One-step synthesis of Pt@ZIF-8 catalyst for the selective hydrogenation of 1,4-butynediol to 1,4-butenediol

Article abstract of DOI:10.1016/S1872-2067(16)62497-X

A catalyst consisting of platinum nanoparticles on a ZIF-8 support (Pt@ZIF-8) was synthesized in a straightforward one-step procedure, by adding a nanostructured platinum sol during the formation of ZIF-8 at room temperature. Pt@ZIF-8 was highly porous an

Full text of DOI:10.1016/S1872-2067(16)62497-X

Chinese Journal of Catalysis 37 (2016) 1555–1561
a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c
Article
One‐step synthesis of Pt@ZIF‐8 catalyst for the selective
hydrogenation of 1,4‐butynediol to 1,4‐butenediol
Chuang Li a, Mingming Zhang a, Xin Di a, Dongdong Yin a, Wenzhen Li b, Changhai Liang a,*
a Laboratory of Advanced Materials and Catalytic Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning,
China
b DCBE, Biorenewables Research Laboratory, Iowa State University, Iowa 50011, USA
A R T I C L E I N F O
A B S T R A C T
Article history:
A catalyst consisting of platinum nanoparticles on a ZIF‐8 support (Pt@ZIF‐8) was synthesized in a
straightforward one‐step procedure, by adding a nanostructured platinum sol during the formation
of ZIF‐8 at room temperature. Pt@ZIF‐8 was highly porous and well crystallized. The Pt nanoparti‐
cles were well dispersed within the ZIF‐8 support. In the hydrogenation of 1,4‐butynediol, Pt@ZIF‐8
exhibited high activity, excellent selectivity for 1,4‐butenediol of greater than 94%, and reusability.
The Pt@ZIF‐8 catalyst did not require further additives. The favorable catalytic performance was
attributed primarily to the modification of the ZIF‐8 support by the platinum nanoparticles.
© 2016, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Received 6 May 2016
Accepted 30 June 2016
Published 5 September 2016
Keywords:
Platinum sol
ZIF‐8
One‐step synthesis
1,4‐Butynediol
Selective hydrogenation
Published by Elsevier B.V. All rights reserved.
1. Introduction
reduce the rate of the subsequent hydrogenation of BED to
1,4‐butanediol (BDO) [1]. The outstanding selectivity of Lindlar
The selective hydrogenation of carbon‐carbon triple bonds
to double bonds is an important process in the fine chemicals
industry, and is relevant to commodities and other specialty
chemicals production [1,2]. The partial hydrogenation of
1,4‐butynediol (BYD) to 1,4‐butenediol (BED) is especially im‐
portant, because BED is an important intermediate for produc‐
ing endosulfan [3], vitamins A and B6, and is used in the syn‐
thesis of n‐methyl pyrrolidone [4]. BED is also used as an addi‐
tive in resin manufacturing [5]. Lindlar catalysts [6] (Pd sup‐
ported on CaCO3 with a secondary doping of lead) are typical
selective supported metal catalysts for the liquid phase hydro‐
genation of BYD. In these catalysts, lead is used as a dopant to
promote the selective reduction of BYD to BED. A basic com‐
pound such as quinoline is also added during the reaction, to
catalysts results from the synergistic effect of the lead com‐
pounds and other soluble additives. Various Pd and Ni‐based
catalysts can also be used in this reaction, but require combin‐
ing with one or more mixed compounds of Cu, Zn, Ca, Cd, and
Ga, and/or an organic base [7–9]. The conversion of BYD is
significantly lower using these catalyst combinations, and toxic
compounds are generally required to obtain high purity prod‐
ucts [10]. Developing alternative reusable catalysts for a more
sustainable transformation is therefore of interest.
Metal‐organic frameworks (MOFs) have attracted much re‐
cent attention in the field of heterogeneous catalysis [11–14].
The high surface area, narrow pore diameter, and specific
composition of MOFs can yield nanoparticles (NPs) with a uni‐
form size distribution and interesting catalytic activity and
* Corresponding author. Tel/Fax: +86‐411‐84986353; E‐mail: changhai@dlut.edu.cn
This work was supported by the National Natural Science Foundation of China (21573031 and 21428301) and the Fundamental Research Funds for
the Central Universities (DUT15ZD106 and DUT15RC(4)09).
DOI: 10.1016/S1872‐2067(16)62497‐X | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 37, No. 9, September 2016

