Laboratoire de Chimie des Processus Biologiques, UMR CNRS 8229, Collège de France-CNRS-Sorbonne Université, PSL Research University, 11 Place Marcelin Berthelot, 75005, Paris, France.
Synchrotron SOLEIL, L'Orme des Merisiers Saint-Aubin-BP 48, 91192, Gif-sur-Yvette, France.
ChemSusChem. 2020 Jan 9;13(1):173-179. doi: 10.1002/cssc.201902859. Epub 2019 Nov 14.
Electroreduction of CO to CO is one of the simplest ways to valorise CO as a source of carbon. Herein, a cheap, robust, Cu-based hybrid catalyst consisting of a polymer of Cu phthalocyanine coated on carbon nanotubes, which proved to be selective for CO production (80 % faradaic yield) at relatively low overpotentials, was developed. Polymerisation of Cu phthalocyanine was shown to have a drastic effect on the selectivity of the reaction because molecular Cu phthalocyanine was instead selective for proton reduction under the same conditions. Although the material only showed isolated Cu sites in phthalocyanine-like CuN coordination, in situ and operando X-ray absorption spectroscopy showed that, under operating conditions, the Cu atoms were fully converted to Cu nanoparticles, which were likely the catalytically active species. Interestingly, this restructuring of the metal sites was reversible.
将 CO 电化学还原为 CO 是将 CO 转化为有价值碳源的最简单方法之一。在此，开发了一种廉价、坚固的基于 Cu 的混合催化剂，由涂覆在碳纳米管上的 Cu 酞菁聚合物组成，该催化剂在相对较低的过电势下表现出对 CO 生成（80%的法拉第产率）的选择性。Cu 酞菁的聚合被证明对反应的选择性有重大影响，因为在相同条件下，分子 Cu 酞菁对质子还原具有选择性。尽管该材料在酞菁样的 CuN 配位中仅显示出孤立的 Cu 位，但原位和操作条件下的 X 射线吸收光谱表明，在操作条件下，Cu 原子完全转化为 Cu 纳米颗粒，这可能是催化活性物种。有趣的是，金属位的这种重构是可逆的。
