{"title":"Metalloporphyrin-based covalent triazine frameworks for efficient photocatalytic CO2 cycloaddition at ambient conditions","authors":"","doi":"10.1016/j.dyepig.2024.112531","DOIUrl":null,"url":null,"abstract":"<div><div>The sunlight-driven CO<sub>2</sub> 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 (<strong>Por-CTFs</strong>) including metal-free <strong>Por-CTF</strong> (<strong>H2Por-CTF</strong>) and metallized <strong>Por-CTFs</strong> (<strong>MPor-CTFs</strong>, M = Co, Zn, Cu) and their photocatalytic activity in CO<sub>2</sub> cycloaddition. All <strong>Por-CTFs</strong> 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 <strong>MPor-CTFs</strong> 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 <strong>CoPor-CTF</strong> exhibits excellent photocatalytic performance achieving a reaction rate of 62.22 mmol g<sup>−1</sup> h<sup>−1</sup>, which is among the state-of-the-art cases for photocatalytic CO<sub>2</sub> cycloaddition and outperforms two other <strong>MPor-CTFs</strong>. This work demonstrates that the photophysical and electronic properties of <strong>Por-CTFs</strong> can be rationally tuned by incorporating various metal ions into porphyrin units to achieve effective photocatalysts for CO<sub>2</sub> cycloaddition.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":null,"pages":null},"PeriodicalIF":4.1000,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dyes and Pigments","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0143720824005977","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
引用次数: 0
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.
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.