Microporous and Mesoporous Materials 197 (2014) 252–261

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Influence of preparation method on the performance of Zn-containing

HZSM-5 catalysts in methanol-to-aromatics
Xianjun Niu a,b, Jie Gao a,b, Qing Miao a,b, Mei Dong a,⇑, Guofu Wang a, Weibin Fan a, Zhangfeng Qin a,⇑,
Jianguo Wang a,⇑
a
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. Box 165, Taiyuan, Shanxi 030001, PR China
b
University of Chinese Academy of Sciences, Beijing 100049, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Zn-containing HZSM-5 zeolites (Zn/ZSM-5) were prepared by four methods including impregnation (IM),
Received 21 March 2014 ion exchange (IE), physical mixing with ZnO (PM), and direct synthesis (DS); the influence of preparation
Received in revised form 26 May 2014 method on the catalytic performance of Zn/ZSM-5 in the process of methanol-to-aromatics (MTA) was
Accepted 23 June 2014
investigated. The results indicated that Lewis acid sites of zinc species (ZnOH+) are formed by introducing
Available online 1 July 2014
zinc into HZSM-5, at the expense of the silanol hydroxyl and proton acid sites. The distribution of acid
sites and the nature of zinc species as well as the subsequent catalytic performance of Zn/ZSM-5 in
Keywords:
MTA are significantly influenced by the preparation method for introducing zinc. In Zn(PM)/ZSM-5, zinc
Methanol to aromatics
Zinc species
is mainly present as macro ZnO particles and trace ZnOH+ is formed by solid state reaction; in Zn(IM)/
Preparation method ZSM-5, ZnOH+ is the main ingredient, together with nano ZnO particles dispersed in the zeolite channel;
Zn-containing HZSM-5 in Zn(IE)/ZSM-5 and Zn(DS)/ZSM-5, however, only ZnOH+ species are observed. There is a linear correla-
Methanol aromatization tion between the amount of ZnOH+ species and the selectivity to aromatics for MTA over the Zn/ZSM-5
catalysts prepared by different methods; ZnOH+ species may promote the dehydrogenation of light
hydrocarbons to aromatics and suppress the hydrogen transfer reaction and the formation of alkanes
by depressing the Brønsted acidity. Zn(DS)/ZSM-5 with small particle size and high mesoporous volume
exhibits the longest catalytic lifetime, whereas Zn(IE)/ZSM-5 with high fraction of surface ZnOH+ species
gives the highest selectivity to aromatics in MTA.
Ó 2014 Elsevier Inc. All rights reserved.

1. Introduction its high stability and adaptability to a broad range of products,

As methanol can be expediently produced via syngas from mul-
tifarious carbon resources such as coal, natural gas and biomass,
the conversion of methanol to hydrocarbons (MTH) over acidic
zeolite catalysts has been turning into an increasingly important
alternative to petroleum processing to get various fuel and chem-
ical products. Accordingly, the MTH process has been extensively
investigated since its discovery by Mobil Oil Corporation in
1970s [1–3]. It is well acknowledged that MTH is a very compli-
cated process concerning numerous reactions; the composition
and distribution of MTH products are dependent on the reaction
conditions as well as the structure, morphology, and acidity of
the zeolite catalysts [4–8]. Among the various molecular sieves
used in MTH, ZSM-5 zeolite is the most attractive one which exhib-
⇑ Corresponding authors. Tel.: +86 351 4046092; fax: +86 351 4041153.
E-mail addresses: mdong@sxicc.ac.cn (M. Dong), qzhf@sxicc.ac.cn (Z. Qin),
iccjgw@sxicc.ac.cn (J. Wang).
from olefin, gasoline to aromatics [8,9].
By modifying ZSM-5 with the ionic metals like gallium and zinc,
aromatics like benzene (B), toluene (T), and xylenes (X) could be
selectively produced from methanol [10–13], which is known as
the process of methanol to aromatics (MTA). The essential role of
gallium or zinc species in promoting the selectivity to aromatics
has been studied and associated with their dehydrogenation capa-
bility; for example, it was found that the presence of zinc ions is
able to enhance the recombination of hydrogen atoms and desorp-
tion of H2 [14–17]. However, the characteristics of the active sites
for aromatization as well as the interaction between the metal ions
and the protonated acidic sites are still rather elusive.
Zinc species can be introduced into ZSM-5 by various methods
such as ion exchange, incipient wet impregnation, Zn/ZnCl2 subli-
mation, solid-state ion exchange with ZnO or metallic zinc, and
directly hydrothermal synthesis [18]; the preparation method
may also have important influence on the existence state of zinc
species, the interaction between zinc ions and acid sites, and the
catalytic performance in MTA as well. Liu, She and coworkers

