Tuning Synergistic Effect of Au-Pd Bimetallic Nanocatalyst for Aerobic Oxidative Carbonylation of Amines

Article abstract of DOI:10.1021/acs.chemmater.7b00544

The activation and utilization of carbon monoxide is of crucial importance to C₁ chemistry. Various catalytic transformation processes have been developed and studied in the last century, and oxidative carbonylation of amines is one of them. Catalysts that have been identified to date for the oxidative carbonylation of amines generally show relatively low activity and/or selectivity. Herein, a metal-organic framework (MOF), i.e., MOF-253 prepared from AlCl₃·6H₂O and 2,2′-bipyridine-5,5′-dicarboxylic acid, was employed as a support of gold-palladium bimetallic nanoparticles (Au-Pd/MOF) for the oxidative carbonylation of amines under mild conditions. Compared to palladium or gold monometallic catalysts, higher catalytic activity (turnover frequency up to 2573 h^-1) and selectivity in the carbonylation of amines were achieved by Au-Pd/MOF bimetallic catalysts through adjusting the molar ratio of gold and palladium within the framework. A breathing effect of Au-Pd/MOF in the catalytic process was further observed from kinetic profiles and powder X-ray diffraction for the first time.

Full text of DOI:10.1021/acs.chemmater.7b00544

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Article
Tuning Synergistic Effect of Au-Pd Bimetallic Nanocatalyst
for Aerobic Oxidative Carbonylation of Amines
Hui Duan, Yongfei Zeng, Xin Yao, Pengyao Xing, Jia Liu, and Yanli Zhao
Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/acs.chemmater.7b00544 • Publication Date (Web): 03 Apr 2017
Downloaded from http://pubs.acs.org on April 3, 2017
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Chemistry of Materials
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Tuning Synergistic Effect of Au-Pd Bimetallic Nanocatalyst for
Aerobic Oxidative Carbonylation of Amines
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†
§
†§
†
†
†
,†,‡
Hui Duan , Yongfei Zeng , Xin Yao , Pengyao Xing , Jia Liu , Yanli Zhao*
†Division of Chemistry and Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological
University, 21 Nanyang Link, 637371 Singapore
‡School of Materials Science and Engineering, Nanyang Technological University, 639798, Singapore
ABSTRACT: The activation and utilization of carbon monoxide (CO) is of crucial importance to the C chemistry.
1
Various catalytic transformation processes have been developed and studied in the last century, and oxidative
carbonylation of amines was one of them. Catalysts that have been identified so far for the oxidative carbonylation of
amines generally show relatively low activity and/or selectivity. Herein, a metal-organic framework (MOF), i.e., MOF-
2
53 prepared from AlCl
3
·6H O and 2,2’-bipyridine-5,5’-dicarboxylic acid, was employed as a support of gold-
2
palladium bimetallic nanoparticles (Au-Pd/MOF) for the oxidative carbonylation of amines under mild conditions.
Compared to palladium or gold monometallic catalysts, higher catalytic activity (turnover frequency up to 2573 h )
and selectivity in the carbonylation of amines were achieved by Au-Pd/MOF bimetallic catalysts through adjusting the
molar ratio of gold and palladium within the framework. A breathing effect of Au-Pd/MOF in catalytic process was
further observed from kinetic profiles and powder X-ray diffraction for the first time.
-1
KEYWORDS: aerobic oxidative carbonylation, bimetallic catalyst, breathing effect, metal-organic frameworks, synergistic
effect
INTRODUCTION
Developing novel heterogeneous catalysts with higher
efficiency and better selectivity is one of the primer goals
in modern catalytic chemistry. Recently, we demonstrated
that mesoporous silica framework supported single site
Pd(II) is an efficient catalyst for the C-H olefination
reactions, confirming that the ligand modified framework
has distinctive capability to immobilize the Pd site and to
remain its catalytic activity during the catalytic process.41
Similar to mesoporous silica, metal-organic frameworks
(MOFs) are a kind of crystalline porous materials
containing organic linkers, metal clusters, and empty space
in nanometer scale, having high surface area and
During the past few decades, many studies had shown
that supported transition-metal nanoparticles could be
1
-8
effective catalysts in various chemical transformations.
