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In Situ Synthesis of Metal-Containing ZSM‑5 and Its Catalytic

Performance in Aromatization of Methanol
Yanjun Zhang, Yao Liu, and Jianwei Li*

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ABSTRACT: Metal-containing ZSM-5 zeolites, denoted as M/

ZSM-5 (M = Ga, Zn, and La), were prepared by an in situ
synthetic method. The structural, textural, and surface acid
properties of M/ZSM-5 were characterized by XRD, N 2
adsorption−desorption, NH3-TPD, and FT-IR. The catalyst pore
size and the distribution of strong acid and weak acid were affected
by the introduction of metal. Considering the methanol-to-
aromatics model reaction, the catalytic performance of these
samples was investigated in a fixed bed reactor under the
conditions of 450 °C and a liquid weight hourly space velocity
(WHSV) of 5 h−1. The results indicated that the Zn/ZSM-5 molecular sieve was most beneficial to aromatization; the relationship
between the change of B/L caused by Zn content and aromatics selectivity was further studied. When the B/L value decreased, the
selectivity of aromatics showed an initial increase and then a decrease. The B/L value was optimal, and the aromatics yield was the
highest when the Zn loading was 0.35%.

1. INTRODUCTION the ZSM-5 molecular sieve by impregnation and isomorphous

Benzene, toluene, and xylene (BTX) are widely used as substitution methods, separately. The experimental results
important industrial intermediates with increasing demand showed that H [Zn, Al] ZSM-5/SiO 2 obtained by
every year.1−3 The main methods for producing BTX are isomorphous substitution possessed more strong and medium
catalytic reforming and steam cracking of naphtha.4,5 However, acid sites, beneficial to cyclization and aromatization in the
as petroleum resources are limited with erratic prices, it is of methanol-to-aromatics (MTA) reaction. The presence of more
paramount importance for governments and researchers to find intercrystalline voids improved the carbon deposition resist-
a nonoil route to produce these aromatics. In recent years, ance of the catalyst. Niu et al.20 synthesized Zn-containing
methanol has been able to be obtained from various resources HZSM-5 zeolites by ion exchange, impregnation, mechanical
such as coal and biomass, resulting in an overcapacity of mixing, and direct synthesis, separately, to influence the nature
methanol.2,6,7 Coincidentally, methanol aromatization can of the Zn species and acid distribution. Molecular sieves
solve the problem of the BTX shortage and excess methanol. synthesized by direct synthesis with small particle size and high
Methanol aromatization is a complex reaction system mesoporous volume with a suitable ratio of B acid to L acid
involving numerous side reactions. The distribution and exhibited the highest selectivity for aromatics and the longest
content of methanol aromatization products are related to catalytic lifetime. The ZSM-5 molecular sieve with low Si/Al is
the reaction conditions, molecular sieve structure, and suitable for the MTA reaction, but when the content of
acidity.8−10 In the methanol aromatization reaction, the framework aluminum is low, the degree of metal cation
ZSM-5 molecular sieve has become the most promising exchange by the ion exchange method is limited,21 and the
catalyst due to its superior shape-selective catalytic perform- metal species formed by the impregnation method exist as
ance, hydrothermal stability, and adjustable acidity.11−14 Many large metal oxide clusters that block the pores or cover the
researchers have modified the ZSM-5 molecular sieve to external surface.22 The metal distribution of in situ synthesis is
