Direct Synthesis of Ultrasmall Ruthenium Nanoparticles on Porous Supports Using Natural Sources for Highly Efficient and Selective Furfural Hydrogenation

Article abstract of DOI:10.1002/cctc.201700262

The synthesis of noble-metal nanoparticles (NPs) with ultrasmall particle sizes (<2 nm) is crucially important but challenging. Making use of the unique structure of natural sources for the preparation of functional materials is an attractive topic. By taking advantage of the coordination effect between polyphenols and metal ions, we report a straightforward strategy for the synthesis of porous heterogeneous catalysts containing ultrasmall Ru NPs. These catalysts exhibit excellent catalytic activity for the selective hydrogenation of furfural. We envisage that this strategy will find a broad range of applications in the near future.

Full text of DOI:10.1002/cctc.201700262

Accepted Article
Title: Direct Synthesis of Ultra-small Ruthenium Nanoparticles on
Porous Supports Using Natural Sources for Highly Efficient and
Selective Furfural Hydrogenation
Authors: Zhanrong Zhang, Jinliang Song, Zhiwei Jiang, Qinglei Meng,
Pei Zhang, and Buxing Han
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
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To be cited as: ChemCatChem 10.1002/cctc.201700262
Link to VoR: http://dx.doi.org/10.1002/cctc.201700262
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ChemCatChem
10.1002/cctc.201700262
COMMUNICATION
Direct Synthesis of Ultra-small Ruthenium Nanoparticles on
Porous Supports Using Natural Sources for Highly Efficient and
Selective Furfural Hydrogenation
[
a]
[a]
[a]
[a]
[a]
[a, b]
Zhanrong Zhang , Jinliang Song* , Zhiwei Jiang , Qinglei Meng , Pei Zhang and Buxing Han*
Abstract: Synthesis of noble metal nanoparticles (NPs) with ultra-
small particle sizes (< 2nm) is crucially important, but challenging.
Making use of the unique structure of natural sources for the
preparation of functional materials is an attractive topic. Taking
advantage of the coordination effect between polyphenols and metal
ions, we report a straightforward strategy for the synthesis of porous
heterogeneous catalysts containing ultra-small Ru NPs. These
catalysts exhibited excellent catalytic activity for selective
hydrogenation of furfural. We envisage this strategy would find a
broad range of applications in the near future.
the fabrication of ultra-small noble metal NPs supported on
porous supports is highly desirable, but represents a grand
challenge, from both fundamental and practical point of view.
In recent years, innovative design and synthesis of
functional materials using natural resources derived compounds
is gaining significant attention.8 Owning to the diverse and
unique structures and properties of some naturally occurring
components, a wide array of functional materials could be
produced with many different applications. For example,
polyphenols are a group of compounds which are widely
distributed in plant tissues and display a diverse spectrum of
chemical and physical properties.9,10 Due to their high
dihydroxyphenyl (catechol) and trihydroxyphenyl (gallic acid)
content, some polyphenols could chelate with metal ions to
generate many functional materials. These materials have found
Heterogeneous catalysis plays a key role for the enhancement
of the efficiency of many chemical reactions. It represents one of
the most important and widely applied chemical processes of
various industries. Many heterogeneous catalysts involve noble
metal nanoparticles (NPs) which provide the active sites and a
support on which the NPs are dispersed. Numerous studies
have verified that the sizes and structures of metal NPs
significantly affect their catalytic performances.1 Reductions in
the sizes of noble metal NPs afford higher surface to volume
ratio and larger proportion of surface atoms, resulting in
11
a diverse range of applications such as cell encapsulation,
12,13
14
15
catalysis,
multifunctional coatings, and capsules.
