高效且稳健的析氢反应:氮化磷酰亚胺纳米管作为锚定单钌位点的载体

Efficient and Robust Hydrogen Evolution: Phosphorus Nitride Imide Nanotubes as Supports for Anchoring Single Ruthenium Sites.

作者信息

Yang Jian, Chen Bingxu, Liu Xiaokang, Liu Wei, Li Zhijun, Dong Juncai, Chen Wenxing, Yan Wensheng, Yao Tao, Duan Xuezhi, Wu Yuen, Li Yadong

机构信息

Department of Chemistry, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), University of Science and Technology of China, Hefei, 230026, China.

Department of Chemistry, Tsinghua University, Beijing, 100084, P.R. China.

出版信息

Angew Chem Int Ed Engl. 2018 Jul 20;57(30):9495-9500. doi: 10.1002/anie.201804854. Epub 2018 Jul 2.

Abstract

Amorphous phosphorus nitride imide nanotubes (HPN) are reported as a novel substrate to stabilize materials containing single-metal sites. Abundant dangling unsaturated P vacancies play a role in stabilization. Ruthenium single atoms (SAs) are successfully anchored by strong coordination interactions between the d orbitals of Ru and the lone pair electrons of N located in the HPN matrix. The atomic dispersion of Ru atoms can be distinguished by X-ray absorption fine structure measurements and spherical aberration correction electron microscopy. Importantly, Ru SAs@PN is an excellent electrocatalyst for the hydrogen evolution reaction (HER) in 0.5 m H SO , delivering a low overpotential of 24 mV at 10 mA cm and a Tafel slope of 38 mV dec . The catalyst exhibits robust stability in a constant current test at a large current density of 162 mA cm for more than 24 hours, and is operative for 5000 cycles in a cyclic voltammetry test. Additionally, Ru SAs@PN presents a turnover frequency (TOF) of 1.67 H  s at 25 mV, and 4.29 H  s at 50 mV, in 0.5 m H SO solution, outperforming most of the reported hydrogen evolution catalysts. Density functional theory (DFT) calculations further demonstrate that the Gibbs free energy of adsorbed H* over the Ru SAs on PN is much closer to zero compared with the Ru/C and Ru SAs supported on carbon and C N , thus considerably facilitating the overall HER performance.

摘要

据报道,非晶态氮化磷酰亚胺纳米管(HPN)是一种用于稳定含单金属位点材料的新型基底。大量悬空的不饱和磷空位起到了稳定作用。钌单原子(SAs)通过钌的d轨道与位于HPN基质中的氮的孤对电子之间的强配位相互作用成功锚定。钌原子的原子分散性可通过X射线吸收精细结构测量和球差校正电子显微镜来区分。重要的是,Ru SAs@PN是0.5 m H₂SO₄中析氢反应(HER)的优异电催化剂,在10 mA cm⁻²时过电位低至24 mV,塔菲尔斜率为38 mV dec⁻¹。该催化剂在162 mA cm⁻²的大电流密度下进行恒流测试时表现出强大的稳定性,持续超过24小时,并且在循环伏安测试中可运行5000次循环。此外,在0.5 m H₂SO₄溶液中,Ru SAs@PN在25 mV时的周转频率(TOF)为1.67 H₂ s⁻¹,在50 mV时为4.29 H₂ s⁻¹,优于大多数已报道的析氢催化剂。密度泛函理论(DFT)计算进一步表明,与负载在碳和C₃N上的Ru/C和Ru SAs相比,PN上Ru SAs上吸附的H*的吉布斯自由能更接近零,从而极大地促进了整体HER性能。

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