Promotional Effects of In on Non-Oxidative Methane Transformation

over Mo-ZSM-5

Yang Zhang1, Michelle Kidder2, Rose E. Ruther1, Jagjit Nanda1, Guo Shiou Foo2, Zili Wu2,

Chaitanya K. Narula1*

1
Materials Science & Technology Division, Oak Ridge National Laboratory, 1 Bethel Valley Road,

Oak Ridge, Tennessee 37831-6133, United States

b
Chemical Sciences Division, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge,

Tennessee 37831, United States

*Corresponding author:

Tel: +1 (865) 574-8445

Email: narulack@ornl.gov
ABSTRACT

We present a new class of catalysts, InMo-ZSM-5, which can be prepared by indium

impregnation of Mo-ZSM-5. The incorporation of indium dramatically decreases coke formation

during methane dehydroaromatization. The benzene and C2 hydrocarbons selectivity among total

hydrocarbons over InMo-ZSM-5 remains comparable to that of Mo-ZSM-5 despite reduced

methane conversion due to decreased coke formation. We found 1 wt% indium to be optimal

loading for reducing coke selectivity to half that of Mo-ZSM-5. Characterization methods were

not helpful in discerning the interaction of In with Mo but experiments with bimetallic 1In2Mo-

ZSM-5 and mechanical mixture 1In+2Mo-ZSM-5 suggest that In and Mo need to be in close

proximity to suppress coke formation. This is supported by temperature programmed reduction

experiments which show that In incorporation leads to lower Mo reduction temperature in In2Mo-

ZMS-5.

KEYWORDS

Methane to benzene, Methane dehydroaromatization, Coking suppression, Heterobimetallic

zeolites, InMo-ZSM-5
1. INTRODUCTION

The catalytic conversion of methane to higher hydrocarbons is a promising approach to utilize

abundant and cheap natural gas resources [1]. The activation of methane is challenging due to its

thermodynamic stability. The indirect methane conversion process via steam reforming is

commercial but is energetically intensive and requires economy of scale in order to be profitable

[2]. Thus, the search for direct methods, such as methane dehydroaromatization (MDA), oxidative-

or non-oxidative coupling, which are energetically favorable and able to operate on a small scale,

remains a topic of great interest [3]. However, a durable catalyst that can effectively convert

methane to desirable products in high yields and selectivity has remained elusive.

Since the first report by Wang et al. in 1993 [4], Mo-loaded zeolites (e. g. ZSM-5) has been

widely studied and has been shown to be one of the most effective catalysts for MDA. In

comparison with other monometallic zeolites, Mo-ZSM-5 exhibits high methane conversion and

product selectivity [5-9]. Depending on the metal loading and preparation method, 5-10% methane

conversion to hydrocarbons and coke can be achieved over Mo-ZSM-5. The reaction was reported

to have 60-70% benzene selectivity among hydrocarbons at 973 K and 1440 mL/g·h space velocity.

The coke formation can vary from 15-30% and leads to gradual deterioration of catalyst activity.

Operando X-ray methods show that metastable MoCxOy species is responsible for C2Hx/C3Hx

formation and the presence of MoC3 clusters coincide with benzene formation. Sintering of MoC3

and accumulation of coke was proposed to reduce catalyst performance [10]. The conclusion of a

detailed study employing a variety of spectroscopy and electron microscopic techniques were
essentially similar and coke and lower Mo-carbide were found to decrease methane conversion.

[11].

The efforts to improve methane conversion, benzene selectivity, and to reduce coke formation

have met with limited success. Zhang et al investigated several metals and found that Fe additive

improve catalytic stability of Mo-ZSM-5 [12]. The catalyst promoters such as Fe, Co [13], Pt [14],

