Water electrolysis is a well-established commercial process. The electrolysis is usually operated at extreme pH conditions due to a combination of facile kinetics and low solution resistance for electrocatalysis. Electricity from renewable energy resources however necessitates additional requirement for versatile, safe and durable water-splitting electrocatalysis. Recent efforts in the water-splitting study include the development of the catalyst materials and the description of the efficiency at near-neutral pH condition. In such a condition, the buffering action is inevitable to achieve high rates. Such electrolyte engineering may lead to the discovery of new reaction environments for water electrolysis in more benign conditions and more towards membrane-less systems. It is even more effective for water-splitting using semiconductor photon absorbers where the extreme pH should be avoided. This contribution discusses the rates that can be described quantitatively, dividing the functions into solution resistance, concentration overpotential, and kinetic contribution in an electrocatalytic system. It also expands the discussion on the effectiveness of electrocatalytic measurements to understand photoelectrochemical and photocatalytic behaviors, mainly focusing on hydrogen evolution catalysis and water-forming back reaction.<br/>

Electrolyte engineering for water splitting at mild pH

2019 Spring National Meeting

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