Fester Jakob, Walton Alex, Li Zheshen, Lauritsen Jeppe V
Interdisciplinary Nanoscience Center (iNANO), Aarhus University, 8000 Aarhus C, Denmark.
ISA, Aarhus University, 8000 Aarhus C, Denmark.
Phys Chem Chem Phys. 2017 Jan 18;19(3):2425-2433. doi: 10.1039/c6cp07901f.
In the present study, we investigate the facile conversion of Co-O bilayer islands on a Au(111) surface into preferentially O-Co-O trilayers in an oxygen atmosphere and O-Co-O-Co-O multilayers at elevated temperature. We characterize and compare the island morphologies with scanning tunneling microscopy, X-ray photoemission spectroscopy (XPS) and valence band spectroscopy, and show that the cobalt oxidation state changes from Co in bilayers to purely Co in trilayers and a mixture of Co and Co in the multilayer morphology. In contrast to bilayers and multilayers, the trilayer structure appears to grow pseudomorphic with the Au(111) substrate, and in addition we reveal the presence of a hydroxyl overlayer on this island type as evidenced by the appearance of a superstructure in STM correlated with the fingerprints of OH species in XPS and valence band spectroscopy. The obtained layered morphology consisting of hydroxylated trilayer islands is identical to an exfoliated sheet of the β-CoOOH which is proposed to be the active phase of the cobalt oxide oxygen evolution reaction catalyst present in the electrochemical environment, and we note that this synthesized structure thus could serve as a valuable model catalyst.
在本研究中,我们探究了在金(111)表面上的钴 - 氧双层岛在氧气气氛中如何轻松转化为择优取向的氧 - 钴 - 氧三层结构,以及在高温下如何转化为氧 - 钴 - 氧 - 钴 - 氧多层结构。我们使用扫描隧道显微镜、X射线光电子能谱(XPS)和价带光谱对岛的形态进行了表征和比较,结果表明钴的氧化态从双层中的Co变为三层中的纯Co,在多层结构中则是Co和Co的混合物。与双层和多层结构不同,三层结构似乎与金(111)衬底呈赝形生长,此外,我们还揭示了这种岛型结构上存在羟基覆盖层,扫描隧道显微镜中的超结构出现与XPS和价带光谱中OH物种的指纹特征相关,这证明了羟基覆盖层的存在。所获得的由羟基化三层岛组成的层状形态与β-CoOOH的剥离片相同,β-CoOOH被认为是电化学环境中钴氧化物析氧反应催化剂的活性相,我们注意到这种合成结构因此可以作为一种有价值的模型催化剂。