An efficient Au catalyst supported on hollow carbon spheres for acetylene hydrochlorination

Article abstract of DOI:10.1039/c9ra06989e

Mesoporous hollow carbon spheres (HCSs) were prepared using SiO₂ spheres as a hard template, and Au nanoparticles were then synthesized using NaBH₄ as a reducing agent on the surface of the HCS support. Transmission electron microscopy characterization indicated that Au nanoparticles were much smaller on the HCS support than those on the active carbon (AC) support. HCl-TPD showed that the Au/HCS catalyst displayed a more active site than on Au/AC. The resulting Au/HCS catalyst showed excellent catalytic activity and stability for acetylene hydrochlorination. Acetylene conversion of Au/HCS can be maintained above 92% even after 500 h of lifetime. The excellent catalytic performance of Au/HCS was attributed to the presence of the HCS support, which limited the aggregation of Au nanoparticles.

Full text of DOI:10.1039/c9ra06989e

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An efficient Au catalyst supported on hollow
carbon spheres for acetylene hydrochlorination
Cite this: RSC Adv., 2019, 9, 31812
ab
Lihua Kangab and Mingyuan Zhu
*
Mesoporous hollow carbon spheres (HCSs) were prepared using SiO2 spheres as a hard template, and Au
nanoparticles were then synthesized using NaBH4 as a reducing agent on the surface of the HCS
support. Transmission electron microscopy characterization indicated that Au nanoparticles were much
smaller on the HCS support than those on the active carbon (AC) support. HCl-TPD showed that the Au/
HCS catalyst displayed a more active site than on Au/AC. The resulting Au/HCS catalyst showed
excellent catalytic activity and stability for acetylene hydrochlorination. Acetylene conversion of Au/HCS
can be maintained above 92% even after 500 h of lifetime. The excellent catalytic performance of Au/
HCS was attributed to the presence of the HCS support, which limited the aggregation of Au nanoparticles.
Received 2nd September 2019
Accepted 29th September 2019
DOI: 10.1039/c9ra06989e
rsc.li/rsc-advances
polyaniline exhibited remarkable stability for acetylene hydro-
chlorination.6 In our previous work, we reported that metallic
1. Introduction
Au nanoparticles exhibited considerable catalytic activity for
acetylene hydrochlorination, and the aggregation of Au nano-
particles was another reason for the deactivation of the Au-
based catalyst in addition to the reduction of Au(III) or Au(I).7
Therefore, this study used metallic Au as an active site for
acetylene hydrochlorination. The use of nitrogen-doped carbon
may be a good strategy for supports to inhibit the aggregation of
Au nanoparticles and promote support stability for acetylene
hydrochlorination.8,9 Recently, Yuan et al. reported that metallic
Au(0) was directly involved in the catalysis of acetylene hydro-
chlorination due to the strong mediating properties of Ce(IV)/
Ce(III) with one-electron complementary redox coupling reac-
tions. Thus, the ceria promotion to Au catalysts gives enhanced
activity and stability.10 The reduction of oxidative Au cations
and aggregation of Au nanoparticles cannot be avoided under
the acetylene hydrochlorination reaction conditions-especially
in long-term testing. Thus, another good strategy to improve
catalyst stability may be the use of an appropriate carbon
support for Au catalysts. We found that larger AC pore sizes
increased the speed of the reaction and efficiently prohibited
carbon deposition.11 Li et al.12 proposed that some of the
oxygenated groups on the surface of AC could improve the
catalytic activity and stability of Au catalysts.
Polyvinyl chloride is mainly produced by polymerization of vinyl
chloride monomer (VCM). Acetylene hydrochlorination is an
important industrial process in the manufacture of VCM in coal
abundant regions, especially in China. Mercuric chloride
(HgCl2) is commonly used as a catalyst for the industrial pro-
cessing of acetylene hydrochlorination,1 but it is highly toxic
and may lead to serious environmental pollution problems.
Therefore, the use of mercury-free catalysts has attracted great
attention in recent years.
