Bimetallic atom synergistic covalent organic framework for efficient electrochemical nitrate reduction

Electrochemical reduction has emerged as an effective method to remove nitrate from industrial wastewater. Nevertheless, this method has been largely restricted by the lack of low-cost and efficient electrocatalysts. Here, we demonstrate a porous two-dimensional covalent organic framework (2D COF) material as a promising electrocatalyst, which is obtained via a Schiff base reaction by combining copper phthalocyanine with bipyridine sites for precise copper coordination. The bidentate coordinated COF material has a robust framework and stable chemical property, allowing the isolated Cu sites to be embedded into the regular pores with controlled and uniformly dispersed active centers. The well-defined design of the reaction monomers makes the COF material to trap nitrate ions more easily from aqueous solution. By rationally combining the synergistic effect of 2D COF and Cu active sites, the CuTAPc-CuBPy-COF electrocatalyst shows much higher nitrate reduction efficiency than CuTAPc-BPy-COF under low superpotential and different nitrate concentrations. The high NO₃^- conversion (90.3 %) and NH₃ selectivity (69.6 %) are achieved. To our best acknowledge, this is the first demonstration of bi-copper-based COF material for NO₃^-RR electrocatalysis, which provides a new direction for the rational design of COFs as significant electrocatalysts for nitrate reduction.