State Key Labor of Urban Water Resource and Environment (Harbin Institute of Technology), Harbin, P R China.
Phys Chem Chem Phys. 2012 Jan 28;14(4):1352-9. doi: 10.1039/c1cp22907a. Epub 2011 Dec 9.
Efficient N-containing TiO(2) nanoparticles with high anatase thermal stability were synthesized via a hexamethylenetetramine (HMT)-modified sol-hydrothermal process. The results showed that modification with proper amounts of HMT is effective in increasing the onset temperature of the phase transformation of TiO(2) from anatase to rutile. The enhancement of the anatase thermal stability of the modified TiO(2) was attributed to ammonia produced slowly by hydrolysis of the HMT molecules in the sol-hydrothermal process and, additionally, to the residual nitrogen species after the thermal treatment at high temperatures, as indicated by the XPS examination. Compared with the unmodified TiO(2), the modified TiO(2) obtained by a thermal treatment at high temperatures exhibited good photocatalytic performance under UV light and was found to even be superior to the commercially available P25-TiO(2). It was suggested that the residual N species (Ti-O-N), formed after the thermal treatment at high temperatures, along with the mixed phase composition, large surface area and the increase in the thermal stability, were responsible for the enhanced photocatalytic activity of modified TiO(2). It was demonstrated, by means of the surface photovoltage responses of the modified TiO(2) in different atmospheres along with the aid of an outer electric field, that the residual N species could effectively capture the photoinduced holes, which was favorable for the effective separation of the photoinduced charges. This work provides a feasible route to fabricate high-performance TiO(2)-based functional nanomaterials with high anatase thermal stability.
通过六亚甲基四胺(HMT)改性溶胶-水热法合成了具有高热稳定性锐钛矿相的高效含 N 的 TiO2 纳米粒子。结果表明,适量 HMT 的修饰可有效提高 TiO2 从锐钛矿相向金红石相转变的起始温度。修饰 TiO2 的锐钛矿热稳定性的增强归因于溶胶-水热过程中 HMT 分子缓慢水解产生的氨,以及高温热处理后残余的氮物种,XPS 测试表明了这一点。与未修饰的 TiO2 相比,高温热处理得到的修饰 TiO2 在紫外光下表现出良好的光催化性能,甚至优于市售的 P25-TiO2。研究表明,高温热处理后形成的残余 N 物种(Ti-O-N)以及混合相组成、大比表面积和热稳定性的提高,是修饰 TiO2 光催化活性增强的原因。通过不同气氛下修饰 TiO2 的表面光电压响应以及外加电场的辅助,证明了残余 N 物种可以有效地捕获光生空穴,有利于光生电荷的有效分离。这项工作为制备具有高热稳定性锐钛矿相的高性能 TiO2 基功能纳米材料提供了一条可行的途径。