CAJ | 학술논문

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。
채용제일성원리계산고찰료음리자(붕、탄、담、불、린、류)참잡적이양화태(포괄예태광상화금홍석상)。심위이계산결과표명,재담참잡적TiO2중,간극참잡류형적N적1s능급재XPS능보상봉적위치요비체대참잡적능급고,유사적결과야재붕、탄、린화류참잡적TiO2상발현。연이대우F참잡적TiO2,체대참잡적봉위치비간극참잡적고,차여TiO2적정상무관。환대음리자참잡적TiO2진행료열역학연구。결과표명,체환참잡적형성함고우간극참잡적,인차체대참잡적TiO2적제비수요가각적조건,이간극참잡TiO2적제비지수온화적습화학조건。
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.