R. Kamal Saravanan, Sanchita Karmakar, Faruk Ahamed Rahimi, Anupam Dey, Rohan Jena, Dipanjan Maity and Tapas Kumar Maji*,
{"title":"Metallo-Porous Organic Polymer as a CO2 Reduction Catalyst toward Selective Solar Fuel Production","authors":"R. Kamal Saravanan, Sanchita Karmakar, Faruk Ahamed Rahimi, Anupam Dey, Rohan Jena, Dipanjan Maity and Tapas Kumar Maji*, ","doi":"10.1021/acs.chemmater.4c00315","DOIUrl":null,"url":null,"abstract":"<p >In photocatalytic CO<sub>2</sub> reduction for solar fuel production, selectivity and efficiency are crucial. Here, we report the design and synthesis of a donor–acceptor imine-based porous organic polymer (<b>POP</b>) <b>Tpa-Phenda</b> and a metallo-porous organic polymer (<b>M-POP</b>) <b>Tpa-Phenda-Ru</b>, by reacting tris(4-formylphenyl)amine (Tpa) and Phenda/[Ru(Phenda)(bpy)<sub>2</sub>]<sup>2+</sup> (Phenda = 4,4′-(1,10-phenanthroline-3,8-diyl)dianiline; bpy = 2,2′-bipyridine) using acid-catalyzed Schiff base condensation reaction under solvothermal conditions. Here, the donor–acceptor dyads in both polymers harvested the visible light and transferred the photoexcited electrons to the active catalytic center, which is elucidated through <i>in situ</i> UV–vis spectroscopy. Both <b>Tpa-Phenda</b> and <b>Tpa-Phenda-Ru</b> produced CO in the acetonitrile–water medium using 1-benzyl-1,4-dihydronicotinamide (BNAH) and triethylamine (TEA) as sacrificial electron donors. <b>Tpa-Phenda</b> and <b>Tpa-Phenda-Ru</b> produced 0.92 and 9.77 mmol g<sup>–1</sup> of CO, respectively. <b>Tpa-Phenda-Ru</b> exhibited a higher rate of CO formation and selectivity compared to bare <b>Tpa-Phenda</b>. This can be attributed to the presence of the coordinated Ru<sup>II</sup> center in <b>Tpa-Phenda-Ru</b>, which acts as a catalytic site. Interestingly, <b>Tpa-Phenda</b> showed a low exciton binding energy (78 meV), which enhances the charge transfer efficiency and minimizes the energy loss. From an <i>in situ</i> diffuse reflectance FTIR spectroscopy (DRIFTS) study together with DFT calculation, a possible catalytic cycle for CO formation was constructed.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2000,"publicationDate":"2024-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry of Materials","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.chemmater.4c00315","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
In photocatalytic CO2 reduction for solar fuel production, selectivity and efficiency are crucial. Here, we report the design and synthesis of a donor–acceptor imine-based porous organic polymer (POP) Tpa-Phenda and a metallo-porous organic polymer (M-POP) Tpa-Phenda-Ru, by reacting tris(4-formylphenyl)amine (Tpa) and Phenda/[Ru(Phenda)(bpy)2]2+ (Phenda = 4,4′-(1,10-phenanthroline-3,8-diyl)dianiline; bpy = 2,2′-bipyridine) using acid-catalyzed Schiff base condensation reaction under solvothermal conditions. Here, the donor–acceptor dyads in both polymers harvested the visible light and transferred the photoexcited electrons to the active catalytic center, which is elucidated through in situ UV–vis spectroscopy. Both Tpa-Phenda and Tpa-Phenda-Ru produced CO in the acetonitrile–water medium using 1-benzyl-1,4-dihydronicotinamide (BNAH) and triethylamine (TEA) as sacrificial electron donors. Tpa-Phenda and Tpa-Phenda-Ru produced 0.92 and 9.77 mmol g–1 of CO, respectively. Tpa-Phenda-Ru exhibited a higher rate of CO formation and selectivity compared to bare Tpa-Phenda. This can be attributed to the presence of the coordinated RuII center in Tpa-Phenda-Ru, which acts as a catalytic site. Interestingly, Tpa-Phenda showed a low exciton binding energy (78 meV), which enhances the charge transfer efficiency and minimizes the energy loss. From an in situ diffuse reflectance FTIR spectroscopy (DRIFTS) study together with DFT calculation, a possible catalytic cycle for CO formation was constructed.
期刊介绍：
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.
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