Pugliese Silvia, Huan Ngoc Tran, Solé-Daura Albert, Li Yun, Rivera de la Cruz Jose-Guillermo, Forte Jérémy, Zanna Sandrine, Krief Alain, Su Bao-Lian, Fontecave Marc
Laboratoire de Chimie des Processus Biologiques, UMR CNRS 8229, Collège de France-CNRS-Sorbonne Université, PSL Research University, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France.
Laboratory of Inorganic Materials Chemistry (CMI), University of Namur, 61 Rue de Bruxelles, B-5000 Namur, Belgium.
Inorg Chem. 2022 Oct 10;61(40):15841-15852. doi: 10.1021/acs.inorgchem.2c01645. Epub 2022 Sep 27.
Molecular catalysis for selective CO electroreduction into CO can be achieved with a variety of metal complexes. Their immobilization on cathodes is required for their practical implementation in electrolytic cells and can benefit from the advantages of a solid material such as easy separation of products and catalysts, efficient electron transfer to the catalyst, and high stability. However, this approach remains insufficiently explored up to now. Here, using an appropriate and original modification of the cyclam ligand, we report a novel [Ni(cyclam)] complex which can be immobilized on carbon nanotubes. This material, once deposited on a gas diffusion layer, provides a novel electrode which is remarkably selective for CO electroreduction to CO, not only in organic solvents but also, more remarkably, in water, with faradic efficiencies for CO larger than 90% and current densities of 5-10 mA cm during controlled potential electrolysis in H-cells.
通过多种金属配合物可实现将CO选择性电还原为CO的分子催化。为了在电解池中实际应用，需要将它们固定在阴极上，并且可以受益于固体材料的优点，例如产物和催化剂易于分离、向催化剂的有效电子转移以及高稳定性。然而，到目前为止，这种方法仍未得到充分探索。在这里，通过对环胺配体进行适当且新颖的修饰，我们报道了一种新型的[Ni(环胺)]配合物，它可以固定在碳纳米管上。这种材料一旦沉积在气体扩散层上，就提供了一种新型电极，该电极对将CO电还原为CO具有显著的选择性，不仅在有机溶剂中，而且更显著的是在水中，在H型电解池中进行恒电位电解时，CO的法拉第效率大于90%，电流密度为5-10 mA/cm²。
