Highly Active and Stable Catalysts of Phytic Acid-Derivative Transition Metal Phosphides for Full Water Splitting

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State Key Laboratory of Environmental Aquatic Chemistry, and Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
§ Department of Chemistry, Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Beijing Key Laboratory for Microanalytical Methods and Instrumentation, Tsinghua University, Beijing 100084, China
Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China
University of Chinese Academy of Sciences, Beijing 100039, China
Cite this: J. Am. Chem. Soc. 2016, 138, 44, 14686–14693
Publication Date (Web):October 19, 2016
https://doi.org/10.1021/jacs.6b08491
Copyright © 2016 American Chemical Society
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Abstract

Application of transition metal phosphide (TMP) catalysts for full water splitting has great potential to help relieve the energy crisis. Various methods have been investigated to obtain high catalytic activity, but the use of electronic structure regulation by incorporation of different elements is of particular simplicity and significance for development of a universal TMP synthesis method. We herein describe a novel approach for fabricating a series of TMPs by pyrolyzing phytic acid (PA) cross-linked metal complexes. The introduction of oxygen atoms into TMPs not only enhanced their intrinsic electrical conductivity, facilitating electron transfer, but activated active sites via elongating the M–P bond, favoring the hydrogen evolution reaction (HER) or oxygen evolution reaction (OER). MoP exhibited relative low HER overpotentials of 118 mV and 93 mV while supporting a current density of 20 mA·cm–2 in 0.5 M H2SO4 and 1 M KOH electrolytes, respectively. When CoP was applied as a catalyst for OER, only 280 mV overpotential was required to reach current density of 10 mA·cm–2. Additionally, PA-containing precursors enabled intimate embedding of TMPs onto a flexible substrate surface (carbon cloth), so that electron injection from substrate and transport to the active sites was facilitated. Remarkably, an alkaline electrolyzer was able to achieve a current density of 40 mA·cm–2 at the low voltage of 1.6 V, demonstrating its potential for practical overall water splitting without the use of noble metals.

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