In situ generation of supported palladium nanoparticles from a Pd/Sn/S chalcogel and applications in 4-nitrophenol reduction and Suzuki coupling

Article abstract of DOI:10.1039/c8ta11772a

Supported ultrafine palladium nanoparticles with uniform distribution exhibit remarkable catalytic capabilities in various applications. Obtaining size-controlled Pd nanoparticles on a support remains challenging and here we present a one-step in situ route to well-defined Pd nanoparticles through reduction of a Pd-containing chalcogel (Pd/Sn/S) with tunable size distribution. The spacings of the Pd nanoparticles on the chalcogel can be controlled by using antimony-containing chalcogels (Pd-Sb/Sn/S). The catalytic performance of Pd nanoparticles supported on the chalcogel surface was assessed in 4-nitrophenol reduction and the Suzuki-Miyaura coupling reaction, and found to exhibit good activities and robust stability. This in situ and one-step synthetic method could be further extended to synthesize a series of noble metal nanoparticles for a variety of applications.

Full text of DOI:10.1039/c8ta11772a

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ISSN 2050-7488
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Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
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In-Situ Generation of Supported Palladium Nanoparticles from a
Pd/Sn/S Chalcogel and Applications in 4-Nitrophenol Reduction
and Suzuki Coupling
Received 00th January 20xx,
Accepted 00th January 20xx
Xinyao Shan,a,b Ning Sui,a,b Wengang Liu,a Manhong Liu,a and Jian Liua,*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Abstract: Supported ultrafine palladium nanoparticles with The in-situ formation of the supported NPs is highly desirable
uniform distribution exhibit remarkable catalytic capabilities in for catalytic applications.16-19 Shumaker-Parry and co-workers
various applications. Obtaining size-controlled Pd nanoparticles on reported that the noble metal precursors incorporated in a
a support remains challenging and here we present a one-step in- polymer matrix can be reduced to anchor Au, Pt, or Pd NPs at
situ route to well-defined Pd nanoparticles through reduction of a the polymer-diamond surface.20 Zhang and co-workers
Pd-containing chalcogel (Pd/Sn/S) with tunable size distribution. reported the synthesis of ultrafine and highly dispersed Pt or Pd
The spacings of the Pd nanoparticles on the chalcogel can be NPs on covalent organic framework.21 Stair and co-workers
controlled by using with antimony containing chalcogels (Pd- reported the use of atomic layer deposition technique to
Sb/Sn/S). The catalytic performance of Pd nanoparticles supported deposit the Pt NPs onto a series of oxides for CO oxidation and
on the chalcogel surface was assessed in 4-nitrophenol reduction water-gas-shift reactions.22 Chalcogels are a new class of
and Suzuki-Miyaura coupling reaction, and found to exhibit good aerogels composed of metal chalcogenide frameworks, offering
activities and robust stability. This in-situ and one-step synthetic numerous exciting properties relevant to catalysis, adsorption,
method could be further extended to synthesize a series of noble separations, environmental remediation, etc.23-25 Similar to
metal nanoparticles for a variety of applications.
MOF,26 a series of metal ions acting as the metal centers and
thioanions such as [SnS4]4- as the linking building blocks are used
to synthesize a broad variety of chalcogels through metathesis
reactions.27 We previously reported a synthesis strategy that
can simultaneously address both the dispersion and
nanointerface by in-situ partly reducing the metal species in the
chalcogel backbone to obtain the supported Pt NPs.28 Because
Pd NPs are useful for promoting and catalyzing C-C coupling
reactions, including Heck, Suzuki and Stille couplings,29-32 it is
therefore of great significance to develop active and stable Pd
NPs catalysts.33
Herein, we report the facile synthesis of ultrafine and well-
dispersed Pd NPs supported on a chalcogel matrix, motivated
by our previous work.28 Due to the flexibility of the chalcogel
synthesis, the Pd content could be tailored by varying the
amount of antimony dopant. The particle size distribution and
loading density of the Pd NPs could be adjusted accordingly. The
dispersed Pd NPs supported in partly reduced chalcogel were
Synthesizing ultrafine noble metal nanoparticles (NPs) with
controllable size distribution is important to uncover their
superior activity and stability in various catalytic applications.1-7
Host materials are generally employed to support the
nanoparticles, inhibit aggregation, simplify separation steps
after the reaction and deliver optimized catalytic behavior and
stability. Various classical supporting materials have been
developed including porous silica, carbon, carbon nitride,
graphene, metal oxide, polymers, and non-classical metal
organic frameworks, and covalent organic frameworks etc.8-15
However, controllable regulation of NPs size and dispersion is
still an outstanding problem which often derives from weak
interactions between the supports and metal NPs. Therefore, it
is imperative to develop novel chemical routes to prepare
ultrafine NPs with high stability and narrow size distribution
simultaneously.