Inspired by the coordination effect between polyphenol
molecules and metal ions as well as the abovementioned
applications, we anticipate that the polyphenol-metal complexes
could also be used as ideal precursors for the synthesis of ultra-
small metal NPs. Herein, we report a novel and straightforward
strategy for synthesis of ultra-small Ru NPs that are uniformly
dispersed on supports with mesoporosity, taking advantage of
2
predominantly edge and corner atoms. To this end, the design
and synthesis of supported ultra-small noble metal NPs (particle
diameter < 2 nm) is gaining increasingly substantial attention.3,4
However, at nano size regime, metal NPs are unstable and
tend to aggregate, owing to their high surface energy and
surface to volume ratio.5 Also, the low affinity between metal
precursors or nano catalysts and their supports generally leads
to NPs with large particle sizes ranging from several nanometers
to micrometers. This renders the conventional fabrication
protocols (e.g., coprecipitation, impregnation) impractical and
ineffective for rational control of particle sizes and dispersion.3
Noble metal NPs with controlled particle sizes and
nanostructures could be produced with the aid of capping agents.
However, in this case, the presence of capping agents might
render the catalysts less effective and/or selective by blocking
the active cites.3 Despite these capping agents could be
removed by thermal decomposition, the small metal NPs tend to
sinter and/or aggregate to form larger particles.6 In another
aspect, introduction of porosity to heterogeneous catalysts
affects the diffusion of reactants and product distribution, and
could generally enhance the catalytic efficiency.5,7 Hence, the
development of general and readily applicable methodologies for
the coordination effect between natural resource derived tannic
acid (TA), Ru3+ and Ti4+.
2
Figure 1. Illustration for the synthesis of Ru@C/TiO catalysts.
Figure 1 highlights our procedure for the preparation of
mesoporous catalysts containing ultra-small Ru NPs using TA,
tetrabutyl titanate and RuCl
3 2
3H O as precursors. TA is a low-
cost, abundant and naturally occurring polyphenol and has a
high dihydroxyphenyl content (Figure S1 and S2). The abundant
dihydroxyphenyl groups in TA could chelate with metal ions.
Hence, the Ru ions could be captured or “grasped” by the OH
groups while stirring in ethanol solution at room temperature.
Subsequently, tetrabutyl titanate was added dropwise into the
mixture and the Ti ions coordinate with the abundant
dihydroxyphenyl groups. The insert in Figure 1 highlights a
proposed possible schematic structure illustrating the
[
a]
Dr. Z. Zhang, Dr. J. Song, Dr. Z. Jiang, Dr. Q. Meng, Dr. P. Zhang,
Prof. B. Han
Beijing National Laboratory for Molecular Sciences, Key Laboratory
of Colloid and Interface and Thermodynamics.
Institute of Chemistry, Chinese Academy of Sciences,
Beijing 100190, P. R. China
University of Chinese Academy of Sciences,
Beijing 100049, P. R. China
E-mail: songjl@iccas.ac.cn, hanbx@iccas.ac.cn
[
b]
Supporting information for this article is given via a link at the end of
the document.
3+
4+
coordination effect between TA, Ru and Ti . This structure
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ChemCatChem
10.1002/cctc.201700262
COMMUNICATION
was speculated according to Wei et al. In their recent work, they
have proposed similar structures demonstrating the self-
assembled Fe-TA12a and Co-TA12b framework. Due to this
be clearly observed and highlighted by the red circles. The
interplanar distance of the Ru NPs for the lattice fringe was
around 0.23 nm, which is the distinct lattice fringe of Ru crystal.
coordination effect, brown precipitates were formed while stirring. The small particle size and narrow size distribution was resulted
Followed by deprotonation with triethylamine, these precipitates
were washed with ethanol, vacuum dried, grinded before heating
from the coordination effect between Ru ions and
dihydroxyphenyl groups of TA. The N adsorption-desorption
method indicates that the Ru@C/TiO -500 was also porous with
2
o
o
o
o
at elevated temperatures (400 C, 500 C, 600 C and 700 C)
under argon atmosphere to afford Ru@C/TiO catalysts.
