氮基载体调控酞菁钴的电子结构实现高选择性电化学还原二氧化碳产甲醇

doi:10.1016/S1872-2067(26)64971-6

催化学报 ›› 2026, Vol. 83: 330-340.DOI: 10.1016/S1872-2067(26)64971-6

氮基载体调控酞菁钴的电子结构实现高选择性电化学还原二氧化碳产甲醇

胡碧华^a^,^b, 曹海邻^c, 陈振^a, 雷志伟^b, 王新^a, Panagiotis Tsiakaras^d^,^*(), 陈忠伟^e^,^*(), 徐保民^b^,^*()

^a浙江万里学院碳中和研究院, 宁波高能量密度电池重点实验室, 浙江宁波 315100, 中国
^b南方科技大学材料科学与工程系, 广东深圳 518055, 中国
^c南方科技大学机械与能源工程系, 广东深圳 518055, 中国
^d色萨利大学工程学院机械工程系, 佩迪昂·阿雷奥斯, 希腊
^e中国科学院大连化学物理研究所, 辽宁大连 116023, 中国

收稿日期:2025-10-30 接受日期:2025-12-02 出版日期:2026-04-18 发布日期:2026-03-04
通讯作者: * 电子信箱: tsiak@mie.uth.gr (P. Tsiakaras), zwchen@dicp.ac.cn (陈忠伟), xubm@sustech.edu.cn (徐保民).
基金资助:
深圳市科技创新委员会重点基础研究基金(JCYJ20200109141014474);深圳市科技创新委员会重点基础研究基金(JCYJ20220818100406014);国家自然科学基金(22379047);国家自然科学基金(U19A2089);宁波市鄞州区创新创业团队项目;浙江省人才科研启动项目(SC1032445280940)

N-supports for electronic regulation of phthalocyanine cobalt to selective carbon dioxide electroreduction toward methanol

Bihua Hu^a^,^b, Hailin Cao^c, Zhen Chen^a, Zhiwei Lei^b, Xin Wang^a, Panagiotis Tsiakaras^d^,^*(), Zhongwei Chen^e^,^*(), Baomin Xu^b^,^*()

^aNingbo Key Laboratory of High Energy Density Battery, Institute of Carbon Neutrality, Zhejiang Wanli University, Ningbo 315100, Zhejiang, China
^bDepartment of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen 518055, Guangdong, China
^cDepartment of Mechanical and Energy Engineering, Southern University of Science and Technology, Shenzhen 518055, Guangdong, China
^dDepartment of Mechanical and Industrial Engineering, School of Engineering, University of Thessaly, Pedion Areos 383 34, Greece
^eDalian Institute of Chemical Physics Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2025-10-30 Accepted:2025-12-02 Online:2026-04-18 Published:2026-03-04
Contact: * E-mail: tsiak@uth.gr (P. Tsiakaras), zwchen@dicp.ac.cn (Z. Chen), xubm@sustech.edu.cn (B. Xu).
Supported by:
Key Fundamental Research Project funding from the Shenzhen Science and Technology Innovation Committee(JCYJ20200109141014474);Key Fundamental Research Project funding from the Shenzhen Science and Technology Innovation Committee(JCYJ20220818100406014);National Natural Science Foundation of China(22379047);National Natural Science Foundation of China(U19A2089);Entrepreneurial and Innovative Team Project of Ningbo Yinzhou District;Talent Research Start-up Project of Zhejiang(SC1032445280940)

