In situ synthesis of sub-nanometer metal particles on hierarchically porous metal-organic frameworks via interfacial control for highly efficient catalysis

Article abstract of DOI:10.1039/c7sc04269h

In this work, we developed a strategy to in situ synthesize sub-nanometer metal particle/hierarchically mesoporous metal-organic framework (MOF) composites in emulsion. In this route, water droplets in the emulsion acted as both a solvent of the metal pre

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DOI: 10.1039/C7SC04269H
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In situ Synthesis of Sub-nanometer Metal Particles on
Hierarchically Porous Metal-Organic Frameworks via Interfacial
Control for Highly Efficient Catalysis
Received 00th January 20xx,
Accepted 00th January 20xx
a,b
a,b
a,b
a,b
a
a,b
DOI: 10.1039/x0xx00000x
Pei Zhang, Chunjun Chen, Xinchen Kang, Lujun Zhang, Congyi Wu, Jianling Zhang, and
a,b
Buxing Han*
www.rsc.org/
In this work, we developed a strategy to in situ synthesize sub-nanometer metal particles/hierarchically mesoporous
metal-organic frameworks (MOFs) composites in emulsion. In this route, water droplets in the emulsion acted as both
solvent of metal precusors and template for hierarchical mesopores of MOFs, and the surfactant was emulsifier and
2+
reductant for generating metal particles. Au/Zn-MOF (MOF formed by Zn and methylimidazole), Ru/Zn-MOF, Pd/Zn-
2
+
MOF, and Au/Cu-MOF (MOF formed by Cu and methylimidazole) were prepared using this method, in which ultrafine
metal particles (e.g. 0.8 nn) were immobilized uniformly on hierarchically mesoporous MOFs. Au/Zn-MOF and Au/Cu-MOF
showed outstanding catalytic performances for selective aerobic oxidation of cyclohexene to 2-cyclohexen-1-one in the
absence of initiator, and Ru/Zn-MOF was very active and selective for hydrogenation of diphenyl sulfoxide to diphenyl
sulfide.
In
addition,
the
catalysts
were
also
very
stable
in
the
reactions.
1
5,16
properties.
Controlling the size of metal particles is very
Introduction
difficult because aggregation readily occurs due to high
7,18
1
cohesive energy and low melting points.
Immobilization of
Metal-organic frameworks (MOFs) represent an emerging class
of crystalline materials with diverse and uniform porosity,
which are very promising for applications in heterogeneous
sub-nanometer metal particels uniformly on hierarchically
porous MOFs is very interesting in different fields, but still
remains a major technical challenge.
1
-3
catalysis.
Hierarchically porous supports are particularly
In this work, we found that the bio-based surfactant
desired in many catalytic processes because they integrate the
advantages of pores with different sizes in diffusion and
1
9
sorbitol˗alkylamine (SAAS-C12, Scheme S1) could form stable
W/O emulsion. A method to synthesize sub-nanometer metal
particles/hierarchically mesoporous MOFs composites was
proposed using water droplets in the emulsion as template of
the hierarchical pore and solvent of precusors, and the
surfactant acted as both emulsifier and reductant in situ.
4
-7
adsorption of the species in reaction systems.
Emulsions are made of liquids, which can dissolve both polar
and non-polar substances. The dispersed droplets in emulsions
are both highly deformable and easily removable after the
accomplishment of templating. Emulsions offer advantages for
preparing a wide variety of materials with controlled particle
2
+
Au/Zn-MOF (MOF formed by Zn and methylimidazole),
-11 Ru/Zn-MOF, Pd/Zn-MOF, and Au/Cu-MOF were prepared using
this method, in which the ultrafine metal particles (e.g. 0.8
nm) were immobilized uniformly on hierarchically mesoporous
MOFs. The catalysts demonstrated outstanding catalytic
performances because they integrated the advantages of
ultrafine metal particle catalysts and the hierarchically porous
supports.
8
size, morphologies and composition at mild condition.
Utilization of emulsions as heterogeneous media is a way to
obtain porous materials with hierarchical porosity and various
structures.
Sub-nanometer metal particles have unique electronic
structures, surface geometric effects, and intrinsic chemical
1
2-14
properties.
For instance, it has been reported that Au
particles smaller than 2 nm were effectively for catalyzing
oxidation reactions and exhibited size-sensitive catalytic
Results and discussion
a.
