High valence state species are significant in the energy-relevant electrochemical oxidation reactions. Herein, the high active state of Ni³⁺ formation induced by Mo⁶⁺ and their efficient synergism in NiS₂-MoS₂ hetero-nanorods powder catalyst with the rough layered structure are demonstrated, as proof of concept, for the urea-assisted water electrolysis. This catalyst can be derived from the sulfidation of NiMoO₄ nanorods that can realize individual metal sulfides sufficiently mixing at a domain size in the nanoscale which creates lots of active sites and nanointerfaces. The high valence state of Mo⁶⁺ and Ni³⁺ formation and increased conductive phase of 1 T MoS₂ in the hetero-nanorods compared to the counterpart pure phases are revealed by spectral study and microscopic analysis; high electrochemical surface area and active site exposure are found due to the nano-interface formation and layered rough nanosheets over the surface of nanorods. They show much higher catalytic performance than their pure phases for urea oxidation, including high catalytic activity, stability, charge transfer ability and catalytic kinetics resulting from more active Ni³⁺ species formation and electronic synergism of high valence metals. Transformation of 1 T MoS₂ to Mo⁶⁺ and increased amount of Mo⁶⁺ and Ni³⁺ after stability test indicate their involvement and synergism for the catalysis reaction. The current work offers a novel understanding of the synergistic effect based on the high valence state synergism for heterogeneous catalysts in electrocatalysis.

高价态物质在与能量相关的电化学氧化反应中很重要。在此，证明了由 Mo ⁶⁺诱导的 Ni ³⁺形成的高活性状态及其在具有粗糙层状结构的NiS ₂ -MoS ₂杂纳米棒粉末催化剂中的有效协同作用，作为概念证明，用于尿素辅助水电解。该催化剂可以源自 NiMoO ₄纳米棒的硫化，该纳米棒可以实现单个金属硫化物在纳米级域尺寸下充分混合，从而产生大量活性位点和纳米界面。Mo ⁶⁺和Ni ^{3+ 的}高价态通过光谱研究和显微分析揭示了与对应的纯相相比，异质纳米棒中 1 T MoS _{2 的}形成和导电相的增加；由于纳米界面的形成和纳米棒表面上的分层粗糙纳米片，发现了高电化学表面积和活性位点暴露。对于尿素氧化，它们显示出比纯相高得多的催化性能，包括高催化活性、稳定性、电荷转移能力和催化动力学，这是由更活跃的 Ni ³⁺物种形成和高价金属的电子协同作用产生的。1 T MoS ₂向Mo ^{6+ 的}转化以及Mo ⁶⁺和Ni ^{3+ 的增加}经稳定性试验表明它们对催化反应的参与和协同作用。目前的工作提供了对基于电催化中多相催化剂的高价态协同作用的协同效应的新理解。