Advances in metal-free carbon catalysts for acetylene hydrochlorination:From heteroatom doping to intrinsic defects over the past decade  

乙炔氢氯化非金属碳催化剂的研究进展:从杂原子掺杂到本征缺陷

作　　者：Shuhao Wei Guojun Lan Yiyang Qiu Di Lin Wei Kong Ying Li 魏抒豪;蓝国钧;邱一洋;林迪;孔薇;李瑛(浙江工业大学化工学院,工业催化研究所,浙江杭州310014)

机构地区：[1]Institute of Industrial Catalysis,College of Chemical Engineering,Zhejiang University of Technology,Hangzhou310014,Zhejiang,China

出　　处：《Chinese Journal of Catalysis》2025年第3期8-43,共36页催化学报(英文)

基　　金：国家重点研发计划(2024YFC3907904);国家自然科学基金企业创新发展联合基金(U23B20162).

摘　　要：The development of metal-free carbon catalysts has garnered significant attention as a promising approach to address the challenges of sustainable catalysis,particularly in the replacement of toxic and environmentally hazardous mercury-based systems for the coal-based PVC industry.Within a decade of development,the catalytic performance of carbon catalysts has been improved greatly and even shows superiorities over metal catalysts in some cases,which have demonstrated great potential as sustainable alternatives to mercury catalysts.This review provides a comprehensive summary of the recent advancements in carbon catalysts for acetylene hydrochlorination.It encompasses a wide range of aspects,including the identification of active sites from heteroatom doping to intrinsic carbon defects,the various synthetic strategies employed,the reaction and deactivation mechanisms of carbon catalysts,and the current insights into the key challenges that are encountered on the journey from laboratory research to scalable commercialization within the field of carbon catalysts.The review offers foundational insights and practical guidelines for designing green carbon catalysts systems,not only for acetylene hydrochlorination but also for other heterogeneous catalytic reactions.聚氯乙烯(PVC)由氯乙烯(VCM)通过聚合反应制得,是我国产能最大的高分子材料之一.鉴于我国“富煤、贫油、少气”的能源结构现状,乙炔氢氯化法已成为国内生产氯乙烯单体的主要工艺.当前,工业界普遍采用活性炭负载氯化汞催化剂作为氯乙烯生产的催化剂.然而,随着全球范围内限汞政策的不断推进,开发新型的无汞催化剂已成为当务之急.尽管已有关于金、铜、钌等金属催化剂的研究报道,但这些催化剂存在金属组分易流失、成本高昂及易因中毒而失活等缺陷.相比之下,无金属碳催化剂以其绿色环保、成本低廉且不存在金属烧结与流失问题等优势,在无汞催化剂领域展现出了巨大的发展潜力.非金属碳催化剂的开发被视为应对可持续催化挑战的重要途径,特别是在替代煤基聚氯乙烯工业中有毒且危害环境的汞基催化剂方面,已引起广泛关注.自2014年乙炔氢氯化非金属碳催化剂被首次报道以来,经过了十年的发展,其催化活性及稳定性都获得了大幅度的提高.在某些情况下,非金属碳催化剂甚至表现出优于金属催化剂的性能,充分展现了其作为汞催化剂可持续替代方案的巨大潜力.本文系统总结了乙炔氢氯化碳催化剂的最新研究进展,从碳催化剂的活性位结构认识的发展历程、催化剂的制备方法、催化反应和失活机理,以及从实验室小试技术迈向大规模工业化应用过程中所面临的诸多挑战等几个方面进行阐述.首先,简要介绍了近十年来乙炔氢氯化碳催化剂的研究进展,特别指出了活性位的识别逐渐深入的过程,并阐述了不同活性位点(如单掺杂、共掺杂、缺陷、缺陷与杂原子的协同效应及曲率结构)在乙炔氢氯化反应中的作用机制.然后,讨论了碳催化剂的合成策略,包括后处理法和直接碳化法制备杂原子掺杂碳催化剂,以及高温脱杂原子和刻蚀等技术制备缺陷碳�

关 键 词：METAL-FREE Carbon catalyst Acetylene hydrochlorination Heteroatom doping Defect engineering 

分 类 号：O643.36[理学—物理化学]