In 1985, Hutchings et al. evaluated the catalytic performance
of more than 20 types of metal chlorides for acetylene hydro-
chlorination.2 They found that their catalytic activity correlated
with the standard electrode potential of the cations present. In
2015, active carbon (AC) supported Au catalysts with ultra-low
metal loading and long lifetimes for acetylene hydro-
chlorination were synthesized. The active sites of the Au catalyst
were proposed to be related to the highly dispersed Au that
cycles between the Au(I)/Au(III) redox couples with
a S-
containing ligand as the so donor atoms.3 Later, Hutchings's
group found that single-site cationic Au entities exhibited
activity that correlated with the ratio of Au(I)/Au(III) in the
catalyst.4 Although the deactivation of the catalyst might be
associated with the formation of metallic Au particles,5 metallic
Au played a role in the catalysis of acetylene hydrochlorination,
when the size of Au nanoparticles was controlled to a very small
scale. Perez-Ramirez et al. found that Au single atoms hosted on
N-doped carbon-derived by the controlled pyrolysis of
HCS has been well reported as catalyst supports due to their
high surface area, large pore size, and abundant oxygenated
groups;13 the hollow structure functions act as a barrier to
prevent encapsulated Au nano-particles from aggregation or
leaching.14 Therefore, we inferred that Au aggregation could
also be restricted during acetylene hydrochlorination, and an
Au catalyst with excellent stability could be obtained by depos-
iting Au nanoparticles on HCS support.
aCollege of Chemistry and Chemical Engineering of Yantai University, Yantai,
Shandong, 264005, PR China. E-mail: zhuminyuan@shzu.edu.cn; Tel:
+86-993-2057277
bSchool of Chemistry and Chemical Engineering of Shihezi University, Shihezi,
Xinjiang, 832000, PR China
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˚
1.5406 A) at 40 kV and 40 mA in the scanning range of 2q
between 10ꢀ and 90ꢀ. The transmission electron microscopy
(TEM) used a JEM 2010 electron microscope at the accelerating
voltage of 200 kV, a line resolution of 0.14 nm, and a point
resolution of 0.23 nm. X-ray photoelectron spectroscopy (XPS)
measurements were recorded in an Axis Ultra spectrometer with
a monochromatized Al-Ka X-ray source (225 W). The tempera-
ture programmed decomposition (TPD) was analyzed using an
Auto Chem 2720 instrument with a TCD detector. The samples
were pretreated in a hydrogen chloride atmosphere at a reactive
temperature of 180 ꢀC for 4 h. High-purity N2 (40 mL minꢁ1) was
then passed through the sampꢁle1 at 100 ꢀC for 20 min. The
sample was heated at 10 ꢀC min from 50 ꢀC to 800 ꢀC during
data collection. Thermogravimetric analysis (TGA) used
a Netzsch STA-449 F3 Jupiter (Germany) analyzer with oxygen
atmosphere, ow rate of 30 mL minꢁ1, and a heating rate of 10
2. Materials and methods
2.1 Materials
Tetraethyl orthosilicate (TEOS), cetyltrimethylammonium
bromide (CTAB), resorcinol, formalin, activated carbon
(coconut carbon, 40–60 mesh, marked as AC), HAuCl4$4H2O
(with 47.8% Au content), NaBH4, C2H2 (gas, 99%), and HCl (gas,
99%) were used here.
2.2 Catalyst preparation
2.2.1 Preparation of the SiO2 template. SiO2 sphere
synthesis was performed using a modied Stober reaction.
15
¨
Water (25 mL), 63 mL of 2-propanol, and 13 mL of ammonia
(27%, aqueous solution) were mixed and heated to 35 ꢀC in
a water bath. Next, 0.6 mL of TEOS was added dropwise under
vigorous stirring for 30 min to generate the silica seeds. TEOS (5
mL) was then added dropwise. The reaction mixture was held
K minꢁ1
.
ꢀ
constant at 35 C for 4 h. The SiO2 spheres were separated by
2.4 Catalyst evaluation
centrifugation, washed with ethanol four times, then air dried.