http://dx.doi.org/10.1016/j.micromeso.2014.06.027
1387-1811/Ó 2014 Elsevier Inc. All rights reserved.
 X. Niu et al. / Microporous and Mesoporous Materials 197 (2014) 252–261
proposed that ZnO and ZnOH+ species were present in Zn/ZSM-5
prepared by impregnation or physical mixing with ZnO [19,20].
Berndt and coworkers used temperature-programmed surface
reaction with CO as probe molecule (TPSR/CO) to distinguish
between Zn2+ ions and oxygenous zinc species [21]; they observed
that equimolar amounts of CO2 and H2 were formed during the
TPSR/CO over Zn/HZSM-5 prepared by ion exchange and impregna-
tion, proving the presence of ZnOH+ species. Kolyagin and cowork-
ers found that three types of zinc species were involved in Zn/H-
MFI zeolite prepared by impregnation with aqueous solution of
Zn(NO3)2, i.e. small ZnO clusters inside the pores, large ZnO clus-
ters on the external surface, and zinc cations (Zn2+ or ZnOH+)
[22]. Ni and coworkers prepared nano-sized H[Zn,Al]ZSM-5 zeolite
by direct synthesis and found that the direct synthesis method was
beneficial to the dispersion of zinc species and part of zinc intro-
duced was incorporated into the zeolite framework [23].
Although a great deal of efforts has been devoted to investigate
zinc states in zeolites, the nature of zinc species in Zn-containing
HZSM-5 and their effect on the subsequent catalytic performance
are still under debate. Biscardi and coworkers suggested that the
ZnOH+ species was unstable and might react further with acidic
–OH groups to form active zinc species bridging two oxygen atoms
(O –Zn2+–O ) [24]. Through pyridine adsorption on Zn-modified
HZSM-5, Yakerson and coworkers gave the similar conclusion that
one Zn2+ cation could replace two protons and interact with two Al
sites [25]. El-Malki and coworkers found that the structure of zinc
species in Zn/HZSM-5 was related to the Si/Al ratio; zinc could be
stable in cationic exchange positions, either for compensating the
charge of two Al-centered tetrahedrons or being ligated with one
internal silanol or –OH group [16]. Kamarudin and coworkers
reported that the Zn2+ cations interacted with extraframework alu-
minum (AlO)+, forming Zn(OAl)2 and Si(OH)Al [26]. Penzien and
coworkers carried out stepwise zinc ion exchange of BEA zeolite
and found that the zinc species in BEA could be present as Zn2+
incorporated in the vicinity of two framework aluminum atoms,
(Zn–O–Zn)2+ created at nearby framework aluminum pairs, and
ZnO, depending on the zinc concentration [27].
In this work, Zn-containing HZSM-5 zeolites (Zn/ZSM-5) were
prepared by four methods including impregnation (IM), ion
exchange (IE), physical mixing with ZnO (PM), and direct synthesis
(DS). The Zn/ZSM-5 zeolites obtained by various methods were
characterized by X-ray diffraction (XRD), nitrogen physical sorp-
tion, scanning electron microscope (SEM), Fourier transform infra-
red (FT-IR) spectra, temperature programmed desorption of NH3
(NH3-TPD), ultraviolet–visible diffuse reflectance spectra (UV–vis
DRS), X-ray photoelectron spectroscopy (XPS), and X-ray absorp-
tion spectroscopy (XAS). The influence of preparation method for
introducing zinc on the distribution of acid sites, the nature of zinc
species, and the subsequent catalytic performance of Zn/ZSM-5 in
MTA was investigated; the relationship between the existence
state of zinc species and the aromatization activity was then
elucidated.
2. Experimental
2.1. Catalyst preparation
ZSM-5 zeolite was synthesized with the molar composition of
SiO2:0.011 Al2O3:0.02 Na2O:0.15 TPAOH:30 H2O, from the mixture
of sodium hydroxide (NaOH), silica sol (40 wt.% SiO2, 0.4 wt.%
Na2O), sodium aluminate (NaAlO2, Al2O3 P 41.0 wt.%), and tetra-
propylammonium hydroxide (TPAOH, 48.67 wt.% in aqueous solu-
tion). To obtain zeolites with a uniform particle size, 0.2 wt.%
silicalite-1 seeds, prepared by following the procedures of Li and
coworkers [28], was added to the above-mentioned synthesis gel.
The crystallization was conducted at 170 °C for 40 h in a Teflon-
253
lined stainless steel autoclave under rotation (20 r/min). The solid
products were recovered by centrifugation and washing with de-
ionized water repeatedly until the mother liquid showed a pH
value of 7–8, followed by drying at 110 °C overnight and calcina-
tion at 550 °C for 10 h in air. The ZSM-5 zeolite in hydrogen form
(HZSM-5) was obtained through ion-exchanging with aqueous
NH4NO3 solution (1 M, m(liquid)/m(solid) = 40) at 80 °C for 4 h
and subsequent calcination at 550 °C for 6 h.
Zn(IM)/ZSM-5 was prepared by incipient wet impregnation of
HZSM-5 in Zn(NO3)2 solution, followed by drying at 100 °C over-
night and calcination at 550 °C for 6 h in air. Zn(IE)/ZSM-5 by ion
exchange was obtained through stirring HZSM-5 powder in
Zn(NO3)2 solution (0.1 M, m(liquid)/m(solid) = 40) at 80 °C for 6 h,
and then filtrating, drying and lastly calcinating at 550 °C for 6 h.
Zn(PM)/ZSM-5 was acquired by mechanically grinding the physical
mixture of HZSM-5 and ZnO powder and subsequent calcination at
550 °C for 6 h. Zn(DS)/ZSM-5 was directly synthesized in a similar
way as HZSM-5, by adding a desired amount of Zn(NO3)2 in the
synthesis gel.
2.2. Catalyst characterization
The actual amount of zinc element in the Zn/ZSM-5 zeolites was
determined by inductively coupled plasma atomic emission spec-
troscopy (ICP-AES, Autoscan16, TJA).
Nitrogen adsorption/desorption isotherms were measured at
195.8 °C on a BELSORP-max gas adsorption analyzer. Prior to
the measurement, the zeolite sample was degassed under high
vacuum at 300 °C for 8 h. The surface area was calculated from
the adsorption branch in the range of relative pressure from 0.05
to 0.25 by Brunauer–Emmett–Teller (BET) method and the pore
size distribution was derived from the adsorption branch by Bar-
rett–Joyner–Halenda (BJH) method. Pore volume was estimated
at a relative pressure of 0.99.
X-ray powder diffraction (XRD) patterns were collected on a
Rigaku MiniFlex II desktop X-ray diffractometer with monochro-
mated Cu Ka radiation (154.06 pm, 30 kV, and 15 mA). By assum-
ing that the zeolite sample having the largest peak area in the
range of 2h from 22° to 25° (here it was HZSM-5) as a reference
had a crystallinity of 100%, the relative crystallinity of each zeolite
sample was then estimated by comparing its total peak area in this
2h range with that of the reference sample.
Temperature programmed desorption of NH3 (NH3-TPD) was
performed on a Micromeritics AutoChem II 2920 chemisorption
analyzer. Approximately 100 mg of the zeolite sample was used
in each measurement, which was first pretreated at 550 °C for
2 h in an argon stream (30 ml/min) and then cooled down to
120 °C. Saturated adsorption of NH3 on the zeolite sample was then
achieved by introducing gaseous NH3 (5 vol% in argon, 30 ml/min)
into the sample tube for 30 min. After that, the physically adsorbed
NH3 was removed by flushing the sample tube with an argon flow
(30 ml/min) at 120 °C for 2 h. To get the NH3-TPD profile, the zeo-
lite sample was then heated up from 120 to 550 °C at a ramp of
10 °C/min; the amount of NH3 released during the heating for
desorption was measured by a thermal conductivity detector
(TCD). The quantities of strong, medium, and weak acid sites are
measured by the amounts of ammonia desorbed at 300–550,
200–300, and 120–200 °C, respectively, through integrating the
NH3-TPD profile in each temperature interval.
Fourier transform infrared (FT-IR) spectra were measured on a
Bruker Tensor 27 FT-IR spectrometer. The zeolite sample was first
pressed into a self-supported wafer. Prior to the measurement, the
sample cell was evacuated to 10 2 Pa at 450 °C for 2 h; the IR spec-
tra were then recorded at room temperature. To get the FT-IR spec-
tra for pyridine adsorption (Py-IR), pyridine vapor was introduced
into the cell at room temperature for 1 h; the spectra were then
254 X. Niu et al. / Microporous and Mesoporous Materials 197 (2014) 252–261

recorded after evacuation at 150 °C for 1 h. The concentrations of decomposition of methanol to carbon oxides [32]. To minimize
different acidic sites were calculated by following the procedures the negative effect of zinc on the MTA reaction, the content of zinc
reported by Madeira and coworkers [29]. in the Zn-containing HZSM-5 zeolites is controlled at around
Diffuse reflectance ultraviolet–visible spectra (UV–vis DRS) 1 wt.%, as listed in Table 1. For the Zn(IE)/ZSM-5 zeolite prepared
were measured on a Varian Cary 300 Scan UV–vis spectrophotom- by ion-exchange and Zn(PM)/ZSM-5 by physical mixing, the sur-
eter equipped with an integration sphere. face zinc contents determined by XPS are obviously higher than
The scanning electron microscopy (SEM) image to characterize the bulk ones measured by ICP (Table 1), suggesting that the zinc
the surface morphology of the as-prepared zeolite sample was species in Zn(IE)/ZSM-5 and Zn(PM)/ZSM-5 is concentrated on
taken on a field emission scanning electron microscope (FESEM, the HZSM-5 zeolite surface. For the Zn(DS)/ZSM-5 zeolite by direct
JSM 7001-F, JEOL, Japan). synthesis and Zn(IM)/ZSM-5 by impregnation, however, the zinc
X-ray photoelectron spectroscopy (XPS) was recorded on a contents determined by XPS are only slightly higher than those
Thermo ESCALAB 250 spectrometer with Al Ka radiation source by ICP. Such a result suggests that in Zn(DS)/ZSM-5 and Zn(IM)/
(hm = 1486.6 eV) and a multichannel detector. Approximately ZSM-5, more zinc is admitted in the zeolite channels and less is
100 mg of the powder sample was compressed into a wafer for concentrated on the zeolite surface, compared with that in
analysis. The binding energy (BE) values were calibrated with the Zn(IE)/ZSM-5 and Zn(PM)/ZSM-5.
signal of contaminated carbon C 1s at 284.6 eV. The detailed Zn
2p3/2 spectra were measured in the ranges of 1030–1018 eV. The
spectra were decomposed by using XPSPEAK software (Ver. 4.1)
after applying a Shirley background subtraction and Gaussian Table 1
(80%)–Lorentzian (20%) decomposition parameters. Atomic ratios Textural properties of HZSM-5 and Zn-containing HZSM-5 zeolites prepared by
were calculated from the peak areas that were calibrated by the different methods.
sensitive factors provided by the equipment manufacturer. Sample Crystallinity Zn content SBET Vmicro Vmeso
X-ray absorption fine structure (XAFS) measurements were car- (%) (wt.%) (m2 g 1
) (cm3 g 1
) (cm3 g 1
)
ried out at the BL14W1 beam line in Shanghai Synchrotron Radia- ICP XPS
tion Facility (SSRF). The extended X-ray absorption fine structure
HZSM-5 100 0 0 390 0.188 0.068
(EXAFS) spectra were analyzed following a standard procedure of Zn(IE)/ 98.2 1.16 1.60 376 0.165 0.085
data reduction and least-square fitting by using the IFEFFIT code ZSM-5
[30]; the phase and amplitude function was calculated by using Zn(DS)/ 93.9 0.98 1.11 364 0.156 0.117
ZSM-5
the FEFF 9.0 code [31]. The structure parameters were calculated
Zn(IM)/ 95.6 1.13 1.15 362 0.172 0.051
in R-space with k = 3–11.5 Å–1, dk = 2, and kweight = 3, using a first ZSM-5
coordination sphere of oxygen atoms and a second coordination Zn(PM)/ 95.7 1.02 1.47 377 0.170 0.050
sphere of zinc or silica atoms, where the mean coordination num- ZSM-5
ber was individually determined in each case. Note: SBET, BET surface area; Vmicro, micropore volume determined by t-plot; Vmeso,
mesopore volume determined by Vtotal – Vmic; the relative crystallinity is estimated
by comparing the total XRD peak area of a zeolite sample in the range of 2h from 22°
2.3. Catalyst tests and analytic procedures
to 25° with that of the parent HZSM-5 having the strongest diffraction intensity.

