Bimetallic Cobalt-Based Phosphide Zeolitic Imidazolate Framework: CoP_x Phase-Dependent Electrical Conductivity and Hydrogen Atom Adsorption Energy for Efficient Overall Water Splitting

详细信息    查看全文

• 作者：Junhua Song ; Chengzhou Zhu ; Bo Z. Xu ; Shaofang Fu ; Mark H. Engelhard ; Ranfeng Ye ; Dan Du ; Scott P. Beckman and Yuehe Lin
• 刊名：Advanced Energy Materials
• 出版年：2017
• 出版时间：January 25, 2017
• 年：2017
• 卷：7
• 期：2
• 全文大小：3914K
• ISSN：1614-6840

文摘

Cobalt-based bimetallic phosphide encapsulated in carbonized zeolitic imadazolate frameworks has been successfully synthesized and showed excellent activities toward both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Density functional theory calculation and electrochemical measurements reveal that the electrical conductivity and electrochemical activity are closely associated with the Co₂P/CoP mixed phase behaviors upon Cu metal doping. This relationship is found to be the decisive factor for enhanced electrocatalytic performance. Moreover, the precise control of Cu content in Co-host lattice effectively alters the Gibbs free energy for H* adsorption, which is favorable for facilitating reaction kinetics. Impressively, an optimized performance has been achieved with mild Cu doping in Cu_0.3Co_2.7P/nitrogen-doped carbon (NC) which exhibits an ultralow overpotential of 0.19 V at 10 mA cm^–2 and satisfying stability for OER. Cu_0.3Co_2.7P/NC also shows excellent HER activity, affording a current density of 10 mA cm^–2 at a low overpotential of 0.22 V. In addition, a homemade electrolyzer with Cu_0.3Co_2.7P/NC paired electrodes shows 60% larger current density than Pt/RuO₂ couple at 1.74 V, along with negligible catalytic deactivation after 50 h operation. The manipulation of electronic structure by controlled incorporation of second metal sheds light on understanding and synthesizing bimetallic transition metal phosphides for electrolysis-based energy conversion.