التفاصيل البيبلوغرافية
| العنوان: |
Electronically Modified Cobalt Aminopyridine Complexes Reveal an Orthogonal Axis for Catalytic Optimization for COâ‚‚ Reduction |
| المؤلفون: |
Chapovetsky, Alon, Liu, Jeffrey J., Welborn, Matthew, Luna, John M., Do, Thomas, Haiges, Ralf, Miller, Thomas F., III, Marinescu, Smaranda C. |
| المصدر: |
Inorganic Chemistry, 59(18), 13709-13718, (2020-09-21) |
| بيانات النشر: |
American Chemical Society |
| سنة النشر: |
2020 |
| المجموعة: |
Caltech Authors (California Institute of Technology) |
| الوصف: |
The design of effective electrocatalysts for carbon dioxide reduction requires understanding the mechanistic underpinnings governing the binding, reduction, and protonation of COâ‚‚. A critical aspect to understanding and tuning these factors for optimal catalysis revolves around controlling the electronic environments of the primary and secondary coordination sphere. Herein we report a series of para-substituted cobalt aminopyridine macrocyclic catalysts 2–4 capable of carrying out the electrochemical reduction of COâ‚‚ to CO. Under catalytic conditions, complexes 2–4, as well as the unsubstituted cobalt aminopyridine complex 1, exhibit i_(cat)/i_p values ranging from 144 to 781. Complexes 2 and 4 exhibit a pronounced precatalytic wave suggestive of an ECEC mechanism. A Hammett analysis reveals that ligand modifications with electron-donating groups enhance catalysis (Ï < 0), indicative of positive charge buildup in the transition state. This trend also extends to the Co^(I/0) potential, where complexes possessing more negative E(CoI/0) reductions exhibit greater i_(cat)/i_p values. The reported modifications offer a synthetic lever to tune catalytic activity, orthogonal to our previous study of the role of pendant hydrogen bond donors. ; © 2020 American Chemical Society. Received: July 14, 2020; Published: August 31, 2020. The research was primarily supported by the National Science Foundation (NSF) under the CAREER Award CHE-1555387 (experimental studies) and the Chemistry of Life Processes Program CHE-1611581 (theoretical studies). S.C.M. acknowledges additional support from the Alfred P. Sloan Foundation through a Sloan research fellowship, the University of Southern California (USC), and the USC Women in Science and Engineering program. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. This research used resources of the ... |
| نوع الوثيقة: |
article in journal/newspaper |
| اللغة: |
unknown |
| Relation: |
https://doi.org/10.1021/acs.inorgchem.0c02086; eprintid:105197 |
| DOI: |
10.1021/acs.inorgchem.0c02086 |
| الاتاحة: |
https://doi.org/10.1021/acs.inorgchem.0c02086 |
| Rights: |
info:eu-repo/semantics/openAccess ; Other |
| رقم الانضمام: |
edsbas.F2BA24F9 |
| قاعدة البيانات: |
BASE |