Constructing a high-performance hydrogen evolution reaction (HER) electrocatalyst is significantly desirable to realize electrochemical splitting of water to massively produce hydrogen. In this work, we have activated rhodium selenides by incorporation of metallic Rh to form Rh–Rh₃Se₄ heterostructure at atomic level to regulate the electronic configuration of Rh₃Se₄. Due to the presence of metallic Rh, the HER activity of Rh–Rh₃Se₄/C is boosted requiring an ultralow overpotentials of 32 mV and 29 mV to attain 10 mA cm⁻² in acidic and alkaline electrolyte with 14.3 μg_Rh cm⁻², respectively, corresponding to 11- and 6.5-fold better mass activity than commercial Pt/C at overpotential of 50 mV. The exceptional HER performance is attributed to the metallic Rh efficiently weakening the strong binding strength between Rh₃Se₄ and hydrogen ions associated with constructing electronic path to decrease the charge transfer resistance due to the electronic enrichment at Fermi level. Besides, owing to the strong electronic interaction between metallic Rh and Rh₃Se₄, a superior HER stability is also achieved.

为了实现水的电化学分解以大量产生氢气，构建高性能的氢气析出反应（HER）电催化剂是非常需要的。在这项工作中，我们通过掺入金属Rh激活了硒化铑，从而在原子水平上形成Rh–Rh ₃ Se ₄异质结构，从而调节Rh ₃ Se ₄的电子构型。由于金属的Rh中，HER铑的Rh活性的存在₃硒₄ / C被升压要求32毫伏和29毫伏的超低超电势达到10毫安厘米^-2在酸性和碱性电解质与14.3微克_的Rh厘米^{- 2个}在50 mV的超电势下，其质量活性分别比市售Pt / C高11倍和6.5倍。优异的HER性能归因于金属Rh有效削弱了Rh ₃ Se ₄与氢离子之间的强结合强度，这与构建电子路径相关联，从而由于费米能级的电子富集而降低了电荷转移阻力。另外，由于金属Rh和Rh ₃ Se ₄之间的强电子相互作用，还实现了优异的HER稳定性。