| Autor: |
Yingzheng Li, Shaoqi Zhan, Lianpeng Tong, Wenlong Li, Yilong Zhao, Ziqi Zhao, Chang Liu, Mårten S. G. Ahlquist, Fusheng Li, Licheng Sun |
| Jazyk: |
angličtina |
| Rok vydání: |
2021 |
| Předmět: |
|
| Zdroj: |
Research, Vol 2021 (2021) |
| Druh dokumentu: |
article |
| ISSN: |
2639-5274 |
| DOI: |
10.34133/2021/9851231 |
| Popis: |
Water oxidation is a vital anodic reaction for renewable fuel generation via electrochemical- and photoelectrochemical-driven water splitting or CO2 reduction. Ruthenium complexes, such as Ru-bda family, have been shown as highly efficient water-oxidation catalysts (WOCs), particularly when they undergo a bimolecular O-O bond formation pathway. In this study, a novel Ru(pda)-type (pda2– =1,10-phenanthroline-2,9-dicarboxylate) molecular WOC with 4-vinylpyridine axial ligands was immobilized on the glassy carbon electrode surface by electrochemical polymerization. Electrochemical kinetic studies revealed that this homocoupling polymer catalyzes water oxidation through a bimolecular radical coupling pathway, where interaction between two Ru(pda)–oxyl moieties (I2M) forms the O-O bond. The calculated barrier of the I2M pathway by density-functional theory (DFT) is significantly lower than the barrier of a water nucleophilic attack (WNA) pathway. By using this polymerization strategy, the Ru centers are brought closer in the distance, and the O-O bond formation pathway by the Ru (pda) catalyst is switched from WNA in a homogeneous molecular catalytic system to I2M in the polymerized film, providing some deep insights into the importance of third coordination sphere engineering of the water oxidation catalyst. |
| Databáze: |
Directory of Open Access Journals |
| Externí odkaz: |
|
