Zeolitic Imidazolate Framework-67-Derived P-Doped Hollow Porous Co3O4 as a Photocatalyst for Hydrogen Production from Water.

As a part of photocatalytic water splitting, the design of low-cost, high-activity catalysts plays an essential role in the development of photocatalytic water splitting. Metal oxides have the advantages of a wide range of sources, many varieties, and easy preparation. Doping engineering on their surface can construct new active sites and adjust their catalytic activity. In this work, a new strategy was developed through anion hybridization to regulate electron delocalization. Using one of the cobalt-based zeolitic imidazole skeletons (ZIF-67) as a precursor material, a two-step calcination method was used to prepare a P-doped Co3O4 mixed anion composite photocatalyst. The hydrogen production rate of P@Co3O4 is 39 times that of ZIF-67 and 6.8 times that of Co3O4. Through density functional theory (DFT) calculations, the electron delocalization state of the sample surface is predicted and the reaction energy barrier is reduced to promote the process of the hydrogen evolution reaction (HER). The special O(δ-)-Co(δ+)-P(δ-) surface bonding state promotes the bridging of isolated electronic states and provides active sites for the adsorption and activation of reaction substrates. The improved electron transport pathway and the synergy between the catalytic sites under the high electron transport rate are the main reasons for the enhanced photocatalytic hydrogen evolution activity. This strategy, including changing the surface bond state and optimizing the structure and composition of the catalyst not only provides a new method for preparing other MOF-derived nanomaterials with porous structures but also inspires the reasonable development of other MOF-based advanced photocatalysts.