Work

Synergy between Fe and Ni in the optimal performance of (Ni,Fe)OOH catalysts for the oxygen evolution reaction

Year: 2018

Type: article

Abstract: The oxygen evolution reaction (OER) is critical to solar production of fuels, but the reaction mechanism underlying the performance for a best OER catalyst, Fe-doped NiOOH [(Ni,Fe)OOH], remains highly controversial. We used grand canonical quantum mechanics to predict the OER mechanisms including kinetics and thus overpotentials as a function of Fe content in (Ni,Fe)OOH catalysts. We find that density functional theory (DFT) without exact exchange predicts that addition of Fe does not reduce the overpotential much. However, DFT with exact exchange predicts dramatic improvement in performance for (Ni,Fe)OOH, leading to an overpotential of 0.42 V and a Tafel slope of 23 mV/decade (dec), in good agreement with experiments, 0.3-0.4 V and 30 mV/dec. We reveal that the high spin [Formula: see text] Fe(IV) leads to efficient formation of an active O radical intermediate, while the closed shell [Formula: see text] Ni(IV) catalyzes the subsequent O-O coupling, and thus it is the synergy between Fe and Ni that delivers the optimal performance for OER.

Source: Proceedings of the National Academy of Sciences

DOI: 10.1073/pnas.1722034115

Authors: Hai Xiao, Hyeyoung Shin, William A. Goddard

Institutions: California Institute of Technology, Joint Center for Artificial Photosynthesis

Language: English

Topic: Electrocatalysts for Energy Conversion

Subfield: Renewable Energy, Sustainability and the Environment

Field: Energy

Domain: Physical Sciences

SDG: Affordable and clean energy

Open Access status: bronze

Funders: U.S. Department of Energy, Office of Science