improve the yield of aromatic hydrocarbons using methods
such as hydrothermal modification, acid−base modification,
metal modification, etc.15−18 Among them, metal modification Received: March 10, 2022
has shown the most improvement in catalytic performance to Accepted: June 24, 2022
achieve a higher aromatics yield. Published: July 10, 2022
The methods of synthesizing a metal bifunctional ZSM-5
molecular sieve include dipping, ion exchange, and isomor-
phous substitution. Pan et al.19 successfully introduced Zn into
© 2022 The Authors. Published by
American Chemical Society https://doi.org/10.1021/acsomega.2c01442
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more dispersed, and the synthesis is more convenient, omitting ments, the samples were outgassed under a vacuum of 1.33
the postprocessing step. × 10−3 Pa at 300 °C for 12 h. The external surface area and
Su et al.23 obtained nanosized H-ZSM-5 zeolites isomor- microporous volume were calculated with the BET equation
phously substituted by Ga and tested their catalytic perform- and the t-plot method, respectively. The mesopore size e
ances in the 1-hexene and FCC gasoline aromatization. The Ga distributions were calculated with the Barrett−Joyner−
isomorphous substitution can facilitate the formation of both B Halenda (BJH) equation.
and L acid sites, leading to higher aromatic yield. Zhang et al.24 The NH3-temperature-programmed desorption (TPD)
prepared an Fe-modified ZSM-5 via a direct method used for experiments were performed in a Quantachrome automated
the conversion of biomass to light olefins, with the results chemisorption analyzer. The TPD profiles were obtained over
showing that the Fe-modified ZSM-5 catalyst increased the a temperature range from 40 to 800 °C at a constant heating
olefins yield significantly. These above experiments prove that rate of 10 °C/min. The pyridine adsorption infrared
transition metals can be synthesized in situ into molecular spectroscopy (Py-IR) of the sample molecular sieve was
sieves to provide excellent catalytic properties. carried out using an Avatar 360 (Nicolet instrument), which
In this work, we introduced three metals (Ga, La, and Zn) measures the distribution of B acid and L acid on the sample
by in situ synthesis, a process more convenient than ion molecular sieve and records the vibration of the molecular
exchange and impregnation, to investigate the effects of these sieve skeleton.
three kinds of metals and Zn content on the reaction of The X-ray photoelectron spectroscopy (XPS) of the samples
methanol to aromatics. The relationship between the B/L of was carried out using an ESCALAB250 (Thermo instrument).
molecular sieves with different Zn contents and their aromatic The test conditions used were as follows: the Al target was an
selectivity was studied. The results provide a reference for a anode, the test voltage was 10 kV, and the current was 20 mA.
simple preparation method of metal-containing molecular The electron binding energy of C 1s of graphite carbon was set
sieves and suitable metal loading used in the methanol-to- to 284.8 eV, and the measured binding energy was corrected
aromatics reaction. by this value.
2.3. Catalyst Testing in the MTA Reaction. The
2. EXPERIMENTAL SECTION experiment was carried out by using MTA as a model reaction.
2.1. Synthesis of the M/ZSM-5 Molecular Sieve. ZSM- These prepared molecular sieve catalysts were evaluated in a
5 zeolite was synthesized with the molar composition of self-made stainless steel fixed bed reactor (L = 300 mm, Φ16 ×
SiO2:0.026Al2O3:0.2Na2O:0.15NaCl:0.2DEA:25H2O from a 3 mm) under atmospheric pressure at 450 °C, with a single