a. College of Materials Science and Engineering, Qingdao University of Science and Technology,
Qingdao, 266042, P.R. China, E-mail: liujian@qust.edu.cn
b. These authors contributed equally.
Electronic Supplementary Information (ESI) available: The experimental details, scheme for
synthesis, structural characterization and catalytic activity of the catalysts, Fig. S1–S17, and Tables
S1. See DOI: 10.1039/x0xx00000x
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confirmed by high-resolution transition electron microscopy
(HRTEM), X-ray photoelectron spectroscopy (XPS) and
elemental mapping. The catalytic behavior of the chalcogel-
supported Pd NPs were investigated in Suzuki-Miyaura coupling
reaction and 4-nitrophenol reduction.
View Article Online
DOI: 10.1039/C8TA11772A
Figure 2. TEM images and corresponding size distribution
profiles of PdxSb1-x-SnSreduced (x=1, 0.4, 0.2 and 0.05) chalcogel:
Scheme 1. Schematic illustration of growing Pd NPs from
chalcogels.
a-c, Pd-SnSreduced
; d-f, Pd0.4Sb0.6-SnSreduced; g-i, Pd0.2Sb0.8-
SnSreduced; j-l, Pd0.05Sb0.95-SnSreduced
.
The Pd NPs supported on reduced chalcogel were prepared by
reducing the pristine PdxSb1-x-SnS (x=1, 0.4, 0.2, and 0.05)
chalcogel with NaBH4, as illustrated in Scheme 1.28 As seen from
Figure 1a, the high-angle annular dark-field scanning
transmission electron microscopy (HAADF-STEM) analysis of the
reduced chalcogel shows uniform Z-contrast (proportional to
atomic number), indicating Pd well distributed in the chalcogel.
The energy dispersive X-ray spectroscopy (EDS) elemental
mapping further reveals that all the elements (i.e., Pd, Sb, S, and
Sn) distribute uniformly within reduced chalcogels. (See Figure
1 and Figure S2-3 of SI). Scanning electron microscopy energy-
dispersive X-ray spectroscopy (SEM-EDS) mapping images
(Figure S4-5 of SI) further confirm the homogeneous
distribution of composed elements in Pd-SnSreduced and
Pd0.05Sb0.95-SnSreduced chalcogel in large area. The inductively
coupled plasma (ICP) analysis shows that the Pd content in Pd-
Figure 1. (a) HAADF-STEM image and (b-e) STEM-EDS mapping
of composition elements in reduced chalcogel.
The Pd based chalcogel was synthesized through the metathesis
reaction between Pd(CH3COO)2 and Na4SnS4·14H2O in
formamide.28 Since K2(SbC4H2O6)2·0.5H2O could also react with
Na4SnS4·14H2O to form Sb4Sn3S12 chalcogel,34 diluting with Sb
could control the content and dispersion of Pd in the hybrid
chalcogel matrix.35, 36 The initial raw ratios of Pd versus Pd+Sb
for forming chalcogels were set at 1, 0.4, 0.2 and 0.05,
respectively. After left standing for certain time in organic
solvent, the gelated chalcogel monolith were ready for washing
and for further characterizations. Area-averaged compositions
of the pristine chalcogels from EDS analysis indicate an
empirical formula close to “PdSn1.2S3.5”, “PdSb2.9Sn0.7S5.8”,
“PdSb5.8Sn0.85S10.69” and “PdSb32.7Sn4.7S52.2”, respectively (See
Figure S1 of Supporting Information, abbreviated as SI in the
following context). The elemental compositions agree well with
the expected values. For simplicity, the pristine chalcogels are
abbreviated according to the initial ratios as PdxSb1-x-SnS (x=1,
0.4, 0.2, 0.05) in the following context.