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Chuang Li et al. / Chinese Journal of Catalysis 37 (2016) 1555–1561
selectivity [15–17]. MOF catalysts with nitrogen‐containing
groups have been investigated for tailoring the acidity/basicity,
solubility/dispersibility, surface area, and selectivity toward
the target products in hydrogenation reactions [18,19]. In our
previous work, a polyvinyl‐pyrrolidone (PVP)‐protected Pd
nano‐sol supported on ZIF‐8 was shown to be a highly active
and selective catalyst for the hydrogenation of BYD [20].
Herein, an acetate‐protected Pt nano‐sol with a uniform
particle size distribution of 1–2 nm was added during the syn‐
thesis of ZIF‐8 at room temperature. The obtained Pt@ZIF‐8
catalyst was used in the hydrogenation of BYD. We investigated
the activity, selectivity, and recyclability of Pt@ZIF‐8, and the
specific role of ZIF‐8 in this reaction.
tima 2000 DV apparatus.
2.3. Catalytic reaction tests
The catalyst was reduced at 200 °C for 1.5 h under an at‐
mosphere consisting of Ar:H2 = 2:1. The freshly reduced cata‐
lyst (0.05 g) was mixed with BYD (0.568 g) and 1,2‐propylene
glycol (an internal standard required for gas chromatography
analysis) in 10 mL of H2O. The mixture was transferred into a
50 mL batch reactor. The reactor was flushed with H2 three
times, and catalytic hydrogenation was then carried out at a
given H2 pressure and temperature. A blank test was per‐
formed following a conventional catalytic test procedure at 120
°C and p(H2) = 2 MPa, using pure ZIF‐8 as the catalyst. Less than
2% conversion was obtained, indicating that ZIF‐8 was inactive
for the hydrogenation of BYD.
2. Experimental
2.1. Preparation of Pt nano‐sol and synthesis of Pt@ZIF‐8
3. Results and discussion
The Pt NP colloid was prepared through the chemical re‐
duction of H2PtCl6·6H2O by ethylene glycol in the presence of
CH3COONa as a stabilizer, at 160 °C for 3 h [21,22]. Then, 11.35
g of 2‐methy imidazole and 12 mL of the as‐prepared Pt colloid
ethanol solution were dissolved in 40 mL of H2O. An aqueous
solution of Zn(NO3)2·6H2O (4 mL) was then added under stir‐
ring. The mixture was stirred for a further 1.5 h at 25 °C, after
which the black powder was collected by centrifugation. The
product was washed twice with H2O and then twice with
methanol. Drying under vacuum at 120 °C for 12 h yielded the
1.0 wt% Pt@ZIF‐8 catalyst. The Pt loading could be controlled
by adjusting the amount of Pt colloid added during the synthe‐
sis. The precise Pt content as determined by inductively cou‐
pled plasma atomic emission spectroscopy (ICP‐AES) was 0.98
wt%. Fig. 1 shows the procedure for preparing Pt@ZIF‐8.
3.1. Characterization of Pt@ZIF‐8
A mild room temperature procedure was used to synthesize
ZIF‐8, which ensured that the structure of the Pt nano‐sol was
preserved. XRD patterns of ZIF‐8 and Pt@ZIF‐8 prepared by
the one‐step synthesis are shown in Fig. 2(a). The XRD patterns
show that introducing the Pt nano‐sol had negligible effect on
the formation of ZIF‐8. Both ZIF‐8 and Pt@ZIF‐8 exhibited very
high crystallinity. The characteristic diffraction peaks of Pt
could not be detected, because of the low Pt loading and high
crystallinity of ZIF‐8. N2 adsorption measurements of ZIF‐8 and
Pt@ZIF‐8 are shown in Fig. 2(b). Type I isotherms were ob‐
served for both ZIF‐8 and Pt@ZIF‐8, according to IUPAC classi‐
fications. High surface areas of 1786 m2/g for ZIF‐8 and 1747
m2/g for Pt@ZIF‐8 were observed, along with narrow pore size
distributions of 1–2 nm. This indicated that the pore structure
remained intact after loading with Pt.
2.2. Characterization
Powder X‐ray diffraction (XRD) patterns were recorded us‐
ing a D/MAX 2400 diffractometer with monochromatic Cu Kα
radiation (λ = 0.15418 nm), operated at 40 kV and 100 mA. The
surface area, pore volume, and pore size distribution of the
ZIF‐8 support and Pt@ZIF‐8 catalyst were determined from N2
TEM images of the Pt NPs and Pt@ZIF‐8 are shown in Fig. 3.
The ZIF‐8 framework was well crystallized. It had a smooth
surface, and consisted of particles of about 100–200 nm in size.
No additional impurities were observed in the TEM images, in
agreement with the XRD results. The TEM images show that the
Pt nano‐sol exhibited very little change after being encapsulat‐
ed in the ZIF‐8 crystals. Pt NPs of size of 1–2 nm were randomly
dispersed throughout the ZIF‐8 support.
adsorption‐desorption isotherms at –196 °C, using
a
Quantachrome Autosorb‐IQ apparatus. The average particle
size and size distribution of the samples were investigated by
transmission electron microscopy (TEM), using a Philips
CM200 apparatus operated at 120 kV. Powder samples were
sonicated in ethanol, and dispersed on copper grids. Elemental
analysis was performed by ICP‐AES, using a Perkin‐Elmer Op‐
3.2. Hydrogenation of BYD over the Pt@ZIF‐8 catalyst
The performance of Pt@ZIF‐8 as a catalyst was tested in a
H2O
Fig. 1. Procedure for preparing Pt@ZIF‐8.

