Ligand Tuning in Cu(pyalk)2 Water Oxidation Electrocatalysis

Autor: Claire C. Cody, Zofia N. Caes, Matt D. Capobianco, Brandon Q. Mercado, Robert H. Crabtree, Gary W. Brudvig
Jazyk: angličtina
Rok vydání: 2023
Předmět:
Zdroj: Inorganics, Vol 11, Iss 6, p 229 (2023)
Druh dokumentu: article
ISSN: 2304-6740
DOI: 10.3390/inorganics11060229
Popis: Molecular copper water oxidation electrocatalysts have been extensively studied in recent years for their potential use in artificial photosynthetic systems for solar energy conversion. Although ligand modification and its ability to influence catalytic properties is a key advantage of molecular systems, there are, as yet, few examples of systematic studies of these effects. Our oxidatively resistant pyalk (2-pyridyl-2-propanoate) ligand forms a complex with copper(II) that catalyzes water oxidation and provides an attractive scaffold for systematic ligand tuning. Here, we report a series of analogous copper complexes with electron-donating (methoxy-) and -withdrawing (methoxycarbonyl-) groups at the para-position of the pyalk ligand. Trends in the pKa and redox potential align with first-principles predictions for the electron-withdrawing and electron-donating groups. While the modified complexes show good activity for water oxidation, lowered faradaic efficiency in comparison to the parent complex highlights the importance of stability considerations for catalyst tuning.
Databáze: Directory of Open Access Journals
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