Abstract
Rational composition design of trimetallic phosphide catalysts is of significant importance for enhanced surface reaction and efficient catalytic performance. Herein, hierarchical CoxNiyFezP with precise control of stoichiometric metallic elements (x:y:z = (1–10):(1–10):1) has been synthesized, and Co1.3Ni0.5Fe0.2P, as the most optimal composition, exhibits remarkable catalytic activity (η = 320 mV at 10 mA cm−2) and long-term stability (ignorable decrease after 10 h continuous test at the current density of 10 mA cm−2) toward oxygen evolution reaction (OER). It is found that the surface P in Co1.3Ni0.5Fe0.2P was replaced by O under the OER process. The density function theory calculations before and after long-term stability tests suggest the clear increasing of the density of states near the Fermi level of Co1.3Ni0.5Fe0.2P/Co1.3Ni0.5Fe0.2O, which could enhance the OH− adsorption of our electrocatalysts and the corresponding OER performance.
摘要
过渡金属磷化物是电催化设计中的新兴材料, 而多元金属磷化物因其能显著提高电催化活性而备受关注. 然而, 由于不同种类金属前驱物之间水解和缩合速率的差异, 当前有关超过两种金属元素和化学计量比精确控制的多元金属磷化物的报道非常少. 因此, 合理设计多元金属磷化物的组成对提高其催化性能具有重要意义. 本工作通过直接磷化二价过渡金属离子氢氧化物的合成策略, 制备了能够精确控制化学计量比(x:y:z = (1–10):(1–10):1)的分级结构CoxNiyFezP, 其中具有最优组分的Co1.3Ni0.5Fe0.2P在析氧反应(OER)中展示了优异的催化活性和高稳定性. 密度泛函理论计算表明, 相对于其他组分的过渡金属磷化物, Co1.3Ni0.5Fe0.2P在费米能级附近的态密度明显增加, 这可以增强催化剂对OH−的吸附, 从而提升OER性能.
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Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (51861135313), Sino-German Center COVID-19 Related Bilateral Collaborative project (C-0046), FRFCU (2021qntd13), the National 111 project (B20002), Guangdong Basic and Applied Basic Research Foundation (2019A1515110436, 2021A1515111131, and 2022A1515011905), Guangdong Province International Scientific and Technological Cooperation Projects (2020A0505100036), Guangzhou Science and Technology Project (202102020463), Shenzhen Science and Technology Program (JCYJ20210324142010029), and DSI/NRF/WITS South African Research Chair Initiative (SARChI) Chair (132739).
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Ying J and Yang X conceived and supervised this study; Chen J carried out the materials fabrication, characterizations, electrochemical measurements, DFT calculations, and computational models; Xiao Y and Dong Y assisted in drawing the pictures. Chen J wrote the paper; Ying J, Yang X, Ozoemena KI, and Lenaerts S revised the paper. All authors discussed the results and commented on the manuscript.
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Jiangbo Chen received his Bachelor degree in materials chemistry at Wuhan Textile University in 2018. He is currently a PhD candidate under the supervision of Prof. Xiaoyu Yang at Wuhan University of Technology. His research interest focuses on non-noble metal compounds in the electrocatalysis field.
Jie Ying received his PhD degree from Wuhan University of Technology in 2016. He then joined the University of Waterloo and Heinrich-Heine-Universität Düsseldorf as a postdoctoral fellow. Currently, he is an associate professor at Sun Yat-sen University. His scientific interest includes the design and synthesis of nanocomposites and their application in catalysis and electrocatalysis.
Xiaoyu Yang earned his BS degree from Jilin University in 2000 and his joint PhD degree from Jilin University, China and FUNDP, Belgium (co-education) in 2007. After a postdoctoral fellowship at the FUNDP, he worked as a “Chargé de Recherches” at the F.N.R.S. of Belgium. He is currently working as a full professor at the State Key Laboratory of Advanced Technology for Material Synthesis and Processing and a visiting professor at Harvard University.
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Chen, J., Ying, J., Xiao, Y. et al. Stoichiometry design in hierarchical CoNiFe phosphide for highly efficient water oxidation. Sci. China Mater. 65, 2685–2693 (2022). https://doi.org/10.1007/s40843-022-2061-x
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DOI: https://doi.org/10.1007/s40843-022-2061-x