镍基磷化物的合成及其在电解水制氢中的应用  

Synthesis and application of nickel-based phosphide in water electrolysis for hydrogen evolution

作　　者：李宇明 徐砚文 刘红宇 马丽娜 王雅君[1] LI Yuming;XU Yanwen;LIU Hongyu;MA Lina;WANG Yajun(State Key Laboratory of Heavy Oil Processing,China University of Petroleum,Beijing 102249,China;Carbon Neutrality Joint Research Institute,Shandong Institute of Petroleum and Chemical Technology,Dongying 257504,Shandong,China)

机构地区：[1]中国石油大学(北京),重质油全国重点实验室,北京102249 [2]山东石油化工学院,碳中和联合研究院,山东东营257504

出　　处：《化工学报》2024年第12期4385-4402,共18页CIESC Journal

基　　金：重质油全国重点实验室自主项目;国家重点研发计划项目(2021YFB4000405,2019YFC1904500);国家自然科学基金项目(52270115,52236003,21777080);碳中和联合研究院自主基金项目(CNIF20230208)。

摘　　要：近年来,以绿氢为代表的零碳能源的推广与使用已成为国家碳中和发展战略的重要组成部分,大力发展包括电解水制氢技术在内的绿氢能源是我国能源转型的重要研究方向。设计和开发高效催化剂是提升电解水制氢(HER)能力的关键因素。镍基过渡金属磷化物是一类重要的非贵金属电解水催化剂,其中磷空穴(P_(v))的存在可以促进H*的解吸,富集催化剂上的电子。同时磷的存在能够降低Ni—H键能,优化析氢活性。这类催化剂不仅在强碱性溶液中,而且在强酸性和中性介质中均具有优异的性能。以镍基磷化物催化剂为基础,介绍了电解水制氢原理及相关催化剂类型,并总结了镍基磷化物中镍、磷物种分别在电解水中的作用机制,可为后续高效镍基电解水催化剂的开发提供一定的理论指导。另一方面,根据镍基磷化物催化剂的制备方法,归纳了镍基磷化物催化剂的制备影响因素,并总结出调整其催化活性的基本策略,包括掺杂金属和非金属元素、制备多金属镍基磷化物以及构建由其他过渡金属磷化物组成的多组分异质结构等。最后讨论了镍基磷化物催化剂在电解水制氢过程中的研究进展,对提高镍基磷化物电解水制氢的催化效率和稳定性提出了一些建议。Energy is one of the most important problems for human society.In recent years,with the proposed goal of carbon neutrality,the development of new environmentally friendly energies has become a key development direction for China.Among the different kinds of new energies,hydrogen with its clean,efficient,pollution-free and other advantages,has become an important part of the national energy strategy development.Green hydrogen refers to the hydrogen obtained from renewable energies without producing extra carbon dioxide in the production process which can realize zero carbon dioxide emissions.With this,the green hydrogen is considered as one of the most promising clean energy sources in the future.Thus,the development of green hydrogen energy including electrolytic water for hydrogen evolution(HER)technology,becomes a focus in China.To meet the requirements of cheap price and stable hydrogen evolution rate in HER process,the design and development of catalysts in high activity is a key factor.Among HER catalysts,precious metal catalysts such as Pt-,Ir-,Ru-based catalysts possess high activity,while their scarcity makes them at a high price.Thus,the development of non-precious metal electrocatalysts has become a research hotspot.Among many non-precious metal catalysts,nickel phosphide based catalyst is one of the important water electrolysis catalysts.The presence of phosphorus can effectively reduce the Gibbs free energy of H*adsorption or H_(2) desorption,which makes its hydrogen evolution efficiency increase,and the catalytic stability can be enhanced.The presence of phosphorus holes(P_(v))formed in nickel phosphide based catalysts can enrich electrons on the catalyst and improve HER performance by promoting the desorption of H*.Moreover,the phosphorus element has a higher electronegativity than the nickel element,and can attract electrons from nickel components,which enables phosphorus atoms to capture positively charged protons during HER process.In addition,the electronegativity of phosphorus is lower than tha

关 键 词：电解水 制氢 镍 磷化物 催化剂制备 反应机理 

分 类 号：O646[理学—物理化学]