Rh [15], Ru [16] and Ga [17], incorporated in Mo-ZSM-5, are not very effective. For example, Liu

et al. observed that the coke selectivity on GaMo-ZSM-5 decreased from 29% to 22% with

increasing Ga loading from 0.1 to 1%, which is still not significantly different from 26% coke

formation for Mo-ZSM-5 [17]. Ichikawa et al. reported that iron impregnation on Mo-ZSM-5,

with an optimized Fe/(Fe+Mo) molar ratio of ~0.2, resulted in 21% coke selectivity which is lower

than 31% coke selectivity for Mo-ZSM-5 under their reaction conditions [13]. Ichikawa et al. also

reported that noble metals, Pt and Rh, suppressed naphthalene formation and coking but they did

not quantify their results [15]. Chen et al. found that 1% Pt loading on 2% Mo-ZSM-5 results in

11% coke selectivity (cf. 21.6% over 2%Mo-ZSM-5) under their reaction conditions [14]. Despite

these advances, coking of the catalysts remains a challenge and it is highly desirable to find a

catalyst that can function effectively for extended periods without requiring a decoking step.

In our efforts to reduce coking, we found that InMo-ZSM-5, prepared by the incorporation of

indium on Mo-ZSM-5, is highly effective at reducing coke formation. Our methane conversion

experiments show that the close proximity between In and Mo results in synergistic suppression

of coke formation. This is further supported by temperature programmed reduction experiments

which show that In incorporation leads to lower Mo reduction temperature in InMo-ZSM-5.

2. RESULTS AND DISCUSSION

2.1. Catalyst Preparation and Characterization

The BET surface area and pore volumes for catalyst samples are summarized in table I. Compared

to H-ZSM-5, metal impregnation does not result in a dramatic decrease in BET surface area or

pore volume. This suggests that the metal oxides, present on the surface, do not block the zeolite

pores. The numbers in front of Mo and In reflect their wt.% in the sample and the total % is 100.

Thus, 1In2Mo-ZSM-5 contains 1 wt% In, 2 wt% Mo, and 97 wt% H-ZSM-5. The physical mixture

includes a + sign between metals and are prepared by mixing monometallic zeolites e.g. 1In+2Mn-

ZSM-5 is a physical mixture which is prepared by mixing 2In-ZSM-5 with 4Mn-ZSM-5.

Table 1. BET Surface areas and pore volumes of H-ZSM-5 and metal-impregnated samples.

BET Surface Pore Volume

Sample
Area / m2 g-1 / cm3 g-1
H-ZSM-5 344 0.19
2In-ZSM-5 311 0.17
2Mo-ZSM-5 326 0.18
1In2Mo-ZSM-5 310 0.17
2In2Mo-ZSM-5 316 0.18
3In2Mo-ZSM-5 300 0.17

XRD patterns of the various Mo-ZSM-5 and InMo-ZSM-5 catalysts exhibit intact ZSM-5

frame (Fig. 1) after metal impregnation and are comparable to that of H-ZSM-5[18]. The

diffraction peaks corresponding to crystalline metal oxides, such as MoO3 (strongest peaks at 23.3,
25.7, 27.3º), In2O3 (strongest peaks at 30.6, 35.5, 51.1, 60.7º) or the mixed-metal oxides were not

observed suggesting that the metals are well-dispersed on zeolite surface.

Fig. 1 XRD patterns (Left) and UV-Vis (right) of metal substituted ZSM-5

The peaks for bulk In2O3 in UV-Vis-NIR are observed at 330 nm [19] and that for MoO3 are

observed at 360, 435, 650, and 850 nm [20]. A broad feature in 250-500 nm range in our samples

can be seen which could be due to oxides. However, no unique peak attributable to In-O-Mo

absorption in 250-2000 nm range (Fig. 1) is observed. IR spectra of H-ZSM-5, Mo-ZSM-5, In-

ZSM-5, and 2In2Mo-ZSM-5 are identical in 4000-500 cm-1 range and the peaks assignable to In-

O, Mo-O or In-O-Mo (Fig. 2 left) are not seen. The Raman spectrum of H-ZSM-5 (Fig. 2 right)

shows broad peaks at 330-500 and 760-820 cm-1 range typical for silica [21]. The spectra of 2Mo-

ZSM-5 and 2In2Mo-ZSM-5 exhibit peaks at 961 and 880 cm-1 assignable to surface

polymolybdate species and 819 and 678 cm-1 peaks due to MoO3 [21-23]. 2In-ZSM-5 shows no

distinguishable peak that can be assigned to In-O vibrations [24], probably due to the overlap of
In-O vibrations with the broad silica features. No peak shift or new feature due to In-Mo or In-O-

Mo bonding is found in the Raman spectrum of 2In2Mo-ZSM-5.

