Two-dimensional conductive pi-conjugated metal-organic frameworks as promising electrocatalysts for highly efficient hydrogen evolution reaction

Two-dimensional conductive pi-conjugated metal-organic frameworks (2D c-MOFs), as a new promising electrocatalytic materials, have spurred great research interests, but the systematic research on the structure -property relationship of c-MOF-based electrocatalysts is scarcely reported. Herein we conduct a first-principles study on the screening of a family of 2D c-MOFs (TM3(HITN)(2)) as HER electrocatalysts, which are constructed by TM atoms and 2,3,8,9,14,15-hexaiminotrinaphthylene (HITN) functional groups. The data suggests that all these 2D TM3(HITN)(2) possess metallic with good conductivity for electrochemical reactions due to their intrinsic pi-electron conjugation and sufficient interaction between the TM atoms and the organic linkers. Through the complete computational screening, the Zr-3(HITN)(2) stands out because of its near-zero delta G*(H) value and low activation energy barrier. Moreover, the distinguished HER performance of Zr-3(HITN)(2 )can be attributed to the extremely enhanced electron density derived from the C-2p orbitals near the Fermi level accompanied by the size increase of the tridentated aromatic linkers. Hence, this study not only highlights a family of promising 2D c- MOF electrocatalysts toward HER, but also supplies a valuable insight on the design of novel and high-performance c-MOF-based materials for better electrocatalysis.