Work

Unraveling the Role of the Nitrate Ion and Solvent Water on the O─O Bond Formation Step in Fe─TAML Catalyzed Water Oxidation

Year: 2024

Type: article

Abstract: Density functional theory‐based molecular dynamics (DFT‐MD) combined with an explicit solvation model were employed to further elucidate the O─O bond formation step in Fe─TAML catalyzed water oxidation reaction. The water nucleophilic attack (WNA) and nitrate nucleophilic attack (NNA) on the oxo group of the high‐valent [TAML+•─Fe5+═O] species were calculated to have comparable active barriers (24 kcal/mol versus 22 kcal/mol). This suggests nitrate ion can behave as a cocatalyst to promote the O─O bond formation. More importantly, a crucial role of the presence and thermal motion of solvent water in the NNA process was observed. This was quantified by an increase of the activation energy barrier by 4 kcal/mol, determined by comparing the explicit solvent DFT‐MD simulation with implicit solvent static DFT calculation.

Source: ChemCatChem

DOI: 10.1002/cctc.202401356

Authors: Ying‐Ying Li, Aaron Eisses, Evert Jan Meijer, Si‐Xiang Chen, Rong‐Zhen Liao

Institutions: Zhengzhou Normal University, Huazhong University of Science and Technology, University of Amsterdam

Language: English

Topic: Metal-Catalyzed Oxygenation Mechanisms

Subfield: Inorganic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: bronze

Funders: Huazhong University of Science and Technology, Natural Science Foundation of Henan Province, Zhengzhou Normal University

Awards: G1393470389, G267530834, G6718938520, G8272181167