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A Pentanuclear Cu(II)-based 2D Bilayer Coordination Polymer for CO2 Fixation Under Mild Conditions

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Abstract

The recovery of carbon dioxide (CO2) through carbon capture and utilization (CCU) technology to produce valuable chemicals has good industrial prospects, and it is also an effective method to solve the problem of global warming and achieve sustainable development. Unfortunately, catalysts are needed to realize the chemical conversion of CO2 due to its low reactivity. In this work, we selected transition metal copper ions and rigid triazole organic ligand 4-(1H-1,2, 4-triazol-1-yl)-benzoic acid to synthesize two-dimensional(2D) bilayer coordination polymer containing pentanuclear copper cluster by solvothermal synthesis method, and its molecular formula is [Cu5(TABC)4(COO)2(μ-O)2(NO3)2(H2O)·11H2O] (Cu-TABC). The pentanuclear [Cu5O2(COO)6] cluster forms a 2D layered structure by connecting to linear ligands, and the three-dimensional(3D) supramolecular structure with one-dimensional(1D) channels is formed by π–π interaction between layers and further parallel stacking, in which the channel window is quadrilateral and the size is 11.6 × 11.5 Å. Simultaneously, coordination unsaturated copper ions can be used as Lewis acid sites to catalyze the cycloaddition reaction of CO2 and epoxides. Importantly, Cu-TABC exhibits excellent catalytic performance, recoverability and significant size effect under solvent-free and mild conditions (0.1 MPa and 25 °C).

Graphical Abstract

A pentanuclear Cu(II)-based 2D bilayer coordination polymer was used as a heterogeneous catalyst for the cycloaddition reaction of CO2 and epoxides with high activity under mild conditions.

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Acknowledgements

This work is supported by National Natural Science Foundation of China (Grant No. 22171121), Liaoning Revitalization Talents Program (Grant No. XLYC2007060), and Scientific Research Foundation of Educational Department of Liaoning Province (Grant No. LJC202004).

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Author notes

  1. Shuo Liu and Li-Hua Liu equally contributed to this work.

Authors and Affiliations

  1. College of Chemistry, Liaoning University, Shenyang, 110036, People’s Republic of China

    Shuo Liu, Li-Hua Liu, Lin Liu & Zheng-Bo Han

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  1. Shuo Liu
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  2. Li-Hua Liu
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  3. Lin Liu
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Contributions

SL: writing-original draft, software, investigation. L-HL: writing-original draft, software, investigation. LL: resources, visualization. Z-BH: conceptualization, methodology, resources, writing-review & editing, supervision.

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Correspondence to Lin Liu or Zheng-Bo Han.

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Supplementary file1 (DOCX 14838 KB)

Appendix 1: Supplementary Data

Appendix 1: Supplementary Data

Experimental details, Crystal structures, PXRD, FT-IR of Cu-TABC, and X-ray crystallographic data for Cu-TABC in CIF format (CIF) and additional tables and figures.

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Liu, S., Liu, LH., Liu, L. et al. A Pentanuclear Cu(II)-based 2D Bilayer Coordination Polymer for CO2 Fixation Under Mild Conditions. Catal Lett 153, 2892–2899 (2023). https://doi.org/10.1007/s10562-022-04225-7

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