Breaking the single-molecule paradigm: Multilayer cobalt phthalocyanine/carbon core-shell structure as the superior active unit for CO2-to-CO electroreduction

Conventional “chemical intuition” attributes the electrocatalytic activity of phthalocyanines (Pc) to idealized single-molecule/carbon models, however, we reveal that a multilayer Pc/carbon architecture more accurately reflects the true active units. Using AI-powered large-scale data mining (AIP-LDM), we examined 220 metal-nitrogen-carbon (M-N-C) materials for CO 2 -to-CO electroreduction, identifying cobalt-phthalocyanine (CoPc) as a promising candidate. When integrated with Ketjen Black (KB), the resulting CoPc/KB electrode achieves a large CO current density of -595 mA cm -2 and a high mass activity of 6537 A g -1 , while maintaining >90% CO selectivity at -100 mA cm -2 for 100 h. Comprehensive analyses reveal CoPc molecules form polycrystalline layers on KB, creating a multilayer CoPc/carbon core-shell structure that induces surface charge transfer (SCT). Theoretical calculations confirm even minimal SCT significantly enhances intrinsic activity. Further AIP-LDM findings show our hybrid surpasses all reported Pc-based catalysts, highlighting this multilayer Pc/carbon architecture’s advantages and affirming its strong industrial potential in Pc materials. Conventional “chemical intuition” attributes the catalytic actvity of cobalt phthalocyanine (CoPc) to idealized single-layer Pc/carbon structures. We reveal a multilayer CoPc core-shell structure on Ketjen Black that induces surface charge transfer, dramatically boosting electrocatalytic CO 2 -to-CO performance. AI-powered large-scale data mining confirms our hybrid surpasses all reported Pc-based catalysts, validating that multilayer architectures better deliver active units than the single-molecule paradigm. • Developed a new multilayer CoPc/carbon structure that delivers superior active units compared to ideal single-molecule models for electrocatalytic CO 2 reduction (ECR). • AI-Powered large-scale data mining (AIP-LDM) of 220 metal-nitrogen-carbon (M-N-C) materials initially guided the selection of electrocatalytic materials. • Achieved a world-record partial current density of -595 mA/cm 2 , with an ultra-high mass activity of 6537 A/g and excellent stability for 100 hours at -100 mA/cm 2 for ECR to CO. • Further AIP-LDM confirms that our performance metrics surpass all previously reported Pc-based catalysts. • Surface charge transfer and unique structural advantages of multilayer CoPc/KB hybrid boost intrinsic activity and improve catalytic efficiency per active site.