Construction of a dual-cage-based MOF with uncoordinated nitrogen sites for CO2 adsorption and fixation

• Published in: Journal of solid state chemistry 2023-01, Vol.317, p.123699, Article 123699
• Main Authors: Zhou, Wen-Feng, Wei, Yi-Min, Xiao, Zhi-Wei, Jiang, Yan, Zhang, Yan-Kai, Zhang, Zhen-Wei, Hu, Hui, Geng, Longlong, Zhang, Da-Shuai, Zhang, Yong-Zheng, Zhang, Xiuling, Zhuang, Shujuan
• Format: Article
• Language: English
• Subjects: Cage-based MOFs; CO2 adsorption; Cycloaddition; Uncoordinated N atom
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/j.jssc.2022.123699

A new dual-cage-based porous metal-organic framework (MOF, termed DZU-113) assembly from the triazole-carboxylate linker and the Cu(II) paddle-wheel unit was solvothermally constructed. The structure of DZU-113 was determined by single-crystal X-ray diffraction, being consisted of the octahedral cage with an internal diameter of approximately 0.4 ​nm, and the spindle nano-cage with internal pores of about 0.8 ​nm ​× ​2.2 ​nm, respectively. Specially, the uncoordinated N atoms of triazole groups are distributed in the bottleneck windows of the spindle nano-cage, serving as open functional sites. DZU-113 has permanent porosity with the Brunauer−Emmett−Teller surface area of 1207 ​m2 ​g−1. The CO2 adsorption test demonstrated that the total uptake of DZU-113 can reach 66.7 ​cm3 ​g−1 ​at 298 ​K, and 112.0 ​cm3 ​g−1 ​at 273 ​K, 1 ​bar. Moreover, it achieves robust catalytic performance for the cycloaddition of CO2 and epoxides under mild conditions. In this paper, a new dual-cage-based porous metal-organic framework (termed DZU-113) assembly from the triazole-carboxylate linker and the Cu(II) paddle-wheel unit was solvothermally constructed, which has good CO2 adsorption capacity and catalytic performance for the cycloaddition of CO2 and epoxides under mild conditions, owing to the cage structure and the uncoordinated N atoms in its structure. [Display omitted] •A porous Cu-MOF (DZU-113) featuring octahedral and spindle cages was successfully synthesized.•Uncoordinated N atoms of ligand were distributed in the bottleneck windows of the spindle cage to serve as functional site.•DZU-113 exhibited good CO2 capture and can catalyze the cycloaddition reaction of CO2 with epoxides under mild environments.•The relatively high solvents and thermal stability endows the DZU-113 with high reusability.