mixture of sodium hydroxide (NaOH, AR), sodium chloride methanol feed. A fixed weight of catalyst (3.5 g) with a 40−60
(NaCl, AR), silica sol (40 wt % SiO2, 0.4 wt % Na2O), mesh was put in the constant temperature zone of the stainless
aluminum sulfate octadecahydrate (Al2(SO4)3·18H2O, AR), steel reactor monitored with a thermocouple and packed with
and diethylamine (DEA, AR). The prereaction and the inert filler quartz sand with a 40−60 mesh at both ends. The
crystallization were conducted at 100 °C for 24 h and 170 catalyst was preheated to the desired temperature for 6 h in a
°C for 72 h in a rotating Teflon-lined stainless steel autoclave flowing nitrogen atmosphere (71 mL/min). The nitrogen gas
(200 rpm), respectively. The solid products were recovered by was turned off at the beginning of the reaction, and the raw
centrifugation and washed with deionized water repeatedly material was pumped into the reactor with a liquid weight
until the mother liquid showed a pH value of 7−8, followed by hourly space velocity (WHSV) of 5 h−1. The reaction was
drying at 100 °C overnight and calcination at 550 °C for 6 h in started at 450 °C; the products were condensed and separated
air. The hydrogen type ZSM-5 zeolite was obtained through by a gas−liquid separator, and the liquid and gas products were
ion-exchanging with an aqueous NH4NO3 solution at 80 °C analyzed by an EWAI GC-4000A instrument connected to an
for 12 h and subsequent calcination at 550 °C for 4 h. The FID detector and an EWAI GC-4000A instrument equipped
HZSM-5 zeolite is marked S-0. with TCD detectors, respectively. The methanol conversion
Selected amounts of GaCl3·6H2O, La(NO3)3·6H2O, or and product selectivity were obtained based on the GC results.
ZnCl2 are added to the above sol (before transfer to autoclave) The calculation formula is as follows:
to obtain S-1 (0.15% Ga), S-2 (0.15% La), S-3 (0.15% Zn), S-4 maro
(0.35% Zn), and S-5 (0.5% Zn), separately, following the steps yield = × 100%
mCH3OH,in
above. The metal loading percentage of the catalyst is the
proportion of the modified metal element in the dry basis of
nimi /M i
the feed. selectivity = × 100%
2.2. Characterization of Samples. The crystallographic (mCH3OH,in mCH3OH,out )/MCH3OH
structures of prepared samples were determined from X-ray
diffraction (XRD) patterns collected with a Bruker D8 Here, maro is the mass of aromatics (benzene, methyl-
Advance diffractometer using Cu Kα (k = 1.5406 Å) radiation benzene, and trimethylbenzene), ni is the number of C
with a fixed power source (40 kV, 40 mA) and 2θ range from contained in product i, mi is the mass of product i, and Mi is
5° to 50°. The relative crystallinity (%) was calculated from the the relative molecular mass of product i.
area in the diffraction angles of 2θ = 23.1°, 23.3°, 23.7°, 23.9°,
and 24.4°, where the area of the S-0 sample was defined as 3. RESULTS AND DISCUSSION
100%. The chemical compositions of the samples were 3.1. Characterization of the ZSM-5 Catalysts. Metal-
determined by X-ray fluorescence (XRF) spectroscopy on a containing ZSM-5 molecular sieves were prepared by an in situ
PANalytical B V Axios-Advanced instrument. synthetic method. Figure 1 shows the XRD patterns of
N2 adsorption−desorption isotherms of the samples were different samples each with different diffraction peak intensities
tested using a TPDRO1100 Series apparatus (Thermo but all containing the characteristic peaks of the MFI structure.
Instruments). Before performing the adsorption measure- The introduction of the metal in situ did not change the
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energies of Zn (2p3/2) in S-3, S-4, and S-5 were 1022.14,

