Catalysis

Science &
Technology
Published on 02 October 2018. Downloaded by CTRO UNIV DE CIENCIA EXACTAS E IGN - (CUCEI) on 10/8/2019 2:24:04 PM.

View Article Online

PAPER View Journal | View Issue

Highly active and stable Zn/ZSM-5 zeolite catalyst

Cite this: Catal. Sci. Technol., 2018,
for the conversion of methanol to aromatics:
8, 5646 effect of support morphology†
abc
Kai Wang, Mei Dong,*b Xianjun Niu,bc Junfen Li,b Zhangfeng Qin, b
b
Weibin Fan and Jianguo Wang *b

Received 19th August 2018,
Accepted 29th September 2018
DOI: 10.1039/c8cy01734d
rsc.li/catalysis
In this study, zinc species were introduced into HZSM-5 zeolite supports with coffin, rod, sphere and hol-
low capsule morphologies by wet impregnation. The regulation of the morphology of HZSM-5 zeolite sup-
ports on modification effect of zinc, as well as subsequent catalytic activities for the methanol-to-
aromatics (MTA) process were investigated by multi-technologies. The results indicated that the catalytic
activities of Zn/HZSM-5 zeolite catalysts were remarkably affected by the morphology of the supports.
Among the different morphologies of Zn/HZSM-5 zeolite catalysts, Hollow-IM possessed superior selectiv-
ity for aromatics (48.59%), and their catalytic activities followed the order of Hollow-IM > Sphere-IM >
Rod-IM > Coffin-IM. The superior catalytic performance of Hollow-IM was attributed to the hollow cap-
sule structure and mesoporous shell, which not only achieved a good synergistic effect between active
(ZnOH)+ and acid sites by facilitating the formation of the highest content and uniform dispersion of
(ZnOH)+ sites, but also increased the contact time as the primary products escaped from the hollow cavity
through the Zn/HZSM-5 shell. Furthermore, this special structure promoted the faster removal of precur-
sors of carbon deposition, as well as facilitating the diffusion and mass transfer of the reactants and prod-
ucts, thereby endowing Hollow-IM with enhanced catalytic stability (156 h).

1. Introduction mance in aromatization and inexpensive price is the most at-

The methanol-to-aromatics (MTA) process refers to a series of
reactions of methanol over solid-acid catalysts, eventually
transforming into aromatics with the presence of liquified pe-
troleum gas (LPG) and gasoline fractions as the main by-prod-
ucts.1,2 This non-oil route is considered as a important alter-
native pathway for the production of aromatics from
petroleum as a result of the continuing depletion of petro-
leum resources and the easy acquisition of methanol from
coal, natural gas and biomasses.3,4 According to the previous
reports, catalysts with loading of the metals from groups IB
and IIB on strongly acidic molecular sieve supports are the
most preferred for the MTA process.5–10 Owing to the shape
selective structure for aromatics, high thermal stability and
easily adjustable acidic property, ZSM-5 zeolites are widely
employed as supports, meanwhile, zinc, with excellent perfor-
a
College of Chemical and Environmental Engineering, Anyang Institute of
Technology, Anyang 455000, PR China
b
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese
Academy of Sciences, 27 South Taoyuan Road, Taiyuan, Shanxi 030001, PR
China. E-mail: mdong@sxicc.ac.cn, iccjgw@sxicc.ac.cn
c
University of Chinese Academy of Sciences, Beijing 100049, PR China
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c8cy01734d
tractive metal adding promoter.11–13
With the zinc modification of HZSM-5 zeolites, the resul-
tant active Zn sites construct bifunctional catalysts by com-
bining with the acid sites in the supports. In general, the cat-
alytic activity of a bifunctional catalyst depends on the
assembly modes of the two active sites.14–16 The traditional
preparation methods, such as mechanical mixing and wet
impregnation, result in the surface enrichment of metal com-
ponents, thus acquiring poor synergy with acid sites through-
out the whole support.17,18 Additionally, high speed flow of
feed gas drives the primary products to escape from the cata-
lyst directly, causing relatively low aromatics selectivity and
insufficient utilization of the core catalysts.19 In addition, the
selectivity for aromatics conflicts with the catalyst stability in
the MTA process. High acid amount is necessary to acquire
the high selectivity for aromatics, however, this in turn accel-
erates the coke formation rate and catalyst deactivation
through secondary reactions.20,21 Also, improving the selectiv-
ity for aromatics via zinc modification is achieved at the ex-
pense of catalyst lifetime. The existence of ZnO nanoparticles
narrows or even blocks the zeolite channels, accelerating the
deactivation of the catalyst.22 Hence, simultaneous acquisi-
tion of high aromatics selectivity and considerable lifetime,
remains a main obstacle in the MTA process.

5646 | Catal. Sci. Technol., 2018, 8, 5646–5656 This journal is © The Royal Society of Chemistry 2018

