Copper nanoparticles socketed in situ into copper phyllosilicate nanotubes with enhanced performance for chemoselective hydrogenation of esters

Article abstract of DOI:10.1039/c7cc02093g

Copper nanoparticles exsoluted in situ under a reducing atmosphere at elevated temperatures are socketed into the parent copper phyllosilicate nanotubes and exhibit excellent catalytic performance and superior stability for the selective hydrogenation of various esters to alcohols.

Full text of DOI:10.1039/c7cc02093g

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Copper nanoparticles socketed in situ into copper phyllosilicate
nanotubes with enhanced performance for chemoselective
hydrogenation of esters†
Received 00th January 20xx,
Accepted 00th January 20xx
Xiaoxiao Gong, Meiling Wang, Huihuang Fang, Xiaoqi Qian, Linmin Ye*, Xinping Duan,
Youzhu Yuan*
DOI: 10.1039/x0xx00000x
www.rsc.org/
interfaces compared with conventional deposition method and
thus can be applied to prepare stable and active supported
catalysts.19 Additional examples of the metallic nanoparticles
in situ exsoluted from perovskite parents inhibited
nanoparticles agglomeration and exhibited excellent activity
Copper nanoparticles exsoluted in situ under reducing atmosphere
at elevate temperature are socketed into the parent copper
phyllosilicate nanotubes (CSNTs) and exhibit excellent catalytic
performance and superior stability for the selective hydrogenation
of various esters to alcohols.
23
−
and stability in electrochemical reaction.20
Berg et al.24
revealed the in situ formation of copper nanoparticles on a
silica support under the H2 atmosphere from homogeneous
copper phyllosilicate platelets precursor using transmission
electron microscopy (TEM). Nevertheless, the structure and
performance of the copper nanoparticles exsoluted and
socketed in situ into the parent CSNTs under reducing
atmosphere at elevate temperatures have not been reported
so far.
In this work, we employ the as-prepared CSNTs as precursor
to prepare a new type of Cu-based catalyst CSNTs-T, (T
represents the reduction temperature) through the in situ
exsolution strategy under reducing atmosphere. Almost
quantitative conversion and high selectivity to corresponding
alcohols are obtained over the optimized catalyst CSNTs-623
for the selective hydrogenation of various esters. In addition,
the catalytic performance of CSNTs-623 has no obvious
deterioration after the reaction on stream for as long as 1000
h. Characteristic studies using several spectroscopic
techniques reveal that the catalyst CSNTs-623 possesses high
Cu dispersion, strong metal-support interactions, and
favourable ratio of active Cu species, thereby exhibiting
excellent performance for the chemoselective hydrogenation
of various esters into corresponding alcohols.
The chemoselective hydrogenation of esters into
corresponding alcohols is a basic reaction in chemical
production, which is widely used in producing various
industrial products, including high-quality polyesters,
chemicals, and fuels.1 For example, recent progress shows
3
−
that the chemoselective hydrogenation of dimethyl oxalate
(DMO) derived via a syngas route may lead to a new non-
petroleum based synthesis procedure for the production of
ethylene glycol (EG), methyl glycolate (MG) and ethanol.4,5 The
inexpensive Cu-based catalyst is proven to be highly active for
the chemoselective hydrogenation of esters to alcohols.6
8
−
However, the conventional Cu-based catalyst presents a
decreasing tendency during hydrogenation reactions, because
of the loss of active Cu surface sites through migration and
aggregation of Cu nanoparticles and the changes in valence
state of surface Cu species under reaction conditions.9,10
Several methods have been introduced to stabilize the Cu
species, such as the introduction of additives and formation of
16
alloys.11
Moreover, Yue et al.17 reported
a copper-
−
impregnated CSNTs for the hydrogenation of DMO to ethanol
with high efficiency and steady performance, given that the
confinement effect of nano-sized channels on Cu particles
could provide the largest amount of surface Cu0 and Cu+.
Correlatively, Zhang et al.18 designed an anti-sintering nickel
phyllosilicate nanotubes and used for reforming reactions. The
phyllosilicate nanotubes could effectively maintain the Ni
particle size during reaction. It has been reported that in situ
The CSNTs were prepared by a modified hydrothermal
method based on literature25 (See ESI† for details of synthesis
of all materials, catalytic activity testing, and characterization
techniques). As shown in Fig. 1A, CSNTs have uniform thin
nanotube morphologies, and the diameter of the nanotubes is
exsolution strategy can generate stronger metal-oxide
approximately 10 nm with a wall thickness of 1−2 nm. XRD
results confirm the formation of a copper phyllosilicate phase.