Chuang Li et al. / Chinese Journal of Catalysis 37 (2016) 1555–1561
1557
1000
0.30
ZIF-8
Pt@ZIF-8
(a)
(b)
0.25
0.20
800
0.15
0.10
0.05
600
0.00
1
2
3
4
Pore Width (nm)
Pore width (nm)
Pt@ZIF-8
ZIF-8
400
200
0
ZIF-8
Pt@ZIF-8
5
10 15 20 25 30 35 40 45 50
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
2 /(o )
Relative pressure (p/p0)
Fig. 2. XRD patterns (a) and N2 adsorption measurements (b) of ZIF‐8 and Pt@ZIF‐8.
(a)
(b)
(c)
Fig. 3. TEM images of Pt nanoparticles (a) and Pt@ZIF‐8 (b, c) via one‐step method.
batch reactor, using H2O as a solvent. The general hydrogena‐
tion pathways of BYD are shown in Scheme 1. BYD can be easily
and completely hydrogenated to BDO by monometallic Pd or Pt
catalysts. The selectivity to mono‐ene products can be sup‐
pressed by poisoning with bismuth, sulfur adatoms, lead, and
Ag [4,9,23–25]. However, these catalytic systems usually pro‐
vide high selectivity to partially hydrogenated products, as well
posing a hazard because of their toxicity. It would advanta‐
geous if a high partial hydrogenation selectivity could be ob‐
tained without using these additives.
When the reaction temperature was 50 °C, a low BYD con‐
version of 10% was obtained when using Pt@ZIF‐8 as a cata‐
lyst under a H2 pressure of 3 MPa for 4 h. The BYD conversion
significantly increased with increasing temperature, and com‐
plete transformation was achieved at 120 °C. Higher tempera‐
tures often lead to the further hydrogenation of BED to BDO.
Scheme 1. Reaction pathway for the hydrogenation of BYD.

