Synergistic Modulation of Non-Precious-Metal Electrocatalysts for Advanced Water Splitting

Electrocatalysis plays a central role in clean energy conversion, enabling a number of sustainable processes for future technologies. This review discusses design strategies for state-of-the-art heterogeneous electrocatalysts and associated materials for several different electrochemical transformations involving water, hydrogen, and oxygen, using theory as a means to rationalize catalyst performance. By examining the common principles that govern catalysis for different electrochemical reactions, we describe a systematic framework that clarifies trends in catalyzing these reactions, serving as a guide to new catalyst development while highlighting key gaps that need to be addressed. We conclude by extending this framework to emerging clean energy reactions such as hydrogen peroxide production, carbon dioxide reduction, and nitrogen reduction, where the development of improved catalysts could allow for the sustainable production of a broad range of fuels and chemicals.

Improving the sluggish kinetics for the electrochemical reduction of water to molecular hydrogen in alkaline environments is one key to reducing the high overpotentials and associated energy losses in water-alkali and chlor-alkali electrolyzers. We found that a controlled arrangement of nanometer-scale Ni(OH)(2) clusters on platinum electrode surfaces manifests a factor of 8 activity increase in catalyzing the hydrogen evolution reaction relative to state-of-the-art metal and metal-oxide catalysts. In a bifunctional effect, the edges of the Ni(OH)(2) clusters promoted the dissociation of water and the production of hydrogen intermediates that then adsorbed on the nearby Pt surfaces and recombined into molecular hydrogen. The generation of these hydrogen intermediates could be further enhanced via Li(+)-induced destabilization of the HO-H bond, resulting in a factor of 10 total increase in activity.