Sun Kang, Liu Meng, Pei Junzhe, Li Dandan, Ding Chunmei, Wu Kaifeng, Jiang Hai-Long
Hefei National Laboratory for Physical Sciences at the Microscale, CAS Key Laboratory of Soft Matter Chemistry, Department of Chemistry, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China.
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning, 116023, P. R. China.
Angew Chem Int Ed Engl. 2020 Dec 7;59(50):22749-22755. doi: 10.1002/anie.202011614. Epub 2020 Oct 6.
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 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 P, Ni P ), are incorporated into a representative MOF, UiO-66-NH , for photocatalytic H production. Compared with the parent MOF and their physical mixture, both TMPs@MOF composites display significantly improved H 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 production. Significantly, the results indicate that Pt is thermodynamically favorable, yet Ni P is kinetically preferred for H production, accounting for the higher activity of Ni P@UiO-66-NH than Pt@UiO-66-NH .
金属有机框架材料（MOFs）已被证明是光催化领域的一个优秀平台。然而，为了抑制电子-空穴复合，通常不可避免地要使用铂助催化剂，尤其是在光催化产氢中，这极大地限制了其实际应用。在此，首次将单分散、小尺寸且不含贵金属的过渡金属磷化物（TMPs；例如，Ni₂P、Ni₃P）掺入代表性的MOF材料UiO-66-NH₂中，用于光催化产氢。与母体MOF及其物理混合物相比，两种TMPs@MOF复合材料均表现出显著提高的产氢速率。热力学和动力学研究表明，TMPs具有与铂类似的能力，极大地加速了连接体到簇的电荷转移，促进了电荷分离，并降低了产氢的活化能。值得注意的是，结果表明铂在热力学上是有利的，但Ni₂P在动力学上更有利于产氢，这解释了Ni₂P@UiO-66-NH₂比Pt@UiO-66-NH₂具有更高活性的原因。
