Multiscale enzyme-mimetic catalysis for aquatic refractory pollutants and CO2 fixation: A roadmap from design frameworks to future prospects.

Enzyme-mimetic catalysts, designed by simulating key structural features of natural enzymes, have shown significant potential in tackling environmental challenges, with the most notable advances currently centered on aquatic refractory pollutant removal and CO2 fixation. The biogeochemical transformation processes of aquatic pollutants and the carbon cycle are deeply coupled, yet a systematic catalytic strategy for their synergistic remediation remains lacking. In this study, a three-level enzyme-mimetic catalytic design framework is proposed spanning atomic, mesoscale, and microenvironmental scales to elaborate the latest advances in tackling aquatic refractory pollutants and CO2 emissions. From the three design dimensions of mimicking active sites, electron/proton transfer structure, and reaction pathways in microenvironment, we systematically review the recent advances focusing on catalytic mechanism and performance mimicking reductive dehalogenases, peroxidases, laccases, photosynthetic enzymes, and CO2 reductases. Critical bottlenecks related to material rational design, synergistic transformation and environmental adaptability are analyzed. Looking forward, we outline a development pathway integrating AI-aided design, dynamic responsive microenvironment, and digital twin-enabled reactor for next-generation enzyme-mimetic catalytic systems. This work provides a systematic design roadmap aiming to facilitate the transition of enzyme-mimetic catalysis from fundamental research toward integrated water purification and CO2 fixation technologies.