Catalysis Science & Technology
Our team has made a lot of efforts to improve the catalytic
activity and stability of Zn/HZSM-5 in the MTA process
Published on 02 October 2018. Downloaded by CTRO UNIV DE CIENCIA EXACTAS E IGN - (CUCEI) on 10/8/2019 2:24:04 PM.
through strategies such as size effects and control of the
preparation methods. The previous research results show the
direct synthesis method of microsized Zn/HZSM-5
strengthens the synergistic effect of the two active sites by
boosting the formation of more active Zn species and their
uniform dispersion.22 However, accompanied with the fast
deactivation caused by the longer zeolite channels,23,24 un-
controllable zinc amount and poor reproducibility make the
direct synthesis method uncompetitive. Contrarily, nanosized
ZSM-5 zeolite as support relieves the surface enrichment of
metal species, as well as enhancing the diffusion of product
molecules, due to the nanoscale size and the shorter zeolite
channels.24,25 Unfortunately, ZSM-5 nanozeolite brings about
difficulties in washing and filtering, reducing catalyst yield
and producing a large amount of waste water in the prepara-
tion process. Meanwhile, nanozeolite powder also causes a
high pressure drop in the fixed bed during the reaction pro-
cess.26,27 So far, it remains a challenge to design a MTA cata-
lyst with a desired structure which retains the advantages
and avoids the drawbacks of the above methods.
Herein, through wet impregnation of ZnIJNO3)2 solution
with four HZSM-5 zeolite supports with different morphol-
ogies, Coffin-IM, Rod-IM, Sphere-IM and Hollow-IM were pre-
pared, respectively. The effects of support morphology on the
physicochemical properties and acid distribution of supports
and the nature of zinc component were investigated in detail,
as well as their effect on the catalytic activities for the MTA
process. According to the obtained results, among the differ-
ent morphologies of Zn/HZSM-5, Hollow-IM exhibits superior
selectivity for aromatics (48.59%) and enhanced lifetime (156
h), thereby providing a new insight for better designing MTA
catalysts.
2. Experimental
2.1 Catalyst synthesis
According to the molar composition listed in Table S1,† so-
dium hydroxide, sodium aluminate, template agents (n-
butylamine or tetrapropylammonium hydroxide), additive
Na2H2EDTA, silica sol (40 wt% SiO2, 0.4 wt% Na2O) and
silicalite-1 seeds (prepared by the procedures of refs. 22, 24,
28 and 29) were successively added into deionized water. Af-
ter stirring for 1 h, the resultant mixture was transferred into
a Teflon-lined stainless steel autoclave, and then crystallized
at 170 °C for 38 h under rotation of 15 rpm. Next, the solid
products were repeatedly washed with deionized water until
the pH value of the mother-liquor was 7–8. Upon subsequent
drying at 100 °C for 12 h and calcination in air at 550 °C for
12 h, the Na-form samples were obtained, which were de-
noted as Coffin-ZSM-5, Rod-ZSM-5, Sphere-ZSM-5 and Hollow-
ZSM-5, respectively. Subsequently, through ion-exchange with
NH4NO3 (1 M, m(liquid)/m(solid) = 40) at 80 °C for 4 h, drying
and calcination at 550 °C for 6 h, H-form zeolites with the
different morphologies were acquired.
This journal is © The Royal Society of Chemistry 2018
View Article Online
Paper
Lastly, Zn/HZSM-5 zeolite catalysts were prepared by iso-
volumic impregnation of HZSM-5 zeolites with ZnIJNO3)2 solu-
tion (Zn = 1 wt%), followed by drying and calcination at 550
°C for 6 h in air, and the resultant Zn/HZSM-5 products were
denoted as Coffin-IM, Rod-IM, Sphere-IM and Hollow-IM,
respectively.
2.2 Catalyst characterization
XRD patterns of samples were recorded on a Rigaku MiniFlex
II desktop X-ray diffractometer with monochromated Cu-Kα
radiation, and the relative crystallinity was estimated by com-
paring the area of the peaks at 2θ = 22.5–25° with that of the
Hollow-ZSM-5 sample as reference. SEM images were taken
on a field emission scanning electron microscope (JEOL, JSM
7001-F). Nitrogen adsorption/desorption was measured on a
gas adsorption analyzer (Micromeritics, TriStar II 3020), and
the test samples were degassed at 300 °C under a high vac-
uum environment for 8 h before measuring.
ICP-AES was determined by a thermo iCAP element ana-
lyzer (TJA, Autoscan16). UV-vis-DRS was measured on a
Varian Cary 500 UV-vis spectrophotometer using BaSO4 as
standard. XPS was collected under ultrahigh vacuum (10−7
Pa) on a Thermo ESCALAB 250 spectrometer using an Al-Kα
radiation source and a multichannel detector. X-Ray absorp-
tion near-edge structure (XANES) was characterized at the
BL14W1 beam line following the procedure of ref. 22 in the
Shanghai Synchrotron Radiation Facility.
NH3-TPD was performed on a chemisorption analyzer
(Micromeritics, AutoChem II 2920). Prior to the adsorption of
NH3, the samples were heated at 550 °C for 2 h and then
cooled to 120 °C in an argon flow of 30 mL min−1; after the sat-
urated adsorption of NH3 at 120 °C for 30 min, the physically
adsorbed NH3 was subsequently degassed from the samples
for 2 h under an argon flow (30 mL min−1); finally, the samples
were reheated to 550 °C with a rate of 10 °C min−1, the
amounts of desorbed NH3 was measured by a thermal conduc-
tivity detector (TCD). FT-IR and Py-IR spectra were both mea-
sured on a Bruker Tensor 27 FT-IR spectrometer. Water and
impurities were removed from the samples under the condition
of 10−2 Pa at 450 °C for 2 h, FT-IR spectra were then collected
at room temperature. Next, pyridine vapor was introduced into
the sample for saturated adsorption; after evacuation at 150 °C
for 1 h, the Py-IR spectra were collected subsequently.
2.3 Catalytic evaluation of zeolites in the MTA reaction
The methanol to aromatics reaction (MTA) was carried out in
a continuous-flow fixed-bed apparatus with an iron tube reac-
tor (10 mm i.d.). The loaded zeolite catalyst was first
pretreated at the reaction temperature (390 °C) under 30 ml
min−1 nitrogen flow for 10 h; then, methanol feed was sy-
ringed into the reactor by a LabAlliance series III pump. The
gas mixtures were analyzed by a gas chromatograph (Agilent
7890A) with two capillary columns (J&W 127-7031 and Agilent
19095P-S25), a thermal conductivity detector (TCD), and two
flame ionization detectors (FID). The oil phase was analyzed
Catal. Sci. Technol., 2018, 8, 5646–5656 | 5647

Paper
by another Agilent 7890A gas chromatograph with a capillary
column (Agilent 19091S-001) and a FID. The aqueous phase
Published on 02 October 2018. Downloaded by CTRO UNIV DE CIENCIA EXACTAS E IGN - (CUCEI) on 10/8/2019 2:24:04 PM.
was analyzed by a third Agilent 7890A gas chromatograph
with a capillary column (Agilent 19091N-136), a TCD, and a
FID. The methanol conversion and selectivity of products
were calculated from the following formulae:
 nCHOff-gas
 shaped ZSM-5 stacked together closely so that the individual
Methanol conversion  wt % : X MeOH  1  Feed3  100%
OH
 nCH OH 
 3  loading content of zinc was controlled at approximately 1
mi
Product selectivity  wt% : Yi   100%
 mi
3. Results and discussion
For investigating the influence of the morphology of ZSM-5
zeolite supports on the modification effect of zinc, four cate-
gories of ZSM-5 zeolite supports with grain size of about 300
nm were prepared, denoted Hollow-ZSM-5, Rod-ZSM-5,
Sphere-ZSM-5 and Coffin-ZSM-5, respectively (Fig. 1). Hollow-
ZSM-5 showed a hollow capsule structure with diameters of
30–50 μm (Fig. 1a and b), and the rod-like single crystals of
ZSM-5 assembled oriented along the c axis into the zeolite
capsule shell with a thickness of about 500 nm (Fig. 1c and
S1d†). The hollow feature was further revealed by the TEM
image of Hollow-ZSM-5 (Fig. S1c†), and the oriented assem-
bly of nano-coffin crystals in the shell caused the formation
of accumulated mesopores (Fig. S1d and e†), which also was
confirmed by the mesopore-related isotherms of Hollow-ZSM-
Fig. 1 SEM images of HZSM-5 zeolite supports: (a) overview, (b)
crushed, and (c) surface in Hollow-ZSM-5; (d) Rod-ZSM-5; (e) Sphere-
ZSM-5; and (f) Coffin-ZSM-5.
5648 | Catal. Sci. Technol., 2018, 8, 5646–5656
View Article Online
Catalysis Science & Technology
5 with a capillary condensation at P/P0 of 0.5–1.0 (Fig. S2†).
Compared to the assembly of the hollow capsule structure,
single rod-like crystals of ZSM-5 were distributed randomly in
Rod-ZSM-5 (Fig. 1d). Sphere-ZSM-5 presented a sphere-like
agglomerative morphology of nanoparticles (Fig. 1e), and
some inter-crystalline voids were observed on the surface and
in the interior of the spheres (Fig. S1a and b†), while coffin-
crystals were not distinguished (Fig. 1f). Furthermore, the
wt% in Zn/HZSM-5 zeolites (Table 1), which was reported to
be the optimized content in the methanol-to-aromatics
process.22,24,26,30
3.1 Physical and textural properties
Compared with each of the ZSM-5 supports, the four Zn/
HZSM-5 zeolites all showed similar diffraction peaks of MFI
structure at 2θ = 7.88, 8.76, 23.0, 23.84 and 24.3° (Fig. 2(I)),31
which suggested that the framework structures of the supports
were not affected with the loading of Zn species. Meanwhile,
slight decreases of the relative crystallinity were observed in
Zn/HZSM-5 zeolites (Table 1), which was ascribed to the inter-
mixing of zinc species with the supports. Furthermore, al-
though the four Zn/HZSM-5 zeolites all had a similar zinc con-
tent of 1 wt%, weak diffraction peaks of ZnO at 2θ = 36.3 and
31.8° were observed in Coffin-IM and Rod-IM, while ZnO peaks
were absent in Sphere-IM and Hollow-IM (Fig. 2(II)), indicating
zinc species were uniformly dispersed in Sphere-IM and Hol-
low-IM, compared with these in Coffin-IM and Rod-IM.
As listed in Table 1, the difference between the surface
zinc content determined by XPS and the bulk zinc content
measured by ICP depended on the morphology of supports:
the surface value was obviously higher than the bulk value in
Coffin-IM, while the difference between the two values was
narrowed in Rod-IM, whereas the surface content was similar
to the bulk content for Sphere-IM and Hollow-IM. This result
indicated that compared with the surface enrichment of Zn
species in Rod-IM and Coffin-IM, the inter-crystalline meso-
pores in Sphere-IM and the hollow capsule structure in
Hollow-IM facilitated the even dispersion of zinc species in
these supports.
Owing to the difference in morphology of the supports,
the effect of introducing zinc species on the surface area,
micropore volume, and pore size distribution of the resultant
Zn/HZSM-5 also differed (Table 1 and Fig. S2†). Comparing
each support, the surface area, micropore volume and pore
size of Coffin-IM almost remained unchanged, while these of
the other three Zn/HZSM-5 decreased to different extents.
Generally, when introduced into the ZSM-5 supports, a part
of zinc species occur as ZnO nanoparticles, which are admit-
ted in the interior of the zeolite, located or accumulated at
the zeolite channels.22,32,33 The existence of ZnO nano-
particles promotes a pore size shift to lower values and may
even block the zeolite channels, thus hindering the diffusion
of nitrogen molecules, decreasing the inner detectable
This journal is © The Royal Society of Chemistry 2018
 View Article Online