The reaction of methanol to aromatics (MTA) was performed in

a continuous flow fixed-bed reactor with an inner diameter of
10 mm. The catalyst sample was pressurized to wafers and then
I * ZnO
crushed and sieved to 20–40 mesh before use. In a typical run,
1.5 g of the zeolite catalyst was loaded and pretreated at the * * e
Intensity (a.u.)

desired reaction temperature for 8 h in a nitrogen flow (60 ml/

d
min); after that, methanol was pumped into the reactor with a
liquid weight hourly space velocity (WHSV) of 3.2 h 1. The reaction c
was carried out at 390 °C and 0.5 MPa.
The gas and liquid products were separated with a cold trap. b
The gaseous products were on-line analyzed by an Aglient 7890A a
gas chromatograph equipped with one thermal conductivity detec-
tor (TCD) and two flame ionization detectors (FID) and two capil- 5 10 15 20 25 30 35 40
lary columns (J&W 127-7031, 30 m  530 lm  0.25 lm; Agilent 2θ
19095P-S25, 50 m  530 lm  15 lm). The liquid organic phase II
was analyzed by another Agilent 7890A gas chromatograph
equipped with a FID and a capillary column (Agilent 19091S-001, e
Intensity (a.u.)

50 m  200 lm  0.5 lm); the liquid aqueous phase, mainly

d
including water, methanol, and oxygenates, was analyzed by the
third Agilent 7890A gas chromatograph equipped with a TCD and c
a FID and a capillary column (Agilent 19091N-136,
b
60 m  250 lm  0.25 lm).
a

3. Results and discussion 30 32 34 36 38 40

3.1. Textural properties and XRD results
The zinc species in HZSM-5 is in general advantageous to the
aromatization of methanol; however, it may also promote the
2θ
Fig. 1. XRD patterns at 2h of 5–40° (I) and scaled-up ones at 2h of 30–40° (II) of
HZSM-5 and Zn-containing HZSM-5 zeolites prepared by different methods: (a)
HZSM-5, (b) Zn(IE)/ZSM-5, (c) Zn(DS)/ZSM-5, (d) Zn(IM)/ZSM-5, and (e) Zn(PM)/
ZSM-5.
 X. Niu et al. / Microporous and Mesoporous Materials 197 (2014) 252–261 255

All HZSM-5 and Zn-containing HZSM-5 zeolites prepared by dif-

ferent methods exhibit similar characteristic diffraction peaks of 250 I e
MFI structure, as shown in Fig. 1(I), suggesting that the introduc-

N2 volume (cm /g)

200 d

3
tion of zinc species in this work has little influence on the frame- c
work structure of the parent HZSM-5. Compared with that of the 150 b
parent HZSM-5, however, Fig. 1(I) also illustrates that the intensity a
of the diffraction peaks of Zn-containing HZSM-5 zeolites is 100
decreased slightly; consequently, as listed in Table 1, the Zn-con- 50
taining HZSM-5 zeolites have a lower crystallinity. The slight
decrease of crystallinity by introducing zinc species should be 0
ascribed to the intermixing of zinc species with HZSM-5 zeolite 0.0 0.2 0.4 0.6 0.8 1.0
0
P/P
rather than any detriment of the crystalline framework.
Although four Zn-containing HZSM-5 zeolites prepared by dif- 0.20 II
ferent methods have a similar bulk zinc content of around 1 wt.%
(Table 1), only very weak diffraction peaks for ZnO at 36.3° and 0.15
31.8° can be discriminated from the XRD patterns of Zn(PM)/ e

ZSM-5 prepared by physical mixing, as illustrated by the scaled-
up XRD patterns at 2h of 30°–40° in Fig. 1(II). The XRD results sug-
gest that the zinc species introduced by ion-exchanging, direct
synthesis, and impregnation are highly dispersed in the parent
HZSM-5, whereas it is difficult to disperse ZnO completely in
monolayer on HZSM-5 surface through the grinding and later heat
treatment of the ZnO and HZSM-5 mixture.
The SEM images of HZSM-5 and Zn-containing HZSM-5 zeolites
shown in Fig. 2 suggest that the introduction of zinc species by post
treatment methods such as impregnation, ion-exchanging, and
physical mixing has little influence on the crystal sizes and the
morphology of the parent HZSM-5 zeolite, which has a crystal size
around 500 nm. The Zn(DS)/ZSM-5 zeolite obtained by direct
hydrothermal synthesis appears in particles of 500 nm, which are
however aggregated from small crystals of around 100 nm
(Fig. 2c). This means that the presence of zinc component in the
synthesis system may have an influence on the nucleation and
crystal growth process, which promotes the formation of nano-
crystals. On the other hand, the SEM picture of Zn(PM)/ZSM-5 zeo-
lite reveals the presence of ZnO crystals with a particle size of 200–
300 nm (Fig. 2e), consistent with the XRD results. Moreover, the
SEM images of ZnO particles were also provided here for a clearer
comparison (Fig. 2f).
dVp/ddp
0.10 d
c
0.05
b
a
0.00
1 10
dp (nm)
Fig. 3. Nitrogen adsorption/desorption isotherms (I) and pore size distribution (II)
of HZSM-5 and Zn-containing HZSM-5 zeolites prepared by different methods: (a)
HZSM-5, (b) Zn(IE)/ZSM-5, (c) Zn(DS)/ZSM-5, (d) Zn(IM)/ZSM-5, and (e) Zn(PM)/
ZSM-5.
Meanwhile, four methods for introducing zinc species are also
different in their influence on the surface area of the resultant
Zn-containing HZSM-5 zeolites, as shown in Table 1. The introduc-
tion of zinc species by four methods all leads to a decrease of sur-
face area, especially for Zn(DS)/ZSM-5 by direct synthesis and
Zn(IM)/ZSM-5 by impregnation. Zn(DS)/ZSM-5 and Zn(IM)/ZSM-5
may have more inaccessible inner micropore surface than Zn(IE)/
ZSM-5 and Zn(PM)/ZSM-5, since in the former two Zn/ZSM-5 sam-
ples, more zinc is admitted in the interior of the zeolite channels, as
revealed by the XPS results.

