Ma Hui-yan, Liu Zheng-jiang, Cheng Lin, Yang Ju-cai, Zhang Qian-cheng
Guang Pu Xue Yu Guang Pu Fen Xi. 2016 Apr;36(4):1133-8.
Ce doped TiO2 was prepared via sol-gel method. The as-prepared Ce doped TiO2 was impregnated with diluted H2SO4 to obtain a H2SO4-treated Ce doped TiO2. In succession, the characterizations of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), pyridine adsorption-FTIR (Py-FTIR), ultraviolet-visible spectroscopy (UV-vis) and X-ray photoelectron spectroscopy (XPS) were carried out to analyze the reasons for the improvement of the light response performance. The visible light photocatalytic degradation of Rhodamine B (RhB) in an aqueous solution was used as a probe reaction to evaluate the photocatalytic activity of the obtained samples. According to the XRD analysis, Ce doping created the lattice defects in TiO2 and minimized the particle size, which promoted the transfer of photo-generated electrons and then improved catalyst activity. The bridged bidentate coordination mode of SO2-4 was proposed based on the FTIR spectra. The pyridine FTIR spectra showed that both Lewis and Brnsted acid sites were formed on the sample surface. The characteristic absorption band as Lewis acid was more intense than that of the Brnsted acid, exhibiting the major Lewis acidity. The presence of the Lewis acid sites resulted in the transfer of photogenerated electrons to the Lewis acid center because of the electron deficiency of the Lewis acid sites, which contributed greatly to the transport of the photogenerated electrons, inhibiting the recombination of the photogenerated electron/hole pairs and leading to the enhancement of the photocatalytic activity of samples. From UV-Vis results, Ce-doping introduced an impurity energy level in the band gap, narrowing the TiO2 band gap. The impurity energy level could capture the photogenerated electrons on the conduct band and photogenerated holes on the valence band, reducing the recombination probability of photogenerated carriers and exciting the electrons captured on the impurity energy band by the photons with lower energy, thus expanding the light response range of TiO2. The XPS results indicated that the doped Ce existed as a mixture of Ce3+/Ce4+ states, which facilitated the efficient separation of the photo-generated electrons and holes because of the electron transfer, enhancing the system’s quantum efficiency. The sulfated Ce doped TiO2 catalysts were very active for the visible photocatalytic degradation of RhB. Results showed that the synergetic effects of Ce doping and acid-treatment improved the visible light response for sulfated Ce-doped TiO2, enhancing the visible photocatalytic activity.
通过溶胶-凝胶法制备了铈掺杂的二氧化钛。将制备好的铈掺杂二氧化钛用稀硫酸浸渍,得到硫酸处理的铈掺杂二氧化钛。随后,进行了X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、吡啶吸附-FTIR(Py-FTIR)、紫外-可见光谱(UV-vis)和X射线光电子能谱(XPS)表征,以分析光响应性能提高的原因。以水溶液中罗丹明B(RhB)的可见光光催化降解作为探针反应,评估所得样品的光催化活性。根据XRD分析,铈掺杂在二氧化钛中产生了晶格缺陷并使粒径最小化,促进了光生电子的转移,进而提高了催化剂活性。基于FTIR光谱提出了SO2-4的桥式双齿配位模式。吡啶FTIR光谱表明,样品表面形成了路易斯酸和布朗斯特酸位点。作为路易斯酸的特征吸收带比布朗斯特酸的更强,显示出主要的路易斯酸性。路易斯酸位点的存在导致光生电子由于路易斯酸位点的电子不足而转移到路易斯酸中心,这极大地促进了光生电子的传输,抑制了光生电子/空穴对的复合,导致样品光催化活性增强。从UV-Vis结果来看,铈掺杂在带隙中引入了杂质能级,使二氧化钛带隙变窄。杂质能级可以捕获导带上的光生电子和价带上的光生空穴,降低光生载流子的复合概率,并通过能量较低的光子激发捕获在杂质能级上的电子,从而扩大了二氧化钛的光响应范围。XPS结果表明,掺杂的铈以Ce3+/Ce4+态的混合物形式存在,由于电子转移,这有利于光生电子和空穴的有效分离,提高了体系的量子效率。硫酸化的铈掺杂二氧化钛催化剂对RhB的可见光光催化降解非常活跃。结果表明,铈掺杂和酸处理的协同效应改善了硫酸化铈掺杂二氧化钛的可见光响应,增强了可见光催化活性。