Modulating the microstructure and surface chemistry of carbocatalysts for oxidative and direct dehydrogenation: A review  

烷烃脱氢制烯烃用碳催化剂的微结构和表面化学调控研究进展(英文)

作　　者：赵忠奎[1] 葛桂芳 李伟作[1] 郭新闻[1] 王桂茹[1] 

机构地区：[1]大连理工大学化工与环境生命学部精细化工国家重点实验室,辽宁大连116024

出　　处：《Chinese Journal of Catalysis》2016年第5期644-670,共27页催化学报（英文）

基　　金：supported by the National Natural Science Foundation of China(21276041);the Program for New Century Excellent Talents in University of Ministry of Education of China(NCET-12-0079);the Natural Science Foundation of Liaoning Province(2015020200);the Fundamental Research Funds for the Central Universities(DUT15LK41)~~

摘　　要：The catalytic performance of solid catalysts depends on the properties of the catalytically active sites and their accessibility to reactants, which are significantly affected by the microstructure（morphology, shape, size, texture, and surface structure） and surface chemistry（elemental components and chemical states）. The development of facile and efficient methods for tailoring the microstructure and surface chemistry is a hot topic in catalysis. This contribution reviews the state of the art in modulating the microstructure and surface chemistry of carbocatalysts by both bottom‐up and top‐down strategies and their use in the oxidative dehydrogenation（ODH） and direct dehydrogenation（DDH） of hydrocarbons including light alkanes and ethylbenzene to their corresponding olefins, important building blocks and chemicals like oxygenates. A concept of microstructure and surface chemistry tuning of the carbocatalyst for optimized catalytic performance and also for the fundamental understanding of the structure‐performance relationship is discussed. We also highlight the importance and challenges in modulating the microstructure and surface chemistry of carbocatalysts in ODH and DDH reactions of hydrocarbons for the highly‐efficient, energy‐saving,and clean production of their corresponding olefins.烯烃是重要的大宗有机化工原料,广泛用于塑料、树脂、橡胶等高分子材料和基础有机化工产品和中间体的生产.同时,烯烃也是重要的精细化工原料和中间体,广泛用于染料、医药、香料、农用化学品、水性油墨和感光树脂等精细化工领域.长链烯烃通常是由小分子烯烃聚合制得,而小分子烯烃和苯乙烯的合成在学术界和工业界备受关注.在脱氢、裂解、脱水等诸多合成方法中,烷烃脱氢制烯烃是直接而中的路线,包括直接脱氢和氧化脱氢.小分子烷烃和乙苯催化脱氢制备对应的烯烃,尤其是乙苯制苯乙烯,目前工业上主要采用铁基催化剂催化直接脱氢工艺.积炭失活是该工艺面临的严峻挑战.工业上采用引入大量过热水蒸气的方法来解决这一难题,同时,还可以为脱氢反应提供热量.但是,这势必造成巨大的能耗和反应器容积效率的显著降低.氧化脱氢工艺是放热反应,并可有效抑制积炭,但又存在过氧化所致的低选择性的问题.直接脱氢和氧化脱氢各有利弊.目前,科学家和工业界都在扬长避短,开展两种脱氢工艺的新结构高性能催化剂的研究,并取得了长足进展.碳催化是近年来发展起来的一类重要的无机非金属固相催化剂,在光催化、电催化,以及热催化领域得到了广泛关注同时也是材料领域研究的前沿和热点.碳材料,尤其是纳米碳,在诸多反应中展示出了比常规金属催化剂更好的催化性能,且具有可持续的特征.因此,碳催化具有广阔的发展空间和巨大的应用前景.众所周知,固体催化剂的催化性能重要依赖于催化剂表面催化活性位的性质及其可及性.元素组成、化学状态及缺陷边角特征决定着活性位的性质,而形貌、尺寸、形状、纹理、表面结构等催化剂的微结构特征决定着固相催化剂活性位的可及性.因此,探索有效的方法和策略,来调节固相催化剂的微结构和表�

关 键 词：Carbocatalysis MICROSTRUCTURE Surface chemistry MODULATION DEHYDROGENATION OLEFIN 

分 类 号：O643.36[理学—物理化学] TQ221.2[理学—化学]