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Chuang Li et al. / Chinese Journal of Catalysis 37 (2016) 1555–1561
100
90
100
80
60
40
20
0
100
90
76
72
68
64
60
56
(a)
(b)
1,4-butenediol
others
1,4-butanediol
butanol
1,4-butenediol
others
1,4-butanediol
butanol
80
6
80
6
4
2
0
4
2
0
40
60
80
100
120
2
3
4
5
Temerature (oC)
Pressure (MPa)
Fig. 4. Hydrogenation of BYD over Pt@ZIF‐8 catalyst at different temperatures (a) and pressure (b).
100
80
60
40
20
0
100
(a)
(b)
80
1,4-butynediol
1,4-butenediol
1,4-butanediol
butanol
1,4-butenediol
others
1,4-butanediol
butanol
60
40
20
0
others
0
1
2
3
4
5
6
0
1
2
3
4
5
Time (h)
Time (h)
Fig. 5. Kinetics for hydrogenation of BYD (a) and BED (b) by Pt@ZIF‐8.
However, a high BED selectivity (>92%) was observed in the
current study, regardless of the BYD conversion. The influence
of temperature is shown in Fig. 4(a).
[27]. At low reaction time (i.e. lower conversions), the hydro‐
genation of BYD primarily produced BED. The selectivity to
BED was approximately 94% after 4 h of reaction time. BYD
was almost completely converted within 4 h, and high selectiv‐
ity was maintained during the entire reaction process. A further
2 h of reaction time after the complete consumption of BYD
yielded no obvious hydrogenation to cis‐BED or isomerization.
The selectivity to BED remained high (93%) after 6 h of reac‐
tion, indicating that the reaction stopped after the first hydro‐
genation. The Pt@ZIF‐8 catalyst in the hydrogenation of BYD in
aqueous solution gave selectivity towards BED of up to 94% at
conversions of up to 100%. This was further confirmed by ki‐
netic data for BED hydrogenation performed under the same
conditions, as shown in Fig. 5(b). Less than 20% of BED was
converted to BDO after 5 h, and no side products were ob‐
served. In comparison, a conventional Pt/C catalyst exhibited
poor selectivity for BED (<60%), under the same condition. The
BED target product was also readily further hydrogenated to
BDO, after the BYD substrate had been completely consumed
[28]. These results suggested that the selectivity of the
Pt@ZIF‐8 catalyst resulted from its structural properties, ra‐
ther than the reaction kinetics.
The pressure also affects the activity (Fig. 4(b)), and a de‐
crease in conversion was anticipated at lower pressure. How‐
ever, an excessively high pressure was also found to decrease
the activity of the catalyst. This was attributed to the high in‐
ternal surface area and the presence of metal cation sites in
ZIF‐8, which facilitated hydrogen adsorption. These properties
mean that ZIF‐8 supported Pt materials are promising candi‐
dates for hydrogen storage [26]. H2 pressure of over 3 MPa
resulted in increased adsorption of H2 molecules into the mi‐
cropores of ZIF‐8, which limited the ability of the BYD substrate
to reach Pt sites encapsulated within the ZIF‐8 framework. The
selectivity to BED was consistently high at approximately 95%,
under various H2 pressure.
Kinetic data for the hydrogenation of BYD over 1 wt%
Pt@ZIF‐8 at 120 °C and 3 MPa of H2 pressure is shown in Fig.
5(a). Analysis of kinetic data can yield information about the
interaction between structural properties and catalytic activity.
Within the first 4 h, the BYD concentration decreased linearly
with increasing reaction time, confirming the zero order kinet‐
ics with respect to BYD. This observation was consistent with
previous results of the hydrogenation of BYD over noble metals
One possible reason for the high partial hydrogenation se‐
lectivity may have been the inhibiting effect from the protective

