Dopant-Induced Charge Redistribution on the 3D Sponge-like Hierarchical Structure of Quaternary Metal Phosphides Nanosheet Arrays Derived from Metal-Organic Frameworks for Natural Seawater Splitting.

Dopant-induced electron redistribution on transition metal-based materials has long been considered an emerging new electrocatalyst that is expected to replace noble-metal-based electrocatalysts in natural seawater electrolysis; however, their practical applications remain extremely daunting due to their sluggish kinetics in natural seawater. In this work, we developed a facile strategy to synthesize the 3D sponge-like hierarchical structure of Ru-doped NiCoFeP nanosheet arrays derived from metal-organic frameworks with remarkable hydrogen evolution reaction (HER) performance in natural seawater. Based on experimental results and density functional theory calculations, Ru-doping-induced charge redistribution on the surface of metal active sites has been found, which can significantly enhance the HER activity.

Hydrogen adsorption mechanism of MOF-74 metal-organic frameworks: an insight from first principles calculations.

The microscopic mechanism of the H adsorption of two Mg-MOF-74 isoreticular frameworks, one with a benzenedicarboxylate (BDC) linker and the other with a dihydroxyfumarate (DHF) linker, were studied on the basis of density functional theory (DFT) method. Possible adsorption sites on the internal surface of the two MOFs were detected using molecular dynamics (AIMD) annealing simulations. The simulations were able to reproduce all adsorption sites which have been experimentally observed for the BDC-based M-MOF-74 frameworks with M = Ni and Zn.