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Title: Inverse Bimetallic RuSn Catalyst for Selective Carboxylic Acid Reduction

Abstract

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-0 nanoparticles with a near-surface bimetallic (RuSn0)-Sn-0 alloy and small SnOx 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 SnOx/Ru, with the SnOx clusters facilitating C-OH scission and Ru enabling hydrogen activation. Intrinsic barriers along nonselective pathways suggest that the RuSn alloy and SnOx resist cracking. SnOx/Ru hydrogenation activity was supported experimentally by inhibiting hydrogenation with phenylphosphonic acid, differentiating the system from fully alloyed RuSn metallic nanoparticles. Overall, this work demonstrates a plausible mechanism for selective reduction of carboxylic acids and proposes a roadmap for rational design of IBCs.

Authors:
 [1];  [1];  [1];  [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Purdue Univ., West Lafayette, IN (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Purdue Univ., West Lafayette, IN (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office
OSTI Identifier:
1577956
Alternate Identifier(s):
OSTI ID: 1775449
Report Number(s):
NREL/JA-5100-75013
Journal ID: ISSN 2155-5435
Grant/Contract Number:  
AC36-08GO28308; FOA-0000996; EEC-1647722; AC02-06CH11357; MCB-09159
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 12; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; propionic acid; 1-propanol; selective hydrogenation; aqueous-phase catalysis; ruthenium; ruthenium-tin alloy; tin oxide

Citation Formats

Vorotnikov, Vassili, Eaton, Todd R., Settle, Amy E., Orton, Kellene, Wegener, Evan C., Yang, Ce, Miller, Jeffrey T., Beckham, Gregg T., and Vardon, Derek R.. Inverse Bimetallic RuSn Catalyst for Selective Carboxylic Acid Reduction. United States: N. p., 2019. Web. https://doi.org/10.1021/acscatal.9b02726.
Vorotnikov, Vassili, Eaton, Todd R., Settle, Amy E., Orton, Kellene, Wegener, Evan C., Yang, Ce, Miller, Jeffrey T., Beckham, Gregg T., & Vardon, Derek R.. Inverse Bimetallic RuSn Catalyst for Selective Carboxylic Acid Reduction. United States. https://doi.org/10.1021/acscatal.9b02726
Vorotnikov, Vassili, Eaton, Todd R., Settle, Amy E., Orton, Kellene, Wegener, Evan C., Yang, Ce, Miller, Jeffrey T., Beckham, Gregg T., and Vardon, Derek R.. Fri . "Inverse Bimetallic RuSn Catalyst for Selective Carboxylic Acid Reduction". United States. https://doi.org/10.1021/acscatal.9b02726. https://www.osti.gov/servlets/purl/1577956.
@article{osti_1577956,
title = {Inverse Bimetallic RuSn Catalyst for Selective Carboxylic Acid Reduction},
author = {Vorotnikov, Vassili and Eaton, Todd R. and Settle, Amy E. and Orton, Kellene and Wegener, Evan C. and Yang, Ce and Miller, Jeffrey T. and Beckham, Gregg T. and Vardon, Derek R.},
abstractNote = {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-0 nanoparticles with a near-surface bimetallic (RuSn0)-Sn-0 alloy and small SnOx 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 SnOx/Ru, with the SnOx clusters facilitating C-OH scission and Ru enabling hydrogen activation. Intrinsic barriers along nonselective pathways suggest that the RuSn alloy and SnOx resist cracking. SnOx/Ru hydrogenation activity was supported experimentally by inhibiting hydrogenation with phenylphosphonic acid, differentiating the system from fully alloyed RuSn metallic nanoparticles. Overall, this work demonstrates a plausible mechanism for selective reduction of carboxylic acids and proposes a roadmap for rational design of IBCs.},
doi = {10.1021/acscatal.9b02726},
journal = {ACS Catalysis},
number = 12,
volume = 9,
place = {United States},
year = {2019},
month = {10}
}

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Figures / Tables:

Scheme 1 Scheme 1: Representations of inverse-prepared catalysts, with inverse defined as a metal oxide sequentially deposited on top of a noble metal. In this figure, M1 represents Ru and M2O represents SnOx. Alloying of the metal oxide and noble metal phase can occur to from a distinct M1M2 alloy phase, resultingmore » in an inverse bimetallic catalyst.« less

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