a b c

d e f

Fig. 2. SEM images of HZSM-5, Zn-containing HZSM-5 zeolites prepared by different methods, and ZnO: (a) HZSM-5, (b) Zn(IE)/ZSM-5, (c) Zn(DS)/ZSM-5, (d) Zn(IM)/ZSM-5,
(e) Zn(PM)/ZSM-5, and (f) ZnO. The images have a magnification of 20,000, with the inserted pictures in a magnification of 100,000 (50,000 for ZnO).
256 X. Niu et al. / Microporous and Mesoporous Materials 197 (2014) 252–261

The porous structure of the Zn-containing HZSM-5 zeolites is
also related to the preparation method for introducing zinc, as
illustrated in Fig. 3. In general, the microporous volume of Zn-con-
taining HZSM-5 zeolites is decreased by the introduction of zinc
species, as the zinc species may be located in the porous channel
and then reduce the accessibility of micropores (Table 1).
It should be emphasized that the mesoporous volume of
Zn(DS)/ZSM-5 by direct synthesis is much higher than that of
the parent HZSM-5 and other Zn-containing HZSM-5 zeolites
(Table 1) and there appears a peak at 5–10 nm in the pore size
distribution diagram of Zn(DS)/ZSM-5 (Fig. 3(II)), which is related
to its agglomerative morphology shown in Fig. 2c, where more
void space is built among the stacked nano-crystals. Ni and
coworkers [23] also observed similar inter-crystalline voids cre-
ated by aggregation of nano-crystals in H[Zn,Al]ZSM-5 and pro-
posed that the inter-crystalline voids might act like intra-
crystalline mesopores, which can effectively alleviate the fast cat-
alyst deactivation due to coke deposition by preventing the
entrance of the micropore from quickly blocking. On the contrary,
the pore size distribution of Zn(IM)/ZSM-5 prepared by impregna-
tion is remarkably narrowed and the pore size becomes much
smaller, compared with other Zn-containing HZSM-5 zeolites.
The shrinkage of pore size in Zn(IM)/ZSM-5 may be ascribed to
the accumulation of a small amount of sub-nanometric ZnO clus-
ters in the channels of HZSM-5 zeolite, which is detrimental to
the effective product diffusion and may accelerate the catalyst
deactivation due to coke deposition. All these suggest that four
Zn-containing HZSM-5 zeolites are also different in the existence
state of zinc species, depending on the preparation method for
introducing zinc.
NH3 desorption (a.u.)
3.2. Acidic properties
The concentration and strength of acid sites in HZSM-5 and Zn-
containing HZSM-5 zeolites are determined by NH3-TPD, as pre-
sented in Fig. 4. Generally, a NH3-TPD profile on HZSM-5 zeolite
shows two desorption peaks, i.e. the high-temperature one located
above 300 °C and the low-temperature one situated below 200 °C,
which are ascribed to ammonia adsorbed on the strong and weak
acid sites, respectively [23]. In this work, the distribution of the
acid sites across the acidic strength is determined by integrating
the NH3-TPD profiles in different temperature intervals, as listed
in Table 2, where the quantities of strong, medium, and weak acid
sites are measured by the amounts of ammonia desorbed at 300–
550, 200–300, and 120–200 °C, respectively.
The introduction of zinc species on HZSM-5 exhibits a signifi-
cant influence on the distribution of acid sites across their acidic
strength, though it has little influence on the total acid quantity
(Table 2). The acidic strength of the Zn-containing HZSM-5 zeolites
is reduced by introducing the zinc species; the extent of tempera-
ture decrease for ammonia desorption follows the sequence of
Zn(IE)/ZSM-5 > Zn(IM)/ZSM-5 > Zn(DS)/ZSM-5 > Zn(PM)/ZSM-5
(Fig. 4). Compared with the parent HZSM-5, it seems that the
amount of the medium acid sites is increased markedly in the
Zn-containing HZSM-5 zeolites at the expense of the strong and
weak acid sites (Table 2); the new medium acid sites should be
ascribed to the interactions between the zinc species and the
intrinsic acid sites in the parent HZSM-5 zeolite. Furthermore,
the quantity of the acid sites with medium strength reduces in
the order of Zn(IE)/ZSM-5 > Zn(IM)/ZSM-5 > Zn(DS)/ZSM-
5 > Zn(PM)/ZSM-5, which may also reflect the degree of the inter-
action between the zinc species and the intrinsic acid sites in the
Zn-containing HZSM-5 zeolites prepared by different methods.
FT-IR spectra in the OH stretching region provide more informa-
tion about the acidic properties. As shown in Fig. 5(I), HZSM-5 con-
tains Brønsted acid groups (3610 cm 1) associated with the
framework aluminum [Si(OH)Al], isolated external silanol groups
(3745 cm 1), free internal silanol groups (3728 cm 1), and delocal-
ized hydrogen-bonded groups (3500 cm 1) of lattice defects

e [22,33]. It is interesting to note that although the external surface

silanol groups (3745 cm 1) are less affected by introducing zinc
d
species, the silanol groups with IR absorption bands at 3728,
c 3610, and 3500 cm 1 are changed considerably, depending on
the preparation methods. Especially, the vibrational intensity at
b 3610 cm 1 is decreased by about 20–35%, suggesting the consump-
tion of protons by introducing the zinc species. For the Zn-contain-
a ing HZSM-5 zeolites, moreover, the vibrational bands at 3728 and
200 300 400 500 3500 cm 1, originated from the internal silanol groups, are also
o severely depressed and even disappear in the IR spectra of
Temperature ( C )
Zn(IE)/ZSM-5 by ion-exchanging and Zn(DS)/ZSM-5 by direct syn-
Fig. 4. NH3-TPD profiles of HZSM-5 and Zn-containing HZSM-5 zeolites prepared by thesis. Such phenomena were attributed to the interaction
different methods: (a) HZSM-5, (b) Zn(IE)/ZSM-5, (c) Zn(DS)/ZSM-5, (d) Zn(IM)/ between the internal silanol groups and ZnOH+ species located in
ZSM-5, and (e) Zn(PM)/ZSM-5. the cationic positions of HZSM-5 zeolite [16], leading to the