2
2
mesopores centered at around 8.8 nm. The surface area and
pore volume was around 293 m2 g-1 and 0.39 cm3 g ,
respectively (Figure 2E). The loading amount of Ru NPs in
-1
Ru@C/TiO
AES analysis (Table S1). The XRD pattern of Ru@C/TiO
Figure 2F) suggests that this material has low crystallinity or is
2
-500 was around 1.16%, as determined by the ICP-
2
-500
(
poorly ordered, indicating that the structure of this material is
nearly amorphous. Meanwhile, no obvious Ru bands exist in the
XRD pattern of Ru@C/TiO -500, resulting from the well
2
dispersion of Ru with ultrafine particles.16 The X-ray
photoelectron spectrum (XPS) showed peaks of Ru 3p3/2 and
3d5/2 at the binding energies of 464.3 eV and 280.6 eV,
respectively, corresponding to Ru 3p3/2 and Ru 3d5/2 of Ru(0),
which further confirmed the generation of Ru NPs. Additionally,
control experiments indicated that the materials prepared
without using TA or tetrabutyl titanate was non-porous with very
low surface area and the Ru NPs in these two materials were
aggregated seriously. These results confirmed the significant
effect of TA and tetrabutyl titanate as discussed above in the
preparation of this supported ultra-small Ru NPs on porous
2
C/TiO .
Figure 2. Characterization of the Ru@C/TiO
TEM image, the insert is particle size distribution histogram of the Ru NPs
Data was obtained from about 200 Ru particles). (D) HRTEM image, the Ru
NPs are highlighted by the red circles, (E) N adsorption-desorption isotherm,
2
-500. (A, B) SEM images, (C)
(
2
the insert is pore size distribution, (F) powder XRD pattern, and (G, H) XPS
spectra.
2
Figure 3. Powder XRD pattern of Ru@C/TiO catalysts.
2
We also synthesized Ru@C/TiO by heating at various
The synthesized Ru@C/TiO
2
catalysts were characterized
o
o
o
temperatures (400 C, 600 C and 700 C) and the samples are
denoted as Ru@C/TiO -400, Ru@C/TiO -600 and Ru@C/TiO
00 accordingly. The Ru@C/TiO -400 has very similar textural
and structural properties to Ru@C/TiO -500 (Table S2, Figure
by a variety of analytical techniques including scanning electron
microscopy (SEM), transmission electron microscopy (TEM),
high-resolution TEM (HRTEM), X-ray diffraction (XRD), X-ray
photoelectron spectroscopy (XPS) and N
method. SEM examinations (Figure 2A and 2B) revealed that
the sample heated at 500 oC (denoted as Ru@C/TiO
-500)
possesses an ununiform shape. The Ru NPs are uniformly
dispersed and the average diameter of these NPs is around 1.6
0.12 nm with a narrow size distribution, as shown in the TEM
2
2
2
-
7
2
2
2
adsorption-desorption
S3 and S6). From Table S2, the pore diameter of the prepared
catalysts at different calcination temperature changed from 7.4
nm to 15.3 nm, while the surface area showed no such obvious
difference. It is known that at higher calcination temperature,
more organic components were decomposed and more gases
2
±
were released, resulting in more micropores. Hence, the surface
image of this sample (Figure 2C and the insert illustrating the
histogram of Ru particle size distribution). From the high-
resolution TEM (HRTEM) image (Figure 2D), the Ru NPs could
17a
area could be potentially increased.
However, higher
calcination temperature could result in the impenetration of
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ChemCatChem
10.1002/cctc.201700262
COMMUNICATION
mesopores in the meantime, which caused the decrease of the
crystallinity (i.e., poorly ordered structure) and mesoporous
structures. In recent years, upgrading of the biomass derived
compounds to value added chemicals and/or fuel products in an
effective and selective manner is important to fully exploit the
chemical potential of these valuable resources.19-21 However,
due to the presence of diverse functionalities in many platform
molecules derived from biomass (e.g., furfural, 5-
hydroxymethylfurfural), hydrotreatment of these substrates
generally results in a mixture of products and the reaction
17b
surface area. Hence, it is possible that the difference between
the surface areas of the prepared catalysts is not very significant
due to the abovementioned two opposite effects. Moreover, the
Ru NPs contained in Ru@C/TiO -600 and Ru@C/TiO -700
2 2
featured large particle sizes with slightly wider size distribution,
as Ru NPs inevitably agglomerated at elevated temperatures
(
Figure S4 and S5). This is also reflected in the XRD patterns of
Ru@C/TiO -600 and Ru@C/TiO -700 (Figure 3). Characteristic
band of Ru(0) at about 2θ=54o ascribing to Ru(102) could be
observed in the XRD patterns of Ru@C/TiO -600 and
-400 and
-500.18 This effect is primarily due to the larger
2
2
22-24
pathways are complicated.
