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Enhanced Activity and Acid pH Stability of Prussian Blue-type Oxygen Evolution Electrocatalysts Processed by Chemical Etching

Author:
Han, Lijuan, Tang, Pengyi, Reyes-Carmona, Álvaro, Rodríguez-García, Bárbara, Torréns, Mabel, Morante, Joan Ramon, Arbiol, Jordi, Galan-Mascaros, Jose Ramon
Source:
Journal of the American Chemical Society 2016 v.138 no.49 pp. 16037-16045
ISSN:
1520-5126
Subject:
carbonates, catalysts, catalytic activity, cobalt, corrosion, cost effectiveness, electrochemistry, electrodes, nanocrystals, oxidation, oxygen, oxygen production, pH, photosynthesis, spectroscopy
Abstract:
The development of upscalable oxygen evolving electrocatalysts from earth-abundant metals able to operate in neutral or acidic environments and low overpotentials remains a fundamental challenge for the realization of artificial photosynthesis. In this study, we report a highly active phase of heterobimetallic cyanide-bridged electrocatalysts able to promote water oxidation under neutral, basic (pH < 13), and acidic conditions (pH > 1). Cobalt–iron Prussian blue-type thin films, formed by chemical etching of Co(OH)₁.₀(CO₃)₀.₅·nH₂O nanocrystals, yield a dramatic enhancement of the catalytic performance toward oxygen production, when compared with previous reports for analogous materials. Electrochemical, spectroscopic, and structural studies confirm the excellent performance, stability, and corrosion resistance, even when compared with state-of-the-art metal oxide catalysts under moderate overpotentials and in a remarkably large pH range, including acid media where most cost-effective water oxidation catalysts are not useful. The origin of the superior electrocatalytic activity toward water oxidation appears to be in the optimized interfacial matching between catalyst and electrode surface obtained through this fabrication method.
Agid:
5594329