Identification of Single-Atom Ni Site Active toward Electrochemical CO2 Conversion to CO
| Autor: | Min Wook Chung, Sung June Cho, Hyung Suk Oh, Da Hye Won, Junseong Lee, Woojin Yang, Ji Yeon Ryu, Jiwon Seo, Haesol Kim, Dongyup Shin, Hyungjun Kim, Sun Hee Kim, Donghyuk Jeong, Chang Hyuck Choi, Keun Hwa Chae |
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| Rok vydání: | 2021 |
| Předmět: |
Electrolysis
Inorganic chemistry chemistry.chemical_element General Chemistry 010402 general chemistry Electrochemistry 01 natural sciences Biochemistry Redox Catalysis 0104 chemical sciences law.invention chemistry.chemical_compound Colloid and Surface Chemistry chemistry law Tetraphenylporphyrin Atom High activity Carbon |
| Zdroj: | Journal of the American Chemical Society. 143:925-933 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | Electrocatalytic conversion of CO2 into value-added products offers a new paradigm for a sustainable carbon economy. For active CO2 electrolysis, the single-atom Ni catalyst has been proposed as promising from experiments, but an idealized Ni-N4 site shows an unfavorable energetics from theory, leading to many debates on the chemical nature responsible for high activity. To resolve this conundrum, here we investigated CO2 electrolysis of Ni sites with well-defined coordination, tetraphenylporphyrin (N4-TPP) and 21-oxatetraphenylporphyrin (N3O-TPP). Advanced spectroscopic and computational studies revealed that the broken ligand-field symmetry is the key for active CO2 electrolysis, which subordinates an increase in the Ni redox potential yielding NiI. Along with their importance in activity, ligand-field symmetry and strength are directly related to the stability of the Ni center. This suggests the next quest for an activity-stability map in the domain of ligand-field strength, toward a rational ligand-field engineering of single-atom Ni catalysts for efficient CO2 electrolysis. |
| Databáze: | OpenAIRE |
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