Fig. 2. IR (left) and Raman (right) spectra of 2In-ZSM-5, 2Mo-ZSM-5 and 2In2Mo-ZSM-5. For
comparison, the IR and Raman spectrum of H-ZSM-5 is also included in the figure.

Thus, the results of standard characterization methods did not offer any evidence for the presence

of In-O-Mo in various InMo-ZSM-5 samples. This is not surprising since we have previously

shown that characterization tools are generally not helpful in discerning the presence of M-O-M’

interactions in CuM-ZSM-5 and CuM-SSZ-13 (M = Sc3+, Fe3+, In3+, La3+) and experimental

evidence is generally necessary to obtain insights into the role of promoters [25]. In order to rule

out the possibility of InMo-ZSM-5 samples to be mechanical mixtures of In-ZSM-5 and Mo-ZSM-

5, we also prepared mechanical mixtures of In-ZSM-5 and Mo-ZSM-5 and compared the catalytic

performance of mechanical mixtures with InMo-ZSM-5 catalysts. The results are described in

section 2.4.
2.2 Temperature Programmed Reduction [TPR] of In2Mo-ZSM-5 and In+2Mo-ZSM-5

The reduction of Mo-ZSM-5 has been previously reported to be exhibit two hydrogen consumption

peaks at ~530 and 660ºC, respectively [17, 26]. Addition of a small amount of Ga in 1Ga3Mo-

ZSM-5 led to reduction temperatures of 470 and 650ºC, respectively [17, 27]. This suggested that

the presence of Ga promotes MoO3 particles on the surface or channels of ZSM-5 and decreased

the reduction temperature of the catalysts. This observed decrease in Mo reduction temperature

and reduction of Brønsted sites was proposed to be responsible for improved performance of Ga

containing Mo-ZSM-5 species.

In our samples, the TPR of the physical mixture, In+2Mo-ZSM-5 exhibits three distinct

hydrogen consumption peaks at 450, 550, and 650ºC. In comparison, the TPR of In2MO-ZSM-5

shows only hydrogen consumption peaks at 500 and 650ºC although the 450ºC peak appears at a

weak shoulder.

Fig. 3. TPR profiles of (a) In+2Mo-ZSM-5 (b) In2Mo-ZSM-5

The 450ºC hydrogen consumption peak has been previously observed for In2O3/H-ZSM-5 and can

be assigned to In2O3 component in In+2Mo-ZSM-5 [28]. Other two peaks at 550, and 660ºC are

due to Mo-ZSM-5. The TPR of In2Mo-ZSM-5 no longer shows In2O3 as a resolved peak but as a

weak shoulder. The Mo hydrogen consumption peak at 550 shifts to 500ºC. As noted previously

for Ga, the presence of In promotes MoO3 particles on the surface or channels of ZSM-5 and

decreased the reduction temperature of the catalysts.

2.3. Catalytic performance of In2Mo-ZSM-5

Methane conversion over 2Mo-ZSM-5, 1In2Mo-ZSM-5, 2In2Mo-ZSM-5 and 3In2Mo-

ZSM-5 is 9.4%, 7.2%, 8.4% and 8.8%, respectively, after one hour on stream (Fig. 4a). Since our

experiments showed that H-ZSM-5, 2In-ZSM-5 and 4In-ZSM-5 are inactive towards methane

dehydroaromatization, the conversions over Indium modified Mo-ZSM-5 samples are primarily

over Mo centers.

Fig. 4. (a) Methane conversions, and (b) hydrocarbons and benzene yields as a function of time
on stream for reactions catalyzed by 2Mo-ZSM-5, In2Mo-ZSM-5, and 2In2Mo-ZSM-5, and
3In2Mo-ZSM-5.
The conversion decreases with time on stream due to catalyst coking. Fresh, 1In2Mo-ZSM-5,

showed lower methane conversion than 2Mo-ZSM-5, which increased with higher indium loading.

