Increasing Iridium Oxide Activity for the Oxygen Evolution Reaction with Hafnium Modification

Zhao, Fang; Wen, Bo; Niu, Wenhan; Chen, Zhu; Yan, Chao; Selloni, Annabella; Tully, Christopher G.; Yang, Xiaofang; Koel, Bruce E.

doi:10.1021/jacs.1c03473

Increasing Iridium Oxide Activity for the Oxygen Evolution Reaction with Hafnium Modification

Journal Article · Wed Sep 01 00:00:00 UTC 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c03473· OSTI ID:1838123

^[1]; Wen, Bo ^[2]; ^[2]; ^[2]; ^[2]; ^[2]; Tully, Christopher G. ^[2]; Yang, Xiaofang ^[2]; ^[2]

Princeton Univ., NJ (United States); Princeton University
Princeton Univ., NJ (United States)

Synthesis and implementation of highly active, stable, and affordable electrocatalysts for the oxygen evolution reaction (OER) is a major challenge in developing energy efficient and economically viable energy conversion devices such as electrolyzers, rechargeable metal-air batteries, and regenerative fuel cells. The current benchmark electrocatalyst for OER is based on iridium oxide (IrO_x) due to its superior performance and excellent stability. However, large scale applications using IrO_x are impractical due to its low abundance and high cost. In this work, we report a highly active hafnium-modified iridium oxide (IrHf_xO_y) electrocatalyst for OER. The IrHf_xO_y electrocatalyst demonstrated ten times higher activity in alkaline conditions (pH = 11) and four times higher activity in acid conditions (pH = 1) than a IrO_x electrocatalyst. The highest intrinsic mass activity of the IrHf_xO_y catalyst in acid conditions was calculated as 6950 A gIrO_x^-1 at an overpotential (η) of 0.3 V. Combined studies utilizing operando surface enhanced Raman spectroscopy (SERS) and DFT calculations revealed that the active sites for OER are the Ir-O species for both IrO_x and IrHf_xO_y catalysts. The presence of Hf sites leads to more negative charge states on nearby O sites, and shortening the bond lengths of Ir-O, and lowering free energies for OER intermediates to accelerate the OER process.

View Accepted Manuscript (DOE)

Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: John Templeton Foundation; National Science Foundation (NSF); Simons Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231; SC0007347

OSTI ID:: 1838123

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 38 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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