Redox-driven atomic-scale changes in mixed catalysts: VOX / WOX / α-TiO2 (110)

Feng, Z.; McBriarty, M. E.; Mane, A. U.; Lu, J.; Stair, P. C.; Elam, J. W.; Bedzyk, M. J.

doi:10.1039/c4ra14140g

Redox-driven atomic-scale changes in mixed catalysts: VO_X / WO_X / α-TiO₂ (110)

Journal Article · Thu Nov 20 00:00:00 EST 2014 · RSC Advances

DOI:https://doi.org/10.1039/c4ra14140g· OSTI ID:1370200

Feng, Z. ^[1]; McBriarty, M. E. ^[2]; Mane, A. U. ^[3]; Lu, J. ^[3]; Stair, P. C. ^[2]; Elam, J. W. ^[3]; Bedzyk, M. J. ^[2]

Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

X-ray studies of vanadium–tungsten mixed-monolayer-oxide catalysts grown on the rutile α-TiO₂(110) single crystal surface show redox behavior not observed for lone supported vanadium or tungsten oxides. Two cases are presented: sub-monolayer (sub-ML) vanadium oxide (vanadia) grown on ML tungsten oxide and ML vanadia grown on sub-ML tungsten oxide. The X-ray standing wave (XSW) and X-ray photoelectron spectroscopy (XPS) observations for both cases show coverage-dependent reversible redox-induced atomic-scale structural and chemical state changes. Atomic force microscopy shows that the mixed VO_X/WO_X overlayers have a conformal film-like structure in the as-deposited state. XSW analysis in light of XPS reveals that the V and W cations that are uncorrelated with the substrate lattice play an important role in catalytic redox reactions. Distinct differences in the redox-induced changes for these two mixed catalysts result from tuning the ratio of V to W, and relationships are drawn between the catalyst composition, structure, and chemistry. In this work, comparison of these V–W mixed cases and the corresponding unmixed cases reveals a synergistic effect in which the reduction of W can be significantly enhanced by the addition of V.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Energy Frontier Research Centers (EFRC) (United States). Institute for Atom-efficient Chemical Transformations (IACT)

Sponsoring Organization:: E. I. duPont de Nemours & Co.; National Science Foundation (NSF); Northwestern University; State of Illinois; The Dow Chemical Co.; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; FG02-03ER15457

OSTI ID:: 1370200

Journal Information:: RSC Advances, Journal Name: RSC Advances Journal Issue: 110 Vol. 4; ISSN 2046-2069; ISSN RSCACL

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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