1022.72, and 1022.45 eV, respectively. The electron binding
energy of Zn-halides (2p3/2) (electron binding energy =
1022.2−1023.0 eV) is relatively close to and slightly larger
than that of the pure ZnO (2p3/2) (electron binding energy is
1021.7−1022.5 eV), indicating that the presence of Zn species
on the surface of the Zn-loaded molecular sieve might be
affected by groups more electronegative than O2−, such as
Zn(OH)+, which are favorable for dehydrogenation.25−27
Table 2 shows that the growth rate gradually decreased, and
the Zn content on the surface of the molecular sieve increased
with increasing Zn loading. The chemical content change was
related to the amount of Zn in the bulk phase as measured by
XRF characterization. The loading ratio of silicon to aluminum
on the surface of the molecular sieve gradually decreased with
the increase in Zn loading, indicating that the surface of the
Figure 1. XRD patterns of M/ZSM-5 zeolites by an in situ synthetic
method. molecular sieve was desiliconized and supplemented with
aluminum, possibly caused by aluminum migration to the
structure of the ZSM-5 skeleton. The metal species loading surface and enrichment of the molecular sieve framework.
weakened the intensity of the diffraction peak and decreased Figure 3 shows the N2 adsorption−desorption curves for
the crystallinity of the molecular sieve compared with S-0. The different samples; there are no significant differences between
different Zn contents led to different amounts of crystallinity in the metal-loaded molecular sieve and the unmodified one. The
the samples (S-4 > S-3 > S-5), but no significant metal curves display a type I isotherm, characteristic of the
diffraction peaks were observed, indicating that the metal microporous molecular sieve.6 The tiny hysteresis loops
species introduced by the in situ synthetic method were highly observed with the S-2 molecular sieve might be caused by
dispersed in the molecular sieve or entered the molecular sieve intergranular intervals. Table 3 shows the specific surface area
skeleton.19 and micropore volume of the molecular sieves reduced after
The elemental analysis results in Table 1 showed the silica− metal loading, which could be metal species occupying the
alumina ratio of molecular sieve increasing after loading with surface and channels, subtly altering the texture properties of
the zeolite.
Table 1. XRF Analysis of M/ZSM-5 Zeolites by an in Situ The concentration and strength of acid sites in different
Synthetic Method samples were determined by NH3-TPD; the results are shown
in Figure 4. Generally, an NH3-TPD profile from a zeolite
element/ wM exhibits two desorption peaks, at high (above 450 °C) and low
samples wSi (%) wAl (%) wO (%) (%) n(SiO2)/n(Al2O3)
(below 400 °C) temperatures, ascribed to ammonia adsorbed
S-0 40.33 2.19 57.23 35.34 on the strong and weak acid sites, respectively. In this work,
S-1 40.44 2.17 56.81 0.35 35.80 the distribution of the acid sites across the two acidic strengths
S-2 41.87 2.25 55.21 0.22 35.79 was determined by integrating the NH3-TPD profiles in
S-3 42.62 2.27 54.52 0.27 36.09 different temperature intervals. These profiles are listed in
S-4 41.31 2.16 55.53 0.53 36.78 Table 4, where the quantities of strong and weak acid sites
S-5 41.41 2.19 55.03 0.78 36.31 were measured by the amounts of ammonia desorbed over
450−600 and 200−350 °C.
the metal species compared with the parent ZSM-5, suggesting After the introduction of metal by the hydrothermal method,
that the metal species substitution into the molecular sieve the loading of Ga causes a larger shift in the acid center
framework replaced the aluminum.2 It was easier for Ga to position than that of La or Zn; as the Zn loading increases, the
enter the skeleton than Zn and La, probably because Ga3+ and proportion of the weak acid peak area increases, and the ratio
Al3+ have similar radii and valence states. The increasing Zn of strong acid peak area decreases, possibly due to the Zn
loading ratio increased the Zn content in the bulk phase species existing on the surface of the molecular sieve in the
reaching a maximum when the loading ratio was 0.5%. form of ZnOH+ (or other forms observed by XPS) that covers
The XPS characterization of molecular sieves with different a part of the strong acid center or turns the strong acid center
Zn contents is shown in Figure 2. The extracted electron into a weak acid center.
binding energy and the relative content of the elements on the The FT-IR spectrum in Figures 5a and 6a showed that the
surface of the different Zn-containing molecular sieves are prepared molecular sieves all have the characteristic ZSM-5
shown in Table 2. structure, and the peak positions of other samples were shifted
Figure 2 and Table 2 show that the binding energy of the Si compared with S-0 due to the metals entering the molecular
2p and Al 2p peaks increased compared with S-0 for sieve framework; however, the relatively low metal loading
hydrothermally modified molecular sieves, with the shift in causes the peak shift to be minimal.
the spectrum indicating that the introduction of Zn ions As seen in Figure 5b, the strong absorption bands of S-0
changed the original chemical environment on the surface of appeared at the five peak positions 1450, 1490, 1540, 1625,
the molecular sieve. The peak shape for the Zn element was and 1635 cm−1.28 The peaks at 1450 and 1625 cm−1 are caused
relatively weak due to the low content of Zn on the surface of by the L acid on the molecular sieve, and the peak at 1540
the molecular sieve and the influence of the Auger electron cm−1 can be attributed to the B acid on the molecular sieve;
peak from the oxygen level near 1017 eV. The electron binding the peaks at 1490 and 1635 cm−1 are the results of the
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Figure 2. XPS spectra of HZSM-5 zeolites under different Zn contents.

