Dithiine-linked metalphthalocyanine framework with undulated layers for highly efficient and stable HO electroproduction.

Realization of stable and industrial-level HO electroproduction still faces great challenge due large partly to the easy decomposition of HO. Herein, a two-dimensional dithiine-linked phthalocyaninato cobalt (CoPc)-based covalent organic framework (COF), CoPc-S-COF, was afforded from the reaction of hexadecafluorophthalocyaninato cobalt (II) with 1,2,4,5-benzenetetrathiol. Introduction of the sulfur atoms with large atomic radius and two lone-pairs of electrons in the C-S-C linking unit leads to an undulated layered structure and an increased electron density of the Co center for CoPc-S-COF according to a series of experiments in combination with theoretical calculations. The former structural effect allows the exposition of more Co sites to enhance the COF catalytic performance, while the latter electronic effect activates the 2e oxygen reduction reaction (2e ORR) but deactivates the HO decomposition capability of the same Co center, as a total result enabling CoPc-S-COF to display good electrocatalytic HO production performance with a remarkable HO selectivity of >95% and a stable HO production with a concentration of 0.48 wt% under a high current density of 125 mA cm at an applied potential of ca. 0.67 V versus RHE for 20 h in a flow cell, representing the thus far reported best HO synthesis COFs electrocatalysts.