Atomic Structural Origin of the High Methanol Selectivity over In2O3–Metal Interfaces: Metal–Support Interactions and the Formation of a InOx Overlayer in Ru/In2O3 Catalysts during CO2 Hydrogenation
Abstract
CO2 hydrogenation to methanol is of great environmental and economic interest due to its potential to reduce carbon emissions and produce valuable chemicals in one single reaction. Compared with the unmodified traditional Cu/ZnO/Al2O3 catalyst, an indium oxide (In2O3)-based catalyst can double the methanol selectivity from 30–50 to 60–100%. It is worth noting that over catalysts involving various active metals dispersed on indium oxide (M/In2O3, M = Pd, Ni, Au, etc.), although the methanol yield is boosted, the selectivity remains similar to that of plain In2O3 despite the distinct chemical properties of the added metals. Here, to investigate the phenomena behind this behavior, we used RuO2/In2O3 as a test catalyst. The results of ambient pressure photoelectron spectroscopy, in situ X-ray absorption fine structure, and time-resolved X-ray diffraction indicate that the structure of the RuO2/In2O3 catalyst is highly dynamic in the presence of a reactive environment. Specifically, under CO2 hydrogenation conditions, Ru clusters facilitate the reduction of In2O3 to generate In2O3–x aggregates, which encapsulate the Ru systems in a migration driven by thermodynamics. In this way, the RuO sites for CH4 production are blocked while creating RuOx–In2O3–x interfacial sites with tunable metal–oxide interactions for selective methanol production. In an inverse oxide/metal configuration,more »
- Authors:
-
[1];
[4];
[4];
[1];
[5];
[5]
- Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Div.
- Stony Brook Univ., NY (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source (APS)
- Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
- Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Div.; Stony Brook Univ., NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1963197
- Report Number(s):
- BNL-224152-2023-JAAM
Journal ID: ISSN 2155-5435
- Grant/Contract Number:
- SC0012704; AC02-06CH11357; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 13; Journal Issue: 5; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; carbon dioxide; hydrogen; methanol; ethanol; platinum; ceria; tin oxide; hydrogenation; methanol synthesis; ruthenium; indium oxide; alcohols; catalysts; oxides; redox reactions; selectivity
Citation Formats
Rui, Ning, Wang, Xuelong, Deng, Kaixi, Moncada, Jorge, Rosales, Rina, Zhang, Feng, Xu, Wenqian, Waluyo, Iradwikanari, Hunt, Adrian, Stavitski, Eli, Senanayake, Sanjaya D., Liu, Ping, and Rodriguez, José A. Atomic Structural Origin of the High Methanol Selectivity over In2O3–Metal Interfaces: Metal–Support Interactions and the Formation of a InOx Overlayer in Ru/In2O3 Catalysts during CO2 Hydrogenation. United States: N. p., 2023.
Web. doi:10.1021/acscatal.2c06029.
Rui, Ning, Wang, Xuelong, Deng, Kaixi, Moncada, Jorge, Rosales, Rina, Zhang, Feng, Xu, Wenqian, Waluyo, Iradwikanari, Hunt, Adrian, Stavitski, Eli, Senanayake, Sanjaya D., Liu, Ping, & Rodriguez, José A. Atomic Structural Origin of the High Methanol Selectivity over In2O3–Metal Interfaces: Metal–Support Interactions and the Formation of a InOx Overlayer in Ru/In2O3 Catalysts during CO2 Hydrogenation. United States. https://doi.org/10.1021/acscatal.2c06029
Rui, Ning, Wang, Xuelong, Deng, Kaixi, Moncada, Jorge, Rosales, Rina, Zhang, Feng, Xu, Wenqian, Waluyo, Iradwikanari, Hunt, Adrian, Stavitski, Eli, Senanayake, Sanjaya D., Liu, Ping, and Rodriguez, José A. Fri .
"Atomic Structural Origin of the High Methanol Selectivity over In2O3–Metal Interfaces: Metal–Support Interactions and the Formation of a InOx Overlayer in Ru/In2O3 Catalysts during CO2 Hydrogenation". United States. https://doi.org/10.1021/acscatal.2c06029. https://www.osti.gov/servlets/purl/1963197.
@article{osti_1963197,
title = {Atomic Structural Origin of the High Methanol Selectivity over In2O3–Metal Interfaces: Metal–Support Interactions and the Formation of a InOx Overlayer in Ru/In2O3 Catalysts during CO2 Hydrogenation},
author = {Rui, Ning and Wang, Xuelong and Deng, Kaixi and Moncada, Jorge and Rosales, Rina and Zhang, Feng and Xu, Wenqian and Waluyo, Iradwikanari and Hunt, Adrian and Stavitski, Eli and Senanayake, Sanjaya D. and Liu, Ping and Rodriguez, José A.},
abstractNote = {CO2 hydrogenation to methanol is of great environmental and economic interest due to its potential to reduce carbon emissions and produce valuable chemicals in one single reaction. Compared with the unmodified traditional Cu/ZnO/Al2O3 catalyst, an indium oxide (In2O3)-based catalyst can double the methanol selectivity from 30–50 to 60–100%. It is worth noting that over catalysts involving various active metals dispersed on indium oxide (M/In2O3, M = Pd, Ni, Au, etc.), although the methanol yield is boosted, the selectivity remains similar to that of plain In2O3 despite the distinct chemical properties of the added metals. Here, to investigate the phenomena behind this behavior, we used RuO2/In2O3 as a test catalyst. The results of ambient pressure photoelectron spectroscopy, in situ X-ray absorption fine structure, and time-resolved X-ray diffraction indicate that the structure of the RuO2/In2O3 catalyst is highly dynamic in the presence of a reactive environment. Specifically, under CO2 hydrogenation conditions, Ru clusters facilitate the reduction of In2O3 to generate In2O3–x aggregates, which encapsulate the Ru systems in a migration driven by thermodynamics. In this way, the RuO sites for CH4 production are blocked while creating RuOx–In2O3–x interfacial sites with tunable metal–oxide interactions for selective methanol production. In an inverse oxide/metal configuration, indium oxide has properties not seen in its bulk phase that are useful for the binding and conversion of CO2. This work reveals the dynamic nature of In2O3-based catalysts, providing insights for a rational design of materials for the selective synthesis of methanol.},
doi = {10.1021/acscatal.2c06029},
journal = {ACS Catalysis},
number = 5,
volume = 13,
place = {United States},
year = {Fri Feb 17 00:00:00 EST 2023},
month = {Fri Feb 17 00:00:00 EST 2023}
}
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