摘要/Abstract

摘要：

CO₂电还原反应(CO₂RR)可在温和条件下将CO₂转化为高附加值化学品, 是实现碳循环和资源化利用的重要途径. 其中甲醇因其能量密度高和用途广泛而备受关注, 但其生成涉及复杂的多电子过程, 高选择性制备仍具挑战. 钴的配位聚合物(CoCPs)结构可控、比表面积高及钴位点配位环境可调, 因而成为研究CO₂转化机理的理想模型体系. 现有CoCPs多以CO或HCOOH为主要产物, 多电子深度还原为甲醇等产物的能力有限, 其关键原因在于钴中心的配位结构对CO₂吸附、活化及CO中间体的后续耦联过程具有决定性影响. 典型的CoN₄结构因对CO吸附过强, 抑制了后续的C-H耦联反应; 相反, 具有扩展配位环境的CoN₄₊_x结构能够调节钴中心的电子性质, 为*CO耦联提供更有利的反应环境, 从而有望实现对甲醇等多电子还原产物的高效生成.
本文提出了一种通过精确调控CoPc基聚合物中钴中心配位环境来提升CO₂RR生成甲醇选择性的策略. 针对传统CoPc催化剂在CO₂深度还原过程中易受限于中间体*CO过强吸附、难以实现C-H偶联的问题, 本研究采用简便的复合材料构筑方法, 将CoPc均匀负载于不同的氮掺杂基底上, 并调变钴中心周围的局域配位结构. 该方法不仅实现了配位环境的有效重构, 也显著改变了CO₂RR的反应路径和产物分布. 电化学测试结果表明, 在多种复合材料中, 所构建的Co-N-Ti配位结构表现最为突出, 在-1.0 V (vs. RHE)条件下实现了高达53.3%的CH₃OH法拉第效率, 并获得68.8 mA cm^‒2的甲醇分电流密度, 展示了优异的多电子转化能力和深度还原性能. 由此可见, 钴中心配位环境的调控对于促进*CO的进一步耦联具有关键作用. 一系列结构表征进一步揭示了性能提升的内在原因. X-射线光电子能谱结果表明, CoPc/(Si)N-MXene, CoPc/TiN和CoPc/C₃N₄三类复合体系中均形成了原始CoPc中所缺失的CoN₄₊_x扩展配位结构. 此外, 原位同步辐射吸收谱分析进一步验证了CoPc/(Si)N-MXene中CoN₄₊_x配位环境的存在, 表明该结构在反应过程中具有良好稳定性. 密度泛函理论计算为机理分析提供了更深入的佐证. 计算结果表明, 扩展配位使钴中心的电子密度重新分布, 增强了Co-N配位键强度, 并显著降低了HCO偶联步骤的反应能垒. 该电子结构调控有效促进了*H与*CO的协同转化, 从而推动CO₂RR向甲醇等多电子产物进行深度还原.
综上, 通过调控CoPc中钴中心的局域配位环境, 可有效调节关键中间体的吸附与活化行为, 从而实现多电子产物甲醇的高选择性合成, 为过渡金属配位聚合物催化CO₂深度还原提供了新的思路, 并为高效催化剂设计开辟了新途径.

关键词: 电催化二氧化碳, 电子调控, 可调选择性, 结构设计, 高效催化剂

Abstract:

Electrocatalytic carbon dioxide reduction (CO₂RR) offers a highly promising strategy for achieving carbon-neutral energy cycles by converting CO₂ into high-value chemicals and fuels. While it remains challenging to modulate the electronic environment precisely and systematically around the active sites of catalysts to steer the reaction toward desired products, especially hydrocarbons such as methanol (CH₃OH). This study reports a strategy that enables highly efficient CO₂RR to CH₃OH under neutral conditions by fine-tuning the electronic environment of cobalt center in cobalt phthalocyanine (CoPc) through nitrogen-rich supports. Among them, CoPc/TiN achieved a high Faradaic efficiency of 53.28% for CH₃OH production at -1.0 V (vs. reversible hydrogen electrode), with a partial current density of 68.76 mA cm^‒2. X-ray photoelectron spectroscopy and extended X-ray absorption fine structure analyses reveal that electronic modulation at Co-N sites of CoPc, which can promote ^*HCO coupling, and it’s a critical step in CH₃OH formation. Theoretical calculations further demonstrate that nitrogen carriers induce electronic redistribution within the Co center coordination environment. The projected density of states of ^*HCO on CoPc loaded on (Si)N-MXene)/TiN/C₃N₄ shown electron deficient characteristics. It promotes the formation of ^*HCO, thereby facilitating CH₃OH synthesis. This work provides new mechanistic insights into CO₂RR for CH₃OH and opens new avenues for designing efficient catalysts.

