Work

Inversed Cation Size Effects on Methanol Formations From CO 2 Electroreduction by Immobilized Cobalt Phthalocyanine

Year: 2026

Type: article

Abstract: ABSTRACT The electrocatalytic reduction of CO 2 to methanol offers a compelling pathway for sustainable fuel synthesis, wherein cations in the electric double layer (EDL) exert a substantial influence on catalytic performance. Although cation modulation of CO 2 ‐to‐CO conversion has been extensively documented, its influence on downstream reduction pathways toward CH 3 OH has received comparatively little attention. Using multiscale simulation, we establish that methanol synthesis over immobilized cobalt phthalocyanine (CoPc) is kinetically governed by the final proton transfer (*CH 2 OH + H 2 O → * + CH 3 OH + OH − ). The EDL environment substantially accelerates this rate‐determining step (RDS). Moreover, the activity exhibits a clear dependence on cation radius, following the trend Li + > Na + > K + > Cs + , with smaller cations systematically lowering the proton transfer barrier. This trend stems from the enhanced accessibility of smaller cations to the transition state, where Li + achieves tighter coordination than Cs + , conferring greater electrostatic stabilization and a correspondingly reduced barrier. Conversely, smaller cations attenuate the hydrogen‐bond network surrounding OH − , potentially impeding OH − transfer from the catalyst surface to the bulk electrolyte. These multifaceted cation effects underscore the complex interplay between kinetic promotion and mass transfer limitations in electrocatalytic systems.

Source: Angewandte Chemie International Edition

DOI: 10.1002/anie.1450878

Authors: Ke Ye, Min Hu, Guozhen Zhang, Mårten S. G. Ahlquist

Institutions: KTH Royal Institute of Technology, Fuyao University of Science and Technology, University of Science and Technology of China

Language: English

Topic: CO2 Reduction Techniques and Catalysts

Subfield: Renewable Energy, Sustainability and the Environment

Field: Energy

Domain: Physical Sciences

SDGs: Affordable and clean energy, Climate action

Open Access status: hybrid

Estimated APC paid: $5,510