The biomolecule DNA with the presence of different functionalities found to interact with different kinds of metal ions and show relatively higher stability over a long period of time when optimized appropriately. With the presence of A-T and G-C pairs, sugar moieties, phosphate functional groups and the double-helical structure, it can assemble both cationic and anionic species and forms a perfect metal-DNA self-assembly. Depending upon the aspect ratio of metal-DNA self-assemblies, metal content and their morphological outcomes, they could deliver variance in the catalytic activities. Such differences can be brought out by varying the synthesis reaction parameters focusing on a specific electrocatalytic application. In this review, recent developments in DNA metallization is elaborated first highlighting the underlying interactions between DNA and cationic/anionic species of various metals following which application of metal-DNA assemblies in electrocatalytic water oxidation and reduction are discussed critically. Knowledge provided in this review thus acts as the guide to various DNA metallization strategies and their subsequent application to water electrolysis for hydrogen generation.
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