Realization of stable and industrial-level H₂O₂ electroproduction still faces great challenge due large partly to the easy decomposition of H₂O₂. 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 H₂O₂ decomposition capability of the same Co center, as a total result enabling CoPc-S-COF to display good electrocatalytic H₂O₂ production performance with a remarkable H₂O₂ selectivity of >95% and a stable H₂O₂ production with a concentration of 0.48 wt% under a high current density of 125 mA cm⁻² at an applied potential of ca. 0.67 V versus RHE for 20 h in a flow cell, representing the thus far reported best H₂O₂ synthesis COFs electrocatalysts.

实现稳定的工业级 H₂O₂ 电生产仍然面临巨大的挑战，这在很大程度上是由于 H₂O₂ 易于分解。在此，通过十六烷氟酞氰酸钴 （II） 与 1,2,4,5-苯四硫醇反应，得到了基于二维二硫因连接的酞菁钴 （CoPc） 基共价有机框架 （COF），CoPc-S-COF。在C-S-C连接单元中引入原子半径大的硫原子和两个孤对电子，通过一系列实验结合理论计算，导致CoPc-S-COF的层状结构起伏，Co中心电子密度增加。前一种结构效应允许暴露更多的 Co 位点以增强 COF 催化性能，而后一种电子效应激活了 2e⁻ 氧还原反应 （2e⁻ ORR），但失去了同一 Co 中心的 H₂O₂ 分解能力，总之使 CoPc-S-COF 表现出良好的电催化 H₂O₂ 生产性能，具有显著的 H₂O₂在 125 mA ^cm-2 的高电流密度下，在 ca 的外加电位下，选择性为 >95%，稳定的 H₂O₂ 产生浓度为 0.48 wt%。0.67 V 与 RHE 在流通池中 20 h 的比较，代表了迄今为止报道的最佳 H₂O₂ 合成 COFs 电催化剂。