The characteristic diffractions of CSNTs (Fig. 1B), centred at
2θ=11.19°, 19.94°, 21.82°, 30.81°, 35.02°, 57.48°, and 62.44°,
are attributed to the chrysocolla phases (JCPDS No. 027-0188).
After the reduction, the Cu2+/Cu+ in CSNT crystal lattice was
reduced to Cu0 while SiO2 appeared in the surrounding. The
XRD peaks of chrysocolla phase were partly substituted by a
couple of new peaks corresponding to metallic Cu. The
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average diameter of Cu nanoparticles is approximately 4.6 nm the Cu+ and Cu0 species according to literature,12 respectively.
(Fig. 1C). Strong metal-support interactions restricted the It has been reported that copper phyllosilicate could produce
accumulation of copper nanoparticles in the reduction, which stable Cu+ species on its surface in the hydrogenation reaction
is attributed to the intrinsic lattice structure. The schematic and enhance the dispersion and metal-support interactions
illustration of the formation of CSNTs (Fig. 1D) implies that Cu significantly.26 In present work, the ratio of Cu+ species in
nanoparticles are strongly anchored by the layered structure CSNTs-T maintained up to 60% when the reduction
at a suitable reduction temperature.
temperature was below 723 K; and rapidly decreased to 43.6%
while increasing the reduction temperature to 823 K. The
characterization results reveal that the CSNTs-T catalyst
reduced at a range of 523 K to 723 K may possess an excellent
thermal stability.
Chrysocolla: 27-0188
Copper: 04-0836
(A)
(B)
The selective hydrogenation of dimethyl 1,4-cyclohexane
dicarboxylate (DMCD) is selected as the first probe reaction to
investigate the Cu-based catalysts. As shown in Scheme 1,
DMCD hydrogenation is a multi-steps reaction. One ester
group of DMCD is hydrogenated to form methyl 4-
CSNTs
CSNTs-623
10 20 30 40 50 60 70 80 90
θ / °
hydroxymethylcyclohexane
carboxylate
(MHMCC)
as
2
intermediate, then the MHMCC is hydrogenated continuously
to produce CHDM as the target product. The over-
hydrogenolysis of CHDM may generate 4-methyl-
cyclohexanemethanol (MCHM) as a by-product. As the target
product of DMCD hydrogenation, 1,4-cyclohexane dimethanol
(CHDM) can be used to produce high-quality and nontoxic
(C)
(D)
30
20
10
0
4.6 nm
polyester fibres with higher corrosion resistance and melting
point than ethylene glycol.27 A series of Cr-free Cu-based
29
−
2 3 4 5 6 7 8
Particle size / nm
layered double hydroxides (LDH) catalysts investigated by Li
et al.30 displayed excellent catalytic performance of DMCD
32
−
Fig. 1 (A) TEM image of CSNTs; (B) XRD patterns of CSNTs and
CSNTs-623; (C) TEM image of reduced CSNTs; (D) Schematic
illustration of the formation of CSNTs.
hydrogenation, which was mainly attributed to the presence of
highly dispersed and stable active metallic copper species in
LDH precursors. However, the lifetime of these catalysts does
not satisfy to industrial requirement. Deactivation is mainly
caused by the aggregation of Cu nanoparticles during the
reaction process. As shown in Table 2, the DMCD conversion
maintained up to 99% when the reduction temperature of
CSNTs was below 623 K. The DMCD conversion and CHDM
selectivity decreased while further increasing the reduction
temperature. A similar variation of turnover frequency (TOF)
value was observed. Combining the XPS result in Table 1 can
lead to the speculation that the ratio of Cu+ species in CSNTs-T
is the key factor for influencing the catalytic performance. The
Table 1 Cu LMM XAES deconvolution results of CSNTs under a
different reduction temperatures
K. E.a / eV
A. P.b / eV
Cu+
Catalyst
XCu+c / %
Cu+
Cu0
Cu0
CSNTs
914.2 918.0 55616.7
–
100
CSNTs-523
CSNTs-623
CSNTs-723
CSNTs-773
CSNTs-823
914.1 918.0 29907.6 17556.7
914.2 918.0 28960.5 14948.9 65.9
914.0 918.0 14451.8 8551.6 62.8
914.3 918.3 24438.2 19718.5 55.3
914.2 918.2 11709.2 15145.5 43.6
63.0
catalyst with
a
proper Cu+ ratio of approximately 60%
exhibited the best catalytic performance in the selective
hydrogenation of DMCD to CHDM.
a
b
c
Kinetic energy. Auger parameter. Ratio between Cu+ and
(Cu++Cu0) by deconvolution of Cu LMM XAES spectra.
