Electrochemical and Photoelectrochemical Water Oxidation by Supported Cobalt–Oxo Cubanes

Abstract

Cobalt–oxo cubane clusters were immobilized on a Nafion film-coated fluorine-doped tin oxide (FTO) electrode and an α-Fe2O3 photoanode as surface catalysts for water oxidation. The performance of electrochemical water splitting indicated that these earth-abundant metal complexes retain their homogeneous reactivity on the electrode. Furthermore, efficient visible light-driven water oxidation was realized by coupling a molecular electrocatalyst with an inorganic semiconductor as a noble metal-free photoanode, showing a stability significantly improved with respect to that of the homogeneous system.

Toward a Low‐Cost Artificial Leaf: Driving Carbon‐Based and Bifunctional Catalyst Electrodes with Solution‐Processed Perovskite Photovoltaics

“…Commonly employed materials for the current collector are bulk or porous metals, [ 15 ] whereas a popular choice for the catalyst is various types of metal-oxides. [24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] From a system-cost and practicality perspective, it is desirable to develop a functional lightweight and low-cost current collector and to identify a catalyst that is bifunctional in that it can drive the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) in the same water solution. [ 14,[39][40][41][42][43][44] Here, we present an artifi cial-leaf device that delivers an STH effi ciency of 6.2% and a Faradaic H 2 evolution effi ciency of 100%.…”

The Principle of Photoelectrochemical Water Splitting

“…Indeed, while a number of p-type semiconductors have been shown to produce Cobalt-based catalyst was modified on the surface of photoanode. Reprinted with permission from [4]. Copyright @ American Chemical Society.…”

“…A typical water splitting cell device includes semiconductors with appropriate bandgap as photoelectrodes (photoanode or photocathode) to absorb sunlight, conductive substrates to transport charges and electrolyte to support the reactions ( Figure 3) [4]. Electrons and holes are generated when the photoelectrodes are irradiated.…”

Catalytic Oxygen Evolution by Cobalt Oxido Thin Films

“…The aim is not to provide a review of the molecular water oxidation catalysts, cobalt-containing or otherwise, but to highlight the results obtained from studying molecules that have refined our thinking with regard to the mechanisms germane to the activity of Co-OEC. [95], were not only shown to be useful for EPR studies, but have also been explored as discrete water oxidation catalysts [101][102][103]. Though some evidence of electrochemical water oxidation was presented in these studies, the primary mode of characterization of the water oxidation activity was through the use of a photochemical assay, utilizing Ru(bpy) 3 2+ /persulfate as the photosensitizer/sacrificial oxidant.…”