Semiconductors and the associated methodologies applied to electrochemistry have recently grown as an emerging field in energy materials and technologies. For example, semiconductor membranes and heterostructure fuel cells are new technological trend, which differ from the traditional fuel cell electrochemistry principle employing three basic functional components: anode, electrolyte, and cathode. The electrolyte is key to the device performance by providing an ionic charge flow pathway between the anode and cathode while preventing electron passage. In contrast, semiconductors and derived heterostructures with electron (hole) conducting materials have demonstrated to be much better ionic conductors than the conventional ionic electrolytes. The energy band structure and alignment, band bending and built-in electric field are all important elements in this context to realize the necessary fuel cell functionalities. This review further extends to semiconductor-based electrochemical energy conversion and storage, describing their fundamentals and working principles, with the intention of advancing the understanding of the roles of semiconductors and energy bands in electrochemical devices for energy conversion and storage, as well as applications to meet emerging demands widely involved in energy applications, such as photocatalysis/water splitting devices, batteries and solar cells. This review provides new ideas and new solutions to problems beyond the conventional electrochemistry and presents new interdisciplinary approaches to develop clean energy conversion and storage technologies. Graphic Abstract

Fuel cells are highly efficient and green power sources. The typical membrane electrode assembly is necessary for common electrochemical devices. Recent research and development in solid oxide fuel cells have opened up many new opportunities based on the semiconductor or its heterostructure materials. Semiconductor-based fuel cells (SBFCs) realize the fuel cell functionality in a much more straightforward way. This work aims to discuss new strategies and scientific principles of SBFCs by reviewing various novel junction types/interfaces, i.e., bulk and planar p-n junction, Schottky junction, and n-i type interface contact. New designing methodologies of SBFCs from energy band/alignment and built-in electric field (BIEF), which block the internal electronic transport while assisting interfacial superionic transport and subsequently enhance device performance, are comprehensively reviewed. This work highlights the recent advances of SBFCs and provides new methodology and understanding with significant importance for both fundamental and applied R&D on new-generation fuel cell materials and technologies.

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