Theoretical Understanding of Electrocatalytic Hydrogen Production Performance by Low-Dimensional Metal-Organic Frameworks on the Basis of Resonant Charge-Transfer Mechanisms.

The exploration of low-cost and efficient electrocatalysts for the hydrogen evolution reaction (HER) is a prerequisite for large-scale hydrogen fuel generation. The understanding of the electronic properties of electrocatalysts plays a key role in this exploration process. In this study, our first-principles results demonstrate that the catalytic performance of the 1D metal-organic frameworks (MOFs) can be significantly influenced by engineering the composite of the metal node. Using the Gibbs free energy of the adsorption of hydrogen atoms as a key descriptor, we found that Ni- and Cr-based dithiolene MOFs possess better hydrogen evolution performance, and the much different efficiencies can be ascribed to their electronic resonance structures [TM3+(L2-)(L2-)]- ↔ [TM2+(L•-)(L2-)]-. The [TM2+(L•-)(L2-)]- structure is preferred due to the higher activity of the catalytic site L with more radical features, and the stabilized [TM2+(L•-)(L2-)]- structure of the Cr- and Ni-based MOFs can be ascribed to the electronic configurations of their TM2+ cations with half-occupied and fully occupied valence orbitals. Our results therefore reveal a novel strategy for optimizing the electronic structures of materials on the basis of the resonant charge-transfer mechanism for their practical applications.