Light-Driven Hybrid\nNanoreactor Harnessing the Synergy\nof Carboxysomes and Organic Frameworks for Efficient Hydrogen Production

Synthetic photobiocatalysts\nare promising catalysts for valuable\nchemical transformations by harnessing solar energy inspired by natural\nphotosynthesis. However, the synergistic integration of all of the\ncomponents for efficient light harvesting, cascade electron transfer,\nand efficient biocatalytic reactions presents a formidable challenge.\nIn particular, replicating intricate multiscale hierarchical assembly\nand functional segregation involved in natural photosystems, such\nas photosystems I and II, remains particularly demanding within artificial\nstructures. Here, we report the bottom-up construction of a visible-light-driven\nchemical–biological hybrid nanoreactor with augmented photocatalytic\nefficiency by anchoring an α-carboxysome shell encasing [FeFe]-hydrogenases\n(H–S) on the surface of a hydrogen-bonded organic molecular\ncrystal, a microporous α-polymorph of 1,3,6,8-tetra(4′-carboxyphenyl)pyrene\n(TBAP-α). The self-association of this chemical–biological\nhybrid system is facilitated by hydrogen bonds, as revealed by molecular\ndynamics simulations. Within this hybrid photobiocatalyst, TBAP-α\nfunctions as an antenna for visible-light absorption and exciton generation,\nsupplying electrons for sacrificial hydrogen production by H–S\nin aqueous solutions. This coordination allows the hybrid nanoreactor,\nH–S|TBAP-α, to execute hydrogen evolution exclusively\ndriven by light irradiation with a rate comparable to that of photocatalyst-loaded\nprecious cocatalyst. The established approach to constructing new\nlight-driven biocatalysts combines the synergistic power of biological\nnanotechnology with the multilength-scale structure and functional\ncontrol offered by supramolecular organic semiconductors. It opens\nup innovative opportunities for the fabrication of biomimetic nanoreactors\nfor sustainable fuel production and enzymatic reactions.