag1Pd9@NPCꢀUiOꢀ66ꢀ800 (B).
To demonstrate the general applicability of this catalyst system,
various substituted nitro compounds were investigated under the
optimized conditions (Table 3).
6 | J. Name., 2012, 00, 1-3
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Journal Name
ARTICLE
Table 3 Reduction of nitro compounds to corresponding amines. [a]
Time
(min)
Conversion
(%)
Selectivity
(%)
T
OF
Entry
Substrate
Product
TON[c]
100
[hꢀ1][b]
1
2
20
20
>99
>99
>99
>99
300
NO2
300
196
300
300
100
3
4
5
6
7
30
20
20
20
20
98
>99
>99
>99
>99
>99
98
>99
>99
>99
>99
100
100
100
100
H2N
NO2
300
300
8
9
20
30
30
20
>99
>99
>99
>99
>99
98
300
200
194
300
100
100
97
10
11
97
>99
100
12
13
5 h
60
96
96
>99
>99
19.2
96
96
96
14
15
60
>99
98
>99
>99
100
100
98
6 h
16.3
16[d]
17[d]
18
30
2 h
6 h
97
98
>99
>99
>94
194
49
97
98
94
>99
15.7
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Journal Name
19
20
>99
>99
>95
>99
95
95
60
60
100
100
NO2
[a]
o
Substrate (1 mmol), FA (4 mmol), HCOONH4 (4 mmol), Ag1Pd9@NPCꢀUiOꢀ66ꢀ800 (1 mol%), methanol (5 mL), 25 C; GC analysis
using nꢀdecane as an internal standard. [b] turnover frequency: mol of substrate transformed per mol of catalyst per hour. [c] turnover number.
[d] 50 oC.
66ꢀ800 catalyst. Then, the next catalytic cycle is started.
The reaction was carried out in methanol at room temperature.
Alkylꢀsubstituted nitroarenes are reduced rapidly in excellent yields
up to 99% (Table 3, entries 2, 3). Moreover, the nitro compounds
4. Conclusions
involving electronꢀrich groups such as oꢀhydroxyl, pꢀhydroxyl, pꢀ
amino, pꢀmethylol and pꢀmethoxy were reduced to corresponding
In summary, bimetallic AgPd nanoparticles supported on Nꢀdoped
porous carbon have been successfully fabricated. With FA and AF as
amine products in an efficient fashion with absolute selectivity
the hydrogen donor, the asꢀprepared Ag1Pd9@NPCꢀUiOꢀ66ꢀ800
(Table 3, entries 4ꢀ8). More importantly, for halogenated nitroarenes,
catalyst exhibited high activity for the catalytic transfer
full conversion is achieved (Table 3, entries 9, 10) and no
hydrogenation of substituted nitroarenes at room temperature. The
dehalogenation product was obtained. Particularly, the nitroarenes
superior catalytic performance can be attributed to the synergistic
functionalized with the most challenging reducible functional
effect between the highly dispersed AgPd NPs and unique structure
moieties, such as aldehydes, ketone and nitrile groups, were
of NPCꢀUiOꢀ66 support, as well as the high adsorption ability of the
successfully transformed into corresponding amines products with
catalyst for the nitroarenes. The approach in this work can be
an excellent selectivity (Table 3, entries 11ꢀ14, 18). The transfer
potentially used to develop novel efficient catalysts for
hydrogenation of oꢀnitroacetophenone over the catalyst needed
hydrogenations in the future.
longer time to gain full conversion (Table 3, entry 12), which
revealing slight space steric hindrance to the hydrogenation of the
nitro group can be well tolerated. When the reaction temperature Acknowledgements
rose to 50 oC, the reaction time for hydrogenation of oꢀ
nitroacetophenone and 1ꢀnitronaphthalene greatly decreased (Table
China (21603054), the Natural Science Foundation of Hebei
3, entries 16, 17), and the TOF were greatly raised. Next, the
reduction of 4ꢀnitrostyrene, which has both olefin and nitro moieties
(Table 3, entry 19) 44, was investigated using Ag1Pd9@NPCꢀUiOꢀ
Talents Foundation of Hebei Provincial Universities (BJ2016027),
66ꢀ800 catalyst. Under the optimal reaction conditions, 4ꢀ
nitrostyrene was converted to the completely reduced product 4ꢀ
Financial supports from the National Natural Science Foundation of
Province (B2015204003, B2016204131), the Young Topꢀnotch
and the Natural Science Foundation of Agricultural University of
Hebei (ZD201506, ZD201613) are gratefully acknowledged.
