Shi Fangbing, Geng Zhibin, Huang Keke, Liang Qingshuang, Zhang Yuan, Sun Yu, Cao Jungang, Feng Shouhua
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry College of Chemistry Jilin University Changchun 130012 P. R. China.
College of Chemistry and Material Fujian Normal University Fuzhou Fujian 350007 P. R. China.
Adv Sci (Weinh). 2018 Jun 10;5(8):1800575. doi: 10.1002/advs.201800575. eCollection 2018 Aug.
Black phosphorus (BP) nanosheet (NS) is an emerging oxygen evolution reaction (OER) electrocatalyst with both high conductivity and abundant active sites. However, its ultrathin structure suffers instability because of the lone pair electrons exposed at the surface, which badly restricts durability for achieving long-term OER catalysis. Herein, a facile solvothermal reduction route is designed to fabricate Co/BP NSs hybrid electrocatalyst by in situ growth of cobalt nanoparticles on BP NSs. Notably, electronic structure engineering of Co/BP NSs catalyst is observed by electron migration from BP to Co due to the higher Fermi level of BP than that of Co. Because of the preferential migration of the active lone pairs from the defect of BP NSs, the stability and high hole mobility can be effectively retained. Consequently, Co/BP NSs electrocatalyst exhibits outstanding OER performance, with an overpotential of 310 mV at 10 mA cm, and excellent stability in alkaline media, indicating the potential for the alternatives of commercial IrO. This study provides insightful understanding into engineering electronic structure of BP NSs by fully utilizing defect and provides a new idea to design hybrid electrocatalysts.
黑磷（BP）纳米片（NS）是一种新兴的析氧反应（OER）电催化剂，具有高导电性和丰富的活性位点。然而，由于其超薄结构表面暴露的孤对电子，导致结构不稳定，这严重限制了其实现长期OER催化的耐久性。在此，设计了一种简便的溶剂热还原路线，通过在BP纳米片上原位生长钴纳米颗粒来制备Co/BP NSs混合电催化剂。值得注意的是，由于BP的费米能级高于Co，电子从BP迁移到Co，从而实现了Co/BP NSs催化剂的电子结构工程。由于活性孤对电子从BP纳米片的缺陷处优先迁移，其稳定性和高空穴迁移率得以有效保持。因此，Co/BP NSs电催化剂表现出优异的OER性能，在10 mA cm时过电位为310 mV，在碱性介质中具有出色的稳定性，这表明其具有替代商业IrO的潜力。本研究通过充分利用缺陷，对BP纳米片的电子结构工程提供了深刻的理解，并为设计混合电催化剂提供了新思路。
