Fabrication of Carboxylic Acid and Imidazolium Ionic Liquid Functionalized Porous Cellulosic Materials for the Efficient Conversion of Carbon Dioxide into Cyclic Carbonates

TY - JOUR

T1 - Fabrication of Carboxylic Acid and Imidazolium Ionic Liquid Functionalized Porous Cellulosic Materials for the Efficient Conversion of Carbon Dioxide into Cyclic Carbonates

AU - Yang, Yunlong

AU - Guo, Yuanlong

AU - Gao, Chengtao

AU - North, Michael

AU - Yuan, Jili

AU - Xie, Haibo

AU - Zheng, Qiang

N1 - Funding Information: This work was financially supported by the National Natural Foundation of China (Grant Nos. 21574030, 21774028, and 51803038) and Science and Technology Department of Guizhou Province (Grant No. Natural Science Key Fund [2016]1402; Grant No. Platform & Talents [2016]5652; [2017]5788; [2019]5607). Publisher Copyright: © 2023 American Chemical Society.

PY - 2023/1/27

Y1 - 2023/1/27

N2 - Cellulosic poly(ionic liquid)s ([Cellmim][Br]) with a degree of substitution (DS) in the range of 0.32-0.89 were synthesized successfully via the homogeneous transesterification reaction of cellulose with 1-(2-methoxyacetyl)-3-methyl imidazole bromide IL ([Mmim][Br]) in a DBU/DMSO/CO2 solvent system. The structure and properties of these novel materials have been fully characterized. Cellulosic poly(ionic liquid) POF polymers (POF-[Cellmim][Br]) were then obtained by an in situ crosslinking reaction without adding an exterior catalyst. The porosity and properties of the POF-[Cellmim][Br] materials can be modulated. The POF-[Cellmim][Br] materials functioned as green, efficient, and highly active catalysts for cycloaddition reactions of epoxides and carbon dioxide under solvent-free and co-catalyst-free conditions. These reactions gave high yields (up to 97%), and the catalyst can be easily separated with excellent reusability and no significant change to its structure. A plausible reaction mechanism for the cycloaddition reaction of epoxide and carbon dioxide by the POF-[Cellmim][Br] catalyst is proposed based on the experimental results. This work provided a new strategy to prepare cellulosic-PIL POF materials and offered a platform to understand the cooperative effects of porous properties and nucleophilic anions on the cycloaddition reaction of carbon dioxide and epoxides.

AB - Cellulosic poly(ionic liquid)s ([Cellmim][Br]) with a degree of substitution (DS) in the range of 0.32-0.89 were synthesized successfully via the homogeneous transesterification reaction of cellulose with 1-(2-methoxyacetyl)-3-methyl imidazole bromide IL ([Mmim][Br]) in a DBU/DMSO/CO2 solvent system. The structure and properties of these novel materials have been fully characterized. Cellulosic poly(ionic liquid) POF polymers (POF-[Cellmim][Br]) were then obtained by an in situ crosslinking reaction without adding an exterior catalyst. The porosity and properties of the POF-[Cellmim][Br] materials can be modulated. The POF-[Cellmim][Br] materials functioned as green, efficient, and highly active catalysts for cycloaddition reactions of epoxides and carbon dioxide under solvent-free and co-catalyst-free conditions. These reactions gave high yields (up to 97%), and the catalyst can be easily separated with excellent reusability and no significant change to its structure. A plausible reaction mechanism for the cycloaddition reaction of epoxide and carbon dioxide by the POF-[Cellmim][Br] catalyst is proposed based on the experimental results. This work provided a new strategy to prepare cellulosic-PIL POF materials and offered a platform to understand the cooperative effects of porous properties and nucleophilic anions on the cycloaddition reaction of carbon dioxide and epoxides.

KW - carbon dioxide conversion

KW - cellulosic poly(ionic liquid)s

KW - porous organic framework

KW - transesterification

UR - http://www.scopus.com/inward/record.url?scp=85147164512&partnerID=8YFLogxK

U2 - 10.1021/acssuschemeng.2c06976

DO - 10.1021/acssuschemeng.2c06976

M3 - Article

AN - SCOPUS:85147164512

SN - 2168-0485

JO - ACS Sustainable Chemistry and Engineering

JF - ACS Sustainable Chemistry and Engineering

ER -