2.2.2 Preparation of mesoporous hollow carbon spheres.
Next, 0.8 g of as-obtained SiO2 spheres was uniformly dispersed
in 70 mL of deionized water by ultrasonication followed by 2.3 g
of CTAB, 0.35 g of resorcinol, 28 mL of ethanol, and 0.1 mL of
ammonia. The mixture was heated to 35 ꢀC in a water bath and
stirred for 30 min to form a homogeneous dispersion. Formalin
was then added to the mixture under stirring. The mixture was
cooled to room temperature aer 6 h and aged at room
temperature overnight without stirring. The resulting
silica@resorcinol-formaldehyde (SiO2@RF) was collected by
centrifugation, washed with water and ethanol several times,
and dried. The SiO2@RF product was then heated under
a nitꢀrogen atmosphere at 5 ꢀC minꢁ1 from room temperature to
150 C and kept at this tempeꢁra1ture for 1 h. The temperature
was then increased by 5 ꢀC min to 800 ꢀC and held for 2 h. The
SiO2@C product was then treated with a 10% HF solution to
remove the silica and generate the hollow carbon nanoparticles.
2.2.3 The preparation of Au/HCS catalyst. The Au/HCS
catalyst was prepared using NaBH4 reduction methods.8 About
1.0 g of the HCS was dispersed in 100 mL water under sonica-
tion for 30 min. A solution of HAuCl4$4H2O (2.1 mL, 1 g/100
mL) was added dropwise to the HCS slurry, and then NaBH4
(21 mL, 0.1 M) was added to this suspension under sonication
and stirred for 30 min. The resulting mixture was vigorous
stirred for 24 h at room temperature. Finally, the solution was
ltered, washed several times with distilled water, dried in
a vacuum at 60 ꢀC, and named as the Au/HCS catalyst. For
comparison, an Au/AC catalyst was prepared with active carbon
as support for comparison. The theoretical loadings of Au metal
were 1% in those two catalysts.
Catalytic performance during acetylene hydrochlorination was
tested using a xed-bed reactor. Nitrogen (50 mL minꢁ1) was
used to remove air and moisture from the reactor system before
the start of the reaction. Hydrogen chloride gas at a ow rate of
20 mL minꢁ1 was passed through the reactor to activate the
catalyst (2 mL). The reactor was heated to 180 ꢀC, and the
hydrogen chloride (33.35 mL minꢁ1
) and acetylene (29
mL minꢁ1) were passed at a gas hourly space velocity (GHSV) of
870 hꢁ1. The reaction products were detected with a GC-2014C
gas chromatograph (Shimadzu).
3. Results and discussion
BET was used to analyze the structure of the HCS. Fig. 1a shows
that the nitrogen adsorption isotherms of the HCS were
consistent with the type IV curve, which indicated that the pore
structures of HCS were mainly mesoporous.16 The surface area
of HCS was calculated to be 762 m2 gꢁ1, which is lower than that
2.3 Catalyst characterization
Surface area analysis was carried out by N2 adsorption–
desorption at 77 K on a Micromeritics ASAP 2020 instrument.
Samples were degassed at 423 K for 15 h before analysis. The X-
ray diffraction (XRD) data were collected using a Bruker D8
Fig. 1 Nitrogen adsorption–desorption isotherms of (a) HCS and (b)
advanced X-ray diffractometer with Cu-Ka irradiation (l ¼ AC.
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of AC (1033 m2 gꢁ1) used as the support of Au nanoparticles in support had no inuence on the reducing process of the Au
the following experiment for comparison.
precursor.
The catalytic activity of the Au/HCS and Au/AC catalysts were
XRD characterization results of Au/HCS and Au/AC are
shown in Fig. 2. Characteristic diffraction peaks appeared at evaluated using a xed-bed reactor containing 2 mL of the
24.4ꢀ, which corresponded to the (002) diffraction of the carbon catalyst. The catalysts were evaluated under the following
material in these two catalysts. In addition, the obvious conditions: GHSV ¼ 870 hꢁ1, VHCl/VC H ¼ 1.15, reaction
2
2
ꢀ
diffraction peaks at 38.5ꢀ, 44.14ꢀ, 64.8ꢀ, and 78ꢀ corresponded temperature ¼ 180 C. The conversion of acetylene and selec-
to the (111), (200), (220), and (311) lattice planes of metallic tivity of VCM during 10 h in the stream are shown in Fig. 5.
