Water oxidation and reduction reactions play vital roles in highly efficient hydrogen production conducted by an electrolyzer, in which the enhanced efficiency of the system is apparently accompanied by the development of active electrocatalysts. Solar energy, a sustainable and clean energy source, can supply the kinetic energy to increase the rates of catalytic reactions. In this regard, understanding of the underlying fundamental mechanisms of the photo/electrochemical process is critical for

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... future development. Combining light-absorbing materials with catalysts has become essential to maximizing the efficiency of hydrogen production. To fabricate an efficient absorber-catalysts system, it is imperative to fully understand the vital role of surface/interface modulation for enhanced charge transfer/separation and catalytic activity for a specific reaction. The electronic and chemical structures at the interface are directly correlated to charge carrier movements and subsequent chemical adsorption and reaction of the reactants. Therefore, rational surface modulation can indeed enhance the catalytic efficiency by preventing charge recombination and prompting transfer, increasing the reactant concentration, and ultimately boosting the catalytic reaction. Herein, the authors review recent progress on the surface modification of nanomaterials as photo/electrochemical catalysts for water reduction and oxidation, considering two successive photogenerated charge transfer/separation and catalytic chemical reactions. It is expected that this review paper will be helpful for the future development of photo/electrocatalysts.