Polypyrrole reinforced ZIF-67 with modulated facet exposure and billion-fold electrical conductivity enhancement towards robust photocatalytic CO_(2) reduction

The implementation of metal organic frameworks(MOFs) as the co-catalysts in hybrid photocatalytic systems puts requirements on both their charge-carrying capability and solvent stability. In the current study, in order to simultaneously promote the electrical conductivity and water stability of ZIF-67, an insitu monomer trapping strategy is deployed to synthesize polypyrrole(PPy)-reinforced ZIF-67 ensembles.Through coordination modulation, the incremental addition of pyrrole monomers enables to alter the crystal morphology of ZIF-67 from rhombic dodecahedra to truncated rhombic dodecahedra, and further to cubes. Upon polymerization, the resulted composite, in comparison to ZIF-67, demonstrates a billionfold conductivity enhancement, much improved chemical stability in pronated solvents, as well as largely retained specific surface area and porosity, enabling it functioning as an outstanding co-catalyst for catalyzing robust photocatalytic CO_(2) reduction. Furthermore, a PPy-mediated electron harvest and relay mechanism is proposed for rationalizing the enhanced photocatalytic performance.