期刊
ACS CATALYSIS
卷 11, 期 12, 页码 7223-7240出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c01395
关键词
water oxidation; copper; electrocatalysis; dioxygen; trinuclear; DFT calculations
资金
- U.S. National Science Foundation [CBET-1805022]
- MAXNET Energy effort
- Max Planck Society
- Helmholtz Energy Materials Foundry (HEMF)
This study presents a trinuclear copper(II) complex as a homogeneous electrocatalyst for water oxidation, exhibiting high catalytic activity and selectivity under different pH conditions. Experimental and computational studies provide insights into the relationship between the copper complex and the catalytic mechanism, highlighting the importance of phosphate and nitrogen-based ligands in facilitating proton transfer processes.
We report a trinuclear copper( II) complex, [(DAM)Cu-3(mu(3)-O)][Cl] 4 (1, DAM = dodecaaza macrotetracycle), as a homogeneous electrocatalyst for water oxidation to dioxygen in phosphate-buffered solutions at pH 7.0, 8.1, and 11.5. Electrocatalytic water oxidation at pH 7 occurs at an overpotential of 550 mV with a turnover frequency of similar to 19 s(-1) at 1.5 V vs NHE. Controlled potential electrolysis (CPE) experiments at pH 11.5 over 3 h at 1.2 V and at pH 8.1 for 40 min at 1.37 V vs NHE confirm the evolution of dioxygen with Faradaic efficiencies of 81% and 45%, respectively. Rinse tests conducted after CPE studies provide evidence for the homogeneous nature of the catalysis. The linear dependence of the current density on the catalyst concentration indicates a likely first-order dependence on the Cu precatalyst 1, while kinetic isotope studies (H2O versus D2O) point to involvement of a proton in or preceding the rate-determining step. Rotating ring-disk electrode measurements at pH 8.1 and 11.2 show no evidence of H2O2 formation and support selectivity to form dioxygen. Freeze-quench electron paramagnetic resonance studies during electrolysis provide evidence for the formation of a molecular copper intermediate. Experimental and computational studies support a key role of the phosphate as an acceptor base. Moreover, density functional theory calculations highlight the importance of second-sphere interactions and the role of the nitrogen-based ligands to facilitate proton transfer processes.
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