5
9-16
Palladium (Pd) and gold (Au)
are popular metals
among these transition metals, due to their high activity
demonstrated in carbon-carbon bond formation and
aerobic oxidation reactions. After the concept of bimetallic
17,18
nanoparticle catalysts was established in 1970’s,
Au-Pd
bimetallic catalysts have been raising as one of the most
attractive systems in the catalysis research. As a new type
of heterogeneous catalyst,1
9-39
the Au-Pd bimetallic
4
2-44
porosity.
Owing to these unique properties, MOFs
nanoparticles have been investigated in the acetoxylation
4
5-63
2
4
34
20,35
show considerable promise in catalysis.
One of
of ethylene, synthesis of H
2
O
2
, oxidation of alcohols,
3
7,40
promising approaches is to use MOFs as the supports of
and carbon monoxide (CO) oxidation.
activation and utilization of CO in organic reactions
catalyzed by Au-Pd bimetallic catalysts still remain
However, the
active metal sites (i.e., metal complexes or
2
7,51,54,56,64-69
nanoclusters).
Based on these pioneering
studies, we herein developed MOF supported Au-Pd
bimetallic catalysts and investigated their catalytic
performance in aerobic oxidative carbonylation reactions
unexplored, although it is an essential part of C chemistry.
1
(
Scheme 1). In this work, MOF-253 prepared from
9
8 %
AlCl ·6H O and 2,2’-bipyridine-5,5’-dicarboxylic acid was
3
2
selected as the catalyst support owing to its high
concentration of 2,2’-bipyridine unit and unique
Scheme 1. Au-Pd bimetallic catalysts for aerobic oxidative
carbonylation.
nanostructure. MOF-253 also showed good capability to
immobilize and disperse the metal sites uniformly,67
demonstrating that it is an excellent support for
heterogeneous catalysis.
1
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To the best of our knowledge, this is the first report of
aerobic oxidative carbonylation reaction catalyzed by Au-
Pd bimetallic catalyst. Carbonylation reaction is an
important reaction in organic chemistry and C1 chemistry.
Both Au and Pd could be used as catalysts in this reaction,
but there are some activity and/or selectivity issues
associated by using only single metal catalysts. On the
other hand, the present Au-Pd bimetallic catalyst shows an
amazing potential in the activation of O2 and CO, making it
highly unique for further developments.
overnight. 2,2'-Bipyridine-5,5'-dicarboxylic acid (684 mg,
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
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1
2.8 mmol, 66 % yield) was obtained as a white solid. H
NMR (DMSO-d , 400 MHz): δ = 13.57 (br. s., 2 H), 9.20 (s, 2
H), 8.57 (d, J = 8.3 Hz, 2 H), 8.42 - 8.47 ppm (m, 2 H);
NMR (DMSO-d , 101 MHz): δ = 166.5, 157.8, 150.8, 138.9,
6
1
3
C
6
127.6, 121.6 ppm.
Synthesis of MOF-253. MOF-253 was synthesized as the
6
8
reported method with slight modifications. A solution of
AlCl ·6H O (151 mg, 0.625 mmol) and glacial acetic acid
3
2
(859 µL, 15.0 mmol) in N,N'-dimethylformamide (DMF, 10
mL) was added to a Teflon-capped 20 mL scintillation vial
containing 2,2'-bipyridine-5,5'-dicarboxylic acid (153 mg,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
0
.625 mmol). The mixture was heated on an oven at 120 °C
EXPERIMENTAL SECTION
for 24 h. The resulting white microcrystalline powder was
then filtered and washed with DMF. The powder was
extracted with methanol via soxhlet extraction for 72 h,
after which the powder was collected by filtration and
heated at 250 °C under dynamic vacuum on a Schlenk line
General information. All the chemicals including non-
aqueous tetrahydrofuran (THF), MeOH and dimethyl
sulfoxide (DMSO) were purchased from Sigma Aldrich and
used as received. All non-aqueous reactions and
for 12 h. The N adsorption isotherm (Figure S1 in the
2
manipulations were performed in a N atmosphere using
2
Supporting Information) and pore size distribution (Figure
S2) of the prepared MOF-253 were determined, showing a
pore size of about 1.2 nm. Its pore size determined by
PXRD was from 1.2 nm to 1.3 nm.
