Construction of Thiazolo[5,4-d]thiazole-based Two-Dimensional Network for Efficient Photocatalytic CO2 Reduction.

The efficient conversion of CO2 to chemical fuels driven by solar energy is still a challenging research area in photosynthesis, in which the conversion efficiency greatly relies on photocatalytic coenzyme NADH regeneration. Herein, a photocatalyst/biocatalyst synergetic system based on a conjugated microporous polymer (CMP) was prepared for sustainable and highly selective photocatalytic reduction of CO2 to methanol. Two thiazolo[5,4-d]thiazole-linked CMPs (TZTZ-TA and TZTZ-TP) were designed and synthesized as photocatalysts. Slight skeleton modification led to a great difference in their photocatalytic performance. Triazine-based TZTZ-TA exhibited an unprecedentedly high NADH regeneration efficiency of 82.0% yield within 5 min. Furthermore, the in situ photocatalytic NADH regeneration system could integrate with three consecutive enzymes for efficient conversion of CO2 into methanol. This CMP-enzyme hybrid system provides a new avenue for accomplishing the liquid sunshine from CO2.