化学学报 ›› 2018, Vol. 76 ›› Issue (7): 501-514.DOI: 10.6023/A18040138 上一篇    下一篇

综述

过渡金属催化的醇类脱氧脱水反应

李翠a, 张琪b, 傅尧a   

  1. a 中国科学技术大学 化学系 合肥 230026;
    b 合肥工业大学 工业与装备技术研究院 合肥 230009
  • 出版日期:2018-07-15 发布日期:2018-05-14
  • 通讯作者: 傅尧,E-mail:fuyao@ustc.edu.cn;Tel.:0086-0551-63606689 E-mail:fuyao@ustc.edu.cn
  • 作者简介:李翠,中国科学技术大学在读硕士生;张琪,合肥工业大学工业与装备技术研究院讲师.主要从事有机化学与材料化学方向的理论计算研究,2013年获得国家杰出青年科学基金资助,2017年入选国家"万人计划"领军人才,获得国家自然科学二等奖(第二完成人)、闵恩泽能源化工奖杰出贡献奖等荣誉.
  • 基金资助:

    项目受国家自然科学基金(Nos.21325208,21572212,21732006,21702041)、国家科技部基金(No.2017YFA0303500)、中国科学院战略性先导项目(No.XDB20000000)、中央高校基本科研专项资金和教育部长江学者和创新团队发展计划资助.

Transition Metal Catalyzed Deoxydehydration of Alcohols

Li Cuia, Zhang Qib, Fu Yaoa   

  1. a Department of Chemistry, University of Science and Technology of China, Hefei 230026;
    b Institute of Industry & Equipment Technology, Hefei University of Technology, Hefei 230009
  • Online:2018-07-15 Published:2018-05-14
  • Contact: 10.6023/A18040138 E-mail:fuyao@ustc.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21325208, 21572212, 21732006, 21702041), Ministry of Science and Technology of China (No. 2017YFA0303500), the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB20000000), Fundamental Research Funds for the Central Universities, and Program for Changjiang Scholars and Innovative Research Team in University.

开发和利用环境保护型的可再生新能源是缓和与解决能源环境问题的重要举措.生物质可作为燃料和可再生平台化学品的来源.高含氧量与过度官能化的生物质原料不能直接使用,因此降低生物质原料的含氧量并将其转化为燃料与增值化学品的方法是实现生物质能广泛应用的关键.还原脱氧的方法主要有热解、水解、氢解、脱羧/脱羰反应、加氢脱氧与脱氧脱水反应等.本综述详细介绍了铼、钼、钒、钌等四种过渡金属催化的由二元醇及多元醇制备相应烯烃的脱氧脱水反应,主要从均相催化、还原剂使用、机理研究和非均相催化等方面做了多角度的总结.铼催化的脱氧脱水反应具有选择性好和烯烃产率高等优点,钼、钒、钌等金属是可能替代昂贵的铼金属的催化剂.

关键词: 脱氧脱水, 过渡金属, 邻二醇, 烯烃, 生物质衍生物

In view of the depletion of fossil fuels, the development and utilization of environment-friendly and sustainable resources widely play an indispensable role in alleviating and resolving problems about resources and environment. Biomass could be utilized as biofuels and renewable platform chemicals. However, biomass-derived molecules are fairly oxygen-rich and hyperfunctionalized. Therefore, new synthetic routes for the regenerative production of chemicals, fuels, and energy from renewable biomass sources are currently investigated especially the routes of transforming high-oxygen-content biomassderived vicinal diols and poly vicinal alcohols into fuels and value-added chemicals. A range of reductive deoxygenation methods consisting of direct deoxygenation, pyrolysis, hydrogenolysis, decarbonylation, decarboxylation, hydrodeoxygenation, and deoxydehydration (DODH) are under investigation. In this review, we detail the recent-evolutionary and efficient strategies of transition metal-catalyzed DODH of vicinal diols into corresponding alkenes, including rhenium, molybdenum, vanadium, and ruthenium catalysts. Rhenium-catalyzed DODH reactions are very selective and active to provide high yields of olefin products, which keep important functionality in place as well as can be readily functionalized. Recent efforts in rhenium-mediated systems include the development of new rhenium catalysts, the application of cheaper and more available reductants, and growing mechanistic understandings owing to both theoretical and experimental studies. A new emerging trend within DODH is the development of heterogeneous rhenium-based catalysts which demonstrates their ability to rival and in some cases surpass their homogeneous counterparts. Furthermore, catalysts based on the transition metals molybdenum, vanadium and ruthenium show great potential as inexpensive alternatives to rhenium catalysts.

Key words: deoxydehydration, transition metal, vicinal diol, olefin, biomass derivatives