物理化学学报 >> 2019, Vol. 35 >> Issue (9): 923-939.doi: 10.3866/PKU.WHXB201810002

所属专题: 碳氢键活化

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甲烷/甲醇光催化转化研究进展

张舒怡1,2,鲍静娴1,3,吴博1,2,钟良枢1,4,*(),孙予罕1,4,*()   

  1. 1 中国科学院上海高等研究院,中科院低碳转化科学与工程重点实验室,上海 201203
    2 中国科学院大学,北京 100049
    3 上海大学理学院,上海 200444
    4 上海科技大学物质科学与技术学院,上海 201203
  • 收稿日期:2018-10-08 发布日期:2018-11-26
  • 通讯作者: 钟良枢,孙予罕 E-mail:zhongls@sari.ac.cn;sunyh@sari.ac.cn
  • 作者简介:钟良枢,2003年本科毕业于北京化工大学,获应用化学学士学位;2008年6月毕业于中国科学院化学研究所,获物理化学博士学位;2008年7月至2010年6月在德国慕尼黑工业大学化学系进行博士后研究。现任中国科学院上海高等研究院研究员。主要从事C1分子高选择性转化制清洁燃料与高附加值化学品相关的催化研究|孙予罕,1983年毕业于郑州大学化学系,获得学士学位;1983年至1989年在中国科学院山西煤炭化学研究所获博士学位。现任中国科学院上海高等研究院低碳转化科学与工程重点实验室主任。主要从事含碳资源与CO2转化利用中催化和工程研究,以及相关纳米材料及其在绿色化学中的应用研究,包括近期的清洁能源战略与解决方案研究
  • 基金资助:
    国家重点研发计划重点专项(2017YFB0602202);国家重点研发计划重点专项(2018YFB0604700);国家自然科学基金(21573271);国家自然科学基金(91545112);国家自然科学基金(21703278);中国科学院前沿科学重点研究划(QYZDB-SSW-SLH035);中国科学院洁净能源先导科技专项(XDA21020600)

Research Progress on the Photocatalytic Conversion of Methane and Methanol

Shuyi ZHANG1,2,Jingxian BAO1,3,Bo WU1,2,Liangshu ZHONG1,4,*(),Yuhan SUN1,4,*()   

  1. 1 CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute
    2 Chinese Academy of Sciences, Shanghai 201203, P. R. China
    3 University of the Chinese Academy of Sciences, Beijing 100049, P. R. China
    4 College of Sciences, Shanghai University, Shanghai 200444, P. R. China
  • Received:2018-10-08 Published:2018-11-26
  • Contact: Liangshu ZHONG,Yuhan SUN E-mail:zhongls@sari.ac.cn;sunyh@sari.ac.cn
  • Supported by:
    This work was supported by the National Key R & D Program of China(2017YFB0602202);This work was supported by the National Key R & D Program of China(2018YFB0604700);National Natural Science Foundation of China(21573271);National Natural Science Foundation of China(91545112);National Natural Science Foundation of China(21703278);Key Research Program of Frontier Sciences, CAS(QYZDB-SSW-SLH035);"Transformational Technologies for Clean Energy and Demonstration" and Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21020600)

摘要:

在能源需求不断上涨及石油供应日益紧张的背景下,开展对煤、天然气或生物质等非油基资源(CO、CO2、CH3OH、CH4等)的高效利用显得尤为重要。C1小分子(CO、CO2、CH3OH、CH4等)经催化转化可得到燃料及多种化学品,一直受到学术界及工业界的广泛关注。甲烷/甲醇作为重要的C1平台分子,其催化转化在C1化学中占据重要地位。为了提高目标产物的选择性,需要有效地控制甲烷/甲醇中C―H键的活化。传统热催化作为甲烷/甲醇最常见的转化方法发展已久,但仍然面临着反应条件苛刻、能耗大、产率和选择性低等问题。光催化反应通过引入光能弥补反应中吉布斯自由能的上升,同时具有反应条件温和、操作简单、能耗低等特点,从而为甲烷/甲醇转化提供了新的途径。通过调节光的波长、强度以及催化剂的氧化能力可以实现甲烷/甲醇的选择性转化,减少副产物的生成。此外,光催化能够选择性活化甲醇的C―H键而非O―H键,从而实现甲醇的C―C偶联反应。本文主要围绕甲烷/甲醇的重整、氧化和偶联反应,总结近年来的光催化转化进展,并对进一步提高光催化性能做了展望。

关键词: C―H键活化, C1化学, 甲烷, 甲醇, 光催化

Abstract:

With the increasing energy demands and the limited petroleum reserves, it is highly desirable to produce fuels and chemicals from non-petroleum feedstocks, such as coal, natural gas and biomass. Catalytic conversion of C1 resources (CO, CO2, CH3OH, CH4, etc.) affords various products and attracts increasing attention from both academia and industries. Methane and methanol are important C1 feedstocks in the production of fuels and chemicals. In order to obtain high selectivity for the target product, it is necessary to control the activation of C―H bonds in methane and methanol. However, this remains a great challenge. Although the traditional thermal catalytic conversion of methane and methanol has been developed over decades, there are still some disadvantages associated with the catalytic process, such as harsh reaction conditions, high energy consumption, and low selectivity. Photocatalysis, which is driven by photoenergy, can compensate for the Gibbs free energy. In the photocatalytic reactions, semiconductor photocatalysts absorb photons and generate electrons and holes in their conduction and valence bands, respectively, to accelerate the reaction rate. The position of the conduction band determines the oxidation capacity, and the bandgap determines the light absorption property. Normally, the oxidation capacity of photocatalysts is regulated by choosing semiconductors with a suitable bandgap or anions/cations doping. Fabrication of heterojunction and loading metalsare recognized as effective methods to promote the separation of electron-hole pairs and improve the photocatalytic efficiency. In contrast to thermal catalysis, photocatalysis can be carried out under mild reaction conditions with low energy consumption. Recently, photocatalysis has been considered an attractive route for the efficient conversion of methane and methanol to fuels and chemicals. Partial oxidation of methane, which is necessary to avoid the formation of byproducts, can be achieved by adjusting the wavelength and intensity of the light and the oxidation capacity of the photocatalysts. In addition, light-induced plasmon resonance improves the efficiency of methane conversion by forming an intrinsic high-energy magnetic field that can polarize methane. In methanol conversion, the C―H bond can be selectively activated, instead of the O―H bond, by light irradiation. Therefore, C―C coupling can be realized for the production of various value-added chemicals from methanol. This review summarizes the recent advances in the photocatalytic conversion of methane and methanol including the reactions of reforming, oxidation, and coupling. Perspectives and challenges for further research on the photocatalytic conversion of methane and methanol are also discussed.

Key words: Activation of C―H bond, C1 chemistry, Methane, Methanol, Photocatalysis

MSC2000: 

  • O644