ethylaniline. To our delight, the reaction can be further extended to
simple aliphatic nitro compounds, which was converted to the Notes and references
related primary amines with high yield in 1 h (Table 3, entry 20).
College of Science
Agricultural University of Hebei
Baoding 071001, Hebei Province, P. R. China
Fax: (+86)312ꢀ7528292
The influence of the substituents on the reduction rate of
nitrobenzenes is represented by the Hammett σ ρ ꢀrelationship :
k
= σρ
log
k0
Eꢀmail: chunwang69@126.com (C. Wang);
fengchengcctv@163.com (C. Feng)
where k is the rate constant of the catalytic reduction of substituted
nitrobenzenes and k0 indicates the rate constant of the unsubstituted
nitrobenzene. The kꢀvalues were evaluated from the initial reduction
Electronic Supplementary Information (ESI) available: Reduction
of nitrobenzene to aniline with different hydrogen source over
Ag1Pd9@NPCꢀUiOꢀ66ꢀ800 catalyst. Various reported catalyst
tested for reduction of nitroarenes into anilines. EDX spectrum,
XPS patterns and recyclability of the catalyst. TEM and XPS of
the reused of the catalyst. Tentative reaction mechanism for the
reduction of nitroarenes over the catalyst. See DOI:
10.1039/b000000x/
45
rates. The corresponding Hammett plot (Fig. S7) reveals that the
rate of reaction is decreased by electron donating groups and
enhanced by electron attracting substituents. The resulting slope (ρ)
of the σρ−relationship obtained by linear regression is 0.347
(correlation coefficient: r2=0.961), indicative of an anionic charge on
the transition state.
According to the precious works, a schematic mechanism was
proposed for the CTH of nitro compounds over the Ag1Pd9@NPCꢀ
UiOꢀ66ꢀ800 catalyst. As shown in Fig S8, nitrobenzene firstly
absorbs on the surfaces of the catalyst. The activation of FA and AF
by AgPd NPs would generate active AgPdꢀH species, which were
used for the hydrogenation of nitrobenzene to amines. Finally, the
product amines release from the surface of the Ag1Pd9@NPCꢀUiOꢀ
1. L. Liu, P. Concepción and A. Corma, J. Catal., 2016, 340, 1ꢀ9.
2. Y. Liu, Y. Lu, M. Prashad, O. Repi and T. J. Blacklock, Adv.
Synth. Catal., 2005, 347, 217ꢀ219.
3. Y. B. Huang, Q. Wang, J. Liang, X. Wang and R. Cao, J. Am.
Chem. Soc., 2016, 138, 10104ꢀ10107.
8 | J. Name., 2012, 00, 1-3
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Please do not adjust margins
New Journal of Chemistry
Page 9 of 10
Journal Name
View Article Online
DOI: 10.1039/C7NJ00442G
ARTICLE
4. Q. Yang, P. Q. Xu, S. H. Yu and H. L. Jiang, Angew. Chem. Int. 31. S. Hu, M. Liu, K. Li, Y. Zuo, A. Zhang, C. Song, G. Zhang and
Ed., 2016, 55.
X. Guo, CrystEngComm, 2014, 16, 9645ꢀ9650.
5. M. J. Gilkey and B. Xu, ACS Catal., 2016, 6, 1420ꢀ1436.
6. K. J. Datta, A. K. Rathi, M. B. Gawande, V. Ranc, G.
32. X. L. Du, L. He, S. Zhao, Y. M. Liu, Y. Cao, H. Y. He and K.
N. Fan, Angew. Chem. Int. Ed., 2011, 50, 7815ꢀ7819.
Zoppellaro, R. S. Varma and R. Zboril, ChemCatChem, 2016, 33. Y. Xiong, J. M. McLellan, Y. Yin and Y. Xia, Angew. Chem.