2
Selective hydrotreatment of furfural to value-added products
over various metal NPs such as Ni,25 Ru, Cu27 and bimetallic
catalysts28 have been extensively studied. Herein, the catalytic
26
Ru@C/TiO
Ru@C/TiO
-700, but not in those of Ru@C/TiO
2 2
2
particle sizes of Ru NPs contained in the former two samples.
XPS analysis confirms the presence of Ru(0) NPs in
properties of the synthesized Ru@C/TiO
hydrogenation of furfural were studied. For the Ru@C/TiO
catalyst, the conversion of furfural gradually increases with
reaction time and reaches around 100% after 4 h at 80 o
2
catalysts for selective
2
-500
Ru@C/TiO
S7 and S8). It is also noteworthy that the Ru@C/TiO
Ru@C/TiO -700 are also mesoporous while the pore sizes are
larger than those of Ru@C/TiO -400 and Ru@C/TiO -500, as
2
-400, Ru@C/TiO
2
-600 and Ru@C/TiO
2
-700 (Figure
2
-600 and
C
2
(Figure 4A). The yield of tetrahydrofurfuryl alcohol (THFA)
reaches around 100% after 5 h reaction at 80 oC and furfural
alcohol (FA) was detected as the intermediate product. For
2
2
more organic matter was decomposed when treated at higher
temperatures (Figure S6, Table S2). This effect also leads to the
2
comparison, the reaction could not proceed without Ru@C/TiO .
decreased amount of the obtained support (C/TiO
2
). Therefore,
By adjusting the reaction conditions, the yield of THFA (ca. 98%)
the loading amount of Ru NPs increased with the increasing
calcination temperature (Table S1) due to the increased weight
could be achieved with nearly 100% furfural conversion at 120
o
C
for
1
h
(Figure 4B). Further increasing the reaction
o
ratio between Ru and C/TiO
temperatures.
2
for the samples prepared at higher
temperature to 140 C leads to ring opening reactions of THFA
and trace amounts of 1, 2-pentanediol was generated as a side
product (Figure 4B).
We anticipate that the synthesized materials could serve as
excellent catalysts for selective hydrogenation reactions, owning
to their ultra-small and uniform particle sizes of Ru NPs, low
Table 1. Hydrogenation of furfural over Ru@C/TiO
2
.[a]
o
Y (S) of FA[b]/%
15 (94)
51 (96)
96 (96)
0
Y (S) of THFA[c]/%
TOF[d]
44
37
40
72
51
50
31
49
28
31
---
CB[e]/%
94
Entry
Catalyst
Temperature/ C
Time/h
Conversion/%
1
2
3
4
5
6
7
8
9
Ru@C/TiO
Ru@C/TiO
Ru@C/TiO
Ru@C/TiO
Ru@C/TiO
Ru@C/TiO
Ru@C/TiO
Ru@C/TiO
Ru@C/TiO
2
-500
2
-500
2
-500
2
-400
2
-400
2
-600
2
-600
2
-700
2
-700
40
40
40
80
40
80
40
80
40
40
1
4
7
5
7
5
7
5
7
7
16
0
53
0
96
>99
>99
>99
>99
>99
>99
>99
92
3 (3)
98 (98)
4 (4)
99 (99)
12 (12)
98 (98)
16 (16)
4 (4)
0
99
98
97 (97)
0
101
99
85 (85)
0
97
98
80 (80)
87 (94)
8.2 (100)
0
96
1
0[f]
Ru/C (5%)
98
1
1[g]
Ru/TiO
2
, RT, H
2
(0.3 MPa), solvent: octane
8.2
---
2[h]
Ru/C, 165 C, H
o
(2.5 MPa), solvent: water
---
1
2
100
7 (7)
---
3[h]
4[h]
o
1
Ru/C, 165 C, H
2
(2.5 MPa), solvent: 1-butanol
(2.5 MPa), solvent: MTHF[i]
89
91
20 (23)
38 (42)
6 (7)
---
---
---
---
o
1
Ru/C, 165 C, H
2
10 (11)
[
2
a] Reaction conditions: furfural: 1 mmol; catalyst: 30 mg; 1-butanol: 3 mL; H pressure: 4 MPa. [b] FA: furfural alcohol; Y: Yield; S: selectivity; [c] THFA:
-
1
tetrahydrofurfuryl alcohol; Y: Yield; S: selectivity; [d] Turnover number (TON)=mol of product per mole of Ru; TOF=TON h . The TOF was obtained based on the
sole product; [e] CB: carbon balance; [f] The amount of Ru/C (5%) was 8 mg; [g] The data was obtained from Ref. 29; [h] The data was obtained from Ref. 30; [i]
MTHF: 2-Methyltetrahydrofuran
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ChemCatChem
10.1002/cctc.201700262
COMMUNICATION
methodology for the preparation of ultra-small noble metal NPs
will find a diverse range of applications.