standard Schlenk techniques. The catalyst amount in each
reaction was weighted on a microbalance (Mettler Toledo
XS3DU). NMR spectra were recorded on Bruker
1
13
spectrometer at 300 MHz ( H NMR) and 75 MHz ( C
1
Preparation of catalysts. All the catalysts were prepared
NMR), or a Bruker spectrometer at 400 MHz ( H NMR) and
00 MHz ( C NMR). Tetramethylsilane (TMS) was used as
13
via an impregnation method using AuCl solution in MeOH
3
1
1
and/or Pd salt solution in dry DMSO. The loaded metal
species were reduced by hydrogen to obtain the metal
particles. The detailed preparation procedure employed is
described below. All the metal concentrations used in
following catalytic experiments were obtained from ICP-
MS tests.
an internal standard. All H NMR spectra were reported in
delta (δ) units, parts per million (ppm) downfield from the
internal standard. Coupling constants were reported in
Hertz (Hz). Brunauer–Emmett–Teller (BET) surface areas
were obtained using a Micromeritics ASAP 2020M
automated sorption analyzer. High-angle annular dark-
field scanning transmission electron microscope (HAADF-
STEM) images and cross-sectional compositional line
profiles were obtained using a JEOL 2100. Powder X-ray
diffraction (PXRD) measurements were performed on a
SHIMADZU XRD-6000 Labx diffractometer at 40 kV and 30
mA using Cu Kα radiation (λ = 1.5418 Å) over 2θ range of
Preparation of Au/MOF. To a mixture of MOF-253 (40
mg) in MeOH (3 mL), an appropriate amount of AuCl
3
solution in MeOH was added. The mixture was stirred and
refluxed for 3 days. After centrifugation and washing by
plenty of MeOH, the retaining solid was dried under
vacuum for two days. Then, the gold immobilized MOF-253
(Au/MOF) catalyst was obtained after treating the solid
.5o - 40o at room temperature. X-Ray photoelectron
2
o
under hydrogen at 80 C for 2 h.
spectroscopy (XPS) was referenced to the carbon species
with C 1s at the binding energy of 284.8 eV. The metal
loading was determined by inductively coupled plasma
mass spectrometry (ICP-MS) using Agilent 7700. All
catalytic reactions were carried out in an autoclave and
monitored by thin-layer chromatography (TLC), NMR and
gas chromatography (GC). The yield and selectivity data in
catalyst scanning reactions were determined by GC with
dodecane as the internal standard. The concentration of
the product in kinetic profiles was determined by Bruker
Preparation of Pd/MOF. To a mixture of MOF-253 (40
mg) in dry DMSO (3 mL), an appropriate amount of
palladium salt (PdCl
2
, Pd(OTFA)
2
or Pd(OAc) ) solution in
2
DMSO was added. The mixture was stirred at room
temperature for 1 day. After centrifugation and washing by
plenty of MeOH, the retaining solid was dried under
vacuum for two days. Then, the palladium immobilized
MOF-253 (Pd/MOF) catalyst was obtained after treating
o
the solid under hydrogen at 80 C for 2 h.
Preparation of Au-Pd/MOF. To a mixture of gold
immobilized MOF-253 (40 mg, before the treatment by
hydrogen) in dry DMSO (3 mL), an appropriate amount of
4
00 MHz NMR with 1,3,5-trimethoxybenzene as the
internal standard.
