Metalloporphyrin-based covalent triazine frameworks for efficient photocatalytic CO2 cycloaddition at ambient conditions

IF 4.1 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments Pub Date : 2024-11-04 DOI:10.1016/j.dyepig.2024.112531

Ji Xiong , Ming-Hui Chen , Xiang-Yu Li , Quan Shi , Yun-Hao Xu , Ya-Qing Feng , Bao Zhang

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Abstract

The sunlight-driven CO₂ fixation into high value-added industrial products constitutes a promising approach to mitigating global warming, offering an alternative to traditional thermally-driven fixation requiring high temperature and/or high pressure. Herein, we design and synthesize four isostructural porphyrinic covalent triazine frameworks (Por-CTFs) including metal-free Por-CTF (H2Por-CTF) and metallized Por-CTFs (MPor-CTFs, M = Co, Zn, Cu) and their photocatalytic activity in CO₂ cycloaddition. All Por-CTFs exhibit wide light adsorption range in visible region via introducing porphyrins into the covalent triazine frameworks (CTFs) skeleton. Different metal ions which are well anchored in the MPor-CTFs skeleton not only offer Lewis acidic sites for substrate interaction but also apparently endow photocatalysts with longer photogenerated carrier lifetimes and higher electron-hole separation efficiency. Encouragingly, under visible light-assisted and mild conditions, the CoPor-CTF exhibits excellent photocatalytic performance achieving a reaction rate of 62.22 mmol g⁻¹ h⁻¹, which is among the state-of-the-art cases for photocatalytic CO₂ cycloaddition and outperforms two other MPor-CTFs. This work demonstrates that the photophysical and electronic properties of Por-CTFs can be rationally tuned by incorporating various metal ions into porphyrin units to achieve effective photocatalysts for CO₂ cycloaddition.

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基于金属卟啉的共价三嗪框架在环境条件下实现高效光催化 CO2 环化

阳光驱动将二氧化碳固定为高附加值的工业产品是减缓全球变暖的一种有前景的方法，为需要高温和/或高压的传统热驱动固定法提供了一种替代方案。在此，我们设计并合成了四种等结构卟啉共价三嗪框架（Por-CTFs），包括无金属 Por-CTFs （H2Por-CTFs）和金属化 Por-CTFs （MPor-CTFs，M = Co、Zn、Cu）及其在 CO2 环加成中的光催化活性。通过在共价三嗪框架（CTFs）骨架中引入卟啉，所有 Por-CTFs 在可见光区域都表现出很宽的光吸收范围。锚定在 MPor-CTFs 骨架中的不同金属离子不仅为底物相互作用提供了路易斯酸性位点，而且明显赋予了光催化剂更长的光生载流子寿命和更高的电子-空穴分离效率。令人鼓舞的是，在可见光辅助和温和条件下，CoPor-CTF 表现出优异的光催化性能，反应速率达到 62.22 mmol g-1 h-1，跻身光催化 CO2 环加成的先进行列，并优于其他两种 MPor-CTF。这项工作表明，可以通过在卟啉单元中加入各种金属离子来合理调节 Por-CTFs 的光物理和电子特性，从而实现二氧化碳环加成的有效光催化剂。

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来源期刊

Dyes and Pigments 工程技术-材料科学：纺织

CiteScore

8.20

自引率

13.30%

发文量

933

审稿时长

33 days

期刊介绍： Dyes and Pigments covers the scientific and technical aspects of the chemistry and physics of dyes, pigments and their intermediates. Emphasis is placed on the properties of the colouring matters themselves rather than on their applications or the system in which they may be applied. Thus the journal accepts research and review papers on the synthesis of dyes, pigments and intermediates, their physical or chemical properties, e.g. spectroscopic, surface, solution or solid state characteristics, the physical aspects of their preparation, e.g. precipitation, nucleation and growth, crystal formation, liquid crystalline characteristics, their photochemical, ecological or biological properties and the relationship between colour and chemical constitution. However, papers are considered which deal with the more fundamental aspects of colourant application and of the interactions of colourants with substrates or media. The journal will interest a wide variety of workers in a range of disciplines whose work involves dyes, pigments and their intermediates, and provides a platform for investigators with common interests but diverse fields of activity such as cosmetics, reprographics, dye and pigment synthesis, medical research, polymers, etc.