2
Figure 4. Hydrogenation of furfural over Ru@C/TiO -500 under different
conditions (furfural: 1 mmol; catalyst: 30 mg; 1-butanol: 3 mL; H
MPa).
2
pressure: 4
2
Figure 5. Reusability of Ru@C/TiO -500 for catalytic conversion of furfural,
o
o
(
A) at 80 C for 5 h, yield and selectivity: THFA; (B) at 120 C for 1 h, yield and
o
selectivity: THFA; (C) at 40 C for 7 h, yield and selectivity: FA. Other reaction
conditions: furfural 1 mmol; catalyst: 30 mg; 1-butanol: 3 mL; H
2
pressure: 4
MPa.
Furfural alcohol (FA) is one of the most attractive molecules
that could be derived from hydrogenation of furfural. Hence, it is
important to achieve selective hydrogenation of the aldehyde
group of furfural while leaving the furan ring intact. We noticed Acknowledgements
that when the reaction was conducted at 40 oC for 1 h with
Ru@C/TiO
2
-500, the selectivity of FA could reach ca. 94% at
The authors acknowledge the National Natural Science
Foundation of China (21603236, 21673249 and 21503238) and
the Youth Innovation Promotion Association of CAS (2017043).
16% conversion (Table 1, entry 1). Further increasing the
reaction time to 7 h, the yield and selectivity of FA could be
increased to around 96% (Table1, entry 2 and 3).
Due to the similar chemical and structural properties of
Ru@C/TiO -400 to Ru@C/TiO -500, their catalytic activities are
2 2
Keywords: Natural resources • polyphenols • heterogeneous
catalysis
•
ultra-small metal nanoparticles
•
furfural
similar. The yield of THFA was ca. 98% with nearly 100%
o
hydrogenation
conversion of furfural at 80 C for 5 h (Table 1, Entry 4) while the
o
yield of FA was ca. 97% at 40 C for 7 h (Table 1, Entry 5) over
[
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1]
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2
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2
-
4747-4765; b) T. Chen and V. O. Rodionov, ACS Catal. 2016, 6, 4025-
6
00 and Ru@C/TiO
selectivity of THFA (> 98%) were achieved at 80 C for 5 h.
2
-700, high conversion furfural (> 99%) and
4033; c) S. Zhang, L. Nguyen, Y. Zhu, S. Zhan, C.-K. Tsung and F. Tao,
o
Acc. Chem. Res. 2013, 46, 1731-1739.
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o
Ru@C/TiO
2
-400 and Ru@C/TiO
2
-500 at 40 C for 7 h (Table 1,
entry 6-9) From our experimental results, there were no other
solid or gaseous products generated from the reaction and the
carbon balance of the reaction system was around 100%.
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Ru@C/TiO
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1
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ChemCatChem
10.1002/cctc.201700262
COMMUNICATION
Entry for the Table of Contents
Mesoporous heterogeneous
catalysts containing ultra-small
Ru NPs were synthesized
using natural precursor and are
highly efficient for selective
furfural hydrogenation.
Zhanrong Zhang, Jinliang Song*,
Zhiwei Jiang, Qinglei Meng, Pei
Zhang and Buxing Han*
Page No. – Page No.
Direct Synthesis of Ultra-small
Ruthenium Nanoparticles on
Porous Supports Using Natural
Sources for Highly Efficient and
Selective Furfural
Hydrogenation
This article is protected by copyright. All rights reserved.