基于4-二甲氨基吡啶(DMAP)亲核催化剂构建结晶性聚金属酞菁基共价有机框架用于高效电催化CO2还原

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

催化学报 ›› 2026, Vol. 83: 319-329.DOI: 10.1016/S1872-2067(26)64966-2

基于4-二甲氨基吡啶(DMAP)亲核催化剂构建结晶性聚金属酞菁基共价有机框架用于高效电催化CO₂还原

魏滔^a^,^b, 梁展鹏^a^,^b, 张博心^a^,^b, 徐赟浩^a^,^b, 孙兆雪^a^,^b, 多名昊^a^,^b, 陈铭晖^a^,^*(), 张生^a^,^b^,^*(), 张宝^a^,^b^,^*()

^a天津大学化工学院, 天津 300350
^b天津化工协同创新中心, 天津 300072

收稿日期:2025-09-11 接受日期:2025-11-29 出版日期:2026-04-18 发布日期:2026-03-04
通讯作者: * 电子信箱: cmh96@163.com (陈铭晖), sheng.zhang@tju.edu.cn (张生), baozhang@tju.edu.cn (张宝).
基金资助:
国家自然科学基金(22478297);国家自然科学基金(22078241);中央高校基本科研业务费专项资金

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

Tao Wei^a^,^b, Zhanpeng Liang^a^,^b, Boxin Zhang^a^,^b, Yunhao Xu^a^,^b, Zhaoxue Sun^a^,^b, Minghao Duo^a^,^b, Minghui Chen^a^,^*(), Sheng Zhang^a^,^b^,^*(), Bao Zhang^a^,^b^,^*()

^aSchool of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
^bCollaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China

Received:2025-09-11 Accepted:2025-11-29 Online:2026-04-18 Published:2026-03-04
Contact: * E-mail: cmh96@163.com (M. Chen), sheng.zhang@tju.edu.cn (S. Zhang), baozhang@tju.edu.cn (B. Zhang).
Supported by:
National Natural Science Foundation of China(22478297);National Natural Science Foundation of China(22078241);Fundamental Research Funds for the Central Universities

摘要/Abstract

摘要：

共价有机框架材料(COFs), 尤其是具备明确M-N₄配位结构的聚金属酞菁基COFs (pMPc-COFs), 因其可调控的活性位点和优异的结构稳定性, 在电催化CO₂还原(CO₂RR)领域展现出广阔的应用前景. 然而, 传统合成方法(如溶剂热法、离子热法)通常需要苛刻的反应条件、较长的反应时间, 并且难以实现材料的规模化制备, 从而严重阻碍了其在基础研究与实际应用中的进一步发展. 因此, 开发一种温和、绿色且可扩展的合成策略, 以高效构建具有优异催化性能的结晶性pMPc-COFs, 具有重要的科学意义和应用价值.
本研究提出了一种基于4-二甲氨基吡啶(DMAP)的热熔合成方法, 在无溶剂、温和的条件下成功制备了不同金属中心配位的结晶性pMPc-COFs. 该方法以熔融态的DMAP同时作为亲核催化剂和反应介质, 在150 ºC反应 12 h, 实现了1,2,4,5-四氰基苯与金属粉末的高效反应, 构建出具有良好结晶性的DMAP-pMPc-COFs材料, 并实现了该类材料10 g级的批量合成. 通过粉末X-射线衍射、固态¹³C核磁共振、X射线光电子能谱等方法对材料的结构与组成进行了系统表征. 尤为重要的是, X-射线吸收精细结构谱与高角环形暗场扫描透射电子显微镜分析明确揭示了金属原子以原子级分散的M-N₄配位结构形式存在, 排除了材料发生分子聚集的可能性. 在电催化CO₂还原性能测试中, 所合成的DMAP-pCoPc-COFs在−0.8至−1.0 V (vs. RHE)的宽电位范围内表现出优异的CO选择性, 其法拉第效率超过88%, 最高可达91%. 此外, DMAP-pBiPc-COFs作为首例报道的铋酞菁COFs材料, 展现出高达85%的甲酸盐选择性, 成为目前最高效的甲酸盐电催化剂之一. 两种材料在长达10 h的电催化测试中均表现出良好的结构与性能稳定性, 进一步验证了其在实际应用中的价值. 为深入阐明金属中心对CO₂还原反应选择性的影响机制, 结合原位衰减全反射-傅里叶变换红外光谱与密度泛函理论计算, 系统研究了不同金属中心在反应过程中的电子行为与中间体吸附特性, 从而从原子尺度揭示了金属种类对产物选择性的调控机制.
综上, 本工作不仅为结晶性pMPc-COFs的绿色、可扩展合成提供了一种创新性策略, 同时也为通过精确调控中心金属实现CO₂电催化还原反应选择性的优化提供新见解.

关键词: 共价有机框架, 合成方法, 酞菁, 二氧化碳还原反应, 电催化

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

魏滔, 梁展鹏, 张博心, 徐赟浩, 孙兆雪, 多名昊, 陈铭晖, 张生, 张宝. 基于4-二甲氨基吡啶(DMAP)亲核催化剂构建结晶性聚金属酞菁基共价有机框架用于高效电催化CO₂还原[J]. 催化学报, 2026, 83: 319-329.

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

图/表 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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基于4-二甲氨基吡啶(DMAP)亲核催化剂构建结晶性聚金属酞菁基共价有机框架用于高效电催化CO₂还原

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

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