Insights into Active Sites and Mechanisms of Benzyl Alcohol Oxidation on Nickel–Iron Oxyhydroxide Electrodes
Abstract
The electrochemical oxidation of bio-derived molecules has recently garnered interest for its potential in opening electrified synthetic pathways toward value-added products. Herein, we investigate the electrochemical conversion of benzyl alcohol (BA) to benzaldehyde and benzoate on nickel–iron (Fe ~ 7–18%) electrodes as a model system to understand reaction mechanisms and environmental conditions that can transform these molecules. Our results indicate a strong correlation between benzyl alcohol oxidation (BAO) onset potentials and Ni(II/III) redox peak positions, highlighting the potential role that lower oxidation states of nickel, i.e., Ni3+, can play in BAO catalysis. Our work on the Ni2+/3+ system complements mechanisms that involve higher oxidation states of Ni as reported by others. We note that the Ni redox position and thus BAO onset is impacted by Fe incorporation during electrochemistry from unpurified electrolytes, which can resemble standard reactor operating conditions. We perform a systematic computational investigation into BAO and provide density functional theory (DFT) insights into how the redox mechanism has been such a prominent focus of alcohol oxidations. This includes the mode of BA adsorption and the nature of the adsorption site; upon conversion of the Ni2+ surface to active Ni3+ via hydroxyl deprotonation, BAO is thermodynamically downhill. Our DFTmore »
- Authors:
-
[1];
[1];
[2];
[2];
[1];
[2];
[3]
- Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)
- OSTI Identifier:
- 2006812
- Grant/Contract Number:
- AC02-76SF00515; AC02-05CH11231; ECCS-2026822
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 13; Journal Issue: 7; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alcohols; electrodes; electrolytes; oxidation; redox reactions; nickel−iron oxyhydroxide; benzyl alcohol; electrocatalysis; electro-oxidation; biomass conversion; redox mechanism; density functional theory
Citation Formats
Wei, Lingze, Hossain, Md Delowar, Boyd, Michael J., Aviles-Acosta, Jaime, Kreider, Melissa E., Nielander, Adam C., Stevens, Michaela Burke, Jaramillo, Thomas F., Bajdich, Michal, and Hahn, Christopher. Insights into Active Sites and Mechanisms of Benzyl Alcohol Oxidation on Nickel–Iron Oxyhydroxide Electrodes. United States: N. p., 2023.
Web. doi:10.1021/acscatal.2c05656.
Wei, Lingze, Hossain, Md Delowar, Boyd, Michael J., Aviles-Acosta, Jaime, Kreider, Melissa E., Nielander, Adam C., Stevens, Michaela Burke, Jaramillo, Thomas F., Bajdich, Michal, & Hahn, Christopher. Insights into Active Sites and Mechanisms of Benzyl Alcohol Oxidation on Nickel–Iron Oxyhydroxide Electrodes. United States. https://doi.org/10.1021/acscatal.2c05656
Wei, Lingze, Hossain, Md Delowar, Boyd, Michael J., Aviles-Acosta, Jaime, Kreider, Melissa E., Nielander, Adam C., Stevens, Michaela Burke, Jaramillo, Thomas F., Bajdich, Michal, and Hahn, Christopher. Tue .
"Insights into Active Sites and Mechanisms of Benzyl Alcohol Oxidation on Nickel–Iron Oxyhydroxide Electrodes". United States. https://doi.org/10.1021/acscatal.2c05656. https://www.osti.gov/servlets/purl/2006812.
@article{osti_2006812,
title = {Insights into Active Sites and Mechanisms of Benzyl Alcohol Oxidation on Nickel–Iron Oxyhydroxide Electrodes},
author = {Wei, Lingze and Hossain, Md Delowar and Boyd, Michael J. and Aviles-Acosta, Jaime and Kreider, Melissa E. and Nielander, Adam C. and Stevens, Michaela Burke and Jaramillo, Thomas F. and Bajdich, Michal and Hahn, Christopher},
abstractNote = {The electrochemical oxidation of bio-derived molecules has recently garnered interest for its potential in opening electrified synthetic pathways toward value-added products. Herein, we investigate the electrochemical conversion of benzyl alcohol (BA) to benzaldehyde and benzoate on nickel–iron (Fe ~ 7–18%) electrodes as a model system to understand reaction mechanisms and environmental conditions that can transform these molecules. Our results indicate a strong correlation between benzyl alcohol oxidation (BAO) onset potentials and Ni(II/III) redox peak positions, highlighting the potential role that lower oxidation states of nickel, i.e., Ni3+, can play in BAO catalysis. Our work on the Ni2+/3+ system complements mechanisms that involve higher oxidation states of Ni as reported by others. We note that the Ni redox position and thus BAO onset is impacted by Fe incorporation during electrochemistry from unpurified electrolytes, which can resemble standard reactor operating conditions. We perform a systematic computational investigation into BAO and provide density functional theory (DFT) insights into how the redox mechanism has been such a prominent focus of alcohol oxidations. This includes the mode of BA adsorption and the nature of the adsorption site; upon conversion of the Ni2+ surface to active Ni3+ via hydroxyl deprotonation, BAO is thermodynamically downhill. Our DFT study also introduces the possibility of a vacancy-driven mechanism, though expected to be less prevalent during catalysis than the redox mechanism for a Ni3+ surface. Through the systematic investigation of experimental reaction conditions and computational free energy thermodynamics, we have gained valuable insights into BAO reaction mechanisms that inform catalytic activity. Our study opens avenues for further design and development of catalyst active sites for the oxidation of related organic molecules.},
doi = {10.1021/acscatal.2c05656},
journal = {ACS Catalysis},
number = 7,
volume = 13,
place = {United States},
year = {Tue Mar 14 00:00:00 EDT 2023},
month = {Tue Mar 14 00:00:00 EDT 2023}
}
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