Catalysis Science & Technology Paper

Table 1 Physical and textural properties of HZSM-5 and Zn/HZSM-5 zeolites with different morphologies

Relative Zn content (wt%)

Published on 02 October 2018. Downloaded by CTRO UNIV DE CIENCIA EXACTAS E IGN - (CUCEI) on 10/8/2019 2:24:04 PM.

crystallinity
Sample (%) ICP XPS SBETa/m2 g−1 Vmicrob/cm3 g−1 Vmesoc/cm3 g−1
Rod-ZSM-5 94.1 — — 341 0.107 0.103
Coffin-ZSM-5 92.9 — — 339 0.107 0.108
Sphere-ZSM-5 86.3 — — 367 0.120 0.128
Hollow-ZSM-5 100.0 — — 347 0.107 0.151
Rod-IM 87.8 0.91 1.18 323 0.098 0.086
Coffin-IM 80.7 0.95 1.32 330 0.105 0.107
Sphere-IM 83.4 0.98 1.04 341 0.101 0.109
Hollow-IM 94.5 0.96 0.94 331 0.099 0.138
a b
SBET, BET surface area was determined by the Brunauer–Emmett–Teller method. Vmicro, micropore volume was determined by t-plot. c Vmeso,
mesopore volume was calculated by Vtotal − Vmicro.

micropore surface area and volume. Compared with the sur-
face enrichment phenomenon found in Coffin-IM, with the
entry of more zinc species into the zeolite channels, the de-
creases of the surface area, micropore volume, and pore size
were intensified for Rod-IM and Sphere-IM, suggesting the
increasing content of ZnO nanoparticles. However, with the
uniform distribution of Zn species, the decreasing degree in
Hollow-IM was less obvious, indicating the existence of other
Zn species rather than ZnO nanoparticles. The above results
Fig. 2 XRD patterns (I) at 2θ of 5–40° and (II) scaled-up patterns at 2θ
of 30–40° of HZSM-5 and Zn/HZSM-5 zeolites: (a) Hollow-ZSM-5, (b)
Hollow-IM, (c) Sphere-ZSM-5, (d) Sphere-IM, (e) Rod-ZSM-5, (f) Rod-
IM, (g) Coffin-ZSM-5 and (h) Coffin-IM.
suggested that with the introduction of zinc species by wet
impregnation, the morphologies of HZSM-5 zeolite supports
were considerably affected by the modification effect of zinc.
3.2 Acidic properties
NH3-TPD, FT-IR spectra of OH groups and pyridine adsorp-
tion were employed to investigate the effect of loading Zn
species on the acidic properties of HZSM-5 zeolites. The simi-
lar NH3-TPD, FT-IR spectra of OH groups and pyridine ad-
sorption, and 27Al MAS NMR spectra in the four HZSM-5 sup-
ports suggested that all four HZSM-5 supports have similar
acidic properties (Fig. 3, 4, S3† and Table 2), and the differ-
ence among them only arising from the morphology differ-
ences. The NH3-TPD profiles of HZSM-5 and Zn/HZSM-5
shown in Fig. 3, reveal that the four HZSM-5 supports
exhibited two peaks at 180 and 375 °C, relating to weak and
strong acid sites, respectively, while the loading of zinc spe-
cies brought about a decrease in the strong and weak acid
sites as a result of the appearance of a new peak at 230–240
°C, corresponding to Zn-acid sites.21,34–36 The appearance of
Zn-acid sites was attributed to the interaction between zinc
species and intrinsic acid sites in the supports, which not
only consumed the strong and weak acid sites, but also made
Zn-acid sites anchoring on the ZSM-5 framework.22,24,31,32 Fur-
thermore, according to the calculation results of acid amount,
compared to each HZSM-5 support, the total acid quantity was
almost unchanged with the observation of a considerable dif-
ference in the amount of Zn-acid sites, which followed the se-
quence of Hollow-IM > Sphere-IM > Rod-IM > Coffin-IM,
depending on the morphologies of the supports (Table 2).
In the OH stretching region (Fig. 4(I)), the peak located at
3610 cm−1 was assigned to Brønsted acid sites (Al–(OH)–
Si).32,37,38 Comparing with each support, the loading of Zn
species caused a decrease in the peak intensity at 3610 cm−1.
Depending on the morphologies of supports, the decreased
degrees of Brønsted acid sites followed the order of Hollow-
IM > Sphere-IM > Rod-IM > Coffin-IM. Furthermore, the
bands at 1545 and 1454 cm−1 after the chemisorption of pyri-
dine (Fig. 4(II)) belonged to Brønsted and Lewis acid sites, re-
spectively. With the introduction of zinc species into the

This journal is © The Royal Society of Chemistry 2018 Catal. Sci. Technol., 2018, 8, 5646–5656 | 5649
 View Article Online

Paper Catalysis Science & Technology

Published on 02 October 2018. Downloaded by CTRO UNIV DE CIENCIA EXACTAS E IGN - (CUCEI) on 10/8/2019 2:24:04 PM.

Fig. 3 NH3-TPD profiles of HZSM-5 and Zn/HZSM-5 zeolites: (a) Rod-ZSM-5, (b) Rod-IM, (c) Coffin-ZSM-5, (d) Coffin-IM, (e) Sphere-ZSM-5, (f)
Sphere-IM, (g) Hollow-ZSM-5 and (h) Hollow-IM.