Table 2
Acidic properties of HZSM-5 and Zn-containing HZSM-5 zeolites prepared by different methods.
a 1 b 1
Sample Acidity by strength (mmol g ) Acidity by type (mmol g )
Strong Medium Weak Total M/(S + W) Brønsted Lewis L/B
HZSM-5 0.285 0.140 0.138 0.563 0.33 0.172 0.047 0.27
Zn(IE)/ZSM-5 0.193 0.230 0.131 0.554 0.71 0.106 0.266 2.51
Zn(DS)/ZSM-5 0.247 0.178 0.128 0.553 0.47 0.138 0.149 1.08
Zn(IM)/ZSM-5 0.212 0.206 0.136 0.554 0.59 0.129 0.190 1.47
Zn(PM)/ZSM-5 0.246 0.143 0.123 0.512 0.39 0.168 0.093 0.55
a
Density of the acid sites, assorted according to the acidic strength, determined by NH3-TPD. Strong, NH3 desorbed at 300–550 °C; medium, NH3 desorbed at 200–300 °C;
weak, NH3 desorbed at 120–200 °C; M/(S + W), the ratio of the amount of medium acidic sites to that of strong plus weak acidic sites.
b
Density of the acid sites, assorted according to the acidic type, determined by Py-IR. L/B, the ratio of the amount of Lewis acidic sites to that of Brønsted acidic sites.
 X. Niu et al. / Microporous and Mesoporous Materials 197 (2014) 252–261
Absorbance (a.u.)
I 3745 3728 3610
d
b
3800 3700 3600 3500 3400
-1
Wavenumber (cm )
II 1613 1545 1454
Absorbance (a.u.)
b
1700 1650 1600 1550 1500 1450
-1
Wavenumber (cm )
Fig. 5. FT-IR spectra of OH groups (I) and pyridine adsorption (II) on HZSM-5 and
Zn-containing HZSM-5 zeolites prepared by different methods: (a) HZSM-5, (b)
Zn(IE)/ZSM-5, (c) Zn(DS)/ZSM-5, (d) Zn(IM)/ZSM-5, and (e) Zn(PM)/ZSM-5.
formation of ZO–Zn–O–Si species via the reaction of ZO–ZnOH+ +
Si OH ? ZO–Zn–O–Si; such a reaction occurs more preferentially
in Zn(IE)/ZSM-5 and Zn(DS)/ZSM-5 with stronger interaction
between the zinc species and the parent HZSM-5 than that in
Zn(IM)/ZSM-5 and Zn(PM)/ZSM-5.
Chemisorption of pyridine on HZSM-5 leads to a conversion of
Brønsted acid sites into pyridinium ions characterized by the IR
absorption band at 1545 cm 1; meanwhile, the less intense band
at 1454 cm 1 is ascribed to Lewis sites because of the zeolite dehy-
droxylation. By introducing the zinc species, as shown in Fig. 5(II),
the Lewis and Brønsted acid sites are redistributed and more Lewis
acid sites are generated at the expense of the Brønsted acid sites,
confirming the above mentioned interaction between Brønsted
acid sites and zinc ions in the Zn-containing HZSM-5 zeolites.
Moreover, four methods for introducing zinc species also differ
markedly in their effects on the interaction between zinc ions
and Brønsted acid sites, which can be deduced by observing the
ratio of Lewis acidic sites to Brønsted ones, as summarized in
Table 2. The ratio of Lewis acidic sites to Brønsted acidic sites is
increased evidently after introducing zinc into HZSM-5. Depending
on the method for introducing the zinc species, the ratio of Lewis
acidic sites to Brønsted ones follows the sequence of Zn(IE)/ZSM-
5 > Zn(IM)/ZSM-5 > Zn(DS)/ZSM-5 > Zn(PM)/ZSM-5. It is interest-
ing to note that this sequence is the same as that of the amount
of the acid sites with medium strength (Table 2), which may
suggest that the newcome acid sites with medium strength deter-
mined by NH3-TPD originate from the Zn-Lewis species as a result
of the interaction between the zinc ions introduced and the
Brønsted acid sites in the parent HZSM-5 zeolites.
The acid properties of HZSM-5 zeolites were well characterized
by NH3-TPD and IR [34,35] and it was reported that the strong acid
sites are composed of both the protonic and the Lewis acid sites,
whereas the weak acid sites are correlated with the silicon hydro-
xyl characterized by 3724–3740 cm 1 band. From the IR and
NH3-TPD results mentioned above, it may be concluded that
257
220 275 368 I
e
Absorbance (a.u.)
c d
c
b
a a
3300 200 300 400 500 600 700 800
Wavelength (nm)
II
e
FT magnitude k χ(k)
3
3
c 2 e
d
1 c
a b
0 a
1400
0.1 0.2 0.3 0.4 0.5 0.6
Radial distance (nm)
Fig. 6. UV–visible DRS spectra (I) and EXAFS Zn K-edge radial distributions (II) of
Zn-containing HZSM-5 zeolites prepared by different methods: (a) Zn(IE)/ZSM-5,
(b) Zn(IM)/ZSM-5, (c) Zn(DS)/ZSM-5, (d) Zn(PM)/ZSM-5, and (e) ZnO.
through the introduction of the zinc species in HZSM-5, part of
the protonic and silanol hydroxyl reacts with the zinc species,
forming the Zn-Lewis acid sites with medium strength at the
expense of strong and weak protonic acid sites. Depending on
the preparation method for introducing zinc species, the quantity
of the newcome acid sites with medium strength (most likely,
the Zn-Lewis ones) in the Zn-containing HZSM-5 zeolites follows
the sequence of Zn(IE)/ZSM-5 > Zn(IM)/ZSM-5 > Zn(DS)/ZSM-
5 > Zn(PM)/ZSM-5, which are related to the interaction between
zinc ions and Brønsted acid sites.
3.3. State of zinc in HZSM-5
Fig. 6(I) shows the UV–vis DRS spectra of the Zn-containing
HZSM-5 zeolites prepared by different methods. Three main
absorption bands are identified at 368, 275 and 220 nm. The band
at about 368 nm, corresponding to the band gap width of macro-
crystalline ZnO [36,37], appears in the spectra of Zn(IM)/ZSM-5
prepared by impregnation and especially Zn(PM)/ZSM-5 by physi-
cal mixing. The band around 275 nm, attributed to ZnO cluster
with a diameter around 10 Å [38,39], is observed in the spectra
of Zn(DS)/ZSM-5 by direct synthesis, Zn(IM)/ZSM-5 by impregna-
tion and Zn(PM)/ZSM-5 by physical mixing, indicating the pres-
ence of ZnO clusters located in the channels of these zeolites. On
the other hand, the absorbance at about 220 or 195 nm is evident
in all four Zn-containing HZSM-5 zeolites, which should be
ascribed to the zinc species tightly interacted with the parent
HZSM-5. Although the absorption bands below 230 nm have been
assigned to the framework zinc species [23,40], it is more reason-
able to ascribe these broad bands to the charge transfer transition
of zinc species with lattice O2–, taking the various preparation
methods used in this work into consideration. Meanwhile, it
should be noted that in Zn(IE)/ZSM-5 prepared by ion exchange,
no evidence is provided for the presence of bulk and nanoparticle
ZnO species by the UV–vis spectra.
258 X. Niu et al. / Microporous and Mesoporous Materials 197 (2014) 252–261
1021.8
e electron clouds, which is smaller than the distance between nuclei,
d 1023.4
Intensity (a.u.)
c 1022.6
1023.6
1023.4
b around Zn in Zn(IM)/ZSM-5, Zn(IE)/ZSM-5, and Zn(DS)/ZSM-5 are
1022.8
1023.7
a
1028 1026 1024 1022 1020 1018
Binding energy (eV)
Fig. 7. XPS spectra of Zn (2p3/2) of ZnO and Zn-containing HZSM-5 zeolites prepared
by different methods: (a) Zn(IM)/ZSM-5, (b) Zn(IE)/ZSM-5, (c) Zn(PM)/ZSM-5, (d)
Zn(DS)/ZSM-5, and (e) ZnO.
The Zn (2p3/2) XPS spectra of Zn-containing HZSM-5 zeolites are
compared with that of pure ZnO, as illustrated in Fig. 7. Depending
on the preparation method, the distinct variation of the XPS spec-
tra in shape and position demonstrates that the prepared method
for introducing zinc species has a significant influence on the exis-
tent state of the surface zinc species. By fitting the XPS spectra, two
types of zinc species are discriminated in the Zn-containing HZSM-
5 zeolites, with binding energies around 1023.4 and 1022.8 eV. As
pure ZnO shows a peak at 1021.8 eV, it is reasonable to attribute
the lower binding energy peaks around 1022.8 eV in Zn(IM)/
ZSM-5 (by impregnation) and Zn(PM)/ZSM-5 (by physical mixing)
to ZnO species, as suggested by the UV–vis spectra. The shift of this
peak for ZnO species to higher binding energy in the Zn-containing
HZSM-5 zeolites is possibly related to the effect of zeolite frame-
work on the ZnO species, as the framework has much stronger
electronegativity than O2– group [36,41].
On the other hand, the peaks at higher binding energy (around
1023.4 eV) suggest the presence of the zinc species having tighter
interaction with the parent zeolite framework. Chen and cowork-
ers attributed the high binding energy peak to ZnOH+ species
[41], which is formed from the strong interaction between the zinc
species and the protonic acid sites. It seems that this kind of zinc
species with high binding energy is exclusive in Zn(IE)/ZSM-5
(from ion-exchanging) and Zn(DS)/ZSM-5 (from direct synthesis),
though the spectrum of later is more severely broadened because
of the high dispersion of zinc species.
The XPS results also prove that the state and distribution of the
surface zinc species in the Zn-containing HZSM-5 zeolites are
related to the preparation method. In Zn(PM)/ZSM-5, the majority
of surface zinc species is present as ZnO which accounts for about
87%, whereas in Zn(IM)/ZSM-5, the portion of surface ZnO species
is about 28%. For Zn(IE)/ZSM-5 and Zn(DS)/ZSM-5, however, the
zeolite surface is exclusively dominated by the zinc species having
tight interaction with the parent zeolite framework.
As XPS is mainly concerned with the surface chemical state and
composition, XAFS is used to investigate the state of zinc species in
bulk Zn-containing HZSM-5 zeolites, which is effective in deter-
mining the local geometry of metal ions in molecular sieves [42].
The Fourier transform of the Zn K-edge EXAFS for ZnO and Zn-con-
taining HZSM-5 zeolites is illustrated in Fig. 6(II). Because the
radial distance measured by EXAFS is the actual distance between
the peaks in Fig. 6(II) appear at a distance shorter than the actual
interatomic distances. The peak around 1.60 Å for ZnO reference
in the radial distribution, which is attributed to the four nearest
oxygen neighbors, is then corresponding to a Zn–O bond length
of 1.97 Å [24].
Compared with that of ZnO reference, the local structure of zinc
species in the Zn-containing HZSM-5 zeolites is changed signifi-
cantly. For Zn(PM)/ZSM-5 prepared by physical mixing, a decrease
of the Zn–O coordination number to 3.8 can be observed, which is
originated from the dispersion of the bulk ZnO in the HZSM-5 zeo-
lites. On the contrary, the coordination numbers of nearest oxygen
increased to 5.5, 5.8, and 6.3, respectively, accompanied with the
increases of Zn–O distance to 2.02, 2.06, and 2.07 Å, respectively.
This observation is consistent with that reported by Biscardi and
coworkers [24], who further suggested that six coordinated oxygen
atoms around zinc were partly contributed by the weakly bonded
water.
The peak in the EXAFS spectra shown in Fig. 6(II) at longer dis-
tance around 2.95 Å is ascribed to the Zn–Zn connections with the
actual distance of 3.20 Å; depending on the preparation methods,
the second coordination shell around zinc is rather diversified.
For Zn(PM)/ZSM-5 prepared by physical mixing, the distinct peak
at 2.95 Å with some decrease of the coordination number suggests
that most of the zinc species remains as ZnO, but is well dispersed
compared with pure ZnO. Compared with Zn(PM)/ZSM-5, the
shrinkage in the coordination of zinc in Zn(IM)/ZSM-5 by impreg-
nation is much more pronounced, which denotes that only a very
small fraction of zinc is present as ZnO, whereas most of the zinc
species is highly dispersed in the zeolite channel of Zn(IM)/ZSM-
5 or interacted with the acidic sites. For Zn(DS)/ZSM-5 and
Zn(IE)/ZSM-5, however, the second coordination shell of Zn–Zn
connections disappears, indicating that ZnO particles are absent
in the Zn-containing HZSM-5 zeolites prepared by direct synthesis
or ion-exchanging and the zinc atoms here are located at the iso-
lated positions.
The state of zinc in HZSM-5 zeolites has also been the subject of
several recent researches. It was proposed that zinc was present in
ZSM-5 zeolites either as ZnOH+ ions that located on Brønsted sites
[21] or as Zn2+ cations that replaced two protons and interacted
with two Al sites bridged by oxygen ((O –Zn2+–O–) or (Zn–O–
Zn)2+) created at nearby framework aluminum pairs [18,24,43].
However, the (Zn–O–Zn)2+ species was formed from two ZnOH
groups via 2Z–ZnOH ? Z–Zn–O–Zn–Z + H2O, which was strongly
endothermic. Moreover, the formation of binuclear structures
was rather unlikely on HZSM-5 zeolites with high Si/Al ratios
[44,45], considering that the introduction of zinc species has little
influence on the overall quantity of the acid sites determined by
NH3-TPD. If zinc is present as ZnOH+ species, each zinc atom intro-
duced will consume one proton, which is concerned only with one
Al site; as a result, each Al or Zn atom in the Zn-containing HZSM-5
zeolites with different Si/Al and Zn/Al ratios could adsorb one
ammonia molecule [16] and then the introduction of zinc would
have little influence on the amount of ammonia adsorbed for
NH3-TPD. On the contrary, if zinc was present as O––Zn2+–O– spe-
cies, one zinc atom introduced would replace two proton, which
would be concerned with two Al sites; in this way, the overall
ammonia uptake on the Zn-containing HZSM-5 zeolites for NH3-
TPD would be less than that on the parent HZSM-5 [20,24]. The
NH3-TPD results shown in Table 2 and Fig. 4 illustrate that the
overall ammonia uptake of the Zn-containing HZSM-5 zeolites is
comparable with that of the parent HZSM-5, supporting that the
Zn-Lewis species here is in the form of ZnOH+.
 X. Niu et al. / Microporous and Mesoporous Materials 197 (2014) 252–261 259

