Abstract:

Using the electricity generated by renewable energy such as wind energy and solar energy to electrocatalyze the reduction of CO₂ into high value-added materials and chemical raw materials is an effective way to achieve carbon balance. By grafting alkynyl polymer on the surface of CoTBrPP metal porphyrin crystal through Sonogashira-Hagihara coupling reaction, a novel CoTBrPP-PTAB-Cu catalyst was synthesized. The catalyst has a high selectivity for methane, and the Faraday efficiency of methane can reach 54.6% when the current density was -200mA/cm². It was found that the surface of metal porphyrin crystal was coated with triacetylene benzene polymer by grafting reaction, which effectively improved the hydrophilic and hydrophobic properties of metal porphyrins, thus reducing HER competition reaction. At the same time, the copper ions introduced in the coupling reaction can interact with the metal ions in the porphyrin center to achieve the regulation of the reduction products.

Key words: metallic porphyrin, 1,3,5-tracetylene benzene, covalent grafting, electrocatalytic CO₂ reduction reaction, methane

摘要：

利用风能、太阳能等可再生能源产生的电能将CO₂电催化还原为高附加值材料和化工原材料，是实现碳平衡的有效途径。通过Sonogashira-Hagihara偶联反应在CoTBrPP金属卟啉结晶体表面接枝炔基聚合物，合成了新型的CoTBrPP-PTAB-Cu催化剂（PTAB为三乙炔苯聚合物）。该催化剂对甲烷具有较高的选择性，在电流密度为-200mA/cm²时，甲烷的法拉第效率可达54.6%。实验证明，在金属卟啉结晶体表面通过接枝反应包覆PTAB，可以有效改善金属卟啉的亲疏水特性，进而减少HER的竞争反应。同时，偶联反应过程中引入的铜离子可与卟啉中心的金属离子相互作用，实现对电催化CO₂还原产物的调节。这项工作为设计和制备高性能的金属卟啉基催化剂，为实现CO₂到高附加值的烃类化合物提供了一种新的思路。

关键词: 卟啉基催化剂, 1,3,5-三乙炔苯, 共价接枝, 电催化二氧化碳还原, 甲烷