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钌作为一种用于碱性析氢的高效电催化剂被掺入含硒空位的钴硒化物中。

Ru incorporated into Se vacancy-containing CoSe as an efficient electrocatalyst for alkaline hydrogen evolution.

作者信息

Liu Li, Yang Ziyi, Gao Weibo, Shi Jianghuan, Ma Jieyun, Liu Zongjian, Wang Lin, Wang Yichao, Chen Zhengfei

机构信息

College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang 310014, China.

School of Biological and Chemical Engineering, Ningbo Tech University, Ningbo, Zhejiang 315100, China.

出版信息

Nanoscale. 2024 Oct 10;16(39):18421-18429. doi: 10.1039/d4nr02735c.

Abstract

In alkaline media, slow water dissociation leads to poor overall hydrogen evolution performance. However, Ru catalysts have a certain water dissociation performance, thus regulating the Ru-H bond through vacancy engineering and accelerating water dissociation. Herein, an excellent Ru-based electrocatalyst for the alkaline HER has been developed by incorporating Ru into Se vacancy-containing CoSe (Ru-V-CoSe). The results from X-ray photoelectron spectroscopy, kinetic isotope effect, and cyanide poisoning experiments for four catalysts (namely Ru-V-CoSe, Ru-CoSe, V-CoSe, and CoSe) reveal that Ru is the main active site in Ru-V-CoSe and the presence of Se vacancies greatly facilitates electron transfer from Co to Ru a bridging Se atom. Thus, electron-rich Ru is formed to optimize the adsorption strength between the active site and H*, and ultimately facilitates the whole alkaline HER process. Consequently, Ru-V-CoSe exhibits an excellent HER activity with an ultrahigh mass activity of 44.2 A mg (20% PtC exhibits only 3 A mg) and a much lower overpotential (29 mV at 10 mA cm) compared to Ru-CoSe (75 mV), V-CoSe (167 mV), CoSe (190 mV), and commercial Pt/C (41 mV). In addition, the practical application of Ru-V-CoSe is illustrated by designing a Zn-HO alkaline battery with Ru-V-CoSe as the cathode catalyst, and this battery shows its potential application with a maximum power density of 4.9 mW cm and can work continuously for over 10 h at 10 mA cm without an obvious decay in voltage.

摘要

在碱性介质中,水的缓慢离解导致整体析氢性能不佳。然而,钌催化剂具有一定的水离解性能,因此通过空位工程调控钌-氢键并加速水的离解。在此,通过将钌掺入含硒空位的硒化钴(Ru-V-CoSe)中,开发出了一种用于碱性析氢反应的优异钌基电催化剂。对四种催化剂(即Ru-V-CoSe、Ru-CoSe、V-CoSe和CoSe)进行的X射线光电子能谱、动力学同位素效应和氰化物中毒实验结果表明,钌是Ru-V-CoSe中的主要活性位点,硒空位的存在极大地促进了电子从钴通过一个桥连硒原子转移到钌。因此,形成了富电子的钌以优化活性位点与H*之间的吸附强度,并最终促进整个碱性析氢反应过程。结果,Ru-V-CoSe表现出优异的析氢活性,具有44.2 A mg的超高质量活性(20%的Pt/C仅为3 A mg),与Ru-CoSe(75 mV)、V-CoSe(167 mV)、CoSe(190 mV)和商业Pt/C(41 mV)相比,过电位低得多(在10 mA cm时为29 mV)。此外,通过设计以Ru-V-CoSe作为阴极催化剂的锌-水碱性电池来说明Ru-V-CoSe的实际应用,该电池显示出其潜在应用,最大功率密度为4.9 mW cm,在10 mA cm下可连续工作超过10小时,电压无明显衰减。

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