Adachi Yuuki, Brndiar Ján, Konôpka Martin, Turanský Robert, Zhu Qiang, Wen Huan Fei, Sugawara Yasuhiro, Kantorovich Lev, Štich Ivan, Li Yan Jun
Department of Applied Physics, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
Institute of Informatics, Slovak Academy of Sciences, 845 07 Bratislava, Slovakia.
Sci Adv. 2023 Sep 29;9(39):eadi4799. doi: 10.1126/sciadv.adi4799. Epub 2023 Sep 27.
Single-atom catalysis of carbon monoxide oxidation on metal-oxide surfaces is crucial for greenhouse recycling, automotive catalysis, and beyond, but reports of the atomic-scale mechanism are still scarce. Here, using scanning probe microscopy, we show that charging single gold atoms on oxidized rutile titanium dioxide surface, both positively and negatively, considerably promotes adsorption of carbon monoxide. No carbon monoxide adsorption is observed on neutral gold atoms. Two different carbon monoxide adsorption geometries on gold atoms are identified. We demonstrate full control over the redox state of adsorbed gold single atoms, carbon monoxide adsorption geometry, and carbon monoxide adsorption/desorption by the atomic force microscopy tip. On charged gold atoms, we activate Eley-Rideal oxidation reaction between carbon monoxide and a neighboring oxygen adatom by the tip. Our results provide unprecedented insights into carbon monoxide adsorption and suggest that the gold dual activity for carbon monoxide oxidation after electron or hole attachment is also the key ingredient in photocatalysis under realistic conditions.
金属氧化物表面上一氧化碳氧化的单原子催化对于温室气体循环利用、汽车催化等领域至关重要，但关于其原子尺度机制的报道仍然很少。在这里，我们使用扫描探针显微镜表明，在氧化金红石二氧化钛表面上对单个金原子进行正电荷和负电荷充电，都能显著促进一氧化碳的吸附。在中性金原子上未观察到一氧化碳吸附。确定了金原子上两种不同的一氧化碳吸附几何结构。我们展示了通过原子力显微镜针尖对吸附的单个金原子的氧化还原状态、一氧化碳吸附几何结构以及一氧化碳吸附/解吸的完全控制。在带电的金原子上，我们通过针尖激活了一氧化碳与相邻氧吸附原子之间的埃里-里德氧化反应。我们的结果为一氧化碳吸附提供了前所未有的见解，并表明电子或空穴附着后金对一氧化碳氧化的双重活性也是实际条件下光催化的关键因素。