The conversion of 3In2Mo-ZSM-5 is comparable to that of 2Mo-ZSM-5. A comparison of

methane conversion efficiency, averaged over 1-12 hours on stream, shows the pattern to be 2Mo-

ZSM-5 ≈ 3In2Mo-ZSM-5 > 2In2Mo-ZSM-5 > 1In2Mo-ZSM-5. Interestingly, the total

hydrocarbon yields and that of individual hydrocarbon components (Fig. 4b) are statistically

identical for all samples after 2.5 h on stream.

The coke selectivity as a function of time on stream for all catalysts (Fig. 5a) is commensurate

with methane conversion efficiency pattern of 2Mo-ZSM-5 > 3In2Mo-ZSM-5 > 2In2Mo-ZSM-5 >

In2Mo-ZSM-5.

Fig. 5. (a) Coke selectivities among all products as a function of TOS, (b) benzene and C2
selectivities among hydrocarbons as a function of TOS, and (c) average (in 2.5-11.5 h range) coke
selectivities among all products, and average benzene selectivities among hydrocarbons, for
reactions catalyzed by 2Mo-ZSM-5 and 2Mo-ZSM-5, In2Mo-ZSM-5, 2In2Mo-ZSM-5, and
3In2Mo-ZSM-5.
In contrast, the selectivity of benzene and C2 hydrocarbons (ethane and ethylene) is not affected

by indium loading (Fig. 5b). The coke selectivity averaged over 2.5–11.5 h range for 2Mo-ZSM-

5, 1In2Mo-ZSM-5, 2In2Mo-ZSM-5, 3In2Mo-ZSM-5 and 6In2Mo-ZSM-5 is 31%, 15%, 19%, 27%

and 30%, respectively (Fig. 5c). This suggests that In does not impact hydrocarbon yield or

distribution, and the lower methane conversion is primarily due to the suppressed coke formation.

Thus, the low indium loading on 1In2Mo-ZSM-5 leads to a dramatic decrease in coke formation

to half that of Mo-ZSM-5 and an increase in hydrocarbon selectivity. Comparable coke selectivity

reduction has previously been reported only for 1Pt2Mo-ZSM-5 which contains expensive

platinum [14].

2.4. Comparison of catalytic performance of the mechanical mixture, 1In+2Mo-ZSM-5, with

that of 1In2Mo-ZSM-5

The TPR results, summarized in 2.2, clearly show that 1In2Mo-ZSM-5 is not a mechanical

mixture. Additional support comes from the catalytic performance of mechanical mixtures of In-

ZSM-5 and 2Mo-ZSM-5 with that of In2Mo-ZSM-5 catalysts. Our results showed that H-ZSM-5,

2In-ZSM-5 and 4In-ZSM-5 are inactive towards methane dehydroaromatization. This suggests

that the mixing In-ZSM-5 and H-ZSM-5 with Mo-ZSM-5 will have no impact on methane

conversion.

There is no difference between methane conversion over 2Mo+H-ZSM-5 and 2Mo-ZSM-5

possibly due either to equal Mo center or redistribution of Mo due to grinding. During the first 5

hours on stream, the methane conversion activity of 1In+2Mo-ZSM-5 matches that of 2Mo-ZSM-
5 suggesting that all activity is due to Mo-ZSM-5 in 1In+2Mo-ZSM-5. After 5.5 h on stream, the

conversion of 1In+2Mo-ZSM-5 started to gradually decrease to approach that of 1In2Mo-ZSM-5.

The differences in the total yield of hydrocarbons and that of benzene from various catalysts at

2.5h and longer are not significant (Fig. 6b) and difference in methane conversion efficiencies are

due to difference in coke selectivity.

Fig. 6. (a) Methane conversions and (b) hydrocarbons and benzene yields over time for reactions
facilitated by 2Mo-ZSM-5, 2Mo+ZSM-5, 1In+2Mo-ZSM-5 and 1In2Mo-ZSM-5.

