Performance of ZIF-67-Derived fold polyhedrons for enhanced photocatalytic hydrogen evolution

Metal-organic framework (MOF) is one of the most promising precursors for the fabrication of advanced photo semiconductors or cocatalysts due to its diverse structures and unique properties. However, the primitive MOF can not show greater potential and application value. Here Co-ZIF-67 dodecahedron was controllably carved via the different ways for efficiently boosting the photo-catalytic property of hydrogen evolution. This reasonable design can not only preserve polyhedron characteristics with the large specific surface area of ZIF-67, but also improve H-2-evolution performance in Eosin Y sensitization system, which depends on the enhanced electro-negativity of the surface of ZIF-6 derived polyhedrons and the quite strong adsorption of H and H2O by Co-site. Meanwhile, ligand group or hetero-atom adjacent to metal Co atom owing to the introduction of electronegative heteroatoms overturns the inherent structure and properties of ZIF-67 to a certain extent thereby rearranging the electron distribution and improving transfer efficiency of charge carriers. Additionally, the structural evolution of ZIF-67 constructs an efficient transport channels for migration of electron, which eliminates the resistance to be overcome when electrons migrate from the inside of a semiconductor to the surface. And the increase of optical absorption density caused by hyperchromicity effect is also a factor that can not be ignored for evolving the co-catalytic performance of ZIF-67.