The formation of emulsion was confirmed by fluorescence
microscopic analysis with water soluble dye (Rhodamine B),
and the size distribution of water droplets in emulsion was
determined using dynamic light scattering (DLS). The sizes of
water droplets ranged from about 5 nm to 60 nm. The results
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Colloid and
Interface and Thermodynamics, Institute of Chemistry, Chinese Academy of
Sciences, Beijing100190, P.R.China, E-mail: hanbx@iccas.ac.cn
University of Chinese Academy of Sciences, Beijing 100049,P.R.China
b.
Electronic Supplementary Information (ESI) available: [Details of the experimental
procedures and other figures and tables]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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are discussed in detail in the supporting information (Fig. S1 1E, Fig. S1), indicating the template function of water droplets.
and the corresponding discussion). Taking the synthesis of The X-ray photoelectron spectroscopy (XPS) analysis of Au (Fig.
Au/Zn-MOF as the example, the proposed method to prepare 1F) emerged two pairs of spin-orbit doublets, indicating the
0
+
metal particles/MOF composites is illustrated in Scheme 1
the details are given in the method section. In the preparation, eV. The positive shift in binding energy of Au 4f7/2 confirmed
, and existence of Au at 84.8 and 88.5 eV and Au at 86.4 and 91.3
2
Zn and Au were dissolved in water droplets, and the ligand the electronic effect of small particle size. Furthermore, a
+
3+
23
methylimidazole was in oil phase. Zn-MOF was firstly formed shift to higher binding energy of Au 4f5/2 was consistent with
2
+
at water/oil interfaces surrounding the water droplets which the negative shift of Zn spectrum with respect to the origin
3
acted as templates for the mesopores. Then Au ions were Zn-MOF (Fig. S3). Thus, the interaction between Au particles
+
2
+
24,25
reduced in situ after heat treatment by the secondary amine and Zn existed in the composites,
and hydroxy groups in the surfactant, which acted both as the immobilization of Au on the support. In this route, the
which also indicated
2
0,21
3+
Therefore, the Au ions were water droplets in emulsion acted both as solvent of the metal
emulsifier and reductant.
reduced by the surfactant in situ after heating from 25 C to 35 precursors (Zn and Au ) and template for the mesopores of
o
2+
3+
o
C, and the yielded Au particles were immobilized on the wall Zn-MOF. The surfactant behaved as emulsifier and reducing
3
of the porous MOFs. Au/Zn-MOF composites were obtained agent of Au , Zn-MOF was firstly formed from Zn and the
+
2+
3
+
after removing the solvents. It can be known that the ligand around water droplets in the emulsion, leaving Au ions
characteristics of the pores of the composites is closely related in water droplets and being isolated by the mesopores of Zn-
with the size of droplets (Fig. S1). In addtion, hierarchically MOF. Due to the wide size distribution of water droplets in the
porous MOFs without metal particels could also be prepared in emulsion, hierarchically mesoporous Zn-MOF was formed.
3
+
3+
the absence of Au (Fig. S2).
After Au ions were reduced in situ, the Au particles were
immobilized uniformly on Zn-MOF. For comparison, the
experiment was conducted by adding HAuCl solution after the
4
formation of Zn-MOF. Clearly, the agglomeration of Au
particles occurred as shown in Fig. S4, further showing the
advantage of the in situ method proposed in this work. In
addition, the size of Au particles could be tuned by the
concentration of Au precursor using the procedures, and
Au/Zn-MOF composites with average Au particle sizes of 0.8
nm, 1.0 nm, 1.5 nm, 2.0 nm were obtained (Fig. 1, Fig. S5).
Scheme 1 Schematic illustration of the method for in situ
preparation of Au/Zn-MOF in emulsion.
The transmission electron microscopy (TEM) images of
Au/Zn-MOF are shown in Fig. 1A. The HRTEM and high-angle
annular dark-field HAADF images with a high magnification
showed that sub-nanometer Au particles (0.8 nm) were
decorated uniformly on the hierarchically porous Zn-MOF (Fig.
1B and 1C). The corresponding energy dispersive X-ray
spectroscopy (STEM-EDX) elemental mapping analysis (Fig. 1C)
also revealed that Au particles were evenly immobilized on the
supports. Powder X-ray diffraction (PXRD) pattern of the
2
2
obtained Zn-MOF was the same as that reported, and
patterns of Zn-MOF and Au/Zn-MOF were nearly the same (Fig.
1D). In the XRD pattern of Au/Zn-MOF, the diffraction peaks
for Au particles were very weak due to their small size. The
porosity of Au/Zn-MOF was characterized by N2
adsorption/desorption measurement. The BET surface area,
total pore volume, and average pore diameter were provided
in Table S1. The size distribution of the mesopores of Au/Zn-
MOF was similar to that of water droplets in the emulsion (Fig.
