Quantification of the Electrostatic Effect on Redox Potential by Positive Charges in a Catalyst Microenvironment.
| Autor: | Loewen ND; Department of Chemistry, University of California, 1 Shields Avenue, Davis, California 95616, United States., Pattanayak S; Department of Chemistry, University of California, 1 Shields Avenue, Davis, California 95616, United States., Herber R; Racah Institute of Physics, The Hebrew University of Jerusalem, Edmond J. Safra Campus, Givat Ram, Jerusalem 91904, Israel., Fettinger JC; Department of Chemistry, University of California, 1 Shields Avenue, Davis, California 95616, United States., Berben LA; Department of Chemistry, University of California, 1 Shields Avenue, Davis, California 95616, United States. |
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| Jazyk: | angličtina |
| Zdroj: | The journal of physical chemistry letters [J Phys Chem Lett] 2021 Apr 01; Vol. 12 (12), pp. 3066-3073. Date of Electronic Publication: 2021 Mar 22. |
| DOI: | 10.1021/acs.jpclett.1c00406 |
| Abstrakt: | Charged functional groups in the secondary coordination sphere (SCS) of a heterogeneous nanoparticle or homogeneous electrocatalyst are of growing interest due to enhancements in reactivity that derive from specific interactions that stabilize substrate binding or charged intermediates. At the same time, accurate benchmarking of electrocatalyst systems most often depends on the development of linear free-energy scaling relationships. However, the thermodynamic axis in those kinetic-thermodynamic correlations is most often obtained by a direct electrochemical measurement of the catalyst redox potential and might be influenced by electrostatic effects of a charged SCS. In this report, we systematically probe positive charges in a SCS and their electrostatic contributions to the electrocatalyst redox potential. A series of 11 iron carbonyl clusters modified with charged and uncharged ligands was probed, and a linear correlation between the ν |
| Databáze: | MEDLINE |
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