Application of metal-organic frameworks in CO2 hydrogenation
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摘要: 大气中二氧化碳(CO2)浓度的急剧增加引起了人们的关注,并提出了许多将CO2转化为高价值化学品的策略。金属有机框架材料(MOFs)由于其独特的孔隙率、大的比表面积、丰富的孔结构、多活性中心、良好的稳定性和可回收性,可用于二氧化碳的捕获和催化转化。基于晶体多孔材料的金属有机骨架(MOF)设计和合成的各种功能纳米材料可以作为多相催化剂或载体/前体来应对这些挑战。在本文中,笔者将主要关注MOFs在催化二氧化碳加氢领域的最新研究进展,包括催化加氢制备一氧化碳、甲烷、甲酸、甲醇和烯烃,分析了基于MOFs的催化剂的合成方法和提高催化活性的原因。介绍了提高新型MOF材料的催化活性和探索新的CO2转化可行的策略。讨论了MOF型催化剂在CO2化学转化中的主要挑战和机遇,对本研究领域中进一步的发展进行了简要的展望。Abstract: The dramatic increase in atmospheric CO2 concentrations has attracted people's attention, and many strategies have been developed to convert CO2 into high-value chemicals. Metal-organic frameworks (MOFs), as a class of versatile materials, can be used in the CO2 capture and conversion because of their unique porosity, large specific surface area, rich pore structure, multiple active centers, good stability and recyclability. Various functional nanomaterials have been designed and synthesized based on metal organic framework (MOF) of crystalline porous materials to meet these challenges. Herein, in this review, the latest processes of MOFs in field the of CO2 hydrogenation to carbon monoxide, methane, formic acid, methanol and olefins are summarized, and the synthesis methods of catalysts based on MOFs and the reasons for their high catalytic activity are analyzed. Besides, a brief introduction to improve the catalytic activity of the new MOF material and explore the feasible strategies for CO2 conversion are advised. Finally, the paper discusses the main challenges and opportunities of MOF-type catalysts in CO2 chemical conversion, and presents a brief outlook on further developments in this research area.
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Key words:
- metal-organic frameworks /
- CO2 hydrogenation /
- catalysis /
- research progress
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图 2 (a)Pt/Au@Pd@UiO-66纳米复合材料的合成过程;(b)Pt/Au@Pd@UiO-66在不同温度下催化CO2还原;(c)Au@Pd@UiO-66和Pt/Au@Pd@UiO-66的CO选择性[30]
Figure 2 (a): Synthesis process of Pt/Au@Pd@UiO-66 nanocomposites; (b): CO2-reduction catalyzed by Pt/Au@Pd@UiO-66 at different temperatures; (c): CO product selectivity of Au@Pd@UiO-66 and Pt/Au@Pd@UiO-66[30]
图 10 (a)
${\rm{Cu}} \subset {\rm{UiO}} {\text{-}} 66$ 活性位点的图示;(b)${\rm{Cu}} \subset {\rm{UiO}} {\text{-}} 66 $ 和Cu/ZnO/Al2O3在各不同反应温度下产物的TOFs;(c)在${\rm{Cu}} \subset {\rm{UiO}} {\text{-}} 66 $ 上和Cu在UiO-66上甲醇的初始TOFs;(d)${\rm{Cu}} \subset {\rm{UiO}} {\text{-}} 66 $ (UiO-66内部的单个CuNC)的TEM;(e)UiO-66上Cu的TEM[50]Figure 10 (a) Illustration of active site of
$ {\rm{Cu}} \subset {\rm{UiO}} {\text{-}} 66 $ catalyst; (b) TOFs of product formation over${\rm{Cu}} \subset {\rm{UiO}} {\text{-}} 66$ catalyst and Cu/ZnO/Al2O3 catalyst as various reaction temperatures; (c) Initial TOFs of methanol formation over${\rm{Cu}} \subset {\rm{UiO}} {\text{-}} 66$ and Cu on UiO-66 ; (d) TEM images of${\rm{Cu}} \subset {\rm{UiO}} {\text{-}} 66$ (single Cu NC inside UiO-66); (e) TEM images of Cu on UiO-66[50]图 11 (a)合成后金属化的UiO-bpy原位还原制备CuZn@UiO-bpy示意图;(b)CH3OH的时空产率随在反应时间的变化;(c)产物的选择性随反应时间的变化;(d)MOF中封装的活性位点以及各种表面位点在催化CO2加氢中的功能[51]
Figure 11 (a): Preparation of CuZn@UiO-bpy via in situ reduction of post-synthetically metalized UiO-bpy; (b): STY of CH3OH vs reaction time on stream; (c) Selectivity of product vs reaction time; (d) Schematic showing the encapsulated active sites in MOF and the functions of the various surface sites in catalytic CO2 hydrogenation [51] (with permission from ACS)
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