Boukhvalov Danil W, Osipov Vladimir Yu, Baldycheva Anna, Hogan Benjamin T
College of Science, Institute of Materials Physics and Chemistry, Nanjing Forestry University, Nanjing, 210037, P. R. China.
Institute of Physics and Technology, Ural Federal University, Yekaterinburg, 620002, Russia.
Sci Rep. 2024 Oct 30;14(1):26185. doi: 10.1038/s41598-024-74423-3.
We report the results of systematic ab initio modelling of various configurations of iron and cobalt impurities embedded in the (110), (101), and (100) surfaces of anatase TiO, with and without oxygen vacancies. The simulation results demonstrate that incorporation into interstitial voids at the surface level is significantly more favourable than other configurations for both iron and cobalt. The calculations also demonstrate the crucial effect of the facet as well as the lesser effects of other factors, such as vacancies and strain on the energetics of defect incorporation, magnetic moment, bandgap, and catalytic performance. It is further shown that there is no tendency towards the segregation or clustering of impurities on the surface. The calculated free energies of the hydrogen evolution reaction in acidic media predict that iron impurities embedded in the (101) surface of anatase TiO can be a competitive catalyst for this reaction.
我们报告了对锐钛矿型TiO₂的(110)、(101)和(100)表面嵌入铁和钴杂质的各种构型进行系统从头算建模的结果，包括有无氧空位的情况。模拟结果表明，对于铁和钴而言，掺入表面层的间隙空位比其他构型明显更有利。计算还表明了晶面的关键作用以及其他因素（如空位和应变）对缺陷掺入能量、磁矩、带隙和催化性能的较小影响。进一步表明，表面不存在杂质偏析或聚集的趋势。在酸性介质中计算得到的析氢反应自由能预测，嵌入锐钛矿型TiO₂(101)表面的铁杂质可能是该反应的一种有竞争力的催化剂。