Table 2. XPS Analysis of Surface Elements of HZSM-5 Zeolites under Different Zn Contents
electron binding energy/eV surface relative content/%
sample Si 2p Al 2p O 1s Zn 2p3 wSi (%) wAl (%) wO (%) wZn (%) n(SiO2)/n(Al2O3)
S-0 103.35 74.04 532.75 24.86 2.31 72.84 20.67
S-3 103.65 74.65 532.85 1022.14 26.35 1.87 71.58 0.20 26.98
S-4 103.55 74.45 532.80 1022.72 24.16 2.25 73.30 0.29 20.60
S-5 103.45 74.25 532.86 1022.45 24.95 2.42 72.30 0.34 19.79

interaction of the B acid and L acid.29 After adding Zn, the Figure 6 shows a pyridine adsorption infrared spectrum and
absorption peak at 1625 cm−1 shifted to 1616 cm−1, but this a hydroxyl group spectrum from a sample molecular sieve
shift was not observed with the addition of Ga or La. Other catalyst. The effect of Zn content on the intensity of each peak
studies have seen the peak at 1616 cm−1 with the introduction in Figure 6b shows that the peak intensities of 1450 and 1616
of Zn species. Figure 5c shows two obvious hydroxyl vibration cm−1 are positively correlated with the Zn content, and the
bands on S-0: one is the vibrational peak of aluminum hydroxy peak intensities of 1490, 1540, and 1635 cm−1 are negatively
correlated with the Zn content. These results are a further
at 3610 cm−1, with strong B acidity, and the other was the
indication that the peaks at 1450 and 1616 cm−1 were caused
terminal silicon oxyhydroxide at 3740 cm−1.30,31 The vibration by the L acid, that the Zn increase enhanced the L acid peak,
peak did not change with the ion exchange and can be used as and that the B acid peak was weakened. Figure 6c shows two
a reference. After hydrothermal modification, the vibration of hydroxyl vibration bands at 3610 and 3740 cm−1 on the
the molecular sieve at 3610 cm−1 weakened, indicating that the samples.32 The introduction of Zn did not create a new
hydrothermal modification would lead to the reduction of the measurable hydroxyl vibration peak, indicating that Zn does
B acid. not form hydroxy Zn ions (Zn(OH)+) on aluminum hydroxyl
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significantly, possibly due to the formation of new Zn-L acid by

Zn2+ and molecular sieves,25 and the number of L acid sites
increased by adding Ga. While adding La, the L acid showed
minimal change, possibly because Zn and Ga filled the
outermost d electron orbital. The introduction of Zn2+ and
Ga3+ makes the original electrons in the molecular sieve
framework tend toward metal ions attracted by the electro-
static field of the extranuclear electrons of the metal cation,
which will activate the hydroxyl groups on the molecular sieve
framework to a certain extent and change the acid properties,
especially for L acid. When adding La, the amount of B acid on
the surface of the molecular sieve was obviously reduced.
Maybe the introduction of the metal was predominately in the
form of an oxide that covered a part of the proton active sites
on the molecular sieve. As the Zn loading increases, the B acid
decreases, and the L acid increases.
Figure 3. N2 adsorption−desorption isotherms of different samples. 3.2. Catalytic Performance of the Catalysts. The
aromatization performance of the above-mentioned catalysts
Table 3. Texture Properties of Different Samples was evaluated under normal pressure using a single methanol
feed, a reaction temperature of 450 °C, and a WHSV of 5 h−1.
SBET Smicro Vtotal Daverage Vmicro DHK Figure 7 shows that the methanol conversion of S-1, S-2, and
samples (m2/g) (m2/g) (mL/g) (nm) (mL/g) (nm)
S-3 reached approximately 100% within the 5 h reaction time
S-0 399 356 0.260 2.61 0.161 0.98
with different aromatics yields S-3 > S-1 > S-2. The lower
S-1 378 312 0.302 3.20 0.158 1.25
content of Zn significantly enhanced the aromatics yield, a 4%
S-2 345 267 0.260 3.02 0.146 1.24
increase compared with S-0, and the highest yields of S-2 and
S-3 397 337 0.258 2.59 0.149 1.28
S-1 did not increase much, possibly because the Zn
S-4 295 235 0.297 4.04 0.119 1.45
modification reduced the amount of B acid and significantly
S-5 307 258 0.244 3.17 0.114 1.34
increased the amount of L acid, while both the B and L acids of
modified Ga and La zeolites were simultaneously reduced.
Compared with the Ga and La, the Zn sites and the acid sites
in ZSM-5 zeolite have a stronger interaction and accessibility,
which can effectively promote the formation of L acid sites.
The regulation of the surface acidity by the metal on the
molecular sieve was directly related to the hydrogen transfer
and the dehydrogenation process. The improvement in
dehydrogenation aromatization performance of the L acid
after Zn modification compensated for the weakening of the
hydrogen transfer aromatization of the B acid, resulting in a
significant increase in the yield. The modification using Ga and
La was simultaneously weakened, and there was little change in
the yield of aromatic hydrocarbons with no side effects.
Therefore, Zn is a more suitable metal species for hydro-
thermal modification under the synthetic conditions of this
experiment.
Figure 4. NH3-TPD patterns of different samples.
As the Zn loading increased, the yield of aromatics initially
increased and then decreased with the loading of S-4 being
groups. The increase in Zn content does cause a weakening in optimal. A suitable Zn loading improved the stability of the
the vibrational peak of the aluminum hydroxy group, indicating catalyst; however, too much or too little loading decreased the
that Zn does interact with the aluminum hydroxy group on the working life of the catalyst due to the pore structure of the
molecular sieve. molecular sieve. The pore size and pore volume were the
Table 5 shows that the amount of B acid decreased slightly largest when the loading was 0.35%, where the larger pore size
when Zn is added, but the amount of L acid increased and developed channels reduce the effect of coking, prolong

