Synthesis Gas Conversion Over Molybdenum-Based Catalysts Promoted by Transition Metals

Zhang, Lifeng; Ball, Madelyn R.; Rivera-Dones, Keishla R.; Wang, Shao-chun; Kuech, Thomas F.; Huber, George W.; Hermans, Ive; Dumesic, James A.

doi:10.1021/acscatal.9b03968

Synthesis Gas Conversion Over Molybdenum-Based Catalysts Promoted by Transition Metals

Journal Article · Wed Nov 27 00:00:00 EST 2019 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.9b03968· OSTI ID:1778254

Zhang, Lifeng ^[1]; ^[2]; ^[2]; Wang, Shao-chun ^[2]; Kuech, Thomas F. ^[2]; Huber, George W. ^[2]; ^[2]; ^[2]

Univ. of Wisconsin, Madison, WI (United States); University of Wisconsin, Madison, Chemical and Biomolecular Engineering Department
Univ. of Wisconsin, Madison, WI (United States)

Catalysts consisting of transition metals (Ni, Co, Cu and Ru) supported on molybdenum oxide synthesized by atomic layer deposition (ALD) on silica were studied for synthesis gas conversion at 523 K and a pressure of 580 psi. Transition-metal-promoted Mo-based catalysts (M/MoO₃/SiO₂) showed different selectivity patterns from the transition metal supported on silica (M/SiO₂). All molybdenum-based catalysts displayed a similar selectivity pattern, consisting of 15%~20% CH₄, 30~40% C₂₊ hydrocarbons, and 35~40% oxygenates. The addition of transition metals to molybdenum oxide promoted the catalytic activity by an order of magnitude. Temperature program reduction indicated hydrogen spillover from the transition metals to molybdenum species. H₂-D₂ exchange rate measurements showed that the addition of the transition metal enhanced the rate of H₂ dissociation on the catalyst. CO chemisorption measurements indicated that transition-metal-promoted molybdenum catalysts consist of similar amount of strong adsorption sites, which may originate from the reduced transition metal, and weak adsorption sites, which may originate from reduced molybdenum oxides. Here, a dual-site mechanism is suggested in which low-valent molybdenum species dissociate CO and generate CH_x groups that are hydrogenated to hydrocarbons or react with adsorbed CO on higher-valent Mo sites to form higher alcohols. Ni, Co and Ru are able to generate CH_x groups and enhance the production of C₂₊ oxygenates whereas all of the transition metals studied are able to provide sites for H₂ dissociation and H spillover to molybdenum oxide, leading to further enhancement in catalytic activity compared to MoO_x/SiO₂.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357; SC0014058

OSTI ID:: 1778254

Alternate ID(s):: OSTI ID: 1591932

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 1 Vol. 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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