On the whole, the results mentioned above demonstrate that Table 3

there are mainly two types of zinc species in the Zn-containing Product distributions of methanol to aromatics over HZSM-5 and Zn-containing
HZSM-5 zeolites prepared by different methods.
HZSM-5 zeolites, i.e. ZnO in macro-particles on the zeolite surface
a
or in nano-particles inside the zeolite pores and Zn-Lewis acid sites Samples Production selectivity (%)
(ZnOH+) originated from zinc species strongly interacted with the C–1– C@ @
2 –C5 (C@
2) C+5 non- Aromatics Others
protonic sites. The state and distribution of zinc species in the C–4 b
aromatic
Zn-containing HZSM-5 zeolites differs markedly according to the HZSM-5 39.4 4.5 (8.1) 18.9 35.6 1.6
preparation methods. Zn(PM)/ZSM-5 prepared by physical mixing Zn(IE)/ZSM-5 25.9 6.1 (25.1) 16.1 46.9 5.0
is dominated by ZnO; for Zn(IM)/ZSM-5 prepared by impregnation, Zn(DS)/ZSM- 32.2 4.6 (22.5) 18.6 43.0 1.6
5
most of zinc is present as Zn-Lewis species, though ZnO in nano
Zn(IM)/ZSM- 30.4 5.9 (23.5) 13.8 43.1 6.8
scale dispersed in the zeolite channel can also be recognized; in 5
Zn(DS)/ZSM-5 prepared by direct synthesis and Zn(IE)/ZSM-5 by Zn(PM)/ZSM- 38.6 3.5 (21.6) 18.4 38.1 1.4
ion-exchanging, however, Zn-Lewis acid species is dominant. 5
a
The reaction was carried out at 390 °C and 0.5 MPa with a liquid WHSV of
3.4. Catalytic performance of Zn-containing HZSM-5 in MTA 3.2 h 1; the data were acquired at the time on stream (TOS) of 12.5 h; in all cases,
the conversion of methanol exceeds 99.5%.
b
The numerals for C@2 in parentheses represent for the mass fraction of ethene in
The catalytic performances of HZSM-5 and Zn-containing the C@ @
2 –C5 olefins products.
HZSM-5 zeolites prepared by different methods in methanol to
aromatics (MTA) are illustrated in Fig. 8. The introduction of zinc
species as well as the preparation method exhibits a significant compared with the catalytic lifetime of the parent HZSM-5, which
influence on the catalyst lifetime, methanol conversion, and prod- shows a conversion of methanol higher than 99% in 60 h (Fig. 8(I)).
uct distribution, as also listed in Table 3. The introduction of zinc On the other hand, Zn(DS)/ZSM-5 prepared by direct synthesis as a
species by ion exchanging and physical mixing (Zn(IE)/ZSM-5 catalyst shows the longest lifetime to 120 h, almost double of that
and Zn(PM)/ZSM-5) has little influence on the catalytic stability, for the parent HZSM-5, whereas for Zn(IM)/ZSM-5 prepared by
impregnation, the lifetime is decreased to 40 h. The stability of
various catalysts decreases in the sequence of Zn(DS)/ZSM-
5 > HZSM-5  Zn(IE)/ZSM-5  Zn(PM)/ZSM-5 > Zn(IM)/ZSM-5.
Selectivity to aromatics (%) Conversion of methanol (%)

