Identification of the active complex for CO oxidation over single-atom Ir-on-MgAl2O4 catalysts
Abstract
Supported single atoms provide the best utilization of noble metals and provide an opportunity to design new heterogeneous catalysts. However, identification of the active single atoms structure is required for understanding the reaction mechanism and guiding catalyst design. We used in-situ infrared spectroscopy, in-operando x-ray adsorption spectroscopy and quantum chemical calculations to show that Ir(CO)/MgAl2O4 is the active single atom complex for low temperature CO oxidation and Ir(CO)(O) is the most stable intermediate. In contrast to poisoning of nanoparticles by CO, the formation of Ir(CO) on single atoms results in a different reaction mechanism and high activity for low temperature CO oxidation. This is due to the ability of single atoms to coordinate with multiple ligands, where CO, in Ir(CO)(O), acts as a facilitator by lowering the reaction barrier between gas phase CO and adsorbed O (Eley-Rideal mechanism).
- Authors:
-
[1];
[1]
- Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1503098
- Alternate Identifier(s):
- OSTI ID: 1502401
- Report Number(s):
- PNNL-SA-138518
Journal ID: ISSN 2520-1158
- Grant/Contract Number:
- AC02-76SF00515; AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Catalysis
- Additional Journal Information:
- Journal Volume: 2; Journal Issue: 2; Journal ID: ISSN 2520-1158
- Publisher:
- Springer Nature
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Lu, Yubing, Wang, Jiamin, Yu, Liang, Kovarik, Libor, Zhang, Xiwen, Hoffman, Adam S., Gallo, Alessandro, Bare, Simon R., Sokaras, Dimosthenis, Kroll, Thomas, Dagle, Vanessa, Xin, Hongliang, and Karim, Ayman M.. Identification of the active complex for CO oxidation over single-atom Ir-on-MgAl2O4 catalysts. United States: N. p., 2018.
Web. doi:10.1038/s41929-018-0192-4.
Lu, Yubing, Wang, Jiamin, Yu, Liang, Kovarik, Libor, Zhang, Xiwen, Hoffman, Adam S., Gallo, Alessandro, Bare, Simon R., Sokaras, Dimosthenis, Kroll, Thomas, Dagle, Vanessa, Xin, Hongliang, & Karim, Ayman M.. Identification of the active complex for CO oxidation over single-atom Ir-on-MgAl2O4 catalysts. United States. https://doi.org/10.1038/s41929-018-0192-4
Lu, Yubing, Wang, Jiamin, Yu, Liang, Kovarik, Libor, Zhang, Xiwen, Hoffman, Adam S., Gallo, Alessandro, Bare, Simon R., Sokaras, Dimosthenis, Kroll, Thomas, Dagle, Vanessa, Xin, Hongliang, and Karim, Ayman M.. Mon .
"Identification of the active complex for CO oxidation over single-atom Ir-on-MgAl2O4 catalysts". United States. https://doi.org/10.1038/s41929-018-0192-4. https://www.osti.gov/servlets/purl/1503098.
@article{osti_1503098,
title = {Identification of the active complex for CO oxidation over single-atom Ir-on-MgAl2O4 catalysts},
author = {Lu, Yubing and Wang, Jiamin and Yu, Liang and Kovarik, Libor and Zhang, Xiwen and Hoffman, Adam S. and Gallo, Alessandro and Bare, Simon R. and Sokaras, Dimosthenis and Kroll, Thomas and Dagle, Vanessa and Xin, Hongliang and Karim, Ayman M.},
abstractNote = {Supported single atoms provide the best utilization of noble metals and provide an opportunity to design new heterogeneous catalysts. However, identification of the active single atoms structure is required for understanding the reaction mechanism and guiding catalyst design. We used in-situ infrared spectroscopy, in-operando x-ray adsorption spectroscopy and quantum chemical calculations to show that Ir(CO)/MgAl2O4 is the active single atom complex for low temperature CO oxidation and Ir(CO)(O) is the most stable intermediate. In contrast to poisoning of nanoparticles by CO, the formation of Ir(CO) on single atoms results in a different reaction mechanism and high activity for low temperature CO oxidation. This is due to the ability of single atoms to coordinate with multiple ligands, where CO, in Ir(CO)(O), acts as a facilitator by lowering the reaction barrier between gas phase CO and adsorbed O (Eley-Rideal mechanism).},
doi = {10.1038/s41929-018-0192-4},
journal = {Nature Catalysis},
number = 2,
volume = 2,
place = {United States},
year = {2018},
month = {12}
}
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