Adjusting the Chemical Reactivity of Oxygen for Propylene Epoxidation on Silver by Rational Design: The Use of an Oxyanion and Cl
Abstract
The development of catalysts for propylene oxide production from direct epoxidation using propylene and oxygen remains a challenge. Compared to ethylene epoxidation, where selectivity on silver catalysts is high, the low selectivity to produce propylene oxide over silver is partially attributed to the lack of electrophilic oxygen under propylene epoxidation reaction conditions. Here, we investigate how to mediate the chemical reactivity of oxygen by theory-inspired experiments for propylene epoxidation. We show how adding electrophilic-O via SO4 oxyanions to the surface of silver increases epoxide selectivity. Moreover, we show how the addition of Cl to the SO4-modified catalyst activates the oxyanion, giving a more than 4-fold increase in selectivity to propylene oxide. Finally, we explore different systems using DFT and draw a picture on how the next catalyst/co-catalyst systems should be tuned to design a catalyst with high selectivity for direct propylene oxidation.
- Authors:
-
[1];
[1];
[4];
[6]
- Catalysis for Energy, CE-GKAT, Energy Materials In-situ Laboratory (EMIL), BESSY II, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Straße 15, 12489 Berlin, Germany, Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
- Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
- Catalysis for Energy, CE-GKAT, Energy Materials In-situ Laboratory (EMIL), BESSY II, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Straße 15, 12489 Berlin, Germany, Department of Heterogeneous Reactions, Max Planck Institute for Chemical Energy Conversion, Stiftstraße 34-36, Mülheim an der Ruhr 45470, Germany
- CNR-IOM DEMOCRITOS, Consiglio Nazionale delle Ricerche─Istituto Officina dei Materiali, c/o SISSA, Via Bonomea 265, 34136 Trieste, Italy
- Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany, Department of Heterogeneous Reactions, Max Planck Institute for Chemical Energy Conversion, Stiftstraße 34-36, Mülheim an der Ruhr 45470, Germany
- Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany, Theoretical Division, Los Alamos National Lab, Los Alamos, New Mexico 00000, United States
- Publication Date:
- Research Org.:
- Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH (Germany); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1972747
- Alternate Identifier(s):
- OSTI ID: 1972666; OSTI ID: 1973822
- Report Number(s):
- LA-UR-23-23269
Journal ID: ISSN 2155-5435
- Grant/Contract Number:
- 89233218CNA000001
- Resource Type:
- Published Article
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Name: ACS Catalysis Journal Volume: 13 Journal Issue: 9; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; silver; propylene epoxidation; chlorine; sulfur; NAP-XPS; operando; alkyls; organic reactions; oxygen; selectivity
Citation Formats
Carbonio, Emilia A., Sulzmann, Frederic, Klyushin, Alexander Yu., Hävecker, Michael, Piccinin, Simone, Knop-Gericke, Axel, Schlögl, Robert, and Jones, Travis E. Adjusting the Chemical Reactivity of Oxygen for Propylene Epoxidation on Silver by Rational Design: The Use of an Oxyanion and Cl. United States: N. p., 2023.
Web. doi:10.1021/acscatal.3c00297.
Carbonio, Emilia A., Sulzmann, Frederic, Klyushin, Alexander Yu., Hävecker, Michael, Piccinin, Simone, Knop-Gericke, Axel, Schlögl, Robert, & Jones, Travis E. Adjusting the Chemical Reactivity of Oxygen for Propylene Epoxidation on Silver by Rational Design: The Use of an Oxyanion and Cl. United States. https://doi.org/10.1021/acscatal.3c00297
Carbonio, Emilia A., Sulzmann, Frederic, Klyushin, Alexander Yu., Hävecker, Michael, Piccinin, Simone, Knop-Gericke, Axel, Schlögl, Robert, and Jones, Travis E. Mon .
"Adjusting the Chemical Reactivity of Oxygen for Propylene Epoxidation on Silver by Rational Design: The Use of an Oxyanion and Cl". United States. https://doi.org/10.1021/acscatal.3c00297.
@article{osti_1972747,
title = {Adjusting the Chemical Reactivity of Oxygen for Propylene Epoxidation on Silver by Rational Design: The Use of an Oxyanion and Cl},
author = {Carbonio, Emilia A. and Sulzmann, Frederic and Klyushin, Alexander Yu. and Hävecker, Michael and Piccinin, Simone and Knop-Gericke, Axel and Schlögl, Robert and Jones, Travis E.},
abstractNote = {The development of catalysts for propylene oxide production from direct epoxidation using propylene and oxygen remains a challenge. Compared to ethylene epoxidation, where selectivity on silver catalysts is high, the low selectivity to produce propylene oxide over silver is partially attributed to the lack of electrophilic oxygen under propylene epoxidation reaction conditions. Here, we investigate how to mediate the chemical reactivity of oxygen by theory-inspired experiments for propylene epoxidation. We show how adding electrophilic-O via SO4 oxyanions to the surface of silver increases epoxide selectivity. Moreover, we show how the addition of Cl to the SO4-modified catalyst activates the oxyanion, giving a more than 4-fold increase in selectivity to propylene oxide. Finally, we explore different systems using DFT and draw a picture on how the next catalyst/co-catalyst systems should be tuned to design a catalyst with high selectivity for direct propylene oxidation.},
doi = {10.1021/acscatal.3c00297},
journal = {ACS Catalysis},
number = 9,
volume = 13,
place = {United States},
year = {Mon Apr 17 00:00:00 EDT 2023},
month = {Mon Apr 17 00:00:00 EDT 2023}
}
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