Inverse Bimetallic RuSn Catalyst for Selective Carboxylic Acid Reduction

Vorotnikov, Vassili; Eaton, Todd R.; Settle, Amy E.; Orton, Kellene; Wegener, Evan C.; Yang, Ce; Miller, Jeffrey T.; Beckham, Gregg T.; Vardon, Derek R.

doi:10.1021/acscatal.9b02726

Title: Inverse Bimetallic RuSn Catalyst for Selective Carboxylic Acid Reduction

Journal Article · 25 October 2019 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.9b02726 · OSTI ID:1577956

Vorotnikov, Vassili ^[1]; Eaton, Todd R. ^[1]; Settle, Amy E. ^[1]; Orton, Kellene ^[1]; Wegener, Evan C. ^[2]; Yang, Ce ^[3];

^[4];

^[1];

^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)
Purdue Univ., West Lafayette, IN (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Purdue Univ., West Lafayette, IN (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

Inverse bimetallic catalysts (IBCs), synthesized by sequential deposition of noble and oxophilic metals, offer potential reactivity enhancements to various reactions, including the reduction of carboxylic acids for renewable fuels and chemicals. Here, we demonstrate that an IBC comprising RuSn exhibits high selectivity for propionic acid reduction to 1-propanol, while Ru alone results in cracking. On RuSn, X-ray absorption spectroscopy identified Ru^o nanoparticles with a near-surface bimetallic Ru^oSn^o alloy and small SnO_x domains. Corresponding model surfaces were examined with density functional theory to elucidate the observed selectivity difference. Only selective hydrogenation is predicted to be favorable on SnO_x/Ru, with the SnO_x clusters facilitating C-OH scission and Ru enabling hydrogen activation. Intrinsic barriers along nonselective pathways suggest that the RuSn alloy and SnO_x resist cracking. SnO_x/Ru hydrogenation activity was supported experimentally by inhibiting hydrogenation with phenylphosphonic acid, differentiating the system from fully alloyed RuSn metallic nanoparticles. Altogether, this work demonstrates a plausible mechanism for selective reduction of carboxylic acids and proposes a roadmap for rational design of IBCs.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office

Grant/Contract Number:: AC36-08GO28308; AC02-06CH11357

OSTI ID:: 1577956

Report Number(s):: NREL/JA--5100-75013

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 12 Vol. 9; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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09 BIOMASS FUELS
1-propanol
aqueous-phase catalysis
propionic acid
ruthenium
ruthenium-tin alloy
selective hydrogenation
tin oxide

Title: Inverse Bimetallic RuSn Catalyst for Selective Carboxylic Acid Reduction

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