Fig.1 Structural characterizations of Au/Zn-MOF. (A) Representative
TEM image of Au/Zn-MOF; (B) High-resolution TEM (HRTEM) image
2
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2
7,28
and down-inset is the particle size distribution of Au particles; (C) oxidation of alkenes, which is a very important reaction.
Representative HAADF-STEM image and STEM-EDX elemental However, performing the oxidation of alkenes without
mapping of Au/Zn-MOF, the selected area is framed in (a); (D) XRD addition of initiator both selectively and efficiently remains a
2
challenge. We studied the catalytic performances of the
9
patterns of the obtained Au/Zn-MOF (b) and Zn-MOF (a); (E) N
2
adsorption/desorption isotherms and the mesopore size Au/Zn-MOF composites with different Au particles sizes for
aerobic oxidation of cyclohexene to 2-cyclohexen-1-one in the
absence of initiator, and the results are given in Table 1.The
catalyst with Au size of 0.8 nm had outstanding activity and
selectivity. Au/Zn-MOF catalysts with larger Au particles
showed lower activity and selectivity. The stability of the
catalyst with Au size of 0.8 nm was studied, and the activity
and selectivity did not change after reused four times (Fig.
S8a). The TEM and XRD characterizations indicated that the
morphology and structure of the catalyst did not change
obviously after four cycles (Fig. S8b and S8c), further indicating
the excellent stability of the catalyst.
distribution (inset); (F) XPS spectra of Au 4f; Au loading was 0.8 wt%
determined by ICP-AES.
Ru/Zn-MOF and Pd/Zn-MOF were also prepared by this
method using RuCl
3 3 2
and Pd(NO ) as metal precursors,
respectively. The characterizations showed that Ru or Pd
particles of 0.8 nm could also be supported on hierarchically
porous Zn-MOF uniformly (Fig. 2). These composites were
2
characterized by TEM, XPS, XRD, N adsorption/desorption
methods, and the corresponding results were provided in Fig.
S6 and Fig. S7. The BET surface area, total pore volume, and
average pore diameters of the composites were listed in Table Table 1. Conversion and selectivity of cyclohexene oxidation over Au/Zn-
[a]
S1.
MOF catalysts with different Au particle sizes.
Selectivity (%)
Au size
Entry
C (%)
(nm)
[
b]
Au/Zn-MOF
0.8
1.0
1.5
2.0
0.8
―
82
79
64
34
77
7.4
98
―
< 2
11
21
―
19
―
―
[
c]
d]
e]
Au/Zn-MOF
95
[
[
Au/Zn-MOF
81
< 3
―
Au/Zn-MOF
Au/Cu-MOF
Zn-MOF
66
97
23
[
f]
< 1
14
[
a] Reaction conditions: 30 mg catalyst, 0.5 mmol cyclohexene, 2 ml
dioxane, 100 °C, 1 MPa O , 8 h; [b] Au loading 0.8 wt%; [c] Au
2
loading 1.1 wt%; [d] Au loading 1.3 wt%; [e] Au loading 2.0%; [f] Au
loading 0.6 wt%; Metal loadings were determined by ICP-AES; The
Fig.2 Characterizations of Ru/Zn-MOF and Pd/Zn-MOF composites. conversion and selectivity were determined by gas chromatography,
A) Representative TEM image of Ru/Zn-MOF; (B) HRTEM images and conversion was defined based on the initial cyclohexene
(
and down-inset is the particle size distribution of Ru particles; (C) present. C = Conversion.
STEM-EDX elemental mapping of Ru/Zn-MOF, Ru elements; the
selected area is framed in (A); (D) XPS spectra of Ru 3d; (E, F)
To further confirm that ultrafine Au particle was crucial for
Representative TEM image and HAADF-STEM image of Pd/Zn-MOF. the high activity and selectivity, Au particles with size of 0.8
Ru loading in Ru/ZIF-8 was 0.6 wt% and Pd loading in Pd/Zn-MOF nm on the Cu-MOF were also prepared by this route, and the
characterizations are provided in Fig. S9. The activity and
selectivity of the reaction over Au/Cu-MOF were also very high
as shown in Table 1.
was 2.3 wt% determined by ICP-AES.
The size of metal particles is a crucial factor for the catalytic
2
performance in heterogeneous catalysis. It has been shown
that Au nanoparticles of small size could selectively catalyze
6
In order to study the catalytic nature of Au particles,
reaction profiles with time over Au/Zn-MOF with Au particles
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of 0.8 nm and 1.5 nm were investigated, and the results are
given in Fig. 3. It can be observed that the conversion and
selectively of the reaction over the catalyst with smaller Au
particles (0.8 nm) were higher at all reaction time. The
[
d]
Ru size
o
[b]
[c]
TOF
Entry
T
( C)
C
Y
-1
(h )
(nm)
3
0,31
[e]
mechanism of reaction has been well studied.
