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  4. 阴离子掺杂TiO2的芯位移和热力学性质的第一性原理研究

催化学报 , 2015, (2): 181-187. doi: 10.1016/S1872-2067(14)60165-0

阴离子掺杂TiO2的芯位移和热力学性质的第一性原理研究

丁戊辰 1, , 李微雪 2,

1.中国科学院大连化学物理研究所,辽宁大连,116023

2.中国科学院大连化学物理研究所,辽宁大连,116023

基金项目:   国家重点基础研究发展计划(973计划,2013CB834603)   中国科学院战略性先导科技专项(XDA09030000)   国家自然科学基金(21173210,21225315,21321002)  

关键词： 二氧化钛 , 芯位移 , X射线光电子能谱 , 阴离子 , 替换掺杂 , 间隙掺杂 , 密度泛函理论 , 热力学性质

A first principles study of the energetics and core level shifts of anion-doped TiO2 photocatalysts

Keywords： Titania , Core level shifts , X-ray photoelectron spectroscopy , Anion , Subtitutional doping , Interstitial doping , Density function theory , Thermodynamics

采用第一性原理计算考察了阴离子(硼、碳、氮、氟、磷、硫)掺杂的二氧化钛(包括锐钛矿相和金红石相)。芯位移计算结果表明,在氮掺杂的TiO2中,间隙掺杂类型的N的1s能级在XPS能谱上峰的位置要比替代掺杂的能级高,类似的结果也在硼、碳、磷和硫掺杂的TiO2上发现。然而对于F掺杂的TiO2,替代掺杂的峰位置比间隙掺杂的高,且与TiO2的晶相无关。还对阴离子掺杂的TiO2进行了热力学研究。结果表明,替换掺杂的形成焓高于间隙掺杂的,因此替代掺杂的TiO2的制备需要苛刻的条件,而间隙掺杂TiO2的制备只需温和的湿化学条件。

We present a comprehensive and improved density functional theory (DFT) calculation of ani‐on‐doped (anion=B, C, N, F, P, S) anatase and rutile TiO2. The first part is a first principles calcula‐tion of the core level shifts (CLS) for various anion dopants in both anatase and rutile TiO2. The CLS results revealed that interstitial N had a higher N 1s binding energy than substitutional N, which agreed well with experimental results. The calculation also showed that for B‐, C‐, S‐, and P‐doped TiO2, the interstitial dopant had an energy that is higher than that of a substitutional dopant, which is similar to N‐doped TiO2. However, for F‐doped TiO2, the energy of the substitutional dopant is higher, and this is irrespective of the TiO2 crystallography. We also calculated the enthalpy of doping and found that the substitutional dopant had a higher enthalpy than the interstitial dopant. The results revealed that substitutional doping required severe experimental conditions, whereas inter‐stitial doping only requires modest wet chemistry conditions.

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