Boron‐Induced Electronic‐Structure Reformation of CoP Nanoparticles Drives Enhanced pH‐Universal Hydrogen Evolution

• Published in: Angewandte Chemie International Edition Vol. 59; no. 10; pp. 4154 - 4160
• Main Authors: Cao, Erping, Chen, Zhimin, Wu, Hao, Yu, Peng, Wang, Ying, Xiao, Fei, Chen, Shuo, Du, Shichao, Xie, Ying, Wu, Yiqun, Ren, Zhiyu
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 02.03.2020
• Edition: International ed. in English
• Subjects: Atomic properties; B-doping; Boron; Carbon nanotubes; carbon nanotubes (CNTs); Catalysts; Chemical bonds; Electrical conductivity; Electrical resistivity; Electronic structure; electronic structure reformation; Free energy; hydrogen evolution reaction (HER); Hydrogen evolution reactions; Nanoparticles; Nanotechnology; Nanotubes; pH effects; Phosphides; Reaction kinetics; transition-metal phosphide catalysts; transition-metal phosphide catalysts; B-doping; hydrogen evolution reaction (HER); electronic structure reformation; carbon nanotubes (CNTs)
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201915254

Even though transition‐metal phosphides (TMPs) have been developed as promising alternatives to Pt catalyst for the hydrogen evolution reaction (HER), further improvement of their performance requires fine regulation of the TMP sites related to their specific electronic structure. Herein, for the first time, boron (B)‐modulated electrocatalytic characteristics in CoP anchored on the carbon nanotubes (B‐CoP/CNT) with impressive HER activities over a wide pH range are reported. The HER performance surpasses commercial Pt/C in both neutral and alkaline media at large current density (>100 mA cm−2). A combined experimental and theoretical study identified that the B dopant could reform the local electronic configuration and atomic arrangement of bonded Co and adjacent P atoms, enhance the electrons’ delocalization capacity of Co atoms for high electrical conductivity, and optimize the free energy of H adsorption and H2 desorption on the active sites for better HER kinetics. The importance of B in HERnest: Boron is introduced into CoP nanoparticles anchored on carbon nanotubes to form a robust pH‐universal hydrogen evolution reaction (HER) catalyst. The boron has a relatively low electronegativity and refines the electronic structure of the CoP catalytic sites, thus enhancing the electrical conductivity and optimizing the free energy of H adsorption, leading to improved electrocatalytic H2 production.