Microenvironment modulation of Fe-porphyrinic metal–organic frameworks for CO2 photoreduction

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis Pub Date : 2024-09-13 DOI:10.1016/j.jcat.2024.115745

Xue Zhao , Chen-Xi Tang , Qiang Xu , Heng Rao , Dong-Ying Du , Ping She , Jun-Sheng Qin

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Abstract

Photocatalytic CO₂ reduction to fuels and chemicals is a promising pathway towards carbon resource recovery. Herein, three isomorphic Fe-porphyrinic MOFs, Zr₆O₄(OH)₄(Fe-TCPP)₃ (MOF-525, Fe-TCPP = iron 5,10,15,20-tetra(4-carboxyphenyl)-porphyrin), Zr₆O₄(OH)₄(Fe-TCPP-NO₂)₃ (MOF-525-NO₂, Fe-TCPP-NO₂ = iron 5,10,15,20-tetra(2-nitro-4-carboxyphenyl)-porphyrin), and Zr₆O₄(OH)₄(Fe-TCBPP-NO₂)₃ (MOF-526-NO₂, Fe-TCBPP-NO₂ = iron 5,10,15,20-tetra[4-(4′-carboxyphenyl)-2-nitrophenyl]-porphyrin) were synthesized and employed as photocatalysts for CO₂ reduction. Among them, MOF-525-NO₂ exhibited the highest catalytic activity with CO and H₂ yields of 10.36 and 0.46 mmol·g⁻¹ without any photosensitizer under visible light. Mechanism investigations suggested that the micro-environments of these MOFs were adjusted by introducing porphyrinic fragments with different lengths and functional groups, resulting in stronger CO₂ affinity, faster photocurrent response, and efficient photogenerated electron-hole separation and transfer, which finally promoted the efficiency for photocatalytic CO₂ reduction.

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用于二氧化碳光还原的 Fe-卟啉金属有机框架的微环境调控

光催化将二氧化碳还原为燃料和化学品是实现碳资源回收的一条前景广阔的途径。在这里，三种同构的铁卟啉 MOF，即 Zr6O4(OH)4(Fe-TCPP)3（MOF-525，Fe-TCPP = 铁 5,10,15,20-四（4-羧基苯基）-卟啉）、Zr6O4(OH)4(Fe-TCPP-NO2)3（MOF-525-NO2，Fe-TCPP-NO2 = 铁 5,10,15、合成了 Zr6O4(OH)4(Fe-TCPP-NO2)3（MOF-525-NO2，Fe-TCPP-NO2 = 5,10,15,20-四[2-硝基-4-羧基苯基]-卟啉）和 Zr6O4(OH)4(Fe-TCPP-NO2)3（MOF-526-NO2，Fe-TCPP-NO2 = 5,10,15,20-四[4-(4′-羧基苯基)-2-硝基苯基]-卟啉），并将其作为光催化剂用于 CO2 还原。其中，MOF-525-NO2 的催化活性最高，在不使用任何光敏剂的情况下，其在可见光下的 CO 和 H2 产率分别为 10.36 和 0.46 mmol-g-1。机理研究表明，通过引入不同长度和官能团的卟啉片段来调整这些 MOFs 的微环境，使其具有更强的 CO2 亲和力、更快的光电流响应以及高效的光生电子-空穴分离和转移，最终提高了光催化还原 CO2 的效率。

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来源期刊

Journal of Catalysis 工程技术-工程：化工

CiteScore

12.30

自引率

5.50%

发文量

447

审稿时长

31 days

期刊介绍： The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes. The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods. The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.