Hydrogenation of Covalent Organic Framework Induces Conjugated π Bonds and Electronic Topological Transition to Enhance Hydrogen Evolution Catalysis

Recently, many topological materials have been discovered as promising electrocatalysts in chemical conversion processes and energy storage. However, it remains unclear how the topological electronic states specifically modulate the catalytic reaction. Here, the two-dimensional metal phthalocyanine-based covalent organic framework (MPc-COF) is studied by ab initio thermodynamic calculations to clearly reveal the promotional effect on the electrochemical hydrogen evolution reaction (HER) induced by topological gapless bands (TGBs). We find that the prehydrogenated (and fluorinated) H4CdPc-COF(F) shows the best HER performance, with 0.016 V (near zero) overpotential. By tracking changes to the electronic structure and free energy as the prehydrogenation and HER processes occur, we are able to separately attribute the high HER efficiency in part due to the increase of the electron bath by donating electrons to the conjugated pi bonds and also to the existence of TGBs. Specifically, the significant catalytic promotion by TGBs is proven to decrease the free energy by 0.218 eV to near zero. When the TGBs are destroyed, e.g., by replacing N with P and opening a band gap, the HER efficiency is reduced. This study opens avenues for deterministically harnessing topological band features to improve electrocatalysis.