Nanochanneling and Local Crystallization Engineering Accelerate Multiphase Single‐Atom Catalysis for Rapid Water Decontamination

Precise engineering of single-atom catalysts (SACs) with optimal hierarchical structures and favorable local chemical environments remains a significant challenge to cater for multiphase heterogeneous processes. Here, we develop a universal strategy for synthesizing channel-digging microspherical SACs that markedly enhance gas-liquid-solid mass transfer and fine-tune the thermodynamics of catalytic ozonation. By catalytically graphitizing carbon microspheres and selectively etching amorphous carbon domains via mild combustion, we fabricate cross-linked hierarchical graphitic nanochannels confining transition metal (e.g., Co, Cr, Mn, Fe, Ni) single atoms (TMCSs-Air). This nanoenvironment engineering increases interfacial ozone (O₃) mass transfer by 3.2-fold and directs O₃ adsorption from a conventional "end-on" to a bidental "side-on" configuration. The enhanced inter-orbital electronic interactions lower the O₃ activation barrier and form highly oxidizing surface-confined O₃ (*O₃). Consequently, the CoCSs-Air catalyst achieves a 3.6-fold higher ozone utilization efficiency and a 4.2-fold greater turnover frequency (TOF = 1580 min^-1) compared with pristine Co-doped carbon microspheres (CoCSs). Technical and economic evaluations further confirm the feasibility of TMCSs-Air nanoreactors in treating real-world petrochemical wastewater, highlighting its broader potential in overcoming gas diffusion barriers and tuning reaction pathways for multiphase heterogeneous catalysis.