Key words: Electrocatalytic CO₂ reduction, Electronic regulation, Customizable selectivity, Well-designed structures, Efficient catalysts

胡碧华, 曹海邻, 陈振, 雷志伟, 王新, Panagiotis Tsiakaras, 陈忠伟, 徐保民. 氮基载体调控酞菁钴的电子结构实现高选择性电化学还原二氧化碳产甲醇[J]. 催化学报, 2026, 83: 330-340.

Bihua Hu, Hailin Cao, Zhen Chen, Zhiwei Lei, Xin Wang, Panagiotis Tsiakaras, Zhongwei Chen, Baomin Xu. N-supports for electronic regulation of phthalocyanine cobalt to selective carbon dioxide electroreduction toward methanol[J]. Chinese Journal of Catalysis, 2026, 83: 330-340.

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图/表 5

Fig. 1. Structural and morphological characterization of CoPc, MXene, CoPc/MXene, and CoPc/N-MXene Hybrid Materials. (a) Schematic illustration of material synthesis (in atomic model: gray, white, royal-blue, green, and sky-blue spheres represent C, H, N, Co and Ti atoms, respectively). (b) XRD patterns of CoPc, (Si)MXene, (Si)N-MXene, CoPc/(Si)MXene, and CoPc/(Si)N-Mxene. (c) STEM image of CoPc/(Si)N-MXene and EDS elemental mapping of Co, Ti, and N. (d,e) HAADF-TEM images of CoPc/(Si)N-MXene.

Fig. 2. In a CO2-saturated 0.5 mol L-1 KHCO3 solution, the CoPc/o-N-MXene, CoPc/(Si)MXene, and CoPc/(Si)N-MXene catalysts over the potential range of -0.7 to -1.2 V (vs. RHE) with a scanning interval of -0.1 V. (a) Current density. FE for CO, H2, and CH3OH at different potentials for CoPc/o-N-MXene (b), CoPc/(Si)MXene (c), and CoPc/(Si)N-MXene (d) catalysts.

Fig. 3. In a CO2-saturated 0.5 mol L?1 KHCO3 solution, the CO2RR performance of CoPc/TiN and CoPc/C3N4 was systematically evaluated over the potential range of ?0.7 to ?1.2 V with a scanning interval of 0.1 V. (a) Current density versus potential. FE for CO, H2, and CH3OH at different potentials for CoPc/TiN (b) and CoPc/C3N4 (c) catalysts. (d) Stability test results of CoPc/TiN at -1.0 V.

Fig. 4. High-resolution XPS spectra of CoPc/(Si)MXene, CoPc/(Si)N-MXene, CoPc/TiN, and CoPc/C3N4. (a,c,e) Co 2p spectra; (b,d,f) N 1s spectra.

Fig. 5. Theoretical calculation analysis. (a) Co K-edge FT-EXAFS spectra of CoPc, CoPc/o-N-MXene, and CoPc/(Si)N-MXene catalysts. PDOS for *CO/*HCO adsorption on Co active sites of CoPc/(Si)N-MXene (b), CoPc/TiN (c), and CoPc/C3N4 (d). Computed free energy plots for CoPc/(Si)MXene and CoPc/(Si)N-MXene (e), CoPc/TiN and CoPc/C3N4 (f). Computational model: gray, white, dark-blue, green, light-blue, and red spheres represent C, H, N, Co, Ti, and O atoms, respectively.

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氮基载体调控酞菁钴的电子结构实现高选择性电化学还原二氧化碳产甲醇

N-supports for electronic regulation of phthalocyanine cobalt to selective carbon dioxide electroreduction toward methanol

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