Surface Charge Transfer Enhanced Cobalt‐Phthalocyanine Crystals for Efficient CO ₂ ‐to‐CO Electroreduction with Large Current Density Exceeding 1000 mA cm ⁻²

Phthalocyanines (Pcs) have garnered significant attention as promising catalysts for electrochemical CO₂ reduction (ECR); however, traditional methods for preparing carbon-supported Pcs are often complex and time-consuming, limiting their industrial applicability. Herein, a rapid spray-growth method is introduced that directly deposits CoPc crystals onto carbon paper (CP) in just 15 min. The resulting CoPc/CP electrode maintains > 90% CO selectivity across a broad ECR window (-0.57 to -1.32 V vs RHE), achieves a record-breaking CO current density of -1034 mA cm^-2, an ultrahigh mass activity of 5180 A g^-1, and demonstrates excellent long-term stability (145 h @ -150 mA cm^-2), surpassing all reported Pc-based catalysts. Comprehensive characterization attributes this high performance to its carbon-supported-crystalline structure and surface charge transfer (SCT). Density functional theory (DFT) calculations further reveal that even minimal SCT effectively optimizes the adsorption energies of key intermediates (^*CO and ^*COOH), thereby significantly enhancing intrinsic activity. Moreover, this spray-grown electrode offers unique structural advantages, such as strong substrate adhesion and internal layers that replenish active sites-features absent in traditional carbon-supported electrodes. It is believed that this facile spray-growth method holds broad potential and enables the application of additional Pc-based materials for industrial-scale ECR.