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Incorporating Transition‐Metal Phosphides Into Metal‐Organic Frameworks for Enhanced Photocatalysis
Author(s) -
Sun Kang,
Liu Meng,
Pei Junzhe,
Li Dandan,
Ding Chunmei,
Wu Kaifeng,
Jiang HaiLong
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202011614
Subject(s) - photocatalysis , transition metal , metal , catalysis , materials science , metal organic framework , electron transfer , dispersity , noble metal , chemical engineering , nanotechnology , chemistry , inorganic chemistry , photochemistry , metallurgy , organic chemistry , adsorption , polymer chemistry , engineering
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 H 2 production, which greatly limits practical application. Herein, for the first time, monodisperse, small‐size, and noble‐metal‐free transitional‐metal phosphides (TMPs; for example, Ni 2 P, Ni 12 P 5 ), are incorporated into a representative MOF, UiO‐66‐NH 2 , for photocatalytic H 2 production. Compared with the parent MOF and their physical mixture, both TMPs@MOF composites display significantly improved H 2 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 H 2 production. Significantly, the results indicate that Pt is thermodynamically favorable, yet Ni 2 P is kinetically preferred for H 2 production, accounting for the higher activity of Ni 2 P@UiO‐66‐NH 2 than Pt@UiO‐66‐NH 2 .