SnSreduced
,
Pd0.4Sb0.6-SnSreduced
,
Pd0.2Sb0.8-SnSreduced
and
Pd0.05Sb0.95-SnSreduced is 28.33, 9.51, 5.15 and 0.98 wt%,
respectively. The obtained Pd ratio among four reduced
chalcogels are comparable with the raw ratio (1:0.4:0.2:0.05),
indicating the negligible leaching of Pd species during reduction
process.
By adjusting the ratio of Sb and Pd in the precursor chalcogel, a
series of Pd NPs with tunable sizes in a range of 1.8-4.5 nm were
synthesized (See the gelation process in Figure S6-7 of SI).
Transmission electron microscope (TEM) images of PdxSb1-x
-
SnSreduced (x=1, 0.4, 0.2, 0.05) confirm the presence of uniformly
distributed Pd NPs on the chalcogel surface (see Figure 2 and
Figure S8 of SI). Across the PdxSb1-x-SnSreduced (x=1, 0.4, 0.2, 0.05)
chalcogel series, the size and loading density of the as-obtained
Pd NPs decreases as a function of x. The HR-TEM images are
shown in Figure 2b, e, h and k, respectively. The lattice spacings
of nanoparticles on the four kinds of reduced chalcogels are
0.23 nm, which correspond to the (111) spacings of metallic Pd.
These TEM results confirm that the Pd2+ species in the chalcogel
network are directly reduced by the NaBH4 to NPs which are
then directly deposited on the remaining chalcogel surface.
X-ray diffraction (XRD) patterns of pristine Pd0.2Sb0.8-SnS
chalcogel and PdxSb1-x-SnSreduced (x=1, 0.4, 0.2, 0.05) chalcogels
(Figure S9 of SI) indicate the amorphous nature, consistent with
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the previous report.23 As there is no discernible NPs in the
pristine Pd0.2Sb0.8-SnS chalcogel (Figure S10 of SI), the observed
Pd NPs in chalcogel skeleton result from the in-situ reduction of
Pd2+ from the Pd-chalcogel. As seen from Figure 2c, f, i and l, the
NPs supported in PdxSb1-x-SnSreduced (x=1, 0.4, 0.2, 0.05)
chalcogel have an average size of 4.5, 4.0, 2.7 and 1.8 nm in
diameter with narrow size distributions.
View Article Online
DOI: 10.1039/C8TA11772A
Figure 4. (a) UV-vis spectra of 4-nitrophenol aqueous solution
Figure 3. (a) Pd 3d XPS spectra of pristine Pd0.2Sb0.8-SnS. (b) Pd
3d XPS spectra of Pd-SnSreduced(i), Pd0.4Sb0.6-SnSreduced(ii),
before (i) and after catalysis with (ii) Pd-SnSreduced, (iii) Pd0.4Sb0.6
-
SnSreduced, (iv) Pd0.2Sb0.8-SnSreduced, (v) Pd0.05Sb0.95-SnSreduced
,
Pd0.2Sb0.8-SnSreduced(iii),
respectively.
and
Pd0.05Sb0.95-SnSreduced(iv),
respectively; (b) typical optical images of reaction mixtures with
Pd0.2Sb0.8-SnSreduced catalyst at 0 and 10 min; (c) recyclability of
the Pd0.2Sb0.8-SnSreduced catalyst; (d) TEM image of recycled
Pd0.2Sb0.8-SnSreduced chalcogel after reduction reaction of 4-
nitrophenol.
X-ray photoelectron spectroscopy (XPS) is used to investigate
the oxidation states of the elements in both the pristine
chalcogels and the reduced counterparts (Figure 3). As shown
in Figure 3a, Pd 3d spectra of pristine Pd0.2Sb0.8-SnS chalcogel
present the doublet peaks corresponding to Pd 3d5/2 and Pd
3d3/2, respectively.37, 38 No metallic Pd 3d5/2 peak at around 335
eV is observed, suggesting the absence of Pd NPs in the pristine
chalcogel. The spectrum of Pd 3d region for the pristine
Pd0.2Sb0.8-SnS chalcogel (Figure 3a) shows a doublet containing
3d5/2 peak and 3d3/2 at 336.8 and 342.11 eV, respectively.
