A Three-Dimensional Azo-Bridged Porous Porphyrin Framework Supported Silver Nanoparticles as the State-of-the-Art Catalyst for the Carboxylative Cyclization of Propargylic Alcohols with CO2 under Ambient Conditions
{"title":"A Three-Dimensional Azo-Bridged Porous Porphyrin Framework Supported Silver Nanoparticles as the State-of-the-Art Catalyst for the Carboxylative Cyclization of Propargylic Alcohols with CO2 under Ambient Conditions","authors":"Yiying Yang, Yingyin Li, Yinghua Lu, Zhiyuan Chen and Rongchang Luo*, ","doi":"10.1021/acscatal.4c02391","DOIUrl":null,"url":null,"abstract":"<p >Designing efficient heterogeneous catalysts for the atmospheric fixation of CO<sub>2</sub> at room temperature remains a formidable challenge due to their high thermodynamic stability and kinetic inertness. Herein, a versatile nanocomposite of <b>Aza-Por-TAPM</b>-immobilized silver nanoparticles (AgNPs), <b>Ag/Azo-Por-TAPM</b>, has been successfully fabricated by adopting a three-dimensional azo-bridged porous porphyrin framework (<b>Azo-Por-TAPM</b>) as the porous support through a simple “liquid impregnation and in situ reduction” strategy. After adjusting the chemical structure of the porphyrin framework, the experimental results reveal that the presence of abundant azo groups and distorted tetrahedral structures is conducive to the preparation of highly dispersed and small-sized AgNPs at its surface. Further studies discover that <b>Ag/Azo-Por-TAPM</b> exhibits a record-level catalytic activity in the carboxylative cyclization of propargylic alcohols with CO<sub>2</sub> at room temperature, achieving maximum turnover frequencies of 4600 h<sup>–1</sup> at 10 bar and 1050 h<sup>–1</sup> at 1 bar, which far exceed that of the previously reported catalysts. In addition, <b>Ag/Aza-Por-TAPM</b> has a high catalytic efficiency with simulated industrial fuel gas under ambient conditions and can be easily recovered and reused at least six times without a significant decrease in catalytic activity. The significantly reduced activation energy, together with the analytical results of NMR spectra, demonstrate that AgNPs-driven alkyne activation is considered as the rate-determining step of the cyclization reaction. This work not only reports a kind of porous porphyrin polymers loaded AgNPs for mild CO<sub>2</sub> conversion but also brings some inspiration to designing highly efficient catalysts for the integration of CO<sub>2</sub> capture and utilization.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3000,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acscatal.4c02391","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Designing efficient heterogeneous catalysts for the atmospheric fixation of CO2 at room temperature remains a formidable challenge due to their high thermodynamic stability and kinetic inertness. Herein, a versatile nanocomposite of Aza-Por-TAPM-immobilized silver nanoparticles (AgNPs), Ag/Azo-Por-TAPM, has been successfully fabricated by adopting a three-dimensional azo-bridged porous porphyrin framework (Azo-Por-TAPM) as the porous support through a simple “liquid impregnation and in situ reduction” strategy. After adjusting the chemical structure of the porphyrin framework, the experimental results reveal that the presence of abundant azo groups and distorted tetrahedral structures is conducive to the preparation of highly dispersed and small-sized AgNPs at its surface. Further studies discover that Ag/Azo-Por-TAPM exhibits a record-level catalytic activity in the carboxylative cyclization of propargylic alcohols with CO2 at room temperature, achieving maximum turnover frequencies of 4600 h–1 at 10 bar and 1050 h–1 at 1 bar, which far exceed that of the previously reported catalysts. In addition, Ag/Aza-Por-TAPM has a high catalytic efficiency with simulated industrial fuel gas under ambient conditions and can be easily recovered and reused at least six times without a significant decrease in catalytic activity. The significantly reduced activation energy, together with the analytical results of NMR spectra, demonstrate that AgNPs-driven alkyne activation is considered as the rate-determining step of the cyclization reaction. This work not only reports a kind of porous porphyrin polymers loaded AgNPs for mild CO2 conversion but also brings some inspiration to designing highly efficient catalysts for the integration of CO2 capture and utilization.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.