Tailoring ligand fields of metal-azolate frameworks for highly selective electroreduction of CO2 to hydrocarbons at industrial current density

doi:10.1016/S1872-2067(23)64519-X

Abstract

Abstract:

The catalytic activity of a metal complex is often contingent upon factors such as its valence state, coordination configuration of the metal ion, and coordination ability of the ligand. Hence, revealing the influence of the ligand field of the active metal center on the selectivity of the product for electrochemical CO₂ reduction is crucial. Herein, three isostructural metal-azolate frameworks (MAFs) (Cu-BTP, Cu-BTTri, and Cu-BTT) with the same cyclic tetracopper(II) cluster units, namely [Cu₃(BTP)₂] (Cu-BTP, H₃BTP = 1,3,5-tris(1H-pyrazol-4-yl)benzene), [Cu₃(BTTri)₂] (Cu-BTTri, H₃BTTri = 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene), and [Cu₃(BTT)₂] (Cu-BTT, H₃BTT = 1,3,5-tris(2H-tetrazol-5-yl)benzene) were synthesized using pyrazolate-, triazolate-, and tetrazolate-based ligands, respectively. The synthesized MAFs were subjected to analysis to evaluate their electrochemical capabilities for reducing CO₂ under identical reaction conditions. Among them, the pyrazolate MAF, Cu-BTP, delivers a current density of 1.25 A cm⁻² in a flow cell device with the highest Faradiac efficiency for hydrocarbons (CH₄, 60%; C₂H₄, 22%). Furthermore, the system shows no obvious degradation over 60 h of continuous operation. The order of selectivity of the three MAFs for hydrocarbon production is consistent with the corresponding pK_a values of the azolate ligands. Theoretical calculations show that a stronger Lewis basicity of the organic ligand, resulting in a stronger ligand field strength, is conducive to strengthening the binding of metal centers with key intermediates, such as *CO and *CHO. This ultimately leads to the deep reduction of CO₂ to hydrocarbons.

Key words: Metal-organic framework, Metal-azolate framework, Hydrocarbons, Electrocatalysis, Copper

Huan Xue, Jia-Run Huang, Zhi-Shuo Wang, Zhen-Hua Zhao, Wen Shi, Pei-Qin Liao, Xiao-Ming Chen. Tailoring ligand fields of metal-azolate frameworks for highly selective electroreduction of CO₂ to hydrocarbons at industrial current density[J]. Chinese Journal of Catalysis, 2023, 53: 102-108.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64519-X

https://www.cjcatal.com/EN/Y2023/V53/I10/102

Figures/Tables 4

Fig. 1. Chemical structures of H3BTP, H3BTTri, and H3BTT ligands (a), the cyclic tetracopper(II) units (b), and corresponding 3D frameworks (c) of Cu-BTP, Cu-BTTri and Cu-BTT. Color codes: Cu, purple; C, gray; N, blue. Note: the hydrogen atoms were omitted for clarity.

Fig. 2. Electrocatalytic performances. (a) LSV curves of Cu-BTP recorded under CO2 and Ar in a flow cell. (b) Long-time durability test of Cu-BTP in flow cell. (c) FEs (hydrocarbons) of Cu-BTP, Cu-BTTri, and Cu-BTT, respectively, at different potentials in an H-type cell. (d) Comparison of FEs (hydrocarbons) and partial current densities of Cu-BTP and other reported electrocatalysts.

Fig. 3. Cu K-edge EXAFS fitting curves (a) before and (b) after electrocatalysis. Wavelet transforms (WT) contour plots of Cu-BTP (c) before and (d) after electrocatalysis.

Fig. 4. (a) Charge density differences of Cu-BTP with an isosurface level of 0.004 e bohr?3. The blue and yellow indicate electron depletion and accumulation. (b) Schematic illustration of d-orbital splitting of Cu(II) ion in Cu-BTP. (c) The energy levels of the VBMs and CBMs of the MAFs. (d) Operando ATR-FTIR spectra of Cu-BTP. (e) Comparison of the CO adsorption energies of the Cu(II) ions in the cyclic tetracopper(II) cluster with and without another intermediate. (f) Comparison of the free energies for the formation of *COCHO through the coupling of CO and *CHO intermediates. (g) Proposed pathways of Cu-BTP for the formation of CH4, CH3OH, C2H4, and C2H5OH. Color codes: Cu, purple; C, gray; N, blue.

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Tailoring ligand fields of metal-azolate frameworks for highly selective electroreduction of CO₂ to hydrocarbons at industrial current density

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