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

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

doi:10.1016/j.jcat.2019.08.041

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

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

Research output: Contribution to journal › Article › peer-review

23 Scopus citations

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 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 Au₂O_3, 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 temperature (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 temperatures, bulk diffusion induces sintering and Ag redistribution, leading to a loss of activity. These findings 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.

Original language	English
Pages (from-to)	366-374
Number of pages	9
Journal	Journal of Catalysis
Volume	380
DOIs	https://doi.org/10.1016/j.jcat.2019.08.041
State	Published - Dec 2019
Externally published	Yes

Funding

This work was supported as part of the Integrated Mesoscale Architectures for Sustainable Catalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under award #DE-SC0012573. It also used resources (beamline 9.3.2) of the Advanced Light Source, which is supported by the Office of Science of the U.S. DOE under Contract No. DE-AC02-05CH11231. Work at LLNL was performed under the auspices of the U.S. Department of Energy by LLNL under Contract DE-AC52-07NA27344. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704. AIF and YL acknowledge the support from the U.S. Department of Energy Grant No. DE-FG02-03ER15476. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. We acknowledge the support at the BL2-2 beamline of the SSRL by the Synchrotron Catalysis Consortium (U.S. Department of Energy, Office of Basic Energy Sciences, Grant No. DE-SC0012335). This work was supported as part of the Integrated Mesoscale Architectures for Sustainable Catalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy , Office of Science, Basic Energy Sciences under award #DE-SC0012573. It also used resources (beamline 9.3.2) of the Advanced Light Source, which is supported by the Office of Science of the U.S. DOE under Contract No. DE-AC02-05CH11231. Work at LLNL was performed under the auspices of the U.S. Department of Energy by LLNL under Contract DE-AC52-07NA27344. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704. AIF and YL acknowledge the support from the U.S. Department of Energy Grant No. DE-FG02-03ER15476. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. We acknowledge the support at the BL2-2 beamline of the SSRL by the Synchrotron Catalysis Consortium (U.S. Department of Energy, Office of Basic Energy Sciences, Grant No. DE-SC0012335).

Funders	Funder number
DOE Office of Science
Energy Frontier Research Center
Office of Basic Energy Sciences	DE-AC02-76SF00515
Synchrotron Catalysis Consortium	DE-SC0012335
U.S. Department of Energy	DE-AC02-05CH11231
Office of Science
Basic Energy Sciences	-SC0012573
Lawrence Livermore National Laboratory	DE-AC52-07NA27344
Brookhaven National Laboratory	DE-FG02-03ER15476, DE-SC0012704

Keywords

Diluted alloys
In situ/operando multimodal approach
Metastability
Nanoporous Au
Selective oxidation of CHOH

Access to Document

10.1016/j.jcat.2019.08.041

Cite this

Zugic, B., van Spronsen, M. A., Heine, C., Montemore, M. M., Li, Y., Zakharov, D. N., Karakalos, S., Lechner, B. A. J., Crumlin, E., Biener, M. M., Frenkel, A. I., Biener, J., Stach, E. A., Salmeron, M. B., Kaxiras, E., Madix, R. J., & Friend, C. M. (2019). Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag_0.03Au_0.97. Journal of Catalysis, 380, 366-374. https://doi.org/10.1016/j.jcat.2019.08.041

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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 temperature (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 temperatures, bulk diffusion induces sintering and Ag redistribution, leading to a loss of activity. These findings 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.",

keywords = "Diluted alloys, In situ/operando multimodal approach, Metastability, Nanoporous Au, Selective oxidation of CHOH",

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

note = "Publisher Copyright: {\textcopyright} 2019 Elsevier Inc.",

year = "2019",

month = dec,

doi = "10.1016/j.jcat.2019.08.041",

language = "English",

volume = "380",

pages = "366--374",

journal = "Journal of Catalysis",

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Zugic, B, van Spronsen, MA, Heine, C, Montemore, MM, Li, Y, Zakharov, DN, Karakalos, S, Lechner, BAJ, Crumlin, E, Biener, MM, Frenkel, AI, Biener, J, Stach, EA, Salmeron, MB, Kaxiras, E, Madix, RJ & Friend, CM 2019, 'Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag_0.03Au_0.97', Journal of Catalysis, vol. 380, pp. 366-374. https://doi.org/10.1016/j.jcat.2019.08.041

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T1 - Evolution of steady-state material properties during catalysis

T2 - Oxidative coupling of methanol over nanoporous Ag0.03Au0.97

AU - Zugic, Branko

AU - van Spronsen, Matthijs A.

AU - Heine, Christian

AU - Montemore, Matthew M.

AU - Li, Yuanyuan

AU - Zakharov, Dmitri N.

AU - Karakalos, Stavros

AU - Lechner, Barbara A.J.

AU - Crumlin, Ethan

AU - Biener, Monika M.

AU - Frenkel, Anatoly I.

AU - Biener, Juergen

AU - Stach, Eric A.

AU - Salmeron, Miquel B.

AU - Kaxiras, Efthimios

AU - Madix, Robert J.

AU - Friend, Cynthia M.

PY - 2019/12

Y1 - 2019/12

N2 - 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 temperature (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 temperatures, bulk diffusion induces sintering and Ag redistribution, leading to a loss of activity. These findings 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.

AB - 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 temperature (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 temperatures, bulk diffusion induces sintering and Ag redistribution, leading to a loss of activity. These findings 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.

KW - Diluted alloys

KW - In situ/operando multimodal approach

KW - Metastability

KW - Nanoporous Au

KW - Selective oxidation of CHOH

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