For comparison, the Cu-based catalysts with similar metal
content were prepared by deposition-precipitation, urea-
assisted gelation, and ammonia evaporation hydrothermal
methods, labelled as D-Cu/SiO2, U-Cu/SiO2, and A-Cu/SiO2,
respectively. The layer structure of copper phyllosilicate exists
in A-Cu/SiO2 as shown in Fig.S8 (ESI†).26 Subsequently, copper
phyllosilicate disappeared after reduction at 623 K, which was
consistent with literature results.11 All samples had the similar
metal content of approximately 30%, as demonstrated by XRF
(Table S1, ESI†). CSNTs-623 exhibited the highest SBET of 469.1
m2 g–1, and the largest VP of 1.15 cm3 g–1 compared with the
comparison catalysts, mainly due to the existence of the
nanotube structure. Fig. 2A displays the hydrogen temperature
program reduction (H2-TPR) profiles of the four Cu-based
catalysts. The D-Cu/SiO2, U-Cu/SiO2, and A-Cu/SiO2 showed a
reduction peak at 471 K, 493 K, and 503 K, respectively;
whereas the reduction of copper species over CSNTs occurred
at a higher temperature of 508 K, revealing metal-support
interactions in CSNTs. All these characterizations indicate that
To understand the status of Cu nanoparticles exsoluted in
situ during the reduction, the CSNTs were reduced in
5%H2-95%N2 at different temperatures to afford the catalyst
CSNTs-T. The physiochemical properties of CSNTs-T are
illustrated in Table S1 (ESI†). The BET surface area decreased
from 486.9 to 404.5 m2 g–1 with the increasing reduction
temperature ranging from 523 K to 823 K. Similar change trend
was observed in Vp and Dp data. This phenomenon implies that
the nanotube structure is partially destroyed in the reduction
process when the temperature is higher than 773 K, as
confirmed by the TEM image in Fig. S1 (ESI†). However, the
XRD profiles of CSNTs-T in Fig. S2 (ESI†) do not show significant
difference in the Cu nanoparticle size of CSNTs-T. The mean
particle sizes are approximately 5 nm. Two types of Cu species
could be identified (Fig. S3, ESI†). The kinetic energy of
approximately 914 eV and 918 eV (Table 1) are attributed to
2 | J. Name., 2012, 00, 1-3
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the nanotube structure of CSNTs is beneficial to the dispersion different LHSVs. The filled square refers to the conversion and the
of Cu species. In Fig. 2B, the CSNTs-623 achieved almost 100% circle refers to the selectivity. Reaction conditions: P(H2) = 5.0 MPa,
DMCD conversion and 96.3% CHDM selectivity under the T = 493 K, and H2/DMCD molar ratio = 260.
optimal conditions (Liquid hourly space velocity (LHSV) = 1.0 h–
1), which was superior to that of the other catalysts. Excellent
catalytic performance is achieved at a relative low LHSV value
To further investigate the stability of CSNTs-623, the
thermal stability of the DMCD hydrogenation reaction over
mainly due to the high ratio of surface active sites to reactant
molecule. As LHSV increases, the retention time of DMCD
four catalysts was evaluated according to our prior literature13
and the results are shown in Table S2 (ESI†). The space time
molecule on catalyst surface is too short to reaction, which
yield (STY) of the fresh catalyst at 493 K was calculated, and
leads to a decrease of hydrogenation rate. The result is that
then the temperature was rising to 623 K for 24 h. Finally, the
both DMCD conversion and CHDM selectivity decreased with
reaction temperature was adjusted to 493 K, and the STY after
an increase of selectivity to MHMCC. However, the CSNTs-623
thermal treatment was obtained. The ratio of these two STY
maintained both the conversion and selectivity up to 90% with
an LHSV as high as 4 h–1. In contrast, the other three catalysts
values reflects the thermal stability of catalysts. The STYT/STYF
ratios for the D-Cu/SiO2, U-Cu/SiO2, and A-Cu/SiO2 catalysts
rapidly deactivated under the same reaction conditions. The
CSNTs-623 exhibited the maximum TOF value of 19.8 h–1,
were 0.55, 0.88, and 0.93, respectively, whereas CSNTs-623
achieved up to 0.99. After thermal treatment, the catalytic
performance of DMCD hydrogenation over CSNTs-623 did not
significantly decline.
which is nearly five times higher than that of D-Cu/SiO2 (Fig. S4,
ESI†). Thus, the in situ exsolution of Cu nanoparticles in the
CSNT crystal lattice improved not only the catalytic
performance, but also the stability of the catalyst.
100
95
90
DMCD Conversion
CHDM Selectivity
85
80
75
Scheme 1 The reaction pathway for selective hydrogenation of
DMCD to CHDM.
