Strengthening Intermediate Adsorption on a Cobalt Phthalocyanine Assembly by Polymeric Modification for Electrochemical Carbon Dioxide Reduction into Methanol

Poe Ei Phyu Win¹, Xin Xu¹, Lilong Zhang², Song Yang²（杨松）*, Shibin Ren³, Yu Chen⁴（陈煜）*, Jiong Wang¹（王炯）*

¹Innovation Center for Chemical Science, Jiangsu Key Laboratory of Advanced Negative Carbon Technologies, College of Chemistry,Chemical Engineering and Materials Science, Soochow University,Suzhou 215123, P.R. China

²National Key Laboratory of Green Pesticide, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, State-Local Joint Laboratory for Comprehensive Utilization of Biomass, Center for R&D of Fine Chemicals, Guizhou University, Guiyang 550025, P.R. China

³Department of Chemistry, School of Pharmaceutical and ChemicalEngineering, Taizhou University, Taizhou 318000, P.R. China

⁴School of Materials Science and Engineering, Shaanxi NormalUniversity, Xi’an 710062, P.R. China

Angew. Chem. Int. Ed. 2025, 64, e202517033

Abstract: Electrochemical carbon dioxide reduction (CO₂R) to generate value added methanol (MeOH) in water has been considered as a potential strategy to realize efficient carbon cycle and reutilization. Cobalt phthalocyanine (CoPc) represents as a classical molecular catalyst carrying precisely tunable active sites, which has been widely explored for the CO₂-to-MeOH conversion, but optimization of performance is suffering from relatively easiness in desorption of *CO intermediate. To this end, we developed a novel molecular assembly of CoPc nanotubes (CoT) driven by van der Waals force with surface being modified by poly(4-vinylpyridine). The as-derived catalyst exhibited an exceptional performance of MeOH production for the turnover frequency enhanced by more than 14-fold compared to the pristine CoT, and the Faradaic efficiency is up to 40% at a moderate potential. It revealed that the pyridyl groups of P4VP axially coordinated with the Co catalytic centers shifted the d-band center toward the Fermi level, which strengthened the chemisorption and activation of *CO intermediates, thereby decreasing the whole barrier to produce MeOH. This work demonstrates a novel insight into intermediate manipulation of CO₂R and highlights the potential of molecular electrocatalysis for carbon valorization.

Article information: https://doi.org/10.1002/anie.202517033