Synthesis of 2,2'-bipyridine-5,5'-dicarboxylic acid. 2,2'-
palladium salt (PdCl
2
, Pd(OTFA)
2
or Pd(OAc) ) solution in
2
Bipyridine-5,5'-dicarboxylic
acid
was
synthesized
4
1
DMSO was added. The mixture was stirred at room
temperature for two days. After centrifugation and
washing by plenty of MeOH, the retaining solid was dried
under vacuum for two days. The Au-Pd immobilized MOF-
following our previous work. To a stirred solution of
potassium permanganate (4383 mg, 27.7 mmol) in water
(60 mL), 5,5'-dimethyl-2,2'-bipyridine (786 mg, 4.3 mmol)
was added. The mixture was heated in an oil bath to reflux
for 5 h. Subsequently, the mixture was cooled down to
room temperature followed by filtration. Then, the filtrate
2
53 (Au-Pd/MOF) catalyst was obtained after treating the
o
solid under hydrogen at 80 C for 2 h.
General catalytic procedures. A test tube was added with
catalyst (Au/MOF, Pd/MOF, Au-Pd/MOF or a mixture of
Au/MOF and Pd/MOF), as well as THF and amine (4 mL).
The mixture was treated by ultrasonication to disperse the
was washed by Et O (100 mL) for three times. After the pH
2
value of the water phase was adjusted to 2, white floc solid
appeared. The mixture was filtered and white solid was
obtained. The solid was dried at 50 °C under vacuum
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Chemistry of Materials
catalyst. The resulting solution was sealed in a 600 mL
Parr reactor and purged by 10 atm of CO gas for five times,
(Table 1, entries 2 and 3). The carbonylation of reactant a1
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in the presence of Au/MOF led to lower selectivity (36 %,
entry 2) with N-cyclohexylformamide as a side product. A
relatively higher selectivity (73 %, entry 3) was obtained
in the presence of Pd/MOF as the catalyst, having di-
carbonylation as the main byproduct. Significantly, the
catalytic efficiency by using Au-Pd/MOF bimetallic catalyst
was improved dramatically through tuning the molar ratio
of Au and Pd (entries 4-6). Compared to Au/MOF
monometallic catalyst, the TON of Au-Pd/MOF (molar ratio
of Au and Pd = 0.27/0.73) increased by almost 26 times
(entry 5), and the selectivity rose to 98 %. When
and then the reactor was filled by CO (6 bar) and O
2
(2
o
bar). After stirring the mixture at 90 C for 20 h, the
reactor was cooled down to room temperature and the
excess gas was released slowly. After dodecane was added
as an internal standard, the residue was analyzed by GC to
obtain the yield and selectivity data. The turnover number
(TON) and turnover frequency (TOF) data were further
calculated in the basis of total metal concentration.
Procedures for kinetic experiments. To a 1.5 mL vial
was added Au-Pd/MOF (0.3 mg), cyclohexanamine (0.014
mmol), 1,3,5-trimethoxybenzene (about 0.2 mg) and THF-
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
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9
0
Pd(OTFA) was used as the Pd precursor and the Au molar
2
d
8
(0.25 mL). The mixture was treated by ultrasonication
ratio was adjusted to 27 %, the TON increased to five times
higher than that of Pd/MOF monometallic catalyst (entry
5). Furthermore, when Au/MOF and Pd/MOF were
physically mixed together under two different ratios and
then used as catalysts in the model reaction (entries 7 and
to disperse the catalyst. The resulting solution was sealed
in a Norell heavy wall NMR tube and filled by the mixture
gases of CO and O
was heated to 90 C and monitored by H NMR.
2
(5 bar, CO:O
2
= 3:1). Then, the mixture
o
1
8
, molar ratio of Au and Pd = 0.55/0.45 and 0.25/0.75), the
catalytic activity and selectivity were similar to Pd/MOF
monometallic catalyst. These results indicate that the
catalytic efficiency was enhanced by Au-Pd bimetallic
nanoparticles rather than the separated gold and
palladium nanoparticles.
Table 1. Comparison of catalytic activity for oxidative
carbonylation of cyclohexanamine using different
supported catalysts.
