Ruthenium Complex of sp Carbon-Conjugated Covalent Organic Frameworks as an Efficient Electrocatalyst for Hydrogen Evolution.

It is still a great challenge to explore hydrogen evolution reaction (HER) electrocatalysts with both lower overpotential and higher stability in acidic electrolytes. In this work, an efficient HER catalyst, Ru@COF-1, is prepared by complexation of triazine-cored sp carbon-conjugated covalent organic frameworks (COFs) with ruthenium ion. Ru@COF-1 possesses high crystallinity and porosity, which are beneficial for electrocatalysis. The large specific surface area and regular porous channels of Ru@COF-1 facilitate full contact between reactants and catalytic sites. The nitrogen atoms of triazines are protonated in the acidic media, which greatly improve the conductivity of Ru@COF-1. This synergistic effect makes the overpotential of Ru@COF-1 about 200 mV at 10 mA cm , which is lower than other reported COFs-based electrocatalysts. Moreover, Ru@COF-1 exhibits exceptionally electrocatalytic durability in the acidic electrolytes. It is particularly stable and remains highly active after 1000 cyclic voltammetry cycles. Density functional theory calculations demonstrate that tetracoordinated Ru-N Cl moieties are the major contributors to the outstanding HER performance. This work provides a new idea for developing protonated HER electrocatalysts in acidic media.