The PdxSb1-x-SnSreduced is readily dispersed in water and other
organic solvents for catalytic applications. The reduction of 4-
nitrophenol to 4-aminophenol with NaBH4 is used to evaluate
the catalytic activity of PdxSb1-x-SnSreduced (x=1, 0.4, 0.2, 0.05),
which serves an important role in industry.39 This reaction is
easily monitored by UV-vis spectroscopy. The blank experiment
without chalcogel catalyst does not show any activity for 4-
nitrophenol reduction (Figure S13 of SI). With 15 mg of PdxSb1-
x-SnSreduced (x=1, 0.4, 0.2, 0.05) loaded into reaction system, the
absorption peak at 400 nm diminishes after 10 min (as shown in
Figure 4a). The complete discoloration of the solution from
bright yellow to colorless is observed (as seen in Figure 4b).
Sb4Sn3S12 chalcogels (Pd-free), whose compositions are close to
SbSn0.32S1.7, show negligible catalytic activity for such reaction,
as illustrated in Figure S14-16 of SI. This indicates that the Pd
NPs supported in PdxSb1-x-SnSreduced is capable of catalyzing 4-
nitrophenol to 4-aminophenol in the presence of NaBH4.
Consecutive experiments are performed to study the stability
and reusability of PdxSb1-x-SnSreduced, which are important
parameters to evaluate a heterogeneous catalyst for practical
applications.40 The Pd0.2Sb0.8-SnSreduced catalyst toward 4-
nitrophenol reduction was investigated in consecutive 20
cycles, with no obvious variation in the conversion ratio. To
show the advantage of Pd0.2Sb0.8-SnSreduced over some other
catalysts, the catalytic role of the Pd0.2Sb0.8-SnSreduced in
reduction reaction of 4-nitrophenol to 4-aminophenol with
NaBH4 was compared with reported catalyst in the literature
(Table S2 of SI). With an overall look at Table S2, we can see that
Pd0.2Sb0.8-SnSreduced is comparable with other reported catalyst
in term of recycled stability. From the HR-TEM image of recycled
Pd0.2Sb0.8-SnSreduced chalcogel in Figure 4d, no apparent
agglomeration of Pd-based NPs could be observed. The above
From Plot (i) in Figure 3b, the Pd 3d5/2 levels of Pd0.2Sb0.8
-
SnSreduced exhibit binding energies of 335.69 eV and 336.38eV,
respectively, indicating that part of Pd2+ was reduced into Pd0.
Apart from the existence of Pd0 species supported on the
surface, a good fraction of Pd2+ ions remain as linking metal ions
with chalcogenide-based clusters ([SnS4]4-) for keeping
chalcogel skeleton intact. In addition, the fitting analysis of Sn
3d spectra shows the coexistence of Sn0, Sn2+ and Sn4+ (Figure
S11 of SI). The peaks at 485.6 eV, 486.2 eV and 486.8 eV are
assigned to Sn0, Sn2+ and Sn4+, respectively. The result suggests
that the Sn4+ in pristine chalcogel was partially reduced to Sn2+
and Sn0. The oxidation state of Sb in the reduced chalcogel
remains unchanged (Figure S12 of SI). The results of Pd and Sn
binding energies of PdxSb1-x-SnSreduced (x=1, 0.4, 0.2, 0.05) and
pristine Pd0.2Sb0.8-SnSreduced are shown in Table S1 of SI,
suggesting that the Pd NPs are successfully prepared.
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results indicate that the Pd NPs supported on PdxSb1-x-SnSreduced leaching of Pd during catalysis reaction. The Pd NPs still
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DOI: 10.1039/C8TA11772A
have a good stability and catalytic activity.
maintained the pristine particle size and well-dispersed on
chalcogel, as evidenced by the TEM image of the recollected Pd-
SnSreduced (see Figure S17 of SI).
Table 1. Catalytic performance of Pd-SnSreduced and Pd0.2Sb0.8
-
SnSreduced in the Suzuki-Miyaura couplings reaction.
R2
I
B(OH)2
Pd-SnSreduced
70oC, ethanol
Conclusions
+
In conclusion, we developed a one-step and in-situ strategy of
size tunable Pd NPs by direct reduction of Pd-based chalcogel.