3
2
2
1
000
500
000
500
TOF
Selectivity
1
00
Cat.a
90
80
70
Entry
Au/Pd
molar
ratio
TON
Selectivity
(%)b
Yield
(%)b
1
2
3
4
5
6
7
MOF-253
Au/MOF
0:0
1:0
0:1
None
545
2841
9786
None
36
73
88
98
38
75
None
6
23
46
54
8
Pd/MOFc
6
0
c
c
c
1000
Au-Pd/MOF
Au-Pd/MOF
Au-Pd/MOF
0.20:0.80
0.27:0.73 14128
0.69:0.31
0.55:0.45
50
40
30
1941
2575
5
00
0
Au/MOF,
40
Pd/MOFc
8
Au/MOF,
0.25:0.75
2325
71
45
Pd/MOFc
0.0
0.2
0.4
0.6
0.8
1.0
Au (molar %)
Reaction conditions: cyclohexylamine (a1, 4.3 mmol), CO
o
(6 bar), O
2
(2 bar), THF as the solvent (4.0 mL), 90 C, 20 h.
Figure 1. Effect of Au/Pd molar ratio on Au-Pd/MOF
catalyzed oxidation carbonylation of cyclohexanamine.
Reaction conditions: cyclohexylamine (4.3 mmol), CO/O2 (8
TON was calculated in the basis of the total metal. (a) The
catalyst mass was around 0.3 mg. The metal
concentrations in catalysts were obtained from ICP-MS
measurements. (b) The yield and selectivity were
determined by GC with dodecane as the internal standard.
o
bar, 3:1), THF as the solvent (4.0 mL), 90 C, 20 h. The metal
contents in catalysts were obtained from ICP. The yield and
selectivity were determined by GC with dodecane as the
internal standard. TOF was calculated in the basis of total
(
c) Pd(OTFA) was used as the Pd precursor.
2
metal. PdCl was used as the palladium precursor for the
2
RESULTS AND DISCUSSIONS
synthesis of Au-Pd/MOF.
To achieve desirable catalytic activity and selectivity, a
series of MOF-253 supported Au-Pd bimetallic catalysts
(Au-Pd/MOF) were synthesized, and their catalytic
performance was tested in a model reaction (Table 1).
Then, we investigated Au-Pd/MOF with different metal
molar ratios in order to achieve the most effective catalyst
(
Table S1 and Figure S3). As shown in Figure S3a, Au was
not an active metal for this reaction by itself, but the
combination of Au and Pd could enhance the product
selectivity as compared with the Pd/MOF monometallic
catalyst. Better catalytic efficiency was reached when the
Au molar percentage was adjusted to 20~30 %. Similar
results were revealed when switching the Pd precursor to
Under eight bar of gas mixture consisting of CO and O (3
2
to 1), no product was found in the blank reaction by
employing only MOF-253 as the catalyst (Table 1, entry 1).
To examine the catalytic efficiency of MOF-253 supported
monometallic
catalysts
in
carbonylation
of
cyclohexanamine, Au/MOF and Pd/MOF were also
synthesized by an impregnation method. Both of Au/MOF
and Pd/MOF could produce carbonylation product a2
Pd(OAc)
2
(Figure S3b), and the highest selectivity was
observed when 30 mol % of Au was used in Au-Pd/MOF.
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We further studied the Au-Pd/MOF bimetallic catalyst
using PdCl as the Pd precursor (Figure 1). The best
In order to investigate the synergistic effect of Au26
-
1
2
3
4
5
6
7
8
9
1
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5
5
5
5
5
5
6
2
Pd74/MOF catalyzed oxidative carbonylation of amines,
more control experiments were designed and carried out
based on the model reaction. As shown in Scheme S1 and
Table S2 in the Supporting Information, no product was
found by GC when using different concentrations of N-
cyclohexylformamide instead of CO. In addition, no di-
carbonylation product was observed when N-
product selectivity and catalytic efficiency were achieved
at the same time when the Au:Pd molar ratio in Au-
Pd/MOF was adjusted to 26/74, and this catalyst (named
as Au26-Pd74/MOF) was chosen for further investigations.
