Edge-oriented phosphatizing engineering of 2D Ni-MOFs with a tailored d-band center for boosting catalytic activity.

Metal-organic framework (MOF)-based heterostructures have aroused widespread interest owing to their extensive compositional tunability and interesting catalytic properties. However, the precise edge-oriented growth of transition metal compounds at the edges of 2D MOFs to construct edge mode heterostructures remains a great challenge due to their inherent thermodynamic instability. Here, edge-oriented growth of NiP at the edges of a 2D Ni-MOF was achieved for the first time by precisely tuning the phosphorus source content and phosphating temperature. Owing to the formation of the edge mode Ni-MOF/NiP heterostructure, the as-prepared heterostructure showed upregulated d-band center, more robust 4-nitrophenol (4-NP) adsorption capacity, lowered energy barrier of the rate-determining step (RDS), and higher specific surface area, resulting in the best performance of the hydrogenation reduction of 4-NP to 4-aminophenol (4-AP) in the presence of non-precious metal catalysts.