An Antimonene/Cp*Rh(phen)Cl/Black Phosphorus Hybrid Nanosheets-based Z-Scheme Artificial Photosynthesis for Enhanced Photo/bio-catalytic CO2 Reduction
Developing biocatalyzed artificial photosynthesis system (APS) with Z-scheme for CO2 conversion has a promising outlook, however, remains unexplored and challenging. Here we present an antimonene (AM) and black phosphorus (BP) hybrid nanosheets (HNSs) based Z-scheme APS for enhanced photo/bio-catalytic CO2 reduction. An “amphipathic” polymer PEI-PEG-C18 with positively charged PEI-head and hydrophobic C18-tail was synthesized, and further modified with an electron mediator (M, Cp*Rh(phen)Cl). Using this PEI-PEG-C18-M as a “double-side tap”, AM/M/BP HNSs based Z-scheme photocatalytic systems was constructed through in turn catenating AM NSs via hydrophobic interaction with the hydrophobic C18-tail and subsequent BP NSs via electrostatic interactions with the positively charged PEI-head. Thereafter, the biocatalytic system, including NAD(H)+ and redox enzymes, are sandwiched between AM and BP layers through electrostatic attraction with the amide groups in the “double-side tap”. Due to the high separation efficiency of the photogenerated electrons and holes and improved reduction and oxidation potentials, the integrated Z-scheme APS shows excellent performance. Especially, although neither AM nor BP was able to catalyze NADH regeneration using H2O as an electron donor under visible light, a 35.18% regeneration of NADH and 160 umol formic acid production were achieved by AM/M/BP HNSs based Z-scheme APS. Moreover, the compatibility and omnipotence of the HNSs based APS for synthesis other high value-added products from CO2 also have been demonstrated through assembling corresponding biocatalysts.