Fig. 4 (I) FT-IR spectra of OH groups and (II) pyridine adsorption on HZSM-5 and Zn/HZSM-5 zeolites: (a) Rod-ZSM-5, (b) Rod-IM, (c) Coffin-ZSM-
5, (d) Coffin-IM, (e) Sphere-ZSM-5, (f) Sphere-IM, (g) Hollow-ZSM-5 and (h) Hollow-IM.

Table 2 Acidic properties of HZSM-5 and Zn/HZSM-5 zeolites with different morphologies

Acidity by strengtha/mmol g−1 Acidity by typeb/mmol g−1

Samples Strong Medium Weak Total Brønsted Lewis L/B
Rod-ZSM-5 0.455 0.000 0.301 0.756 0.315 0.059 0.187
Coffin-ZSM-5 0.275 0.000 0.360 0.635 0.271 0.076 0.280
Sphere-ZSM-5 0.394 0.000 0.265 0.659 0.313 0.053 0.169
Hollow-ZSM-5 0.469 0.000 0.297 0.765 0.304 0.048 0.158
Rod-IM 0.364 0.163 0.222 0.750 0.219 0.223 1.018
Coffin-IM 0.260 0.148 0.219 0.627 0.210 0.207 0.985
Sphere-IM 0.303 0.201 0.147 0.650 0.188 0.255 1.356
Hollow-IM 0.343 0.255 0.168 0.766 0.177 0.290 1.638
a
Determined by NH3-TPD. b Determined by Py-IR.

supports, the amount of Lewis acid sites increased at the ex- supports, these variation trends decreased in the order of
pense of Brønsted acid sites in Zn/HZSM-5, thus increasing Hollow-IM > Sphere-IM > Rod-IM > Coffin-IM. These coinci-
the ratio of L/B (Table 2). According to the morphologies of dences among the NH3-TPD, FT-IR spectra of OH groups and

5650 | Catal. Sci. Technol., 2018, 8, 5646–5656 This journal is © The Royal Society of Chemistry 2018
 View Article Online

Catalysis Science & Technology Paper

pyridine indicated that the Brønsted acid sites in the sup- Fig. 6(I), three main bands were observed at 368, 275 and 236
ports were the interaction sites with Zn species for the forma- nm, respectively, corresponding to surface enriched ZnO
Published on 02 October 2018. Downloaded by CTRO UNIV DE CIENCIA EXACTAS E IGN - (CUCEI) on 10/8/2019 2:24:04 PM.

tion of Zn-acid sites. On the other hand, with the introduc- macroparticles, ZnO nanoparticles and (ZnOH)+ sites distrib-
tion of zinc species over supports with different uted through the whole zeolites.22,44,45 The three characteris-
morphologies, a good linear relationship was observed be- tic peaks all appeared in Coffin-IM, and the intensity of the
tween the amount of Zn-acid sites and the increase of Lewis peak at 368 nm was high. Compared with that in Coffin-IM,
sites (Fig. S4†), which further confirmed Zn-acid sites existed the intensity of peak at 368 nm decreased along with an in-
as medium acid and Lewis acid sites simultaneously. crease in the intensity of the peaks at 236 and 275 nm in
With the introduction of zinc species into HZSM-5 sup- Rod-IM. The sphere-like agglomerative morphology of
ports, the state of Zn-acid sites have been discussed in sev- Sphere-IM promoted the almost complete disappearance of
eral recent researches.35,39,40 Berndt et al. have reported that the peak at 368 nm and a further increase of intensity of the
one Zn2+ interacted with one proton, and the resultant Zn- peaks at 236 and 275 nm. However, upon complete disap-
acid sites were present as (ZnOH)+, which anchored on the pearance of the peak at 368 nm, the intensity of the peak at
ZSM-5 framework through Zn–O–Al bonds.41 Hence, each Al 236 nm drastically increased with a decrease of that at 275
or Zn atom in Zn/HZSM-5 adsorbed one ammonia molecule, nm in Hollow-IM. Owing to the coexistence of minute quanti-
which did not affect the overall ammonia adsorption quantity ties of ZnO macroparticles and the higher amount of ZnO
in NH3-TPD. On the contrary, Yakerson et al. have concluded nanoparticles, SEM and HRTEM of Sphere-IM were carried
that Zn-acid sites existed as (Al–O−–Zn2+–O−–Al) via the inter- out to reveal these two species visually. It was found that ZnO
actions of one Zn2+ with two Al sites bridged by oxygen at macroparticles were amorphous with a grain size about 200–
nearby framework aluminum pairs.42 This connection mode 400 nm, while ZnO nanoparticles existed as clusters with
decreased the overall ammonia adsorption quantity over Zn/ sizes in the range of 2–5 nm (Fig. S5†).
HZSM-5 zeolites for NH3-TPD, compared with that over the
unmodified support. As shown in Table 2, the comparable
overall ammonia uptake between HZSM-5 and Zn/HZSM-5 ze-
olites indicated that the Zn-acid sites here existed in the form
of (ZnOH)+. In addition, the X-ray absorption near-edge struc-
ture (XANES) spectra of Zn/HZSM-5 were further used to de-
termine the state of Zn-acid sites. Owing to the difference in
the oxidation state of Zn atoms, the absorption edges of Zn
foil (Zn0) and ZnO (Zn2+) reference materials are located at
9659.5 and 9669.0 eV, respectively (Fig. 5). The absorption
edges of the four Zn/HZSM-5 samples were observed at about
9663.0 eV, which lie between these of Zn0 and Zn2+, indicat-
ing that Zn-acid sites existed as (ZnOH)+.43

3.3 Distribution and state of Zn species

The UV-vis DRS spectra of the four Zn/HZSM-5 zeolites were
used to examine the state of bulk zinc species. As shown in

Fig. 6 (I) UV-visible DRS spectra and (II) XPS spectra of Zn (2p3/2) of
Fig. 5 Zn near-edge XANES spectra of Zn/HZSM-5 with different Zn/HZSM-5 zeolites: (a) Rod-IM, (b) Coffin-IM, (c) Sphere-IM and (d)
morphologies. Hollow-IM.

This journal is © The Royal Society of Chemistry 2018 Catal. Sci. Technol., 2018, 8, 5646–5656 | 5651

