Partial Oxidation of Methanol on MoO3 (010): A DFT and Microkinetic Study

Choksi, Tej; Greeley, Jeffrey

doi:10.1021/acscatal.6b01633

Partial Oxidation of Methanol on MoO₃ (010): A DFT and Microkinetic Study

Journal Article · Fri Sep 09 04:00:00 EDT 2016 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.6b01633· OSTI ID:1542659

Choksi, Tej ^[1]; Greeley, Jeffrey ^[1]

Purdue Univ., West Lafayette, IN (United States)

Methanol oxidation is employed as a probe reaction to evaluate the catalytic properties of the (010) facets of molybdenum trioxide (MoO₃), a reducible oxide that exhibits a rich interplay of catalytic chemistry and structural transformations. The reaction mechanism is investigated with a combination of electronic structure calculations, using the BEEF-vdW and HSE06 functionals, and mean-field microkinetic modeling. Considered pathways include vacancy formation and oxidation, monomolecular dehydrogenation of methanol on reduced and nonreduced surfaces, bimolecular reactions between dehydrogenated intermediates, and precursor steps for hydrogen molybdenum phase (H_yMoO_3–x) formation. Methanol dissociation begins with C–H or O–H scission, with the O–H route found to be kinetically and thermodynamically preferred. Dehydrogenation of CH₂O* to CHO* is slow in comparison to desorption, leading to complete selectivity toward CH₂O. C–H scission of CH₃O* and recombination of dissociated OH* to form H₂O* are kinetically significant steps exhibiting positive degrees of rate control, while oxidation of the reduced surface through adsorbed O₂ has a negative degree of rate control. The energetics of the latter elementary step are somewhat sensitive to the choice of density functional, and although this does not affect the predicted reaction orders, the overall rate may change. To estimate the impact of the surface oxidation state on the kinetics, the external pressure of oxygen is varied in the microkinetic model, and the reaction rate is found to follow a volcano-like dependency, with the optimum rate located where surface oxidation neither promotes nor inhibits the overall rate. In conclusion, the methodology demonstrated in this study should be more broadly applicable to modeling catalytic kinetics on reducible oxide single-crystal surfaces.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1542659

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 11 Vol. 6; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Anisotropic thermal expansion of layered MoO 3 crystals Negishi, Hiroshi; Negishi, Saiko; Kuroiwa, Yoshihiro Physical Review B, Vol. 69, Issue 6 https://doi.org/10.1103/PhysRevB.69.064111	journal	February 2004
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Learning from the past: Are catalyst design principles transferrable between hydrodesulfurization and deoxygenation? Kasiraju, Sashank; Grabow, Lars C. AIChE Journal, Vol. 64, Issue 8 https://doi.org/10.1002/aic.16151	journal	March 2018
Effect of particle shape on methanol partial oxidation in a fixed bed using CFD reactor modeling Partopour, Behnam; Dixon, Anthony G. AIChE Journal, Vol. 66, Issue 5 https://doi.org/10.1002/aic.16904	journal	January 2020
Exploring the methanol decomposition mechanism on the Pt ₃ Ni(100) surface: a periodic density functional theory study Du, Pan; Gao, Yuan; Wu, Ping Physical Chemistry Chemical Physics, Vol. 20, Issue 15 https://doi.org/10.1039/c8cp00768c	journal	January 2018
Polymorphic expressions of ultrathin oxidic layers of Mo on Au(111) Lee, Taehun; Lee, Yun-Jae; Palotás, Krisztián Nanoscale, Vol. 11, Issue 13 https://doi.org/10.1039/c8nr10278c	journal	January 2019
Pathways, mechanisms, and kinetics: a strategy to examine byproduct selectivity in partial oxidation catalytic transformations on reducible oxides Miller, Jacob H.; Bui, Linh; Bhan, Aditya Reaction Chemistry & Engineering, Vol. 4, Issue 5 https://doi.org/10.1039/c8re00285a	journal	January 2019
Surface chemistry and reactivity of α-MoO 3 toward methane: A SCAN-functional based DFT study Zhang, Tianyu; Yang, Xiaofeng; Ge, Qingfeng The Journal of Chemical Physics, Vol. 151, Issue 4 https://doi.org/10.1063/1.5113787	journal	July 2019
Quasi-degenerate states and their dynamics in oxygen deficient reducible metal oxides Daelman, Nathan; Hegner, Franziska Simone; Rellán-Piñeiro, Marcos The Journal of Chemical Physics, Vol. 152, Issue 5 https://doi.org/10.1063/1.5138484	journal	February 2020

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DFT
MoO3
adsorption
defects in solids
kinetics
methanol oxidation
microkinetic modeling
oxidation
oxygen
reducible oxide