During the first 5.5 h on stream, the coke selectivity curve for 1In+2Mo-ZSM-5 remains in

between those of 2Mo-ZSM-5 and 2Mo+ZSM-5. In comparison, 1In2Mo-ZSM-5 exhibits

significantly lower coke selectivity (Fig. 7a). At 7h, the coke selectivity of 1In+2Mo-ZSM-5 is

higher than that of 2Mo-ZSM-5 and 2Mo+ZSM-5. These results suggest that InMo-ZSM-5

samples are not mechanical mixtures of In-ZSM-5 and Mo-ZSM-5 and the spatial proximity of In

and Mo in InMo-ZSM-5 may account for coke suppression.

 Unlike coke selectivity, benzene or C2 selectivity are not significantly affected by In in the

catalyst (Fig. 7b). The selectivity analysis of coke and benzene, averaged over the reaction period

of 2.5 – 11.5 h (Fig. 7c), shows that the coke selectivity of 2In2Mo-ZSM-5 is approximately half

that of 2Mo-ZSM-5 and 2Mo+ZSM-5, but benzene selectivity is ~65% for all catalysts.

Fig. 7. (a) Coke selectivities, (b) benzene and C2 (ethylene and ethane) selectivities over time, and
(c) the average (2.5 h – 11.5 h range) hydrocarbons selectivities for reactions catalyzed by 2Mo-
ZSM-5, 2Mo+ZSM-5, 1In+2Mo-ZSM-5 and 1In2Mo-ZSM-5.

3. CONCLUSIONS

In this work, we examined the reactivity indium incorporated Mo-ZSM-5 catalysts for methane

dehydroaromatization. Our results clearly show that indium incorporation (especially with 1%

loading) in Mo-ZSM-5 leads to a dramatic reduction in coke selectivity without affecting

hydrocarbon production. Standard characterization methods (XRD, UV-Vis, IR, and Raman) did

not provide information on the interaction of In and Mo on ZSM-5 surface. Experimental evidence,

derived from the methane conversion efficiency of 1In+2Mo-ZSM-5 (mechanical mixture) and
1In2Mo-ZSM-5, shows that In and Mo need to be in close proximity for coke suppression. This is

supported by temperature programmed reduction experiments which show that In incorporation

leads to reduced Mo reduction temperature.

4. EXPERIMENTAL

4.1. Chemicals

NH4-ZSM-5 (SiO2/Al2O3 molar ratio: 23, surface area: 425 m2/g) was purchased from Zeolyst. H-

ZSM-5 was obtained by calcining NH4-ZSM-5 in air at 773 K for 4 h. Ammonium molybdate

((NH4)6Mo7O24·xH2O) was purchased from Alfa-Aesar and indium nitrate (In(NO3)3·xH2O) from

Sigma-Aldrich. Methane (99.99% purity), helium (99.999%), and compressed air were purchased

from Air Liquide. All reagents were used as received without further purification.

4.2. Catalyst preparation

The preparation of 2Mo-ZSM-5 and 4Mo-ZSM-5 (the number in front of metal refers to wt%

metal, e.g., 2 or 4 refer to wt% of Mo in H-ZSM-5) was carried out by a modified literature method

[4]. H-ZSM-5 (10.0 g) was impregnated via incipient wetness with 0.38 g of (NH4)6Mo7O24·xH2O

dissolved in deionized water. The resulting powder was dried at room temperature for 2 days with

continuous stirring and then transferred to a furnace for calcination in air at 773 K for 4 h.

Elemental analysis of 2Mo-ZSM-5 shows a 1.89% Mo loading. The samples of monometallic 2In-

ZSM-5 and 4In-ZSM-5 were prepared by a similar manner from 10 g of H-ZSM-5 and m×0.26 g

of In(NO3)3·xH2O (0.26 for 2In-ZSM-5 and 0.52 g for 4In-ZSM-5).

 The mixed-metallic 1In2Mo-ZSM-5, 2In2Mo-ZSM-5, and 3In2Mo-ZSM-5 were prepared in

two steps. First, H-ZSM-5 was impregnated via incipient wetness with appropriate amount of

In(NO3)3·xH2O and the resulting powder was dried for 2 days at room temperature with continuous

stirring. Then, incipient wetness impregnation with (NH4)6Mo7O24·xH2O was carried out. The

dried powder was calcined at 773 K for 4 hours. Elemental analysis of 1In2Mo-ZSM-5 showed

0.98% In and 1.97% Mo loading.

