Chinese Journal of Catalysis

Chinese Journal of Catalysis ›› 2026, Vol. 83: 330-340.DOI: 10.1016/S1872-2067(26)64971-6

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

Bihua Hua,b, Hailin Caoc, Zhen Chena, Zhiwei Leib, Xin Wanga, Panagiotis Tsiakarasd,*(), Zhongwei Chene,*(), Baomin Xub,*()   

  1. 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: Panagiotis Tsiakaras, Zhongwei Chen, Baomin 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)

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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