Au0.17 This result shows that the Au nanoparticles were Fig. 5b shows that the differences between HCS and AC
successfully deposited on the HCS and AC support. The Au (111) supports have a very slight effect on the selectivity of VCM
peak was used to calculate the particle size according to the during acetylene hydrochlorination. The acetylene conversion
Scherrer's equation. The Au nanoparticles size in Au/AC and Au/ of Au/AC catalyst was about 57%, being similar to our previous
HCS catalysts were 13.7 nm and 6.3 nm, respectively. The results results of metallic Au nano-particles.7 However, acetylene
showed that the Au nanoparticles displayed a small particle size conversion via the Au/HCS catalyst was much higher versus the
in the Au/HCS catalyst versus the Au/AC catalyst.
Au/AC catalyst (Fig. 5a); the enhanced catalytic activity of Au/
The TEM images shown in Fig. 3 represent the structures of HCS may be assigned with the good dispersion of the Au
the HCS, the Au/HCS catalyst, and the Au/AC catalyst. Fig. 3a nanoparticles.
and b shows that the contrast difference between the edge and
Next, TPD experiments were performed to analyze the
the center of the spheres is obvious, indicating that the HCS adsorption strength of hydrogen chloride on the different
was, indeed, hollow. The wall thickness was around 25 nm, and supports. This study can help elucidate the mechanism
the diameter of the core is 190–220 nm. The TEM images of Au/ underlying enhanced acetylene conversion via Au/HCS. Fig. 6
HCS and Au/AC catalysts are shown in Fig. 3c–f. Fig. 3c and shows that the Au/AC catalyst has two desorption peaks at
d shows that the Au nanoparticle dispersion is dispersed 195 ꢀC and 410 ꢀC. The desorption peaks in the Au/HCS catalyst
uniformly on the surface of the HCS, and some aggregation can were observed at 195 ꢀC and 400 ꢀC. It is obvious that the second
be observed on AC. The average particle diameter of Au/HCS peak of the Au/HCS catalyst was larger than that of the Au/AC
was 3.94 nm (Fig. 3h), and the average particle diameter of catalyst. The adsorption of hydrogen chloride was the rate-
Au/AC was 11.43 nm (Fig. 3g). This result demonstrated that the controlling step in acetylene hydrochlorination.20 This
HCS support was benecial for controlling the size of Au phenomenon demonstrates that hydrogen chloride has
nanoparticles and is consistent with the results.18
stronger adsorption on the HCS during acetylene hydro-
XPS was performed because the catalytic activity of Au cata- chlorination than on active carbon. This might be the reason for
lyst could be inuenced by the gold valence (Fig. 4). The binding the enhanced catalytic activity of Au/HCS.