The mechanical mixtures, 1In+2Mo-ZSM-5, were obtained by grinding 5 g of 2In-ZSM-5 and

5 g of 4Mo-ZSM-5 for 1 h. The 2Mo+H-ZSM-5 sample was similarly obtained by mixing equal

weights of 4Mo-ZSM-5 and H-ZSM-5. No further calcination or post-treatment was conducted for

this mixture before catalytic runs.

4.3. Characterization

Nitrogen sorption experiments were carried out on a Quantachrome Autosorb-1 workstation to

obtain BET surface area. Total pore volume is derived from the adsorbed nitrogen at a relative

pressure close to unity. Powder X-ray diffraction (XRD) scans were performed on the Panalytical

X’pert diffractometer from 5 to 80° 2θ in 30 minute scans using CuKα radiation (45kV, 40mA,

λ=1.5406 Å). Diffuse-reflectance UV-vis-NIR spectra were collected on Cary 5000 UV-vis-NIR

spectrophotometer under R% mode. FT-IR data was collected on Bio-Rad FTS 575C

spectrophotometer in 4000 to 500 cm-1 range employing NaCl pellets. Raman spectra were

acquired with an Alpha 300 confocal Raman microscope (WITec, GmbH) using a solid-state 532
nm excitation laser, a 20x objective, and a 600 grooves per millimeter grating. Elemental analyses

were performed by Galbraith Incorporated, Knoxville, TN, United States.

Temperature-programmed reduction (TPR) was performed using an Altamira AMI-300

system. Each sample (100 mg) was pretreated under 5% O2/He flow (30 ml/min) by heating up to

450 °C at a ramp rate of 10 °C/min, held for 1 h, and cooled down to 35 °C. Subsequently, the gas

flow was switched to 4% H2/Ar (30 ml/min), and the thermal conductivity detector (TCD) was

stabilized for 30 min. The temperature was then increased to 950 °C at a ramp rate of 10 °C/min.

During this period, a cold trap at downstream was cooled by an acetone/dry ice slurry, which was

kept stable at -80 °C to condense any water vapor generated from the reduction.

4.4. Catalytic Tests

A 2 g sample was placed in a fixed-bed continuous-flow tubular quartz reactor (tube diameter: 2

cm) connected to Agilent 6890 gas chromatograph fitted with PLOT-Q capillary column and

thermal conductivity detector (TCD). The catalyst was heated to 973 K under a helium purge for

1 h. Then the helium flow was switched to a gas mixture consisting of 98 mol% methane and 2

mol% argon (as an internal standard). The GHSV for these experiments was 1440 mL/h·g-catalyst.

In-line samples were taken after the 1st hour and then every subsequent 1.5 hours. Methane

conversion and product selectivity (Sproduct) were calculated on carbon basis employing the

Ichikawa protocol [13]. Briefly, the total hydrocarbons selectivity Shydrocarbons was set as ΣSproduct.

The selectivity of coke (soft and hard carbons and undetected heavy aromatics), was estimated by

subtracting Shydrocarbons from total 100%. The selectivity of a particular product among
hydrocarbons was simply, Sproduct/Shydrocarbons. All experiments (including catalyst preparation)

were carried out twice to ensure reproducibility and average of two parallel data points were used

in all plots.

ACKNOWLEDGEMENTS

This research is sponsored by the Laboratory Directed Research and Development Program of Oak

Ridge National Laboratory, managed by UT-Battelle, LLC, for the U. S. Department of Energy.

Authors thank Andrew Lepore for critical reading of manuscript. We also thank Shreya Celly, a

summer undergraduate intern, for assistance with some of the experiments. Raman microscopy

work is supported by Assistant Secretary for Energy Efficiency and Renewable Energy, Office of

Vehicle Technologies of the U.S. Department of Energy. TPR work was supported by U.S.

Department of Energy, Office of Science, Basic Energy of Science, Chemical Science, Geoscience

and Bioscience Division.

