Electronic Modulation of Hierarchical Spongy Nanosheets toward Efficient and Stable Water Electrolysis

Abstract The energy conversion efficiency of water electrolysis is determined by the activity of selected catalysts. Ideal catalysts should possess not only porous architecture for high‐density assembly of active sites but also a subtle electronic configuration for the optimized activity at each site. In this context, the development of stable porous hosting materials that allow the incorporation of various metal elements is highly desirable for both experimental optimization and theoretical comparison/prediction. Herein, MOF‐derived spongy nanosheet arrays constructed by assembly of carbon encapsulated hetero‐metal doped Ni2P nanoparticles is presented as a superior bifunctional electrocatalyst for water splitting. This hierarchical structure can be stably retained when secondary metal dopants are introduced, providing a flexible platform for electronic modulation. The catalytic origin of activity enhancement via metal (Fe, Cr, and Mn) doping is deciphered through experimental and theoretical investigations. Combining the advantages in both morphological and electronic structures, the optimized catalyst NiMn–P exhibits remarkable activity in both hydrogen and oxygen evolution in the alkaline media, with an ultrasmall cell voltage of 1.49 V (at 10 mA cm−2) and high durability for at least 240 h.