Metalation of tetraphenylporphyrin with nickel on a TiO2(110)-1 × 2 surface.
Metalation of tetraphenylporphyrin with nickel on a TiO2(110)-1 × 2 surface.
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四苯基卟啉与镍在 TiO2(110)-1 x 2 表面上的金属化
DOI：
10.1039/c5nr03134f
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发表时间：
2016-01-14
期刊：
影响因子：
6.7
通讯作者：
Zhu J
中科院分区：
文献类型：
--
作者：
Wang C;Fan Q;Han Y;Martínez JI;Martín-Gago JA;Wang W;Ju H;Gottfried JM;Zhu J
用同步辐射光电子能谱（SRPES）、扫描隧道显微镜（STM）和从头算密度泛函理论（DFT）研究了Ni与四苯基卟啉（2 HTPP）在TiO 2（110）-1 × 2表面上的原位金属化反应，得到了吸附的Ni（II）-四苯基卟啉（NiTPP）.金属化可以在室温下实现的Ni和2 HTPP的沉积顺序无关，但这导致不同的金属化程度。提高衬底温度或Ni：2 HTPP比率导致更高的金属化程度，对于Ni的后沉积和预沉积，其最终分别达到其极限~85%（Ni：2 HTPP = 3：1）和~49%（Ni：2 HTPP = 1：1）。从2 HTPP到NiTPP的反应伴随着分子吸附构象和吸附位点的变化，从添加的Ti 2 O3行上的倾斜的两瓣特征到TiO 2（110）-1 × 2表面的槽或交联的顶部的四瓣特征。这种解释的STM数据支持DFT为基础的STM模拟。
The in situ metalation of tetraphenylporphyrin (2HTPP) with Ni on the reconstructed TiO2(110)-1 × 2 surface, resulting in the formation of adsorbed nickel(II)-tetraphenylporphyrin (NiTPP), has been investigated by synchrotron radiation photoemission spectroscopy (SRPES), scanning tunnelling microscopy (STM) and ab initio Density Functional Theory (DFT) calculations. The metalation can be realized at room temperature irrespective of the deposition order of Ni and 2HTPP, which however leads to different metalation degrees. Increasing the substrate temperature or Ni : 2HTPP ratio results in higher metalation degree, which ultimately reaches its limit at ~85% (Ni : 2HTPP = 3 : 1) and ~49% (Ni : 2HTPP = 1 : 1) for post- and pre-deposition of Ni, respectively. The reaction from 2HTPP to NiTPP is accompanied by changes of the molecular adsorption conformation and the adsorption site from a tilted two-lobed feature on added Ti2O3 rows to a four-lobed feature on top of troughs or cross-links of the TiO2(110)-1 × 2 surface. This interpretation of the STM data is supported by DFT-based STM simulations.