Paper
In addition, the state of surface zinc species over Zn/
HZSM-5 zeolites with different morphologies was further in-
Published on 02 October 2018. Downloaded by CTRO UNIV DE CIENCIA EXACTAS E IGN - (CUCEI) on 10/8/2019 2:24:04 PM.
vestigated by Zn (2p3/2) XPS spectra. As shown in Fig. 6(II), by
fitting the XPS spectra, two peaks of zinc species were identi-
fied at around 1022.4 and 1023.4 eV, attributed to ZnO and
(ZnOH)+ species, respectively.24,46,47 Similar to the UV-vis re-
sults, the morphology of supports considerably affected the
state of the surface zinc species. Zn species on the surface of
Coffin-IM predominantly existed as ZnO, whether as macro-
particles or nanoparticles, which accounted for 71.60% area.
However, for the surface of Rod-IM, the totality of ZnO
macroparticles and nanoparticles decreased to 65.12%. With
the almost complete disappearance of surface ZnO macro-
particles, comparable quantities of ZnO nanoparticles and
(ZnOH)+ species (42.03% vs. 57.97%) were observed in the
surface of Sphere-IM, while zinc species were mainly present
as (ZnOH)+ (71.54%) in the surface of Hollow-IM.
On the whole, three types of zinc species were present in
the Zn/HZSM-5 zeolites: surface enriched ZnO macro-
particles, ZnO nanoparticles and (ZnOH)+ species throughout
the whole zeolites. The state of zinc species, whether in bulk
or surface of Zn/HZSM-5, was remarkably affected by the
morphology of the supports: the close stacking of large
coffin-shaped HZSM-5 was not conducive to the dispersion of
Zn species. Hence, zinc species were enriched in the surface
of zeolites, where ZnO macroparticles were the main form
with the observation of a small amount of ZnO nanoparticles
and (ZnOH)+ species. The monocrystalline rod-like morphol-
ogy of Rod-IM promoted the migration of more surface ZnO
macroparticles into the zeolite channels and their partial
interaction with the acid interior of the zeolite channels. This
migration and interaction increased the ratio of (ZnOH)+ spe-
cies at the surface, and generated a higher amount of ZnO
nanoparticles and (ZnOH)+ species in the bulk of zeolite.
Driven by the intracrystalline mesopores among the agglom-
erative nanocrystals of Sphere-IM, the almost complete disap-
pearance of surface ZnO macroparticles indicated the in-
crease in the degree of the above migration and interaction,
which further increased the ratio of (ZnOH)+ species in the
surface and afforded a high number of ZnO nanoparticles
and (ZnOH)+ species in the bulk. However, the hollow struc-
ture and mesoporous shell with an oriented assembly in
Hollow-IM not only facilitated the disappearance of surface
ZnO macroparticles and uniform dispersion of zinc species,
but also promoted the interaction between Zn species and
the acid interior of the zeolite, thus generating more (ZnOH)+
rather than ZnO nanoparticles inside the zeolites.
3.4 Catalytic evaluation in MTA process
Fig. 7 showed the catalytic activities of HZSM-5 and Zn/
HZSM-5 zeolites with different morphologies in the MTA pro-
cess, and the product distributions are listed in Table 3 un-
der the circumstances with carbon mass balances in the
range of 95–105% (Fig. S6†). The selectivity for aromatics
over three HZSM-5 catalysts with the morphologies of coffin,
5652 | Catal. Sci. Technol., 2018, 8, 5646–5656
View Article Online
Catalysis Science & Technology
rod and sphere were 34.30, 33.90 and 35.27%, respectively.
Compared with the above three morphologies of HZSM-5 cat-
alysts, Hollow-HZSM-5 catalyst exhibited a higher selectivity
for aromatics (40.10%) by suppressing the formation of C2=–
C5= alkenes and C5+ non-aromatic hydrocarbons. Classically,
as shown in Scheme 1(I), the MTA process refers to a series
of tandem reactions; methanol first transforms into dimethyl
ether or light alkenes by consecutive dehydration, which fur-
ther forms C5+ non-aromatic hydrocarbons (C6=–C9= high al-
kenes and C5+ saturated hydrocarbons) undergo continuous
methylation and oligomerization; subsequently, C5+ non-
aromatic hydrocarbons are converted into aromatics via a
“cracking–methylation–oligomerization” cycle and alkene aro-
matization accompanied with hydrogen transfer reaction.48–50
The relatively long contact time is propitious to the occur-
rence of this tandem process and the formation of a higher
amount of aromatics.36,49–51 When diffusing to the surface of
Coffin-HZSM-5, Rod-HZSM-5 and Sphere-HZSM-5 catalysts,
the methanol molecules first transform into the primary
products over the acid sites. The diffusion resistance inside
the zeolite channels limits the further mass transfer of the
primary products from the surface to the core of zeolites. To-
gether with the promotion effect of the high-speed CH3OH
flow, the generated primary products then escape from the
catalyst rapidly.19,31 However, for Hollow-ZSM-5 catalyst,
along with the diffusion inward into the internal cavity
through the HZSM-5 shell, methanol molecules first trans-
form into the primary products over the acid sites in ZSM-5
shell; then, instead of directly escaping as from the above
three HZSM-5 zeolites, all the primary products enriched in
the core cavity must diffuse outside from the hollow capsule
and further contact the HZSM-5 shell again, increasing the
contact time with the acid sites in the shell (Scheme 1
(II)).11,19,31,50 The longer contact time promoted not only the
conversion of C5+ saturated hydrocarbons and light alkenes
into high alkenes via the “cracking–methylation–oligomeriza-
tion” cycle, but also promote the further transformation of
high alkenes into aromatics via hydrogen transfer
reaction.24,36
Meanwhile, according to the morphologies of the ZSM-5
zeolite supports, the catalytic lifetimes of the four HZSM-5
catalysts differed markedly, which decreased in the order of
Hollow-ZSM-5 (187 h) > Sphere-ZSM-5 (142 h) > Rod-ZSM-5
(112 h) > Coffin-ZSM-5 (78 h). The close stacking of coffin-
shaped HZSM-5 with grain size of 300 nm in Coffin-HZSM-5
catalyst was not conducive for the diffusion of product mole-
cules, and hence, exhibited a short lifetime; compared with
the dense stacking mode of Coffin-HZSM-5 catalyst, single
crystal Rod-HZSM-5 catalyst led to improved diffusion and
mass transfer of product molecules, increasing the catalyst
stability; with the same grain size, the intracrystalline meso-
pores among the agglomerative nanocrystals of Sphere-
HZSM-5 catalyst facilitated the faster removal of the precur-
sors of carbon deposition formed in micropores to the sur-
face of the zeolite, thus showing the stronger resistance to
carbon deposition;39,52 as for Hollow-HZSM-5 catalyst, the
This journal is © The Royal Society of Chemistry 2018
 View Article Online

Catalysis Science & Technology Paper

Published on 02 October 2018. Downloaded by CTRO UNIV DE CIENCIA EXACTAS E IGN - (CUCEI) on 10/8/2019 2:24:04 PM.

Fig. 7 (I) Methanol conversion and (II) selectivity for aromatics of the MTA process with the time on stream (TOS) over HZSM-5 and Zn/HZSM-5
zeolites: (a) Rod-ZSM-5, (b) Rod-IM, (c) Coffin-ZSM-5, (d) Coffin-IM, (e) Sphere-ZSM-5, (f) Sphere-IM, (g) Hollow-ZSM-5 and (h) Hollow-IM (reac-
tion conditions: T = 390 °C, P = 0.5 MPa, WHSVMethanol = 3.18 h−1).

