Molybdenum oxide and sulfide active sites for isobutane dehydrogenation with methanol as a probe molecule

Emily Cheng; Justin Notestein

doi:10.1016/j.jcat.2022.07.007

Molybdenum oxide and sulfide active sites for isobutane dehydrogenation with methanol as a probe molecule

Emily Cheng, Justin Notestein^*

^*Corresponding author for this work

Chemical and Biological Engineering

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

Molybdenum oxides and sulfides are alternative catalysts for several reactions, including alkane dehydrogenation. Correlations have been developed between reactivity and structure, but it is difficult to compare different catalysts without determining numbers of active sites. Here, methanol temperature programmed surface reaction (TPSR) is applied to bulk MoS₂ and a series of supported molybdenum oxides and sulfides used for isobutane dehydrogenation. Rates and deactivation behavior are similar between supported molybdenum oxides and sulfides. Coking increases with loading and correlates well with the fraction of Mo-based CO₂-forming sites from methanol TPSR. Normalizing isobutane dehydrogenation rates by formaldehyde-forming sites unifies rates over oxide and sulfide materials. These measurements confirm earlier hypotheses that MoS₂ and higher loadings of oxides and sulfides are intrinsically fast catalysts, but they have few active sites and are prone to coking. In general, methanol TPSR is proposed as an accessible route to count sites on both supported oxides and sulfides.

Original language	English (US)
Pages (from-to)	498-508
Number of pages	11
Journal	Journal of Catalysis
Volume	413
DOIs	https://doi.org/10.1016/j.jcat.2022.07.007
State	Published - Sep 2022

Funding

This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Grant No. DGE-1324585. This work is also supported as part of the Institute for Catalysis in Energy Processes funded by the U.S. Department of Energy, Office of Basic Energy Sciences under Award DE-FG02-03ER15457. Metal analysis was performed at the Northwestern University Quantitative Bio-element Imaging Center. The REACT Facility of the Northwestern University Center for Catalysis and Surface Science is supported by a grant from the DOE (DE-SC0001329). This work also made use of the Keck-II facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), the International Institute for Nanotechnology (IIN), and Northwestern’s MRSEC program (NSF DMR-1720139).

Keywords

Isobutane dehydrogenation
Metal oxides and sulfides
Methanol TPSR
MoO
MoS

ASJC Scopus subject areas

Catalysis
Physical and Theoretical Chemistry

Access to Document

10.1016/j.jcat.2022.07.007

Cite this

@article{13d3651697814072b3814b98027abd1d,

title = "Molybdenum oxide and sulfide active sites for isobutane dehydrogenation with methanol as a probe molecule",

abstract = "Molybdenum oxides and sulfides are alternative catalysts for several reactions, including alkane dehydrogenation. Correlations have been developed between reactivity and structure, but it is difficult to compare different catalysts without determining numbers of active sites. Here, methanol temperature programmed surface reaction (TPSR) is applied to bulk MoS2 and a series of supported molybdenum oxides and sulfides used for isobutane dehydrogenation. Rates and deactivation behavior are similar between supported molybdenum oxides and sulfides. Coking increases with loading and correlates well with the fraction of Mo-based CO2-forming sites from methanol TPSR. Normalizing isobutane dehydrogenation rates by formaldehyde-forming sites unifies rates over oxide and sulfide materials. These measurements confirm earlier hypotheses that MoS2 and higher loadings of oxides and sulfides are intrinsically fast catalysts, but they have few active sites and are prone to coking. In general, methanol TPSR is proposed as an accessible route to count sites on both supported oxides and sulfides.",

keywords = "Isobutane dehydrogenation, Metal oxides and sulfides, Methanol TPSR, MoO, MoS",

author = "Emily Cheng and Justin Notestein",

note = "Publisher Copyright: {\textcopyright} 2022 Elsevier Inc.",

year = "2022",

month = sep,

doi = "10.1016/j.jcat.2022.07.007",

language = "English (US)",

volume = "413",

pages = "498--508",

journal = "Journal of Catalysis",

issn = "0021-9517",

publisher = "Academic Press Inc.",

}

TY - JOUR

T1 - Molybdenum oxide and sulfide active sites for isobutane dehydrogenation with methanol as a probe molecule

AU - Cheng, Emily

AU - Notestein, Justin

PY - 2022/9

Y1 - 2022/9

N2 - Molybdenum oxides and sulfides are alternative catalysts for several reactions, including alkane dehydrogenation. Correlations have been developed between reactivity and structure, but it is difficult to compare different catalysts without determining numbers of active sites. Here, methanol temperature programmed surface reaction (TPSR) is applied to bulk MoS2 and a series of supported molybdenum oxides and sulfides used for isobutane dehydrogenation. Rates and deactivation behavior are similar between supported molybdenum oxides and sulfides. Coking increases with loading and correlates well with the fraction of Mo-based CO2-forming sites from methanol TPSR. Normalizing isobutane dehydrogenation rates by formaldehyde-forming sites unifies rates over oxide and sulfide materials. These measurements confirm earlier hypotheses that MoS2 and higher loadings of oxides and sulfides are intrinsically fast catalysts, but they have few active sites and are prone to coking. In general, methanol TPSR is proposed as an accessible route to count sites on both supported oxides and sulfides.

AB - Molybdenum oxides and sulfides are alternative catalysts for several reactions, including alkane dehydrogenation. Correlations have been developed between reactivity and structure, but it is difficult to compare different catalysts without determining numbers of active sites. Here, methanol temperature programmed surface reaction (TPSR) is applied to bulk MoS2 and a series of supported molybdenum oxides and sulfides used for isobutane dehydrogenation. Rates and deactivation behavior are similar between supported molybdenum oxides and sulfides. Coking increases with loading and correlates well with the fraction of Mo-based CO2-forming sites from methanol TPSR. Normalizing isobutane dehydrogenation rates by formaldehyde-forming sites unifies rates over oxide and sulfide materials. These measurements confirm earlier hypotheses that MoS2 and higher loadings of oxides and sulfides are intrinsically fast catalysts, but they have few active sites and are prone to coking. In general, methanol TPSR is proposed as an accessible route to count sites on both supported oxides and sulfides.

KW - Isobutane dehydrogenation

KW - Metal oxides and sulfides

KW - Methanol TPSR

KW - MoO

KW - MoS

UR - http://www.scopus.com/inward/record.url?scp=85134330752&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85134330752&partnerID=8YFLogxK

U2 - 10.1016/j.jcat.2022.07.007

DO - 10.1016/j.jcat.2022.07.007

M3 - Article

AN - SCOPUS:85134330752

SN - 0021-9517

VL - 413

SP - 498

EP - 508

JO - Journal of Catalysis

JF - Journal of Catalysis

ER -

Molybdenum oxide and sulfide active sites for isobutane dehydrogenation with methanol as a probe molecule

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this