energy of Au 4f showed no change in the Au/AC and Au/HCS
The most important parameter of the Au catalyst for acety-
catalysts. The peaks at 84.1 eV and 87.8 eV were ascribed to lene hydrochlorination was its stability under harsh reaction
the 4f7/2 and 4f5/2 peaks of metallic Au, respectively.17,19 No conditions. Therefore, we compared the running life-times of
oxidative valences of Au(III) and Au(I) were found in the XPS Au/HCS and Au/AC at GHSV ¼ 360 hꢁ1, VHCl/VC H ¼ 1.15, and
2
2
spectras of Au/AC and Au/HCS catalysts, indicating all oxidative reaction temperature ¼ 180 ꢀC. As shown in Fig. 7, the acetylene
Au was reduced by NaBH4 reduing agent in the catalyst conversion of the Au/AC catalyst reduced from 82% to 43% aer
preparing process. The results mean that the structure of the 400 h of running time. The Au/HCS catalyst exhibited excellent
catalytic activity for acetylene hydrochlorination, and its acety-
lene conversion remained above 94% even aer 500 h running
time. Considered the harsh reaction conditions (GHSV ¼ 360
hꢁ1), the lifetime of Au/HCS under industrial condition (GHSV
¼ 36 hꢁ1) could be predicted to be higher than previous results
reported in the literatures.21,22
ICP-AES was used to test the actual Au loading. The actual Au
loading was 0.89 wt% and 0.88 wt% in the fresh and spent Au/
HCS catalyst, respectively. The results revealed that Au nano-
particles did not leached in the acetylene hydrochlorination
process. Oxidative Au reduction, aggregation of Au nano-
particles, and carbon deposition from acetylene polymerization
might be the three reasons for Au deactivation.7 However, an
oxidative Au reaction could be excluded because the XPS char-
acterization only showed metallic Au(0) in Au/HCS and Au/AC
catalysts. Next, TGA was used to characterize the carbon depo-
sition of the catalysts, and TEM of the spent catalysts showed
the dispersion of Au nanoparticles on HCS and AC support aer
Fig. 2 XRD patterns of the (a) 1% Au/AC and (b) 1% Au/HCS catalysts. the lifetime testing. These experiments could help further
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Fig. 3 TEM data on the (a and b) HCS, (c and e) Au/HCS, (d and f) Au/AC. The figure also shows the catalysts and particle size histograms of (g) Au/
HCS and (h) Au/C catalysts.
explain why the Au/HCS catalyst showed excellent stability for the Au/AC is 4.71%. Carbon deposition resulted in clogged
acetylene hydrochlorination. Fig. 8 indicates that the amount of pores and reduced surface areas in the carrier—both of these
carbon deposited on the Au/HCS catalyst is 1.73%, and that on decreased catalyst activity. The carbon cokes in the Au/HCS and
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Fig. 4 XPS spectra for the Au 4f of the (a) Au/AC and (b) Au/HCS
Fig. 6 TPD-HCl profiles of the (a) Au/AC and (b) Au/HCS catalysts.
catalysts.
Au/AC were minor, and thus carbon deposition was not the
main reason for the quick deactivation of Au/AC catalyst. TEM
was performed to determine whether the Au particle aggrega-
tion was the main reason for the deactivation rapid of the Au/AC
catalyst (Fig. 9). Fig. 9b shows the spent Au/AC catalyst—the
particle size of Au nanoparticles obviously increased aer 400 h
running, which indicates that the Au nanoparticles form
aggregates during acetylene hydrochlorination. This indicates
that aggregation of the Au nanoparticles was the main reason
for the deactivation of the Au/AC catalyst. However, no obvious
aggregation was seen in Au/HCS. The Au nanoparticles were still
uniformly dispersed even aer 500 h running, which means
that the hollow structure of HCS could restrict the aggregation
of Au nanoparticles during the acetylene hydrochlorination
process. Mesopores originated from the decomposition of
micelles could protect the interior Au nano-particles from
aggregating with Au in other hollow carbon.23 In addition, the
hollow shell of HCS can act as a barrier, which may be another
Fig. 7 Long lifetime testing of Au/AC and Au/HCS catalysts (GHSV ¼
360 hꢁ1, VHCl/VC H ¼ 1.15, reaction temperature ¼ 180 ꢀC).
2
2
Fig. 5 Conversion of acetylene (a) and selectivity of VCM (b) in acetylene hydrochlorination catalyzed by the Au/HCS and Au/AC catalysts (GHSV
¼ 870 hꢁ1, VHCl/VC H ¼ 1.15, reaction temperature ¼ 180 ꢀC).
2
2
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Fig. 8 TGA curves of (a) Au/AC and (b) Au/HCS catalysts.
Fig. 9 TEM images of the (a) spent Au/AC and (b) Au/HCS catalysts.
reason for the weill dispersion of Au nanoparticles.24 The good Development Project of China (2016YFB0301603), and the
dispersion of the Au nanoparticles due to the HCS structure may International Corporation of S&T Project in Xinjiang Bingtuan
be the reason for the excellent stability of the Au/HCS catalyst. (2018BC003) and the International Corporation of S&T Project
in Shihezi University (GJHZ201701).
4. Conclusions
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