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

Abstract

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 Ag0.03Au0.97 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.

Authors:
 [1];  [2];  [3];  [4];  [5];  [6]; ORCiD logo [1];  [3];  [7];  [8]; ORCiD logo [9];  [8];  [6];  [3];  [4];  [4];  [10]
  1. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
  2. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  4. Harvard Univ., Cambridge, MA (United States). Paulson School of Engineering and Applied Sciences
  5. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
  6. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  8. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  9. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States)
  10. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology, Paulson School of Engineering and Applied Sciences
Publication Date:
Research Org.:
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 Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1606185
Alternate Identifier(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 ID: ISSN 0021-9517
Grant/Contract Number:  
SC0012704; AC52-07NA27344; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 380; Journal Issue: C; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Nanoporous Au; Diluted alloys; Selective oxidation of CH3OH; In situ/operando multimodal approach; Metastability

Citation Formats

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., and Friend, Cynthia M. Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag0.03Au0.97. United States: N. p., 2019. Web. doi:10.1016/j.jcat.2019.08.041.
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. Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag0.03Au0.97. United States. https://doi.org/10.1016/j.jcat.2019.08.041
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., and Friend, Cynthia M. Tue . "Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag0.03Au0.97". United States. https://doi.org/10.1016/j.jcat.2019.08.041. https://www.osti.gov/servlets/purl/1606185.
@article{osti_1606185,
title = {Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag0.03Au0.97},
author = {Zugic, Branko and van Spronsen, Matthijs A. and Heine, Christian and Montemore, Matthew M. and Li, Yuanyuan and Zakharov, Dmitri N. and Karakalos, Stavros and Lechner, Barbara A. J. and Crumlin, Ethan and Biener, Monika M. and Frenkel, Anatoly I. and Biener, Juergen and Stach, Eric A. and Salmeron, Miquel B. and Kaxiras, Efthimios and Madix, Robert J. and Friend, Cynthia M.},
abstractNote = {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 Ag0.03Au0.97 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.},
doi = {10.1016/j.jcat.2019.08.041},
journal = {Journal of Catalysis},
number = C,
volume = 380,
place = {United States},
year = {2019},
month = {10}
}

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Cited by: 23 works
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Figures / Tables:

Fig. 1 Fig. 1: Restructuring and redistribution of Ag at the surface of free-standing np Ag0.03Au0.97 under steady-state conditions, related to the high selectivity for methyl formate (MF) production. Exposure of the as-prepared catalyst to O3 forms an oxide layer that is a few nanometers thick, with Ag concentrated in nanometer-scale patchesmore » on the surface. Under steady-state conditions, Ag redistributes into a silver-rich AgAu alloy that is kinetically confined to nanometer-scale regions near the surface. Dioxygen can be activated on these alloy regions, but requires multiple Ag atoms, based on DFT results. This work demonstrates the strong interplay between activation and kinetic trapping of a metastable state for steady-state catalytic function. The schematic is based on a combination of results from environmental transmission electron microscopy (E TEM), ambient-pressure X-ray photoelectron spectroscopy (AP XPS), and operando X-ray absorption fine-structure (XAFS) analysis. Color coding: Au matrix (dark yellow), Ag-rich regions (black speckles), AgAu oxide (pink), and AgAu alloy (dark purple).« less

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.