Artificial photo-enzyme catalysis for sustainable light-driven chemical transformations and energy conversion

Photoenzymatic catalysis combines the exquisite selectivity of enzymes with the activation modes of photocatalysis, thereby expanding the scope of biocatalysis beyond its natural repertoire. This strategy enables the controlled generation and utilization of radical intermediates, offering powerful opportunities for asymmetric synthesis and challenging bond constructions. In this review, we comprehensively discuss the role of photoactive cofactors and external sensitizers, strategies for integrating light-harvesting modules with enzymes, and approaches to pathway engineering that enhance efficiency and stereocontrol. Particular attention is also given to naturally light-responsive enzymes that directly utilize visible photons. Applications spanning solar-driven CO 2 reduction, selective organic synthesis, environmental conversion, and therapeutic photochemistry illustrate how a common photon-to-chemical transduction framework can produce fundamentally different functional outcomes. Particular emphasis is placed on distinguishing solar-energy storage in fuels and feedstocks from the controlled utilization of photochemical redox equivalents in remediation and biomedical systems, thereby positioning artificial photoenzymatic catalysis as a broader platform for sustainable light-driven chemical transformations.