Bai Xiaowan, Li Qiang, Shi Li, Niu Xianghong, Ling Chongyi, Wang Jinlan
School of Physics, Southeast University, Nanjing, 211189, China.
Small. 2020 Mar;16(12):e1901981. doi: 10.1002/smll.201901981. Epub 2019 Jun 13.
The mixing of charge states of metal copper catalysts may lead to a much improved reactivity and selectivity toward multicarbon products for CO reduction. Here, an electrocatalyst model composed of copper clusters supported on graphitic carbon nitride (g-C N ) is proposed; the connecting Cu atoms with g-C N can be oxidized to Cu due to substantial charge transfer from Cu to N atoms, while others stay as Cu . It is revealed that CO can be captured and reduced into *CO on the Cu site, owing to its zero oxidation state. More importantly, C-C coupling reaction of two *CHO species on the Cu -Cu atomic interface can occur with a rather low kinetic barrier of 0.57 eV, leading to the formation of the final C product, namely, C H OH. During the whole process, the limiting potential is just 0.68 V. These findings may open a new avenue for CO reduction into high-value fuels and chemicals.
金属铜催化剂电荷态的混合可能会显著提高其对CO还原生成多碳产物的反应活性和选择性。在此，提出了一种由负载在石墨相氮化碳（g-C₃N₄）上的铜簇组成的电催化剂模型；由于从Cu到N原子的大量电荷转移，与g-C₃N₄相连的Cu原子可被氧化为Cu⁺，而其他的则保持为Cu⁰。研究表明，由于其零氧化态，CO可在Cu⁰位点上被捕获并还原为CO。更重要的是，两个CHO物种在Cu⁺-Cu⁰原子界面上的C-C偶联反应可以在相当低的0.57 eV动力学势垒下发生，从而导致最终C产物即CH₃OH的形成。在整个过程中，极限电位仅为0.68 V。这些发现可能为将CO还原为高价值燃料和化学品开辟一条新途径。
