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The electrochemical nitrogen reduction reaction (NRR) has the potential to replace the Haber–Bosch process for ammonia synthesis under ambient conditions. However, the selectivity and yield of the NRR are impractical, owing to the preferential binding of the electrocatalyst to H and the consequential coverage of active sites. In this study, VO2, with N2 strongly adsorbed over H atoms, is used as a support to provide a N2 source to avoid the hydrogen evolution reaction. Mo, with a high NRR activity, is introduced as the active site to promote the NRR. Meanwhile, the electronic metal–support interaction between the support and Mo creates electron‐deficient sites, which weakens H adsorption and lowers the energy barrier of the first step, protonation, thereby kinetically enhancing the NRR activity. The average NH3 yield of Mo/VO2 is 190.1 µgNH3 mgcat.−1 h−1 and the Faradaic efficiency is 32.4% at −0.5 V versus reversible hydrogen electrode, which is 10.8 and 2.8 times greater than that of VO2, respectively. [ABSTRACT FROM AUTHOR]

Coating photoanodes with transition‐metal hydroxides (TMH) is a promising approach for improving photoelectrochemical (PEC) water oxidation. However, the present system still suffers from high charge recombination and sluggish surface reactions. Herein, effective charge separation is achieved at the same time as boosting the surface catalytic reaction for PEC water splitting through decoration of plasmon metal (Ag) in a semiconductor/TMH coupling system. The kinetic behavior at the semiconductor/TMH and TMH/electrolyte interfaces is systematically evaluated by employing intensity modulated photocurrent spectroscopy, scanning photoelectrochemical microscopy, and oxygen evolution reaction model. It is found that both charge transfer and surface catalysis dynamics are enhanced through local surface plasmon resonance of Ag nanoparticles. The as‐prepared BiVO4/Co(OH)x‐Ag exhibits remarkable activity (≈4.64 times) in PEC water splitting in comparison with pure BiVO4. Notably, this smart approach can be also applied to other TMH (Ni(OH)2), reflecting its universality. This work provides a guiding design method for solar energy conversion with the semiconductor‐TMH system. [ABSTRACT FROM AUTHOR]