100 As the deactivation of zeolite catalyst in MTA can be mainly

I
ascribed to the carbonaceous deposition which may block the
e
entrance of micropores and invalidate the active sites, it is specu-
80 a lated that the small particle size and high mesoporous volume
are responsible for the high stability of the Zn(DS)/ZSM-5 catalyst
(Figs. 2 and 3). Li and coworkers prepared the hierarchical meso-
60 porous ZSM-5 and Zn/ZSM-5 zeolites by the post-synthesis with
b
c alkali treatment [46,47]; the catalysts with hierarchical pore struc-
d
40 ture exhibited enhanced activity and stability in aromatization of
1-hexene, as the path for the diffusion of reactants and products
50 was shortened and the opportunity for channel blockage was then
II
reduced. Rownaghi and coworkers [48] also discovered that meso-
40
porous ZSM-5 zeolites had long-term catalytic stability and high
selectivity to alkyl aromatics in methanol to gasoline reaction,
30 d b e compared with the conventional ZSM-5 zeolites. Ni and coworkers
observed that the nitrogen adsorption–desorption isotherms of
20 a
c H[Zn,Al]ZSM-5 prepared by direct synthesis exhibited a hysteresis
loop, which was ascribed to the capillary condensation in inter-
10
crystalline voids created by aggregates of nano crystals [23]; the
0 20 40 60 80 100 120 140 inter-crystalline voids may act in a manner similar to intra-crystal-
Time on stream (h) line mesopores and provide space to deposit cokes and prevent the
micropore entrance from quickly blocking, which endue the
III (b) Zn(IE)/ZSM-5
Selectivity to aromatics (%)

