Ligand Tuning in Cu(pyalk)2 Water Oxidation Electrocatalysis

Cody, Claire C.; Caes, Zofia N.; Capobianco, Matt D.; Mercado, Brandon Q.; Crabtree, Robert H.; Brudvig, Gary W.

doi:10.3390/inorganics11060229

Title: Ligand Tuning in Cu(pyalk)2 Water Oxidation Electrocatalysis

Journal Article · Fri May 26 00:00:00 EDT 2023 · Inorganics

DOI:https://doi.org/10.3390/inorganics11060229· OSTI ID:1975432

; Caes, Zofia N.; Capobianco, Matt D.; Mercado, Brandon Q.; Crabtree, Robert H.;

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.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: DEFG02-07ER15909

OSTI ID:: 1975432

Journal Information:: Inorganics, Journal Name: Inorganics Vol. 11 Journal Issue: 6; ISSN 2304-6740

Publisher:: MDPI AGCopyright Statement

Country of Publication:: Switzerland

Language:: English

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