Table 3 Product distributions of the MTA process over HZSM-5 and Zn/HZSM-5 zeolites with different morphologies

Production selectivitya (%) H2

Sample C1−–C4− C2=–C5= C5+ non-aromatic Aromatics Others selectivityb Lifetimec/h
Rod 35.44 6.31 23.18 33.90 1.15 2.31 112
Coffin 36.63 7.43 20.46 34.30 1.19 2.98 78
Sphere 36.36 6.23 20.77 35.27 1.36 2.55 142
Hollow 37.68 4.87 16.09 40.10 1.27 2.77 187
Rod-IM 32.43 6.77 20.28 37.35 3.18 26.79 60
Coffin-IM 35.35 7.66 18.73 36.83 1.42 22.42 54
Sphere-IM 31.37 7.58 17.57 40.26 3.22 32.14 103
Hollow-IM 25.11 6.43 14.10 48.69 5.77 52.07 156
a b
The product distributions were acquired at TOS = 12.5 h (the methanol conversion exceeded 99.5% in this time). mol% of H2 in the gas
phase. c When the methanol conversion was lower than 90%, the catalyst was designated to be deactivated.

internal cavities and the mesopores in the shell resulted in
lower bulk density and strong permeability of the shell,11,36
which not only facilitated the faster removal of precursors of
carbon deposition, but also accelerated the inward diffusion
and the outward diffusion of methanol and product mole-
cules, giving rise to the most prolonged catalytic lifetime.31,50
As a result, owing to the hollow capsule structure and meso-
porous shell, Hollow-HZSM-5 showed the highest selectivity
to aromatics (40.10%) and the best catalyst stability (187 h).
In addition, comparing with the lifetimes and the product
distributions in each HZSM-5 support, the loading of zinc
species led to a decrease in lifetime, C1–C4 alkane selectivity
and C5+ non-aromatic hydrocarbon selectivity, but an in-
crease of H2 molar percentage in the gas phase and aro-
matics selectivity in products, and these variations followed
the similar tendency over each Zn/HZSM-5 with different
morphologies (Table 3). With modification effect of zinc,
ZnO macroparticles, ZnO nanoparticles and (ZnOH)+ species
were found to be present over Zn/HZSM-5 zeolites. The sur-
face enrichment of ZnO macroparticles had little influence
on the physical and textural properties of the zeolites, while
the location or accumulation of ZnO nanoparticles at the
pore openings or inside the zeolite channels hindered effec-
tive mass transfer and product diffusion, and shortened the
catalyst lifetime. Meanwhile, the interaction between zinc
species and Brønsted acid sites of the supports consumed

This journal is © The Royal Society of Chemistry 2018 Catal. Sci. Technol., 2018, 8, 5646–5656 | 5653

Paper
Published on 02 October 2018. Downloaded by CTRO UNIV DE CIENCIA EXACTAS E IGN - (CUCEI) on 10/8/2019 2:24:04 PM.
Scheme 1 (I) Reaction routes for the MTA processes over HZSM-5 and Zn/HZSM-5 zeolites; (II) schematics of the catalytic reaction processes
over Hollow-IM.
Brønsted acid sites, which was compensated with (ZnOH)+
sites. The decrease in number of Brønsted acid sites resulted
in the formation of less C1–C4 alkanes by suppressing the hy-
drogen transfer reaction22,48 while the new (ZnOH)+ sites not
only served as active sites for the cracking of C5+ saturated
hydrocarbons into more alkenes, but also promoted the fur-
ther dehydrogenation aromatization of alkenes (Scheme 1(I)
).9,24,53 Although the Brønsted acidity and hydrogen transfer
reaction were reduced, due to the appearance of active
(ZnOH)+ species and their recombinative effect, the “crack-
ing–methylation–oligomerization” cycle and dehydrogenation
reaction were enhanced, affording a decreased amount of C5+
non-aromatic hydrocarbons and increased number of aro-
matics in products and H2 molar percentage in the gas phase
(Scheme 1(I) and Table 3). Therefore, after the modification
effect of Zn, the existence of ZnO nanoparticles reduced the
catalyst stability, while (ZnOH)+ sites synergized with
Brønsted acid sites to improve the selectivity for aromatics:
Brønsted acid sites were responsible for dehydration, methyl-
ation, oligomerization, and hydrogen transfer, (ZnOH)+ sites
played the role of cracking and dehydrogenation.
Nevertheless, with the introduction of Zn species, the en-
hancement level of aromatics selectivity and the decreased
degree in catalyst lifetime both depended on the distribution
of Zn species (Fig. 7 and Table 3). The low proportion and
the surface enrichment of (ZnOH)+ species and ZnO nano-
particles in Coffin-IM catalyst were disadvantageous to syner-
gism with Brønsted acid sites through the whole ZSM-5 zeo-
lites, as well as causing the catalyst lifetime to be reduced by
30.77% (Table S2†), compared with that of the unmodified
Coffin-HZSM-5 support; with the alleviation of surface enrich-
5654 | Catal. Sci. Technol., 2018, 8, 5646–5656
View Article Online
Catalysis Science & Technology
ment and the increase in amount of (ZnOH)+ species and
ZnO nanoparticles in the channels of Rod-IM catalyst, the
synergistic effect strengthened but with an increased catalyst
lifetime reduction of 46.43% (Table S2†), compared with
Rod-HZSM-5 support, which was the biggest reduction rate
among the four Zn/ZSM-5 catalysts. Driven by the inter-
crystalline mesopores among the agglomerated nano-crystals,
the high dispersion and the further increasing content of
(ZnOH)+ species and ZnO nanoparticles through the Sphere-
IM catalyst, this achieved a better synergistic effect, mean-
while the faster removal of the precursors for carbon deposi-
tion alleviated rapid catalyst deactivation effectively and re-
duced the decrease of lifetime to 27.46%, compared with
Sphere-HZSM-5 support. With regard to Hollow-IM catalyst,
the hollow capsule structure and mesoporous shell promoted
the uniform dispersion of Zn species, as well as facilitating
the formation of (ZnOH)+ species with highest content rather
than ZnO nanoparticles, hence, obtaining the best synergistic
effect and the smallest reduction in the lifetime (16.58%),
compared to Hollow-HZSM-5 support.19,31,54 Meanwhile, sim-
ilar to the situation in Hollow-HZSM-5, the hollow capsule
structure not only increased the extra opportunity for inter-
mediate products contacting the Zn/HZSM-5 shell as they
enriched in and diffused outside from the core cavity
(Scheme 1(II)), but also facilitated the diffusion and mass
transfer of the reactants and products. As summarized above,
among the Zn/HZSM-5 catalysts with different morphologies,
Hollow-IM exhibited the best synergistic effect between
(ZnOH)+ species and Brønsted acid sites, the highest aro-
matics selectivity (48.59%) and the most stable catalytic life-
time (156 h).
This journal is © The Royal Society of Chemistry 2018

