Incorporating Transition‐Metal Phosphides Into Metal‐Organic Frameworks for Enhanced Photocatalysis

Metal-organic frameworks (MOFs) have been shown to be an excellent platform in photocatalysis. However, to suppress electron-hole recombination, a Pt cocatalyst is usually inevitable, especially in photocatalytic H2 production, which greatly limits practical application. Herein, for the first time, monodisperse, small-size, and noble-metal-free transitional-metal phosphides (TMPs; for example, Ni2 P, Ni12 P5 ), are incorporated into a representative MOF, UiO-66-NH2 , for photocatalytic H2 production. Compared with the parent MOF and their physical mixture, both TMPs@MOF composites display significantly improved H2 production rates. Thermodynamic and kinetic studies reveal that TMPs, behaving similar ability to Pt, greatly accelerate the linker-to-cluster charge transfer, promote charge separation, and reduce the activation energy of H2 production. Significantly, the results indicate that Pt is thermodynamically favorable, yet Ni2 P is kinetically preferred for H2 production, accounting for the higher activity of Ni2 P@UiO-66-NH2 than Pt@UiO-66-NH2 .