Jump to main content
Jump to site search

Issue 21, 2020
Previous Article Next Article

A highly stable polyoxovanadate-based Cu(i)–MOF for the carboxylative cyclization of CO2 with propargylic alcohols at room temperature

Author affiliations

Abstract

A novel polyoxovanadate-based copper(I)–organic framework, [CuI(bib)]4{VV4O12} (V–Cu–MOF, bib = 1,4-bis(1H-imidazoly-1-yl)benzene), is facilely synthesized under mild hydrothermal conditions. The structure of the V–Cu–MOF is constructed from a cyclic {V4O12}4− polyanion cluster and a 1D chain Cu(I)–MOF ([CuI(bib)]+). The presence of the {V4O12}4− cluster stabilizes the Cu(I)–MOF with Cu(I) as the center, thereby improving the stability of the V–Cu–MOF and enabling it to stably exist in various solvents and pH = 2–12 solutions. Additionally, the V–Cu–MOF as a heterogeneous catalyst can catalyze the carboxylative cyclization of CO2 and propargylic alcohols to high value-added α-alkylidene cyclic carbonates at room temperature, and the conversion and selectivity are almost 100%. More importantly, no obvious decrease in the yield of the α-alkylidene cyclic carbonate is observed after ten cycles. These results indicate the excellent catalytic activity and sustainability of the V–Cu–MOF. Research on the mechanism of the catalytic reaction suggests that the high-density Cu(I) sites in the V–Cu–MOF are the catalytically active centers for activating the C[triple bond, length as m-dash]C bonds of propargylic alcohols. To the best of our knowledge, this is the first example of polyoxometalate-based metal–organic framework catalyst for catalyzing the conversion of CO2 to value-added α-alkylidene cyclic carbonates at room temperature.

Graphical abstract: A highly stable polyoxovanadate-based Cu(i)–MOF for the carboxylative cyclization of CO2 with propargylic alcohols at room temperature

Back to tab navigation

Supplementary files

Article information


Submitted
18 Aug 2020
Accepted
24 Sep 2020
First published
25 Sep 2020

Green Chem., 2020,22, 7513-7520
Article type
Paper

A highly stable polyoxovanadate-based Cu(I)–MOF for the carboxylative cyclization of CO2 with propargylic alcohols at room temperature

H. Tian, Z. Zhang, S. Liu, T. Dang, Z. Li, Y. Lu and S. Liu, Green Chem., 2020, 22, 7513
DOI: 10.1039/D0GC02812F

Social activity

Search articles by author

Spotlight

Advertisements