0
200
400
600
800
1000
Time on steam / h
Table
2 Catalytic performance of CSNTs-T for the selective
Fig. 3 Long-term performance of DMCD hydrogenation over
CSNTs-623. Reaction conditions: P(H2) = 5.0 MPa, T = 493 K,
H2/DMCD molar ratio = 260, and LHSV = 1.0 h–1.
hydrogenation of DMCD to CHDMa
TOFb
/ h–1
Conversion
/ %
Selectivity / %
Catalyst
CHDM MHMCC MCHM
0.9
0.5
2.3
1.4
1.5
CSNTs-523
CSNTs-623
CSNTs-723
CSNTs-773
CSNTs-823
20.1
19.8
17.5
12.7
10.8
99.1
100
89.7
83.2
70.3
96.3
96.3
92.6
87.5
82.5
2.8
3.2
5.1
11.1
15.5
The XRD and XPS measurements were conducted to
investigate the difference of catalysts after thermal treatment.
As shown in Fig. S5 (ESI†), the Cu nanoparticles sintered
obviously after thermal treatment except for CSNTs-623,
which is consistent with TEM images (Fig. S6, ESI†). The Cu+
ratios were calculated according to Fig. S7 (ESI†) and are
illustrated in Table S3 (ESI†). CSNTs-623 had the highest initial
Cu+ ratio of 65.9%, compared with D-Cu/SiO2 (50.2%), U-
Cu/SiO2 (54.8%), and A-Cu/SiO2 (60.6%). After the thermal
treatment, the Cu+ ratios of D-Cu/SiO2, U-Cu/SiO2, and A-
Cu/SiO2 decreased, whereas the CSNTs-623 maintained its Cu+
ratio of 61.4%. Cu active sites in the hydrogenation of esters
showed a synergetic effect between Cu+ and Cu0, that is, the
dissociative activation of H2 molecules on Cu0 and Cu+ species
as electrophilic or Lewis acid sites that can polarize the
carbonyl group via the lone pair electron on oxygen.33 Above
all, the Cu nanoparticle size and Cu+ ratio are two key factors
which influenced the catalytic performance and stability of Cu-
based catalysts in the hydrogenation of DMCD. The strong
metal-support interactions of CSNTs-623 prepared by in situ
exsolution strategy are proved to effectively maintain Cu
nanoparticle size and Cu+ ratio during the reaction. The long
term performance of CSNTs-623 was evaluated under optimal
reaction conditions and is shown in Fig. 3. CSNTs-623 exhibited
almost a full conversion and up to 95% CHDM selectivity over
a Reaction conditions: P(H2) = 5.0 MPa, T = 493 K, H2/DMCD molar
ratio = 260, and LHSV = 1.0 h–1. b The TOF value was calculated by
Cu dispersion when the conversion was controlled under 30%.
100
90
80
70
60
50
40
30
(A)
(B)
d
c
a
b
b
a
c
d
1
2
3
4
5
6
7
8
9
400 500 600 700 800 900
Temperature / K
LHSV / h -1
Fig. 2 (A) H2-TPR profiles of (a) CSNTs, (b) as-prepared A-Cu/SiO2, (c)
as-prepared U-Cu/SiO2, and (d) as-prepared D-Cu/SiO2. (B) Catalytic
performance of (a) CSNTs-623, (b) A-Cu/SiO2, (c) U-Cu/SiO2, and (d)
D-Cu/SiO2 for the selective hydrogenation of DMCD to CHDM under
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Ester
P /
MPa
5
T / Product
K
Conversion Selectivity
/ %
/ %
Diethyl
483 1,3-
Propanediol
493 Ethanol
98.4
79.9
malonatea
Ethyl
3
3
99.2
99.6
98.5
98.3
acetateb
Dimethyl
oxalatec
453 Ethylene
glycol
Reaction conditions: a H2/ester molar ratio = 250, and LHSV=0.6 h–1
.
b H2/ester molar ratio = 80, and LHSV = 1.0 h–1. c H2/ester molar
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This work was supported by the Natural Science Foundation
of China (21403178, 91545115, 21473145, and 21503173), the
Program for Innovative Research Team in Chinese Universities
(No. IRT_14R31), the Fundamental Research Funds for the
Central Universities (20720150096, 20720170026, and
20720170024), and the Natural Science Foundation of Fujian
Province of China (No. 2017J05027).
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Graphical abstract
Copper nanoparticles socketed in situ into copper phyllosilicate
nanotubes with enhanced performance for chemoselective
hydrogenation of esters
Xiaoxiao Gong, Meiling Wang, Huihuang Fang, Xiaoqi Qian, Linmin Ye*, Xinping Duan,
Youzhu Yuan*
State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for
Green Chemical Productions of Alcohols-Ethers-Esters, iChEM, College of Chemistry and Chemical
Engineering, Xiamen University, Xiamen 361005, China