These data demonstrate a clear synergistic effect between
Au and Pd in Au-Pd/MOF bimetallic catalyst, which could
influence the catalytic performance in oxidative
carbonylation of amine.
cyclohexylformamide was reacted with O
of the Au26-Pd74/MOF catalyst. When employing CO instead
of the CO/O mixture, no product was detected in the
2
in the presence
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
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0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Further investigation on Au26-Pd74/MOF bimetallic
catalyst was carried out through high-resolution
transmission electron microscopy (HR-TEM). Fine metal
clusters from Au26-Pd74/MOF bimetallic catalyst were
observed in HAADF-STEM images (Figure 2a and Figure
S4c). These clusters fall in the range of 0.7 to 2.0 nm in
diameter, and intermediate particles were 1.2 nm in size
reaction mixture. When the model reaction was tested
using Au-Pd loaded TS-1 zeolite catalyst prepared under a
similar method, only a trace amount of product was found
by GC.
Basically, there are three interpretations of the
synergetic effect, i.e., bifunctional mechanism, electronic
3
7
(Figure 2b), matching well with the pore size of MOF-253.
effect and geometric ensemble effect. Above results
indicate that this bimetallic catalyst does not work as a
kind of “bifunctional” catalyst in this model reaction,
confirming the synergistic effect in Au26-Pd74/MOF
catalyzed oxidative carbonylation reaction. The study
about the electronic and geometric effect generated from
the Pd–Au interfaces in the catalyst in terms of an increase
or decrease of Pd–Pd and Au–Au bond lengths in Pd-
Au/MOF as compared with that of Au/MOF and Pd/MOF
should be useful for better understanding the mechanism.
We will try to address the detailed synergetic mechanism
in our future research.
Due to the interference of porous framework, the
crystalline lattice of Au-Pd bimetallic nanoparticles was
only observed on some larger nanoparticles (Figure 2c).
Corresponding fast Fourier transformation (FFT) patterns
(Figure 2d) further support the structure of the metal
nanoparticles with body-centered cubic (BCC) morphology
that was same to the reported Au-Pd bimetallic nanoalloy
and different to the Pd-only and Au-only alloy (face-
70-72
centered cubic, FCC).
The cell length was about 0.40
68
nm, which also matches to pervious reports.
The XPS spectra of Au26-Pd74/MOF also confirmed the
presence of Pd, and only weak signal of Au was found due
to the low concentration of Au in the catalyst (Figure S5). A
negative shift (0.3-0.5 eV) of Pd 3d in Au26-Pd74/MOF was
observed as compared to that of Pd/MOF, further
supporting the conclusion that the Au-Pd nanoalloy was
formed in the catalyst. Relatively high binding energy of Pd
3d in the catalyst may be due to small particle size of the
The kinetic investigation was then carried out. As
shown in the first hour from curve a in Figure S9a, an
induction period was observed. However, no induction
period was observed when the Au26-Pd74/MOF catalyst
was immersed into THF-d for 20 h before the kinetic
8
experiments (curve b in Figure S9a). This observation
indicates that the induction period was not caused by the
pre-activation of metal species inside the MOF-253
support. Only possible explanation is the breathing effect
induced by the flexibility of MOF-253, which may restrict
the diffusion process of the reactants and products. The
breathing effect of a MOF is its ability to exhibit displacive
phase transition behavior, where the unit cell volume of
the MOF varies in response to an external stimulus.7
2
7,34
metals.
In addition, a peak splitting of N 1s was found
after the loading of metals in Au26-Pd74/MOF (Figure S6).
No significant peak change was found through FT-IR
analysis (Figure S7). The compositional line profiles
(Figure S8) further indicate the presence of both Au and Pd
in a nanocluster, implying that the two metal precursors
3,74
were reduced into bimetallic clusters by H
preparation.
