Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag0.03Au0.97

Zugic, Branko; van Spronsen, Matthijs A.; Heine, Christian; Montemore, Matthew M.; Li, Yuanyuan; Zakharov, Dmitri N.; Karakalos, Stavros; Lechner, Barbara A. J.; Crumlin, Ethan; Biener, Monika M.; Frenkel, Anatoly I.; Biener, Juergen; Stach, Eric A.; Salmeron, Miquel B.; Kaxiras, Efthimios; Madix, Robert J.; Friend, Cynthia M.

doi:10.1016/j.jcat.2019.08.041

Title: Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag_0.03Au_0.97

Journal Article · Tue Oct 22 00:00:00 EDT 2019 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2019.08.041· OSTI ID:1606185

Zugic, Branko ^[1]; van Spronsen, Matthijs A. ^[2]; Heine, Christian ^[3]; Montemore, Matthew M. ^[4]; Li, Yuanyuan ^[5]; Zakharov, Dmitri N. ^[6];

^[1]; Lechner, Barbara A. J. ^[3]; Crumlin, Ethan ^[7]; Biener, Monika M. ^[8];

^[9]; Biener, Juergen ^[8]; Stach, Eric A. ^[6]; Salmeron, Miquel B. ^[3]; Kaxiras, Efthimios ^[4]; Madix, Robert J. ^[4]; Friend, Cynthia M. ^[10]

Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Harvard Univ., Cambridge, MA (United States). Paulson School of Engineering and Applied Sciences
Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States)
Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology, Paulson School of Engineering and Applied Sciences

Activating pretreatments are used to tune surface composition and structure of bimetallic-alloy catalysts. Herein, the activation-induced changes in material properties of a nanoporous Ag_0.03Au_0.97 alloy and their subsequent evolution under steady-state CH₃OH oxidation conditions are investigated. Activation using O₃ results in AgO and Au₂O₃, strongly enriching the near-surface region in Ag. These oxides reduce in the O₂/CH₃OH mixture, yielding CO₂ and producing a highly Ag-enriched surface alloy. At the reaction tem-perature (423 K), Ag realloys gradually with Au but remains enriched (stabilized by surface O) in the top few nanometers, producing methyl formate selectively without significant deactivation. At higher tem-peratures, bulk diffusion induces sintering and Ag redistribution, leading to a loss of activity. These find-ings demonstrate that material properties determining catalytic activity are dynamic and that metastable (kinetically trapped) forms of the material may be responsible for catalysis, providing guiding principles concerning the activation of heterogeneous catalysts for selective oxidation.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: SC0012704; AC52-07NA27344; AC02-05CH11231

OSTI ID:: 1606185

Alternate ID(s):: OSTI ID: 1575804; OSTI ID: 1616393; OSTI ID: 1637299; OSTI ID: 1647451

Report Number(s):: BNL-213755-2020-JAAM; LLNL-JRNL-774771; LLNL-JRNL-777470

Journal Information:: Journal of Catalysis, Vol. 380, Issue C; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 23 works

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37 INORGANIC
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PHYSICAL AND ANALYTICAL CHEMISTRY
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Selective oxidation of CH3OH
In situ/operando multimodal approach
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Title: Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag0.03Au0.97

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Title: Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag_0.03Au_0.97