Efficient electrocatalytic CO2 reduction by crystalline polymetallophthalocyanine covalent organic frameworks unprecedentedly constructed involving 4-dimethylaminopyridine (DMAP)-type nucleophilic catalyst

doi:10.1016/S1872-2067(26)64966-2

Abstract

Abstract:

Polymetallophthalocyanine covalent organic frameworks (pMPc-COFs) exhibit considerable promise in the electrocatalytic CO₂ reduction reaction (CO₂RR) due to their tunable active sites and excellent structural stability. Nevertheless, preparation of crystalline pMPc-COFs under mild conditions remains a significant challenge. Herein, we developed a mild and scalable synthetic strategy, which can realize the construction of pMPc-COFs with different metals embedded. Thus, in the presence of different metal atoms (Co, Bi and Cu), the nucleophilic catalyst 4-dimethylaminopyridine (DMAP) flux-mediated formation of pMPc-COFs occurred efficiently leading to crystalline DMAP-pCoPc-COFs, DMAP-pBiPc-COFs and DMAP-pCuPc-COFs, respectively, incorporated with well-defined single-metal-atom reactive centers at a temperature of 150 °C with no other solvents required. Intriguingly, in the electrocatalytic CO₂RR, as-prepared DMAP-pCoPc-COFs demonstrated remarkable CO Faradaic efficiencies above 88% and up to 91% over a wide potential range (-0.8 to -1.0 V vs. RHE). More interestingly, DMAP-pBiPc-COFs, as the first example of Bi phthalocyanine COFs to date, exhibited an encouraging formate selectivity of up to 85%, making it one of the most efficient formate electrocatalysts. The tuning of CO₂RR selectivity by the center metal was further revealed from the atomic level through in-situ infrared spectroscopy technique and theoretical calculations, providing new insights for the design of efficient electrocatalysts involving pMPc-COFs.

Key words: Covalent organic framework, Synthesis method, Phthalocyanine, Carbon dioxide reduction reaction, Electrocatalysis

Tao Wei, Zhanpeng Liang, Boxin Zhang, Yunhao Xu, Zhaoxue Sun, Minghao Duo, Minghui Chen, Sheng Zhang, Bao Zhang. Efficient electrocatalytic CO₂ reduction by crystalline polymetallophthalocyanine covalent organic frameworks unprecedentedly constructed involving 4-dimethylaminopyridine (DMAP)-type nucleophilic catalyst[J]. Chinese Journal of Catalysis, 2026, 83: 319-329.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64966-2

https://www.cjcatal.com/EN/Y2026/V83/I4/319

Figures/Tables 6

Scheme 1. Synthesis methods for pMPc-COFs.

Fig. 1. Structure and characterization of DMAP-pMPc-COFs. (a) PXRD of DMAP-pBiPc-COFs, TCB and DMAP. (b) Top and side views of a graphical representation of DMAP-pMPc-COFs (M = Co, Cu, and Bi) with eclipsed stacking (C, light gray; N, blue; M, red). TEM image (c) and HAADF-STEM image (d) of DMAP-pBiPc-COFs. (e) SEM and EDS image of DMAP-pBiPc-COFs. (f) SEM and EDS image of DMAP-pCoPc-COFs.

Fig. 2. Electronic properties of DMAP-pMPc-COFs. (a) XPS Co 2p spectra of DMAP-pCoPc-COFs. (b) XPS Bi 4f spectra of DMAP-pBiPc-COFs. (c) XPS Cu 2p spectra of DMAP-pCuPc-COFs. EPR spectra of DMAP-pCoPc-COFs (d), DMAP-pBiPc-COFs (e), and DMAP-pCuPc-COFs (f).

Fig. 3. Coordination states of DMAP-pMPc-COFs. XANES spectra of DMAP-pCoPc-COFs (a) and DMAP-pBiPc-COFs (c). FT-EXAFS of DMAP-pCoPc-COFs (b) and DMAP-pBiPc-COFs (d). WT-EXAFS spectrum of DMAP-pCoPc-COFs (e) and DMAP-pBiPc-COFs (f).

Fig. 4. Electrochemical performances for CO2 reduction of DMAP-pMPc-COFs. (a) Target product Faradaic efficiency and current density plots of DMAP-pCoPc-COFs and DMAP-pBiPc-COFs. (b) Comparison on FE of DMAP-pCoPc-COFs and DMAP-pBiPc-COFs with other reported phthalocyanine-based COFs electrocatalysts. (c) Capacitive current against the scan rate of DMAP-pCoPc-COFs and DMAP-pBiPc-COFs. (d) LSV curves of DMAP-pCoPc-COFs and DMAP-pBiPc-COFs. (e) DRT spectra of DMAP-pMPc-COFs. (f) Stability test of DMAP-pCoPc-COFs at -0.8 V (vs. RHE) and DMAP-pBiPc-COFs at -1.05 V (vs. RHE).

Fig. 5. CO2RR mechanism research. In-situ FT-IR at various applied potentials for DMAP-pCoPc-COFs (a) and DMAP-pBiPc-COFs (b) at applied potentials ranging from -0.2 to -1.3 V (vs. RHE). DOS, PDOS and EDD of DMAP-pCoPc-COFs (c) and DMAP-pBiPc-COFs (d). The optimized structure diagram and ED plots of DMAP-pCoPc-COFs (e) and DMAP-pBiPc-COFs (f). ELF plots of DMAP-pCoPc-COFs (g) and DMAP-pBiPc-COFs (h). Free energy diagram for CO2RR to the CO (i) and HCOO− (j) process.

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Efficient electrocatalytic CO₂ reduction by crystalline polymetallophthalocyanine covalent organic frameworks unprecedentedly constructed involving 4-dimethylaminopyridine (DMAP)-type nucleophilic catalyst

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