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. 2020 Dec 7;59(50):22749-22755.
doi: 10.1002/anie.202011614. Epub 2020 Oct 6.

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

Kang Sun  1 , Meng Liu  2 , Junzhe Pei  1 , Dandan Li  3 , Chunmei Ding  4 , Kaifeng Wu  2 , Hai-Long Jiang  1
Affiliations

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

Kang Sun et al. Angew Chem Int Ed Engl. .

Abstract

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 .

Keywords: cocatalysts; hydrogen production; metal-organic frameworks; photocatalysis; transition-metal phosphides.

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