Spatially separated single atom/nanaoparticle dual sites on porous carbon for synergistic electrochemical CO2 reduction to syngas

Electrochemical CO 2 reduction reaction (CO 2 RR) to syngas represents a promising strategy to mitigate CO 2 emission and achieve carbon neutrality. Dual-site metal catalysts have emerged as an effective candidates for syngas production, however, challenges such as limited catalytic activity and inadequate control over the H 2 /CO ratio persist. Herein, a spatially separated dual-site catalyst containing cobalt phthalocyanine (CoPc) and ∼18 nm hollow Co 3 O 4 nanoparticles (NPs) was developed, in which CoPc and Co 3 O 4 are confined outside and inside the N-doped carbon (N–C) support, respectively. Experimental and calculation analyses reveal that the CoPc sites promote CO production, while the Co 3 O 4 NPs are responsible for H 2 production. The strong electronic coupling effect among CoPc, N–C and Co 3 O 4 NPs optimizes the electronic structure of catalyst and modulates the adsorption behaviors of reaction intermediates, leading to superior catalytic performance. A consistent H 2 /CO ratio of 2:1 is achieved across an extensive potential window ranging from −0.6 to −1.1 V vs . RHE, which is highly advantageous for industrial applications. Furthermore, adjustments in catalyst composition and microenvironment enable precise tuning of the H 2 /CO ratio from 1 to 2. This study provides a straightforward approach to designing dual-site catalysts for efficient syngas production.