2
during the
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c
d
Figure 2. (a) HAADF-STEM image of Au26-Pd74/MOF bimetallic catalyst, (b) size distribution of Au-Pd nanoclusters in Au26
Pd74/MOF, (c) crystalline lattice of Au-Pd nanoclusters in Au26-Pd74/MOF, and (d) corresponding FFT patterns of these Au-
Pd nanoclusters.
-
to the product. The breathing effect of the catalyst can be
accounted for the structural flexibility of MOF-253 (Figure
To further confirm whether the distinct induction
S9c). While the breathing effect of MOFs has been
period in kinetic profiles of dry Au26-Pd74/MOF is resulted
extensively
conductivity and sensor,
been observed in catalytic process so far.
reported
in
adsorption,
this phenomenon has not
separation,
from the structural change of MOF-253 or not, PXRD
measurements of dry and wet Au26-Pd74/MOF samples
were carried out (Figure S9b). The diffraction shifts in
PXRD between Au26-Pd74/MOF and MOF-253 may be
caused by the filling of Au and Pd metals in the MOF pores,
leading to a slight change of the framework. The PXRD
pattern of wet sample is in a good agreement with that of
the simulated structure having larger pores, while that of
the dry sample matches well with the calculated structure
having smaller pores. The pore sizes of the framework
under two states were further simulated (Figure S10). For
the dry sample, the Al–Al–Al angle (θ) in the framework is
7
5-78
o
o
6
4 . Comparatively, the angle (θ) increased to 80 when
the sample was changed to the wet state (Figure S10a),
and the ID (inner diameter) of the pores increased to
nearly 13 Å. Combining the changes of the ID and the
molecular sizes of cyclohexylamine and product (Figure
S10b), it is obvious that the porous framework shall have a
notable confinement to the diffusion process, specifically
Figure 3. Au26-Pd74/MOF catalyzed oxidation carbonylation of
different amines. 2 % NH
urea generation test, and no additional solvent was employed.
3
aqueous solution was used in the
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In addition, a preliminary study on the reusability of
ACKNOWLEDGMENT
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Au26-Pd74/MOF for the model reaction over five runs was
carried out, showing that both of the reaction yield and
selectivity dropped slightly after five cycles (Figure S11).
The recycled Au-Pd/MOF was tested by PXRD. As shown in
Figure S12, those peaks in the recycled Au-Pd/MOF were
weaker than the peaks from original catalyst, indicating its
relatively low stability after five cycles. Finally, the
This work is supported by the Singapore Academic Research
Fund (RG112/15 and RG19/16). We thank Dr. Steve Heald
and Dr. Tianpin Wu from Argonne National Laboratory for
helpful discussions.
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the integration of Au with Pd in Au-Pd/MOF bimetallic
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catalyst efficiency for the carbonylation reaction of amines.
The best Au/Pd molar ratio for oxidative carbonylation of
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bimetallic catalyst was revealed from the catalytic results.
Compared to Au and Pd monometallic catalysts, the TOF of
Au26-Pd74/MOF increased by 95 and 16 times, respectively.
Moreover, the breathing effect of MOF-253 has been
identified from the kinetic profiles for the first time. Thus,
this newly developed MOF-253 supported Au-Pd bimetallic
catalyst could offer an effective catalytic protocol to
aerobic oxidative carbonylation of amines. Further
mechanistic and kinetic investigations as well as studies on
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AUTHOR INFORMATION
(
20) Villa, A.; Dimitratos, N.; Chan-Thaw, C. E.; Hammond, C.; Prati, L.;
Corresponding Author
Email: zhaoyanli@ntu.edu.sg
Author Contributions
§
(22) Zhang, L.-F.; Zhong, S.-L.; Xu, A.-W. Highly Branched Concave
Au/Pd Bimetallic Nanocrystals with Superior Electrocatalytic Activity
and Highly Efficient SERS Enhancement. Angew. Chem., Int. Ed. 2013,
These authors contributed equally to this work.
Notes
The authors declare no competing financial interests.
52, 645-649.
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