8, 2351ꢀ2355. Int. Ed., 2007, 46, 790ꢀ794.
7. J.ꢀw. Zhang, G.ꢀp. Lu and C. Cai, Catal. Commun., 2016, 84, 34. Y. Ping, J.ꢀM. Yan, Z.ꢀL. Wang, H.ꢀL. Wang and Q. Jiang, J.
25ꢀ29. Mater. Chem. A, 2013, 1, 12188.
8. S. Byun, Y. Song and B. M. Kim, ACS Appl. Mater. Int., 2016, 35. K. Gurushantha, K. S. Anantharaju, L. Renuka, S. C. Sharma,
8, 14637ꢀ14647.
H. P. Nagaswarupa, S. C. Prashantha, Y. S. Vidya and H.
Nagabhushana, RSC Adv., 2017, 7, 12690ꢀ12703.
9. P. Zhou, D. Li, S. Jin, S. Chen and Z. Zhang, Int. J. Hydrogen
Energy, 2016, 41, 15218ꢀ15224.
10. J. Feng, C. Yang, D. Zhang, J. Wang, H. Fu, H. Chen and X. Li,
Appl. Catal. A: Gen., 2009, 354, 38ꢀ43.
11. H. Heeres, R. Handana, D. Chunai, C. Borromeus Rasrendra, B.
Girisuta and H. Jan Heeres, Green Chem., 2009, 11, 1247.
36. Y.ꢀZ. Chen, Y.ꢀX. Zhou, H. Wang, J. Lu, T. Uchida, Q. Xu, S.ꢀ
H. Yu and H.ꢀL. Jiang, ACS Catal., 2015, 5, 2062ꢀ2069.
37. G. Wienhofer, I. Sorribes, A. Boddien, F. Westerhaus, K.
Junge, H. Junge, R. Llusar and M. Beller, J. Am. Chem. Soc.,
2011, 133, 12875ꢀ12879.
12. J. Mondal, Q. T. Trinh, A. Jana, W. K. Ng, P. Borah, H. Hirao 38. A. Corma, P. Serna and H. García, J. Am. Chem. Soc., 2007,
and Y. Zhao, ACS Appl. Mater. Int., 2016, 8, 15307ꢀ15319. 129, 6358ꢀ6359.
13. L. Yu, Q. Zhang, S. S. Li, J. Huang, Y. M. Liu, H. Y. He and Y. 39. M. Boronat, P. Concepción, A. Corma, S. González, F. Illas and
Cao, ChemSusChem, 2015, 8, 3029ꢀ3035. P. Serna, J. Am. Chem. Soc., 2007, 129, 16230ꢀ16237.
14. I. Sorribes, G. Wienhofer, C. Vicent, K. Junge, R. Llusar and 40. G. Postole, B. Chowdhury, B. Karmakar, K. Pinki, J. Banerji
M. Beller, Angew. Chem. Int. Ed., 2012, 51, 7794ꢀ7798. and A. Auroux, J. Catal., 2010, 269, 110ꢀ121.
15. R. V. Jagadeesh, K. Natte, H. Junge and M. Beller, ACS Catal., 41. Q. Y. Bi, X. L. Du, Y. M. Liu, Y. Cao, H. Y. He and K. N. Fan,
2015, 5, 1526ꢀ1529. J. Am. Chem. Soc., 2012, 134, 8926ꢀ8933.
16. Y.ꢀB. Huang, M. Shen, X. Wang, P.ꢀC. Shi, H. Li and R. Cao, 42. D. A. Bulushev, M. Zacharska, A. S. Lisitsyn, O. Y.
J. Catal., 2015, 330, 452ꢀ457.
17. H. C. Zhou and S. Kitagawa, Chem. Soc. Rev., 2014, 43, 5415ꢀ
5418.