Catalysis Science & Technology
Finally, the carbon depositions of the four used Zn/HZSM-
5 catalysts after the MTA process were investigated by TG
Published on 02 October 2018. Downloaded by CTRO UNIV DE CIENCIA EXACTAS E IGN - (CUCEI) on 10/8/2019 2:24:04 PM.
curves. As shown in Fig. S7,† the admitting capacity for car-
bon deposition in monocrystalline Rod-IM was increased to
11.39%, as compared to 8.72% in Coffin-IM with the close
stacking of large coffin crystals. The intracrystalline meso-
pores and hollow structure further strengthened the admit-
ting capacity for coke to 13.05% in Sphere-IM and 13.83% in
Hollow-IM, respectively. Besides, the average carbon deposi-
tion rate over Coffin-IM, Rod-IM, Sphere-IM and Hollow-IM
were 0.016, 0.019, 0.013 and 0.009 mg h−1, respectively. Com-
pared with Coffin-IM, more ZnO nanoparticles inside the zeo-
lites led to an increase of the average carbon deposition rate
in Rod-IM. However, with the further increase of ZnO nano-
particles in Sphere-IM, the average carbon deposition rate in-
stead decreased, which was attributed to the presence of the
intracrystalline mesopores. Introducing mesopores shortened
the diffusion path-length, so that carbon precursors can be
removed from the channels quickly.39,52 As for Hollow-IM, to-
gether with the lowest amount of ZnO nanoparticles, the hol-
low structure and mesoporous shell alleviated the carbon de-
position effectively in a similar way with Sphere-IM, but to a
greater degree, thus further decreasing the average carbon
deposition rate.31,50 Hence, the stability of Zn/ZSM-5 catalysts
depended on not only the admitting capacity for carbon depo-
sition but also the average carbon deposition rate. The hollow
structure, mesoporous shell and the lowest amount of ZnO
nanoparticles in Hollow-IM strengthened the admitting capac-
ity for carbon deposition, as well as decreasing the average car-
bon deposition rate, giving rise to the highest catalyst stability.
4. Conclusions
Zinc species were introduced into ZSM-5 zeolites with the
morphologies of coffin, rod, sphere and hollow capsule by
wet impregnation. The regulation of the morphology of ZSM-
5 zeolite supports on the distribution and state of zinc spe-
cies was systematically investigated. The results indicated
that three types of zinc species were present, viz., ZnO macro-
particles on the zeolite surface, ZnO nanoparticles and
(ZnOH)+ species dispersed throughout the whole zeolites.
The distribution and state of Zn species were significantly
influenced by the morphology of the HZSM-5 zeolite sup-
ports. Zinc species predominantly existed as surface ZnO
macroparticles with the presence of a small amount of ZnO
nanoparticles and ZnIJOH)+ species in Coffin-IM and Rod-IM.
However, zinc species were found to be uniformly dispersed
through Sphere-IM and Hollow-IM with the disappearance of
surface ZnO macroparticles. Comparable proportions of ZnO
nanoparticles and ZnIJOH)+ species were observed in Sphere-
IM, while zinc species were mainly present as ZnIJOH)+ spe-
cies in Hollow-IM.
The selectivity for aromatics of bifunctional Zn/HZSM-5
depended on the synergy between the Brønsted acid and
(ZnOH)+ species, meanwhile, the location or accumulation of
inactive ZnO nanoparticles inside the zeolite channels re-
This journal is © The Royal Society of Chemistry 2018
View Article Online
Paper
stricted the mass transfer and product diffusion, reducing
the catalyst stability. According to the distribution and state
of Zn species, the catalytic activities and catalyst lifetime over
different morphologies of Zn/HZSM-5 exhibited a consider-
able difference. The surface enrichment and low proportion
of (ZnOH)+ species in Coffin-IM and Rod-IM were disadvanta-
geous to the synergy with Brønsted acid sites. However, with
the increased quantity of ZnO nanoparticles from Coffin-IM
to Rod-IM, the reduction rate of catalyst lifetime intensified,
compared with the unmodified supports. The intracrystalline
mesopores in Sphere-IM not only led to high dispersion and
increased content of (ZnOH)+ species, but also facilitated the
faster removal of precursors of carbon deposition, achieving
the enhanced synergistic effect and alleviating the reduction
of the lifetime. The hollow capsule structure and mesoporous
shell in Hollow-IM promoted the uniform dispersion and the
formation of highest (ZnOH)+ content rather than ZnO nano-
particles, increased the contact time as the primary products
escaping from the hollow cavity passed through the Zn/
HZSM-5 shell, as well as facilitating the diffusion and mass
transfer of the reactants and products, and thereby exhibited
the best synergistic effect between (ZnOH)+ species and
Brønsted acid sites, superior catalytic activity (48.59%) and
enhanced catalytic stability (156 h).
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors are grateful for the financial support of the Na-
tional Key R&D Program of China (2018YFB0604802), the Stra-
tegic Priority Research Program of the Chinese Academy of
Sciences (XDA21020500), the National Natural Science Foun-
dation of China (21573270, U1510104, and 21773281), the
Natural Science Foundation of Shanxi Province of China
(2015021003), the Innovative Talent Program of Shanxi Prov-
ince (201605D211001), the CAS/SAFEA International Partner-
ship Program for Creative Research Teams (2015YC901), the
Youth Innovation Promotion Association, CAS (2016161), and
the School foundation of Anyang Institute of Technology. The
calculations were performed on the Computer Network Infor-
mation Center of the Chinese Academy of Sciences and Na-
tional Supercomputer Centers in Lvliang, China.
Notes and references
1 S. Teketel, W. Skistad, S. Benard, U. Olsbye, K. P. Lillerud, P.
Beato and S. Svelle, ACS Catal., 2012, 2, 26–37.
2 S. Ilias and A. Bhan, ACS Catal., 2013, 3, 18–31.
3 C. Mesters, Annu. Rev. Chem. Biomol. Eng., 2016, 7, 223–238.
4 P. Schwach, X. L. Pan and X. H. Bao, Chem. Rev., 2017, 117,
8497–8520.
5 U. Olsbye, S. Svelle, M. Bjorgen, P. Beato, T. V. W. Janssens,
F. Joensen, S. Bordiga and K. P. Lillerud, Angew. Chem., Int.
Ed., 2012, 51, 5810–5812.
Catal. Sci. Technol., 2018, 8, 5646–5656 | 5655