The obtained PdxSb1-x-SnSreduced (x=1, 0.4, 0.2, 0.05) chalcogels
have variable noble metal loading by adjusting the ratio of Pd
and Sb. The catalysts show high catalytic activity, good stability
and easy recyclability for the reduction of 4-nitrophenol to 4-
aminophenol with NaBH4. Pd-SnSreduced is further used to
catalyze Suzuki-Miyaura coupling and shows high catalytic
activity and stability. Further diversifying the size of the Pd NPs
would provide more versatility to synthesize composite
nanomaterials supported on reduced chalcogels for different
catalytic applications. The present work shows the superiority
of chalcogel as a starting platform for in-situ formation of
R2
R1
R1
Entrya
Aryl halide
Arylboronic acid Yield (%)b
1
2
3
4
4-Me–C6H4–I
3-Me–C6H4–I
4-OH–C6H4–I
C6H5–I
C6H5–B(OH)2
C6H5–B(OH)2
C6H5–B(OH)2
C6H5–B(OH)2
4-Me-C6H5–
B(OH)2
93.6
99.6
93.0
97.4
5
C6H5–I
99.1
0
6c
4-Me–C6H4–I
C6H5–B(OH)2
aReaction condition: aryl haide (1 mmol), arylboronic acid (1.1
mmol), NaOH (1.5 mmol), Pd-SnSreduced (28.33 wt% Pd loading,
10 mg), ethanol (12 mL), 70 °C, 24 h. bDetermined by GC analysis
using an internal standard method. The yield was averaged over
five independent runs. cThe catalysis is Pd0.2Sb0.8-SnSreduced (5.15
wt% Pd loading, 15mg).
transition-metal NPs. Nevertheless, for
a
profound
understanding of the structure-activity relationship of reduced
chalcogel, further work is needed. We believe that chalcogels
offer new opportunities for designing highly active catalysts
with hierarchic architectures and tailored compositions.
The Suzuki-Miyaura reaction is a widely investigated synthetic
tool in fundamental research and industrial applications.41, 42
The catalytic activity of Pd NPs catalysts was further studied in
the Suzuki-Miyaura coupling reaction between aryl halide and
arylboronic acid. A mixture of aryl halide, arylboronic acid,
NaOH, and Pd-based catalysts in ethanol was stirred with
heating, and the product was analyzed by gas chromatograph
(GC). The 4-phenyltoluene yield was 93.6% after 24 h reaction
(Table1, Entry 1). The yield of 3-phenyltoluene was 99.6% (Entry
2) and the yield of 4-phenylphenol was 93.0% (Entry 3),
respectively. Iodobenzene was used for further tests; 97.4%
yield for diphenyl and 99.1% yield for 4-phenyltoluene were
obtained, respectively (Entry 4, 5). The Pd0.2Sb0.8-SnSreduced
catalyst was tested for comparison (Entry 6). Unfortunately, the
Sb doping completely inhibited the activity towards Suzuki-
Miyaura coupling reaction. As mentioned above, Pd0 species as
catalytic active sites for Suzuki-Miyaura reaction will become
inactive due to stronger coordination with the chalcogel
skeleton via electron transfer from Pd0 species to Sb. From XPS
spectra shown in Figure 3b, the 3d5/2 peak position of Pd0
species for Pd-SnSreduced chalcogel which is before catalytic
reaction distinctly shifted to higher binding energy with the
doping content of Sb species, which implied the electron
transfer from Pd0 species to Sb via chalcogenide-based cluster
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was financially supported by the National Science
Foundation of China (No. 21802080), Natural Science
Foundation of Shandong Province (No. ZR2018MB018),
Doctoral Fund of QUST and Thousand Young Talent Program.
J.L. acknowledged Prof. Mercouri G. Kanatzidis of Northwestern
University for mentoring and Dr. Zupeng Chen of ETH for helpful
discussion.
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Journal of Materials Chemistry A
Page 6 of 6
View Article Online
DOI: 10.1039/C8TA11772A
In-Situ Generation of Supported Palladium Nanoparticles from a Pd/Sn/S
Chalcogel and Applications in 4-Nitrophenol Reduction and Suzuki Coupling
ToC figure
A one-step in-situ route to obtain well-defined and controllable Pd nanoparticles was reported and
employed for catalytic applications.