摘要
有限的化石燃料与不断增长的能源需求的矛盾和因温室气体大量排放导致的异常气候变化这两大相关问题引起全世界范围内的关注。二氧化碳(CO_(2))是一种主要的温室气体,同时也是合成燃料和化学品的重要C1资源。利用CO_(2)参与合成化学品能有效减少温室气体的排放。然而,高度氧化、热力学稳定的CO_(2)的化学转化仍然是一较大挑战,需要引入还原剂等参与CO_(2)的化学转化。作为理想的还原剂,氢气(H_(2))可将CO_(2)逆水煤气变换(RWGS)转化为一氧化碳(CO),考虑到有毒CO的繁琐分离和运输,众多研究利用原位生成的CO参与到各种羰基化反应中,既得到了高附加值的化学品,又避免了CO的直接使用。基于此,过渡金属催化CO_(2)/H_(2)参与的羰基化反应得到了广泛地关注和研究,实现了CO_(2)/H_(2)参与的烯烃羰基化生成醇、羧酸、胺、醛等产物。同时多相催化的烯烃羰基化的实现为该领域开发了新的催化体系。在烯烃羰基化的基础上,该领域得到了进一步的发展,CO_(2)参与羰基化的反应路径变得更加丰富,如出现了CO_(2)加氢到甲酸(HCOOH),HCOOH到CO的间接生成CO的路径和CO_(2)直接参与羰基化的反应路径,实现了CO_(2)/H_(2)参与的卤代烃、甲醇(MeOH)及其衍生物等的羰基化反应,获得芳醛、乙酸、乙醇等大宗或精细化学品。CO_(2)/H_(2)参与的羰基化研究的快速发展拓展了CO_(2)资源化利用的途径,获得高附加值的大宗或精细化学品,促进了绿色化学的发展。本文主要围绕过渡金属催化CO_(2)/H_(2)参与的多种羰基化生成高附加值化学品的反应,总结了近年来的研究进展,并对该方向的发展做了展望。
Ever-increasing energy demands due to rapid industrialization and urban population growth have drastically reduced petroleum reserves and increased greenhouse-gas production,and the latter has consequently contributed to climate change and environmental damage.Therefore,it is highly desirable to produce fuels and chemicals from nonpetroleum feedstocks and to reduce the atmospheric concentrations of greenhouse gases.One solution has involved using carbon dioxide(CO_(2)),a main greenhouse gas,as a C1 feedstock for producing industrial fuels and chemicals.However,this requires high energy input from reductants or reactants with relatively high free energy(e.g.,H_(2)gas)because CO_(2)is a highly oxidized,thermodynamically stable form of carbon.H_(2)can be generated through water photolysis,making it an ideal reductant for hydrogenating CO_(2)to CO.In situ generation of CO such as this has been developed for various carbonylation reactions that produce high value-added chemicals and avoid deriving CO from fossil fuels.This is beneficial because CO is toxic,and when extracted from fossil fuels it requires tedious separation and transportation.This combination of CO_(2)and H_(2)allows for functional molecules to be synthesized as entries into the chemical industry value chain and would generate a carbon footprint much lower than that of conventional petrochemical pathways.Based on this,CO_(2)/H_(2)carbonylations using homogeneous transition metal-based catalysts have attracted increasing attention.Through this process,alkenes have been converted to alcohols,carboxylic acids,amines,and aldehydes.Heterogeneous catalysis has also provided an innovative approach for the carbonylation of alkenes with CO_(2)/H_(2).Based on these alkene carbonylations,the scope of CO_(2)/H_(2)carbonylations has been expanded to include aryl halides,methanol,and methanol derivatives,which give the corresponding aryl aldehyde,acetic acid,and ethanol products.These carbonylations revealed indirect CO_(2)-HCOOH-CO pathways and direct CO_(2)insertion pathways.The use of this process is ever-increasing and has expanded the scope of CO_(2)utilization to produce novel,high value-added or bulk chemicals,and has promoted sustainable chemistry.This review summarizes the recent advances in transition-metal-catalyzed carbonylations with CO_(2)/H_(2)and discusses the perspectives and challenges of further research.
作者
华凯敏
刘晓放
魏百银
张书南
王慧
孙予罕
Kaimin Hua;Xiaofang Liu;Baiyin Wei;Shunan Zhang;Hui Wang;Yuhan Sun(CAS Key Laboratory of Low-Carbon Conversion Science and Engineering,Shanghai Advanced Research Institute,Chinese Academy of Sciences,Shanghai 201203,China;University of the Chinese Academy of Sciences,Beijing 100049,China;School of Physical Science and Technology,ShanghaiTech University,Shanghai 201203,China;Shanghai Institute of Clean Technology,Shanghai 201620,China)
出处
《物理化学学报》
SCIE
CAS
CSCD
北大核心
2021年第5期133-148,共16页
Acta Physico-Chimica Sinica
基金
国家自然科学基金(21776296,21905291)
国家重点研发计划(2017YFB0602203)
中国科学院战略性先导科技专项(XDA21090201)
中国科学院重点项目(ZDRW-ZS-2018-1-3)
上海市扬帆计划(19YF1453000)资助。
关键词
二氧化碳加氢
羰基化反应
过渡金属催化
醇
醛
羧酸
乙醇
乙酸
Carbon dioxide hydrogenation
Carbonylation
Transition metal catalysis
Alcohols
Aldehydes
Carboxylic acids
Ethanol
Acetic acid