REFERENCES
[1]. BP Statistical Review of World Energy 2013. Document retrieved from: www.bp.com on
16th of October, 2014.
[2]. Rostrup-Nielsen JR (1993) Catal. Today 18:305-324.
[3]. Spivey J, Hutchings G (2014) Chem. Soc. Rev. 43:792-803, and references therein.
[4]. Wang L, Tao L, Xie M, Xu G, Huang J, Xu Y (1993) Catal. Lett. 21:35-41.
[5]. Majhi S, Mohanty P, Wang H, Pant KK (2013) J. Energy Chem. 22:543-554, and
references therein.
[6]. Ismagilove Z, Matus E, Tsikoza L (2008) Energy Environ. Sci. 1:526-541, and references
therein.
[7]. Zeng J-L, Xiong Z-T, Zhang H-B, Lin G-D, Tsai KR (1998) Catal. Lett. 53:119-124.
[8]. Weckhuysen BM, Wang D, Rosynek MP, Lunsford JH (1998) J. Catal. 175:338-346.
[9]. Wang H, Liu Z, Shen J, Liu H, Zhangn J (2005) Catal. Commmun. 6:343-346.
[10]. Lezcano-Gonzalez I, Oord R, Rovezzi M, Glatzel P, Botchway SW, Weckhuysen BM,
Beale, AM (2016) Angew. Chem. Inter. Ed., 55:5215-5219
[11]. Tempelman CHL, Hensen EJM (2015) App. Cata. B, 176: 731-739
[12]. Xu YB, Wang JD, Suzuki Y, Zhang ZG (2012) Catal. Today, 185:41-46
[13]. Liu S, Dong Q, Ohnishi R, Ichikawa M (1997) Chem. Commun. 1455-1456.
[14]. Chen L, Lin L, Xu Z, Zhang T, Li X (1996) Catal. Lett. 39:169-172.
[15]. Kojima R, Kikuchi S, Ma H, Bai J, Ichikawa M (2006) Catal. Lett. 110:15-21.
[16]. Shu Y, Xu Y, Wong S-T, Wang L, Guo X (1997) J. Catal. 170:11-19.
[17]. Liu B, Yang Y, Sayari A (2001) Appl. Catal. A. 214: 95-102.
[18]. Al-Dughaither AS, de Lasa H (2014) Ind. Eng. Chem. Res. 53:15303-15316
[19]. Liu Q, Lu W, Tang J, Lin J, Fang JY (2005) J. Am. Chem. Soc. 127:5276-5277
[20]. O’Brien MG, Beale AM, Jacques SDM, Buslabs T, Honimaki V, Weckhuysen BM
(2009) J. Phys. Chem. C. 113:4890-4897
[21]. Xu Y, Shu Y, Liu S, Huang J, Guo X (1995) Catal. Lett. 35:233-243.
[22]. Williams CC, Ekerdt JG, Jehng J-M, Hardcastle FD, Turek AM, Wachs IE (1991) J.
Phys. Chem. 95:8781-8791.
[23]. Berengue OM, Rodrigues AD, Dalmaschio CJ, Lanfredi AJC, Leite ER, Chiquito AJ
(2010) J. Phys. D: Appl. Phys. 43:040501.
[24]. Du J, Yang M, Cha SN, Rhen D, Kang M, Kang DJ (2008) Cryst. Growth Des. 8: 2312-
2317.
[25]. Yang X, Wu Z, Moses-Debusk M, Mullins DR, Mahurin SM, Geiger RA, Kidder M,
Narula CK (2012) J. Phys. Chem. C 116:23322-23331.
[26]. Borry III RW, Lu EC, Kim YH, Iglesia E, Non-Oxidative Conversion of Methane with
Continuous Hydrogen Removal, US Dept. of Energy/NETL, Morgantown, WV, Contract
DE-AC03-76SF00098.
[27]. Jiang H, Wang L, Cui W, Xu Y (1999) Catal. Lett. 57:95-102.
[28]. Mihalyi RM, Schay Z, Szegedi A (2009) Catal. Today, 143:253-260.