In the
1
0.8
2.5
1.6
95
>99
21
98
19
207.6
2.4
reaction, cyclohexene was oxidized to form hydroperoxide,
which can be further transformed into 2-cyclohexen-1-one
immediately, or react with substrate to form cyclohexen-1-ol
and epoxide. It can be deduced from the results in Fig. 3 that
both reaction rates from cyclohexene to intermediate
hydroperoxide and further to 2-cyclohexen-1-one over the
smaller Au particles were higher, yielding higher conversion
and selectivity.
[f]
2
95
[g]
3
100
>99
>99
20.8
[
a] Reaction conditions: catalyst (40 mg), diphenyl sulfoxide (0.5
mmol), 1,4-dioxane (2 ml), 5 atm H , 1 h; [b, c] Determined by GC
2
using isopropanol as internal standard; [d] TOF denotes moles of
sulfide per mole of Ru per hour; The Ru loading was 0.6 wt% as
determined by ICP-AES; [e] Ru/Zn-MOF catalysts synthesized by the
route proposed herein; [f] Commercial Ru/C catalyst with 5 wt% Ru
loading; [g] Ref 17; C= Conversion %; Y= Yield %.
Conclusions
In conclusion, Au/Zn-MOF, Au/Cu-MOF, Ru/Zn-MOF, and
Pd/Zn-MOF with sub-nanometer metal particles were in situ
synthesized in emulsion using surfactant SAAS-C12 as emulsifier
and reductant. In this route, metal precusors of MOFs (e.g.
Fig.3 Dependence of cyclohexene conversion and 2-cyclohexene-1-
one selectivity on reaction time over Au/Zn-MOF catalysts at the
reaction conditions of Table 1. (a, c) Conversion and selectivity with
2
+
3+
Zn ) and metal particles (e.g. Au ) were dissolved in water
droplets, and the ligand existed in oil phase. MOFs were firstly
formed around water droplets to produce hierarchically
mesoporous structure. Then, the metal precursors isolated in
the mesopores were reduced in situ by the surfactant, leaving
metal particles immobilized uniformly on the hierarchical
porosity of MOFs. In addition, the size of metal particles could
be easily controlled by the content of metal precursors. The
Au/MOFs with sub-nanometer Au particles (0.8 nm) had much
higher activity and selectivty for aerobic oxidation of
cyclohexene to 2-cyclohexen-1-one than those with larger Au
particles, and the Ru/Zn-MOF with Ru particles of 0.8 nm was
much more effective than those with larger Ru particels
catalyst for hydrogenation of diphenyl sulfoxide to diphenyl
sulfide. We believe that this simple one-step method can also
be used to synthesize some other supported metal catalysts, in
which sub-nanometer metal particles are decorated uniformly
on hierarchically mesoporous MOFs.
0
.8 nm Au particle; (b, d) Conversion and selectivity with 1.5 nm Au
particle.
Oxidation and reduction of sulfur-based compounds have
3
2
been studied widely. However, designing of highly efficient
catalysts is still desirable. It was reported that heterogeneous
Ru nanoparticle catalyst could accelerate the hydrogenation of
3
3
sulfoxides to sulfides. Herein, we studied the catalytic
performance of the obtained Ru/Zn-MOF with particle size of
0.8 nm, and the results are presented in Table 2. The activity of
Ru/Zn-MOF was much higher than commercial Ru/C catalyst
with Ru size of 2.5 nm (characterization in Fig. S10) and the
3
3
reported Ru/TiO
2
catalyst with Ru particle of 1.6 nm.
Moreover, the reusability of the Ru/Zn-MOF with Ru particle
size of 0.8 nm was checked, which showed no change of the
activity after recycling 5 times (Fig. S11a). The morphology and
XRD pattern of the used catalyst were not changed (Fig. S11 b
and c), showing excellent stability of the catalyst.
Acknowledgements
The authors are grateful to the support from National Natural
Science Foundation of China (21503238), National Key
Research
and
Development
Program
of
China
Table 2. Catalytic performances of Ru/Zn-MOF for the hydrogenation of (2017YFA0403003), and Chinese Academy of Sciences(QYZDY-
[
a]
diphenyl sulfoxide.
SSW-SLH013).
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TOC Graphic
Sub-nanometer metal particles/hierarchically mesoporous metal-organic framework composites can be
synthesized in situ in bio-based surfactant emulsion.
1