Radio frequency plasma-engraved vacancy engineering towards robust hydrogen-evolving catalysts with large-current stable catalytic activity for over 1000 h  

射频等离子体蚀刻缺陷工程用于开发在大电流下具有超过1000小时稳定催化活性的耐久性析氢催化剂

作　　者：Yong Zhang Haiman Huang Weiqiang Xie Qian Zhou Xuliang Hu Guanghua Wang Wangbing Yu Haiqing Zhou Fang Yu 章勇;黄海漫;谢伟强;周倩;胡旭亮;王光华;禹旺兵;周海青;余芳

机构地区：[1]Key Laboratory of Low-Dimensional Quantum Structures and Quantum Control of Ministry of Education,Institute of Interdisciplinary Studies,Key Laboratory for Multifunctional Ionic Electronic Materials and Devices of Hunan Normal University,Changsha 410081,China [2]Hunan Guohe Kuntai Innovation Technology Co.,Ltd.,Changsha 410301,China

出　　处：《Science China Materials》2025年第4期1129-1137,共9页中国科学(材料科学)(英文版)

基　　金：supported by the National Natural Science Foundation of China(22309051,52302248 and 52172197);the Youth 1000 Talent Program of China,the Major Projects"Takes the lead"of Natural Science Foundation(2021JC0008 and 2023JJ40427)of Hunan Province;the Interdisciplinary Research Program(2023JC201)from Hunan Normal University in Changsha,China。

摘　　要：The proper incorporation of defects in existing materials,including cationic and anionic vacancies,would act as suitable promoters for enhancing the energy efficiency of water electrolysis at large current densities,but controllably creating effective vacancies in electrocatalysts remains a formidable challenge.Here we report that a sandwich-like nanoporous hybrid catalyst consisting of double-layer nickel nitride(Ni_(3)N)intercalated by a metallic Ni layer is creatively synthesized through room-temperature ionized nitrogen radio frequency plasma bombardment with short reaction times.This unique strategy not only ensures good electron transfer between Ni and Ni_(3)N,but also provides abundant nitrogen vacancies as the active species ameliorating initial water dissociation and subsequent hydrogen adsorption as evidenced by the density functional theory(DFT)calculations,thus greatly enhancing the hydrogen evolution kinetics.Owing to the introduction of nitrogen vacancies and the synergistic interaction between Ni_(3)N and Ni species,the resultant catalyst exhibits excellent hydrogen-evolving activity approaching the state-of-the-art Pt catalysts,featured by considerably low overpotentials of 14 and 180 mV to achieve 10 and 500 mA cm^(-2),superior to most available non-precious electrocatalysts,thus considerably facilitating the electrochemical hydrogen production at low voltages under large current density.Remarkably,this catalyst exhibits outstanding durability at large current densities(200-500 mA cm^(-2))for over 1000 h,which is in sharp contrast to most of the non-noble electrocatalysts with tens of hours of stability.This simple strategy does not involve any cumbersome synthetic procedures,paving a new avenue toward the rapid synthesis of robust hydrogen-evolving electrocatalysts for alkaline water electrolysis.在现有材料中适当引入缺陷,包括阳离子和阴离子空位,可以作为提高大电流密度下电解水能量效率的有效促进剂,但在电催化剂中可控地创建有效空位仍然是一个巨大的挑战.在此,我们报道了一种通过室温射频氮等离子体轰击,在短时间内创造性地合成双层氮化镍(Ni_(3)N)夹层和金属镍的三明治状纳米多孔混合催化剂.这一独特策略不仅确保了镍和Ni_(3)N之间的良好电子传输,还提供了丰富的氮空位作为活性物种,改善了初始水解离和随后的氢吸附,这得到了密度泛函理论计算的验证,从而大大增强了析氢动力学.由于氮空位的引入以及Ni_(3)N和镍物种之间的协同作用,所得催化剂表现出接近最先进铂催化剂的优异析氢活性,在10和500 mA cm^(-2)时仅需14和180 mV的极低过电位,优于大多数现有的非贵金属电催化剂,从而在大电流密度下以较低电压大幅促进电化学氢气生产.值得注意的是,该催化剂在大电流密度(200-500 mA cm^(-2))下展现出超过1000小时的出色耐久性,这与大多数仅能稳定数十小时的非贵金属电催化剂形成了鲜明对比.这一简单策略不涉及任何复杂、苛刻和有毒的合成过程,为快速合成用于碱性水电解的高耐久性析氢电催化剂开辟了新途径.

关 键 词：plasma technology ELECTROCATALYST hydrogen evolution long-term stability water electrolysis 

分 类 号：O643.36[理学—物理化学]