46 H[Zn,Al]ZSM-5 catalyst with long lifetime in MTA. On the other

hand, Zn(PM)/ZSM-5 and Zn(IE)/ZSM-5 are dominated by bulk
44 (d) Zn(IM)/ZSM-5 ZnO on the extra surface of HZSM-5 zeolite and Zn-Lewis acid spe-
42 (e) Zn(DS)/ZSM-5 cies in acid sites, respectively, which have little influence on the
40 (c) Zn(PM)/ZSM-5 porous structure and subsequent mass transfer and diffusion
behaviors. As Zn(IE)/ZSM-5 and Zn(PM)/ZSM-5 resemble the par-
38
ent HZSM-5 in their porous structure and textural properties
36 (Fig. 3), they exhibit similar catalytic stability in MTA with a life
(a) HZSM-5
34 time of about 60 h.
0.0 0.2 0.4 0.6 0.8 1.0 1.2 In Zn(IM)/ZSM-5 obtained by impregnation, however, a small
+
Amount of ZnOH (wt.%) amount of sub-nanometric ZnO clusters may accumulate at the
pore apertures or locate in the channels of HZSM-5 zeolite, besides
Fig. 8. Methanol conversion (I) and selectivity to aromatics (II) of MTA with the the bulk ZnO on the zeolite surface and Zn-Lewis acid species inter-
time on stream (TOS) over HZSM-5 and Zn-containing HZSM-5 zeolites prepared by acted with the protonic acid sites [36]. The presence of ZnO cluster
different methods: (a) HZSM-5, (b) Zn(IE)/ZSM-5, (c) Zn(PM)/ZSM-5, (d) Zn(IM)/
ZSM-5, and (e) Zn(DS)/ZSM-5. Correlation between the selectivity to aromatics at a
with a diameter around 10 Å is approved by the band around
TOS of 12.5 h and the surface amount of ZnOH+ species (III) in the Zn-containing 275 nm in the UV–vis spectra (Fig. 6(I)). Although such fine ZnO
HZSM-5 catalysts prepared by various methods. clusters may also be present in Zn(PM)/ZSM-5, they are probably
260 X. Niu et al. / Microporous and Mesoporous Materials 197 (2014) 252–261
well dispersed on the outer surface of Zn(PM)/ZSM-5 and have lit-
tle influence on the porous structure, as shown in Fig. 3(II); the XPS
results also indicate that more zinc is concentrated on the surface
in Zn(PM)/ZSM-5 than that in Zn(IM)/ZSM-5 (Table 1). That is to
say, the pores in Zn(IM)/ZSM-5 catalyst are remarkably shrunk
due to the deposition of the sub-nanometric ZnO clusters at the
pore apertures or in the channels of HZSM-5, which is detrimental
to the effective product diffusion and may accelerate the catalyst
deactivation due to coke deposition; as a result, the Zn(IM)/ZSM-
5 catalyst exhibits a much shorter life time in MTA than the parent
HZSM-5 and other Zn/ZSM-5 catalysts (Fig. 8(I)).
Meanwhile, the preparation methods for introducing zinc spe-
cies also differ markedly in the selectivity to aromatics for the
resultant Zn-containing HZSM-5 catalysts. In general, the presence
of zinc species in HZSM-5 can enhance the selectivity to aromatics,
as shown in Fig. 8(II). After the MTA reaction comes into the period
with a relatively stable catalyst activity, for example, with a time
on stream of 12.5 h, the selectivity to aromatics over various cata-
lysts follows the sequence of Zn(IE)/ZSM-5 > Zn(DS)/ZSM-
5  Zn(IM)/ZSM-5 > Zn(PM)/ZSM-5 > HZSM-5; Zn(IE)/ZSM-5 pre-
pared by ion exchange gives the maximum selectivity of 46.9% to
aromatics, which is much higher than that of 35.6% on the parent
HZSM-5. However, the selectivity to aromatics decreases gradually
with the time on stream.
The products distribution over various catalysts, as listed in
Table 3, suggests that the presence of zinc not only influences
the selectivity to aromatics, but also the selectivity to light alkanes
and olefins. Over different catalysts, the total selectivity to light
alkanes and olefins shows the reversed tendency compared with
the selectivity to aromatics, suggesting that the formation of aro-
matics may be accompanied by the suppression of light alkanes
and olefins. Ono and coworkers [13] proposed that light olefins
could be dehydrogenated to form aromatics by the zinc ions or
transformed into alkanes and aromatics through hydrogen transfer
reaction under the action of protons. Later, it was found that the
zinc species could also act as a catalyst for the dehydrogenation
of alkanes [49,50]. Therefore, it is rational in this work to assume
that the improvement of the selectivity to aromatics in MTA over
Zn/ZSM-5 by introducing zinc species is related to its ability in
enhancing the catalytic activity for alkanes dehydrogenation. In
addition, the formation of less alkanes over the Zn-containing
HZSM-5 zeolites may also be associated with the alteration in acid-
ity by introducing zinc species, as hydrogen transfer between car-
benium ions and alkenes (or alkanes) is catalyzed by the acid sites.
For methanol conversion over HZSM-5, both aromatic- and ole-
fin-based cycles may contribute to the formation of olefins [6,51];
ethene was predominantly produced via the aromatic-based cycle,
whereas propene and higher alkenes were probably formed to a
considerable extent from successive alkene methylation and crack-
ing reactions via the olefin-based cycle [52]. Table 3 illustrates that
the selectivity to aromatics together with the portion of ethene in
olefins are enhanced over the Zn-containing HZSM-5 catalysts,
which approves the fact that the introduction of zinc species is pro-
pitious to the dehydrogenation of alkenes and alkanes to aromatics
and then strengthens the aromatic-based cycle. In a word, the zinc
species incorporated into the parent ZSM-5 is effective in suppress-
ing hydrogen transfer reaction, reducing the generation of alkanes,
and promoting the aromatization of alkenes, which all contribute
to low yield of light alkanes and high selectivity to aromatics over
the Zn-containing HZSM-5 zeolites.
3.5. Active zinc species for the formation of aromatics from methanol
MTA is a complicated process which involves various reactions
like dehydration, oligomerization, methylation, cracking, hydrogen
transfer, dehydrogenation, and cyclization [53,54]. Brønsted acid
sites in zeolites are essential for the formation of olefins from
methanol, which then undergo dehydro-cyclooligomerization and
hydrogen transfer reactions to generate aromatics and alkanes.
The introduction of zinc species is able to reduce the Brønsted acid
sites, leading to the formation of less alkanes by inhibiting the
hydrogen transfer reaction. Moreover, the Zn-Lewis sites origi-
nated from the introduction of zinc were also favorable for the
dehydrogenation of alkenes to aromatics [15]. As a result, the for-
mation of aromatic products is related to both the Brønsted acid
sites and the Zn-Lewis species. Song and coworkers [55] proposed
that the strong acid sites were necessary for the transformation of
methanol, ethanol and olefins to aromatics, whereas the inter-con-
version of olefins was catalyzed both by strong and weak acid sites
over HZSM-5 zeolites. After poisoning of some strong acid sites,
HZSM-5 showed much lower aromatization activity in MTA; how-
ever, HGaMFI zeolites exhibited high aromatization activity due to
the high dehydrogenation activity of metal Ga [56]. The introduc-
tion of zinc species causes a decrease of the strong acid sites, which
is however compensated by the zinc metal centers with high activ-
ity for dehydrogenation and aromatization. The formation of aro-
matics from methanol over the Zn-containing HZSM-5 zeolites is
then attributed to the synergy between the Brønsted and the Zn-
Lewis acid sites.
As summarized above, in the Zn-containing HZSM-5 zeolites,
zinc is mainly present as ZnO and ZnOH+ species. Because
Zn(PM)/ZSM-5 prepared by physical mixing, which is dominated
by ZnO, exhibits the worst activity for aromatization, it is specu-
lated that ZnO is inactive for MTA. Rojasová and coworkers [57]
found that ZnO as an extra-framework phase was an inactive com-
ponent in ZnO/ZSM-5 for n-hexane aromatization. Berndt and
coworkers also thought that ZnO species was inactive in conver-
sion of propane to aromatics [21]. Therefore, in this work, the
ZnOH+ species are suggested as the active component in the Zn-
containing HZSM-5 catalysts for MTA; moreover, the content of
surface ZnOH+ species can be estimated from the decomposition
of the XPS spectra (Fig. 7). If the amount of surface ZnOH+ species
in the Zn-containing HZSM-5 zeolites is correlated with the selec-
tivity to aromatics, as shown in Fig. 8(III), it is clearly illustrated
that the selectivity to aromatics over various catalysts is enhanced
almost linearly with the amount of ZnOH+ species, no matter what
method is used to introduce the zinc species.
In summary, the introduction of zinc species to HZSM-5 is effec-
tive in enhancing the aromatization activity for MTA through two
approaches: on the one hand, ZnOH+ species is formed, which is
active for the dehydrogenation of light hydrocarbons; on the other
hand, zinc cations may reduce the Brønsted acid sites, which is
helpful in suppressing the formation of alkanes by inhibiting the
hydrogen transfer reaction. The enhancement of the selectivity to
aromatics is linearly related to the amount of ZnOH+ species in
the Zn-containing HZSM-5 zeolites, no matter what method is used
to introduce the zinc species. Zn(IE)/ZSM-5 prepared by ion
exchange is provided with the highest fraction of surface ZnOH+
species and then also gives the highest selectivity to aromatics.
4. Conclusions
Zn-containing HZSM-5 zeolites were prepared by four methods
including impregnation, ion exchange, physical mixing with ZnO,
and direct synthesis; the influence of preparation method on their
textural and acidic properties, existence state of zinc species, as
well as catalytic performance in MTA was investigated.
The results indicated that Lewis acid sites of zinc species
(ZnOH+) are formed by introducing zinc into HZSM-5, at the
expense of the silanol hydroxyl and proton acid sites. The distribu-
tion of acid sites and the nature of zinc species as well as the sub-
sequent catalytic performance are significantly influenced by the
 X. Niu et al. / Microporous and Mesoporous Materials 197 (2014) 252–261
preparation method for introducing zinc. In Zn(PM)/ZSM-5 pre-
pared by physical mixing, zinc is mainly present as macro ZnO
particles and trace ZnOH+ is formed by solid state reaction; in
Zn(IM)/ZSM-5 by impregnation, ZnOH+ is the main ingredient,
with nano ZnO clusters dispersed in the zeolite channel; in
Zn(IE)/ZSM-5 and Zn(DS)/ZSM-5, however, only ZnOH+ species
are identified.
Owing to the small particle size and high mesoporous volume of
the Zn(DS)/ZSM-5 zeolite prepared by direct synthesis, it exhibits
the longest catalytic lifetime in MTA, almost double of that for
the parent HZSM-5. The inter-crystalline voids may act in a man-
ner similar to intra-crystalline mesopores and provide certain
space to deposit cokes and prevent the micropore entrance from
quickly blocking. On the contrary, the sub-nanometric ZnO clusters
in Zn(IM)/ZSM-5 at the pore apertures or in the channels of HZSM-
5 may prohibit the product diffusion and deteriorate the catalyst
deactivation, which endue the Zn(IM)/ZSM-5 catalyst with a much
shorter life time in MTA.
The amount of surface ZnOH+ species in the Zn-containing
HZSM-5 zeolites is decisive to the selectivity to aromatics from
methanol. There is a linear correlation between the amount of sur-
face ZnOH+ species and the selectivity to aromatics for MTA over
the Zn/ZSM-5 catalysts prepared by different methods. ZnOH+
species may act as the active sites for the dehydrogenation of light
hydrocarbons and meanwhile, zinc cations can reduce the
Brønsted acidity, which is also helpful in suppressing the formation
of alkanes by inhibiting the hydrogen transfer reaction. Zn(IE)/
ZSM-5 prepared by ion exchange is provided with the highest
fraction of surface ZnOH+ species and then also gives the highest
selectivity to aromatics.
Acknowledgments
The authors are grateful for the help with EXAFS measurements
by Dr S. Zhang and Prof. Y. Huang at Shanghai Synchrotron
Radiation Facility. This work is financially supported by National
Basic Research Program of China (2011CB201400), the National
Natural Science Foundation of China (21273263, 21273264,
21227002), and Natural Science Foundation of Shanxi Province of
China (2012011005-2, 2013021007-3).
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