Development of an Integrated System for Highly Selective Photoenzymatic Synthesis of Formic Acid from CO2

• Published in: ChemSusChem Vol. 16; no. 5; pp. e202201956 - n/a
• Main Authors: Xing, Xiu, Liu, Yan, Lin, Ru‐De, Zhang, Yang, Wu, Zhong‐Liu, Yu, Xiao‐Qi, Li, Kun, Wang, Na
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 08.03.2023
• Subjects: Carbon dioxide; Catalytic activity; Chemical synthesis; CO2 photoreduction; Electrochemical analysis; Electron transfer; Electrons; formate dehydrogenase; Formic acid; Ligands; Metal-organic frameworks; MOF; NADH regeneration; Nicotinamide adenine dinucleotide; Photocatalysis; Photocatalysts; Photoelectric effect; Photoelectricity; photoenzymatic synthesis; Photosensitivity; Valence band; Zirconium
• ISSN: 1864-5631; 1864-564X
• DOI: 10.1002/cssc.202201956

Herein, a Zr‐based dual‐ligand MOFs with pre‐installed Rh complex was employed for NADH regeneration in situ and also used for immobilization of formic acid dehydrogenase (FDH) in order to realize a highly efficient CO2 fixation system. Then, based on the detailed investigations into the photochemical and electrochemical properties, it is demonstrated that the introduction of the photosensitive meso‐tetra(4‐carboxyphenyl) porphin (TCPP) ligands increased the catalytic active sites and improved photoelectric properties. Furthermore, the electron mediator Rh complex, anchored on the zirconium‐based dual‐ligand MOFs, enhanced the efficiency of electron transfer efficiency and facilitated the separation of photogenerated electrons and holes. Compared with UiO‐66‐NH2, Rh‐H2TCPP‐UiO‐66‐NH2 exhibits an optimized valence band structure and significantly improved photocatalytic activity for NAD+ reduction, resulting the synthesis of formic acid from CO2 increased from 150 μg mL−1 (UiO‐66‐NH2) to 254 μg mL−1 (Rh‐H2TCPP‐UiO‐66‐NH2). Moreover, the assembled photocatalyst‐enzyme coupled system also allows facile recycling of expensive electron mediator, enzyme, and photocatalyst. Tailor made! An environmentally friendly and highly effective semi‐artificial photosynthetic system (FDH@Rh‐TCPP‐UiO‐66‐NH2) was developed for transforming CO2 into formic acid. The incorporation of NADH‐dependent formic acid dehydrogenase (FDH), photosensitive porphyrin ligands and Rh complex lead to highly selective and recyclable system.