Ligand Mediated Assembly of CdS Colloids in 3D Porous Metal-Organic Framework Derived Scaffold with Multi-Sites Heterojunctions for Efficient CO2 Photoreduction

The inclusion of colloidal particles into 3D porous constructs to realize heterostructure ensembles enhances surface interactions and energy transfer that can transform the catalytic properties of conventional catalysts. However, assembling hydrophobic colloidal nanoparticles within hydrophilic 3D porous matrices to create tailored heterostructures and catalytic properties is particularly challenging. Here, a modified ligand grafting method is presented to spontaneously assemble CdS inorganic colloidal quantum dots within a metal-organic framework (MOF) derived porous framework for efficient photocatalytic CO2 reduction. The grafted long chain molecular ligands effectively suppress phase separation and endow a molecular-recognition effect to form ordered assembly microstructures. The proof-of-concept assembly of CdS and Prussian blue analogues (PBA) derived Co3O4 facilitates a high density of heterojunctions formation, improving charge transfer and extended lifetimes of photo-induced electrons. Consequently, CdS/Co3O4 assembly exhibits exceptionally active and stable photocatalytic CO2 reduction activity, with a CO production rate of 73.9 mu mol g(-1) h(-1) and CO selectivity of 98.9%. Importantly, the ligand grafting method can be generalized to achieve spontaneous assembly of quantum dots within various metal organic framework derived porous scaffolds. This work provides a rational strategy for precise self-assembly of colloidal nanoparticles within porous microstructures, allowing tailored heterointerfaces for functional materials and applications.