Table 4. Comparison of Strong/Weak Acid of Different Samples

total acid weak acid peak/ strong acid peak/ weak acid peak area strong acid peak area strong acid/weak
sample amount/mmol g−1 °C °C fraction/% fraction/% acid
S-0 1.23 270 500 58.15 41.85 0.720
S-1 1.23 323 567 63.16 36.84 0.583
S-2 1.09 279 508 59.21 40.79 0.689
S-3 1.33 282 511 62.65 37.35 0.596
S-4 0.89 265 492 63.32 36.68 0.579
S-5 0.73 249 469 66.38 33.62 0.507

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Figure 5. IR spectra of different samples: (a) skeleton IR spectra, (b) Py-IR spectra, and (c) IR spectra of hydroxyl.

Figure 6. IR spectra of different samples with different Zn loading: (a) skeleton IR spectra, (b) Py-IR spectra, and (c) IR spectra of hydroxyl.

Table 5. Acid Distribution of Different Samples in the product is high, and the selectivity of BTX is low. When
the loading is between 0.15 and 0.35, the B/L is reduced to
sample B acid L acid B/L
about 0.7, and the aromatics selectivity is obviously improved
S-0 0.265 0.127 2.294 under the cooperation of the two. When the load increases to
S-1 0.160 0.115 1.393 0.5, the advantage of route b is obvious, and the olefin
S-2 0.179 0.120 1.486 selectivity increases significantly; however, the increase in CO
S-3 0.233 0.190 1.466 + CO2 selectivity indicates that the proportion of methanol
S-4 0.174 0.330 0.695 decomposition increases, accelerating catalyst deactivation, and
S-5 0.137 0.378 0.509 the aromatics selectivity drops instead. It can be seen that B/L
needs to be within a certain appropriate range, and the two
the life of the molecular sieve, and improve the stability. Figure pathways can match each other to play the best role.
8a demonstrates the effect of the B/L value on the molecular Therefore, in this work, when the value of B/L was 0.695,
sieve selectivity of aromatics after a 2 h time on stream. The B/ the reaction of methanol to aromatic hydrocarbons was most
L value decreased as the Zn content increased, and the favorable, giving the highest selectivity to aromatics and
aromatic hydrocarbon selectivity first increased and then providing excellent stability.
decreased. Figure 8b shows that, with increased Zn loadings,
the low carbon olefin selectivity increased. The authors suggest 4. CONCLUSION
that the introduction of Zn covers the original B acid, resulting
in a decrease of the center of the B acid that inhibits the ZSM-5 molecular sieves containing Zn, La, and Ga and with
gathered olefin and suppresses the aromatics alkylation different Zn contents were synthesized by the in situ synthetic
reaction. The increased selectivity for high carbon aromatics method, and their textural and acidic properties and catalytic
is more likely to lead to catalyst coking and a reduction in the performance in MTA were investigated. The results indicated
stability of the catalyst. that the acid distribution was associated with the aromatics
As shown in Figure 9, the generation of aromatics can be yield and was significantly influenced by the type and amount
divided into two pathways: (a) cycloalkane and alkene of metal. Zn was the most favorable metal for the MTA
hydrogen transfer (HT) at the B acid site and (b) cycloalkane reaction. When the loading is 0.35%, the aromatics selectivity
dehydrogenation (DH) at the Zn-L acid site. When the loading reaches 56%, 26% higher than the parent ZSM-5. The in situ
is less than 0.15%, the acid content of B is higher than that of L synthesis method used in this work provides a more
acid, and a is more dominant than b; the selectivity of alkanes convenient and efficient method for synthesizing metal−
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Figure 7. (a) Aromatization properties of different samples. (b) Aromatization properties of different samples.

Figure 8. (a) Effect of B/L ratio on the selectivity of aromatics. (b) Product selectivity of different samples.

Yao Liu − State Key Laboratory of Chemical Resources

Engineering, Beijing University of Chemical Technology,
Beijing 100029, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.2c01442
Figure 9. Brief reaction pathway to generate aromatics in the MTA
reaction on Zn/ZSM-5. Notes
The authors declare no competing financial interest.

zeolite bifunctional catalysts, which is more conducive to the

industrial production of catalysts.
■ ACKNOWLEDGMENTS
This work was financially supported by the National Key R&D
Program of China (2018YFB0604802).
■ AUTHOR INFORMATION
Corresponding Author ■ REFERENCES
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