Axial Boron Coordination Reconstructs Stereostructure of Cu Single‐Atom Nanozymes for Efficient Water‐Phase Chemical Sensing

ABSTRACT Developing single‐atom nanozymes with stereoconfigurations is a new paradigm for biomimetic construction of next‐generation natural enzyme alternatives and for achieving high enzyme‐like selectivity and activity. This work developed a high‐temperature pyrolysis tandem chemical vapor deposition technique to produce Cu SAzymes (Cu‐B/N‐C) with axial B coordination as laccase mimics, with Cu‐B axial N 3 ‐C as the core structure. Axial ligands modulate the d‐band center of Cu SAzymes to identify the equilibrium point between the energy barriers of reactant adsorption and product desorption. Transforming product desorption from an endothermic process to a spontaneously exothermic process promotes the regeneration of nanozymes after catalytic cycles. This results in Cu‐B/N‐C exhibiting higher kinetic parameters and specific activity than natural laccase. Subsequently, a sensor array for high‐throughput detection of phenolic pollutants in seawater was constructed based on the time‐dependent changes in the laccase‐like catalytic kinetics of Cu SAzymes before and after modification. On this basis, a stepwise prediction model was further developed using machine‐learning artificial neural network algorithms to enhance the sensor array's detection accuracy for blind samples. Overall, this work provides new insights into the rational design of artificial enzymes from a stereochemical perspective.