18. Y. B. Huang, J. Liang, X. S. Wang and R. Cao, Chem. Soc.
Rev., 2017, 46, 126ꢀ157.
Podyacheva, F. S. Hage, Q. M. Ramasse, U. Bangert and L. G.
Bulusheva, ACS Catal., 2016, 6, 3442ꢀ3451.
43. X. Xu, Y. Li, Y. Gong, P. Zhang, H. Li and Y. Wang, J. Am.
Chem. Soc., 2012, 134, 16987ꢀ16990.
44. A. Corma and P. Serna, Science, 2006, 313, 332ꢀ334.
19. H. L. Jiang, B. Liu, Y. Q. Lan, K. Kuratani, T. Akita, H. 45. M. Lauwiner, P. Rys and J. Wissmann, Appl. Catal., A, 1998,
Shioyama, F. Zong and Q. Xu, J. Am. Chem. Soc., 2011, 133,
11854ꢀ11857.
172, 141–148.
20. Y.ꢀZ. Chen, C. Wang, Z.ꢀY. Wu, Y. Xiong, Q. Xu, S.ꢀH. Yu
and H.ꢀL. Jiang, Adv. Mater., 2015, 27, 5010ꢀ5016.
21. L. Zhang, C. Feng, S. Gao, Z. Wang and C. Wang, Catal.
Commun., 2015, 61, 21ꢀ25.
22. Y. Li, Y. X. Zhou, X. Ma and H. L. Jiang, Chem. Commun.,
2016, 52, 4199ꢀ4202.
23. C. Feng, Y. Wang, S. Gao, N. Shang and C. Wang, Catal.
Commun., 2016, 78, 17ꢀ21.
24. Y. Z. Chen, C. Wang, Z. Y. Wu, Y. Xiong, Q. Xu, S. H. Yu and
H. L. Jiang, Adv. Mater., 2015, 27, 5010ꢀ5016.
25. Y. Luan, Y. Qi, H. Gao, N. Zheng and G. Wang, J. Mater.
Chem. A, 2014, 2, 20588ꢀ20596.
26. C. S. Hinde, W. R. Webb, B. K. Chew, H. R. Tan, W. H.
Zhang, T. S. Hor and R. Raja, Chem. Comm., 2016, 52, 6557ꢀ
6560.
27. Z. Xu, L. Yang and C. Xu, Anal. Chem., 2015, 87, 3438ꢀ3444.
28. S.ꢀT. Gao, W. Liu, C. Feng, N.ꢀZ. Shang and C. Wang, Catal.
Sci. Technol., 2016, 6, 869ꢀ874.
29. M. J. Katz, Z. J. Brown, Y. J. Colon, P. W. Siu, K. A. Scheidt,
R. Q. Snurr, J. T. Hupp and O. K. Farha, Chem. Commun.,
2013, 49, 9449ꢀ9451.
30. T. Ahnfeldt, N. Guillou, D. Gunzelmann, I. Margiolaki, T.
Loiseau, G. Ferey, J. Senker and N. Stock, Angew. Chem. Int.
Ed., 2009, 48, 5163ꢀ5166.
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New Journal of Chemistry
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DOI: 10.1039/C7NJ00442G
High catalytic activity of bimetallic AgPd alloy
supported on UiO-66 derived porous carbon for
transfer hydrogenation of nitroarenes using formic
acid-formate as hydrogen source
Saisai Cheng, Ningzhao Shang, Xin Zhou, Cheng Feng*, Shutao Gao, Chun Wang*[a],
Zhi Wang
College of Science, Hebei Agricultural University, Baoding 071001, China
Bimetallic AgPd nanoparticles supported on metal-organic framework (UiO-66)
derived
N-doped
porous
carbon
(NPC-UiO-66).
The
as-synthesized
Ag1Pd9@NPC-UiO-66 catalyst exhibited extraordinary catalytic activity toward the
hydrogenation of nitroarenes to anilines at room temperature.