Paper
6 Y. Q. Song, X. X. Zhu and L. Y. Xu, Catal. Commun., 2006, 7,
218–223.
Published on 02 October 2018. Downloaded by CTRO UNIV DE CIENCIA EXACTAS E IGN - (CUCEI) on 10/8/2019 2:24:04 PM.
7 M. Bjørgen, F. Joensen, U. Olsbye, K. P. Lillerud and S.
Svelle, Appl. Catal., A, 2008, 345, 43–50.
8 F. Bleken, W. Skistad, K. Barbera, M. Kustova, S. Bordiga, P.
Beato, K. P. Lillerud, S. Svelle and U. Olsbye, Phys. Chem.
Chem. Phys., 2011, 13, 2539–2549.
9 L. L. Yu, S. J. Huang, S. Zhang, Z. N. Liu, W. J. Xin, S. J. Xie
and L. Y. Xu, ACS Catal., 2012, 2, 1203–1210.
10 M. Conte, J. A. Lopez-Sanchez, Q. He, D. J. Morgan, Y.
Ryabenkova, J. K. Bartley, A. F. Carley, S. H. Taylor, C. J.
Kiely, K. Khalidc and G. J. Hutchings, Catal. Sci. Technol.,
2012, 2, 105–112.
11 P. P. Zhang, L. Tan, G. H. Yang and N. Tsubaki, Chem. Sci.,
2017, 8, 7941–7946.
12 M. Trombetta, A. G. Alejandre, J. R. Solis and G. Buscaa,
Appl. Catal., A, 2000, 198, 81–93.
13 J. H. Ahn, R. Kolvenbach, S. S. Al-Khattaf, A. Jentys and J. A.
Lercher, Chem. Commun., 2013, 49, 10584–10586.
14 P. Gao, S. G. Li, X. N. Bu, S. S. Dang, Z. Y. Liu, H. Wang,
L. S. Zhong, M. H. Qiu, C. G. Yang, J. Cai, W. Wei and Y. H.
Sun, Nat. Chem., 2017, 9, 1019–1024.
15 A. Corma and H. García, Chem. Rev., 2003, 103, 4307–4366.
16 K. Cheng, W. Zhou, J. C. Kang, S. He, S. L. Shi, Q. H. Zhang,
Y. Pan, W. Wen and Y. Wang, Chem, 2017, 3, 1–14.
17 Z. Z. Zhu, G. Z. Lu, Z. G. Zhang, Y. Guo, Y. L. Guo and Y. Q.
Wang, ACS Catal., 2013, 3, 1154–1164.
18 Z. D. Wang, Y. M. Liu, J. G. Jiang, M. Y. He and P. Wu,
J. Mater. Chem., 2010, 20, 10193–10199.
19 P. F. Zhu, G. H. Yang, J. Sun, R. G. Fan, P. P. Zhang, Y.
Yoneyam and N. Tsubaki, J. Mater. Chem. A, 2017, 5,
8599–8607.
20 J. Liu, C. X. Zhang, Z. H. Shen, W. M. Hua, Y. Tang, W.
Shen, Y. H. Yue and H. L. Xu, Catal. Commun.,
2009, 1506–1509.
21 J. G. Zhang, W. Z. Qian, C. Y. Kong and F. Wei, ACS Catal.,
2015, 5, 2982–2988.
22 X. J. Niu, J. Gao, Q. Miao, M. Dong, G. F. Wang, W. B. Fan,
Z. F. Qin and J. G. Wang, Microporous Mesoporous Mater.,
2014, 197, 252–261.
23 L. Z. Yang, Z. Y. Liu, Z. Liu, W. Y. Peng, Y. Q. Liu and C. G.
Liu, Chin. J. Catal., 2017, 38, 683–690.
24 X. J. Niu, J. Gao, K. Wang, Q. Miao, M. Dong, G. F. Wang,
W. B. Fan, Z. F. Qin and J. G. Wang, Fuel Process. Technol.,
2017, 157, 99–107.
25 K. Shen, N. Wang, W. Qian, Y. Cui and F. Wei, Catal. Sci.
Technol., 2014, 4, 3840–3844.
26 N. Wang, W. Z. Qian, K. Shen, C. Su and F. Wei, Chem.
Commun., 2016, 52, 2011–2014.
27 C. Pagis, A. R. M. Prates, D. Farrusseng, N. Bats and A. Tuel,
Chem. Mater., 2016, 28, 5205–5223.
28 Q. Li, B. Mihailova, D. Creaser and J. Sterte, Microporous
Mesoporous Mater., 2000, 40, 53–62.
29 F. Xu, M. Dong, W. Gou, J. Li, Z. Qin, J. Wang and W. Fan,
Microporous Mesoporous Mater., 2012, 163, 192–200.
5656 | Catal. Sci. Technol., 2018, 8, 5646–5656
View Article Online
Catalysis Science & Technology
30 H. A. Zaidi and K. K. Pant, Ind. Eng. Chem. Res., 2008, 47,
2970–2975.
31 K. Wang, X. Huang and D. B. Li, Appl. Catal., A, 2018, 556,
10–19.
32 J. Gao, Y. T. Zheng, J. M. Jehng, Y. Tang, I. E. Wachs and
S. G. Podkolzin, Science, 2015, 348, 686–690.
33 Y. G. Kolyagin, V. V. Ordomsky, Y. Z. Khimyak, A. I. Rebrov,
F. Fajula and I. I. Ivanova, J. Catal., 2006, 238, 122–133.
34 F. F. Madeira, K. B. Tayeb, L. Pinard, H. Vezin, S. Maury and
N. Cadran, Appl. Catal., A, 2012, 443–444, 171–180.
35 Y. Ni, A. Sun, X. Wu, G. Hai, J. Hu, T. Li and G. Li,
Microporous Mesoporous Mater., 2011, 143, 435–442.
36 J. Xu, A. M. Zheng, X. M. Wang, G. D. Qi, J. H. Su, J. F. Du,
Z. H. Gan, J. F. Wu, W. Wang and F. Deng, Chem. Sci.,
2012, 3, 2932–2940.
37 Y. H. Kim, K. H. Lee, C. M. Nam and J. S. Lee,
ChemCatChem, 2012, 4, 1143–1153.
38 Y. H. Quan, S. Y. Li, S. Wang, Z. K. Li, M. Dong, Z. F. Qin, G.
Chen, Z. H. Wei, W. B. Fan and J. G. Wang, ACS Appl. Mater.
Interfaces, 2017, 9, 14899–14910.
39 J. A. Biscardi, G. D. Meitzner and E. Iglesia, J. Catal.,
1998, 179, 192–202.
40 J. Xu, A. Zhang, X. Wang, G. Qi, J. Su, J. Du, Z. Gan, J. Wu
and F. Deng, Chem. Sci., 2012, 3, 2932–2940.
41 H. Berndt, G. Lietz and J. Volter, Appl. Catal., A, 1996, 146,
365–379.
42 V. I. Yakerson, T. V. Vasina, L. I. Lafer, V. P. Sytnyk, G. L.
Dykh, A. V. Mokhov, O. V. Bragin and K. M. Minachev,
Catal. Lett., 1989, 3, 339–345.
43 G. D. Qi, J. Xu, J. H. Su, J. F. Chen, X. M. Wang and F. Deng,
J. Am. Chem. Soc., 2013, 135, 6762–6765.
44 J. X. Liu, A. S. N. L. Hong, N. He, G. D. Liu, C. C. Liang, X. F.
Zhang and H. C. Guo, Chem. Eng. J., 2013, 218, 1–8.
45 S. Bordiga, C. Lamberti, G. Ricchiardi, L. Regli, F. Bonino, A.
Damin, K. P. Lillerud, M. Bjorgen and A. Zecchina, Chem.
Commun., 2004, 2300–2301.
46 J. Chen, Z. Feng, P. Ying and C. Li, J. Phys. Chem. B,
2004, 108, 12669–12676.
47 Z. H. Wei, L. F. Chen, Q. S. Cao, Z. H. Wen, Z. Zhou, Y. RXu
and X. D. Zhu, Fuel Process. Technol., 2017, 162, 66–77.
48 A. G. Stepanov, S. S. Arzumanov, A. A. Gabrienko, A. V. Toktarev,
V. N. Parmon and D. Freude, J. Catal., 2008, 253, 11–21.
49 G. H. Yang, N. Tsubaki, J. Shamoto, Y. Yoneyama and Y.
Zhang, J. Am. Chem. Soc., 2010, 132, 8129–8136.
50 K. Wang, M. Dong, J. F. Li, P. Liu, K. Zhang, J. G. Wang and
W. B. Fan, Catal. Sci. Technol., 2017, 7, 560–564.
51 M. Z. Zhang, S. T. Xu, Y. X. Wei, J. Z. Li, J. B. Wang, W. N.
Zhang, S. S. Gao and Z. M. Liu, Chin. J. Catal., 2016, 37,
1413–1422.
52 A. A. Rownaghi and J. Hedlund, Ind. Eng. Chem. Res.,
2011, 50, 11872–11878.
53 E. A. Pidko and R. A. V. Santen, J. Phys. Chem. C, 2007, 111,
2643–2655.
54 N. B. Chu, J. Q. Wang, Y. Zhang, J. H. Yang, J. M. Lu and
D. H. Yin, Chem. Mater., 2010, 22, 2757–2763.
This journal is © The Royal Society of Chemistry 2018