Chuang Li et al. / Chinese Journal of Catalysis 37 (2016) 1555–1561
1559
100
100
80
60
40
20
0
1,4-butynediol
1,4-butenediol
1,4-butanediol
butanol
(a)
1,4-butynediol
1,4-butenediol
1,4-butanediol
butanol
(b)
80
60
40
20
0
others
others
0
1
2
3
4
5
6
0
1
2
3
4
5
6
7
8
Time (h)
Time (h)
Fig. 6. Kinetics for hydrogenation of BYD over Pt nano‐sol (a) and Pt@SBA‐15 (b).
agent around the Pt NPs. This hypothesis can be verified by
testing the catalytic performance of the Pt nano‐sol, and the
result is shown in Fig. 6(a). The acetate‐protected Pt nano‐sol
exhibited a higher activity, requiring only 2 h to fully convert
BYD. This may have resulted from the better contact between
the Pt nano‐sol and reactants, in the absence of the ZIF‐8 sup‐
port. The highest selectivity to BED (68%) was obtained at 1.5
h, and further hydrogenation and isomerization occurred as the
reaction continued. Similar catalytic performance was ob‐
served when the ZIF‐8 support was replaced with SBA‐15, as
shown in Fig. 6(b). Good selectivity was not observed in the
absence of the ZIF‐8 support, indicating that the favorable hy‐
drogenation properties of Pt@ZIF‐8 resulted from the role of
ZIF‐8. Zn‐ and N‐containing organic ligands contained within
the ZIF‐8 structure are a common poison. Metal and organic
inhibitors were also present to adjust the selectivity of the cat‐
alyst for the hydrogenation of BYD. The narrow pore diameter
of ZIF‐8 may also have suppressed isomerization.
shown in Fig. 7(a). The kinetic data for BYD hydrogenation in
Fig. 5(a) showed that BYD was fully converted in approximate‐
ly 4 h. Thus, the reaction data in Fig. 7(a) was collected after 4
h. The sample exhibited reproducible performance over five
runs, sustaining very good conversion of BYD (>91%) and ex‐
cellent selectivity for BED (>92%).
The XRD patterns of Pt@ZIF‐8 before and after reaction are
shown in Fig. 7(b). No obvious differences were observed be‐
tween the patterns of fresh Pt@ZIF‐8 and that after two reac‐
tion cycles, indicating that the ZIF‐8 structure remained intact.
The characteristic XRD peaks of ZnO began to emerge after four
reaction cycles, indicating the decomposition of ZIF‐8. The
characteristic XRD peaks of ZIF‐8 completely disappeared after
five reaction cycles, indicating complete decomposition of the
support at the high reaction temperature. The residual XRD
peaks were consistent with ZnO. BET results showed that the
specific surface area decreased from 1747 to 40 m2/g, over the
five reaction cycles. The metal composition remained largely
unchanged, at 21.3% and 19.8% for fresh Pt@ZIF‐8 and that
subjected to five reaction cycles. This indicated that the high
surface area and narrow pore dimeter of ZIF‐8 were not the
main reasons for the high selectivity of the Pt@ZIF‐8 catalyst
for BED. ZnO was obtained by calcining ZIF‐8 in air at 500 °C
for 3 h. The Pt/ZnO catalyst was prepared by adding ZnO to the
3.3. Recyclability of Pt@ZIF‐8 catalyst for BYD hydrogenation
The Pt@ZIF‐8 catalyst could be reused without reactivation
treatment, except requiring washing twice with H2O. The recy‐
clability of 1.0 wt% Pt@ZIF‐8 at 120 °C and p(H2) = 3 MPa is
100
90
100
90
(a)
(b)
after 5 runs of reaction
after 4 runs of reaction
1,4-butenediol
others
1,4-butanediol
80
80
6
20
10
0
after 2 runs of reaction
Pt@ZIF-8
4
2
0
1
2
3
4
5
5
10 15 20 25 30 35 40 45 50
Number of recycles
2 /(o )
Fig. 7. Recyclability (a) and XRD patterns (b) of Pt@ZIF‐8 before and after 4 h reaction cycles.

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Chuang Li et al. / Chinese Journal of Catalysis 37 (2016) 1555–1561
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Pt colloid. Dilute hydrochloric acid was then added to lower the
pH to <3. This in turn lowered the concentration of the glyco‐
late colloid stabilizer. The kinetics for the hydrogenation of BYD
by the Pt/ZnO catalyst are shown for comparison. The Pt/ZnO
catalyst exhibited poor selectivity for BED (<65%). After four
reaction cycles, the crystal structure of ZIF‐8 began to degrade,
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decompose and adsorb to the Pt surface, which affected the
catalysts performance. These results showed that nitro‐
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the partial hydrogenation. A possible reason for the good reus‐
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most of the Pt nano‐sol was located on the outer surface of
ZIF‐8.
4. Conclusions
We prepared a catalyst containing Pt supported on ZIF‐8,
via a rapid dynamic crystallization method at room tempera‐
ture. The Pt@ZIF‐8 catalyst exhibited enhanced selectivity for
1,4‐butenediol in the hydrogenation of 1,4‐butynediol, because
of the role of Zn2+ and N‐containing organic ligands in ZIF‐8.
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high specific surface area and well‐dispersed Pt NPs. Pt@ZIF‐8
exhibited excellent performance and reusability, although the
ZIF‐8 structure began to degrade after more than two reaction
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Graphical Abstract
Chin. J. Catal., 2016, 37: 1555–1561 doi: 10.1016/S1872‐2067(16)62497‐X
One‐step synthesis of Pt@ZIF‐8 catalyst for the selective
hydrogenation of 1,4‐butynediol to 1,4‐butenediol
1,4-butynediol
1,4-butenediol
others
1,4-butanediol
butanol
100
80
60
40
20
0
Chuang Li, Mingming Zhang, Xin Di, Dongdong Yin, Wenzhen Li,
Changhai Liang *
Dalian University of Technology, China;
Iowa State University, USA
HO
OH
2-butyne-1,4-diol
Pt@ZIF-8
OH
OH
cis-2-butene-1,4-diol
Pt@ZIF‐8 was synthesized by a one‐step method, and applied in the hy‐
drogenation of 2‐butyne‐1,4‐diol to 2‐butene‐1,4‐diol, exhibiting high ac‐
tivity, selectivity, and absolute reusability.
0
1
2
3
4
5
6
7
8
Time (h)

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