新型可见光响应的InVO4-Cu2O-TiO2三元纳米异质结:制备及其光催化性能

doi:10.1016/S1872-2067(15)61105-6

催化学报 ›› 2016, Vol. 37 ›› Issue (6): 855-862.DOI: 10.1016/S1872-2067(15)61105-6

新型可见光响应的InVO₄-Cu₂O-TiO₂三元纳米异质结:制备及其光催化性能

冯海波^a,b, 李亚萍^a, 罗冬明^a, 谭功荣^a, 蒋剑波^a, 袁惠敏^a, 彭三军^a, 钱东^a,b

a 中南大学化学化工学院, 湖南长沙 410083;
b 中南大学粉末冶金国家重点实验室, 湖南长沙 410083

收稿日期:2016-01-31 修回日期:2016-04-13 出版日期:2016-05-30 发布日期:2016-05-30
通讯作者: Dong Qian
基金资助:
国家自然科学基金(21171174); 湖南省自然科学基金(09JJ3024); 湖南省环境科学技术基金.

Novel visible-light-responding InVO₄-Cu₂O-TiO₂ ternary nanoheterostructure: Preparation and photocatalytic characteristics

Haibo Feng^a,b, Yaping Li^a, Dongming Luo^a, Gongrong Tan^a, Jianbo Jiang^a, Huimin Yuan^a, Sanjun Peng^a, Dong Qian^a,b

a College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, Hunan, China;
b State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, Hunan, China

Received:2016-01-31 Revised:2016-04-13 Online:2016-05-30 Published:2016-05-30
Contact: Dong Qian
Supported by:
This work was supported by the National Natural Science Foundation of China (21171174), Provincial Natural Science Foundation of Hunan (09JJ3024), and Provincial Environmental Science and Technology Foundation of Hunan.

摘要/Abstract

摘要：

由于日益严重的环境和能源危机, 可见光催化剂的开发已成为当今最具挑战和紧迫的任务之一. 将 TiO₂和其它窄禁带半导体复合, 已被证明是一种有效的可提高其可见光光催化性能的策略. Cu₂O 是一种禁带宽度为 2.0 eV 的 p 型窄禁带半导体, InVO₄则是一种禁带宽度为 2.0 eV 的 n 型半导体, 因它们可用于可见光光解水产氢和有机污染物的可见光降解而在过去的数年中引起了人们广泛的关注. 但是纯的 Cu₂O 和 InVO₄由于光生电子空穴对在其内部快速地复合, 光催化活性通常都比较低. 基于能带工程的策略本文设计了一种新型的可见光响应的 InVO₄-Cu₂O-TiO₂三元纳米异质结, 并通过普通的湿化学法进行制备: 先通过水热法制备 InVO₄, 再通过溶胶-凝胶法制备 InVO₄-TiO₂二元复合物, 最后通过沉淀和还原过程制备得到 InVO₄-Cu₂O-TiO₂三元纳米异质结.
在 10%InVO₄-40%Cu₂O-50%TiO₂三元纳米异质结的 X-射线衍射谱中没有观察到明显的杂质峰; 通过透射电子显微技术和高分辨透射电子显微技术观察到了它们之间异质结的形成, 纳米颗粒的尺寸范围在 5-20 nm; 经紫外可见漫反射光谱估算得到 10%InVO₄-40%Cu₂O-50%TiO₂的禁带宽度为 2.78 eV, 在可见光区域具有较强的吸收. 以普通的 9 W 节能灯作为可见光光源光照甲基橙 5 h 后, 纯的 InVO₄, TiO₂和 Cu₂O 几乎没有光催化活性; 10%InVO₄-90%TiO₂的光催化活性也很低, 甲基橙降解率为 8%; 70%Cu₂O-30%TiO₂对甲基橙降解率达 84%, 但初始活性较低; 10%InVO₄-40%Cu₂O-50%TiO₂对甲基橙降解率接近 90%, 并且循环使用 6 次后, 其光催化活性的保持率还维持在 90% 以上, 而 50%Cu₂O-50%TiO₂光催化活性的保持率只有 74%.
经对使用过的 10%InVO₄-40%Cu₂O-50%TiO₂进行 X 射线光电子能谱表征发现, 存在一弱小的 Cu(II) 震动卫星峰, 表明在 InVO₄-Cu₂O-TiO₂的光催化过程中 Cu₂O 的光蚀并不严重. 从能带工程的角度分析, InVO₄-Cu₂O-TiO₂三元纳米异质结具有优异的可见光催化性能的主要原因为: InVO₄的导带电极电位约为-0.5 eV(vs. SHE, 下同), 价带电位约为+1.5 eV, Cu₂O 的分别约为-1.6 和+0.4 eV, 与 TiO₂(导带和价带电极电位分别约为-0.23 和+2.97 eV) 相比, 它们的导带位置更负, 将它们组装成三元复合结构, 可见光激发的导带电子就可能从 InVO₄和 Cu₂O 的导带迁移到 TiO₂的导带上去. 同时, n 型的 TiO₂和 InVO₄都与 p 型的 Cu₂O 形成 p-n 异质结, n 型的 TiO₂和 InVO₄之间形成 n-n 异质结, 由于 p-n 异质结中内电场的存在以及不同能级相互耦合, 可进一步促进可见光激发的导带电子从 InVO₄和 Cu₂O 的导带迁移到 TiO₂的导带上去, 以及可见光激发的价带空穴从 InVO₄的价带迁移到 Cu₂O 的价带上去, 从而实现光生载流子空间上的有效分离. 本文有望为新型可见光响应的半导体复合催化剂的设计和制备提供新的思路.

关键词: 钒酸铟, 氧化亚铜, 二氧化钛, 纳米异质结, 可见光, 光催化降解, 甲基橙

Abstract:

A novel visible-light-responding InVO₄-Cu₂O-TiO₂ ternary nanoheterostructure was designed on the basis of the strategy of energy gap engineering and prepared through ordinary wet chemistry methods. The as-prepared nanoheterostructure was characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and diffuse reflectance ultraviolet-visible spectroscopy (UV-vis/DRS). The TEM and HRTEM images of 10%InVO₄-40%Cu₂O-50%TiO₂ confirm the formation of nanoheterostructures resulting from contact of the nanosized TiO₂, Cu₂O and InVO₄ in the size of 5-20 nm in diameter. The InVO₄-Cu₂O-TiO₂ nanoheterostructure, when compared with TiO₂, Cu₂O, InVO₄, InVO₄-TiO₂ and Cu₂O-TiO₂, shows significant enhancement in the photocatalytic performance for the degradation of methyl orange (MO) under visible-light irradiation. With a 9 W energy-saving fluorescent lamp as the visible-light source, the MO degradation rate of 10%InVO₄-40%Cu₂O-50%TiO₂ reaches close to 90% during 5 h, and the photocatalytic efficiency is maintained at over 90% after six cycles. This may be mainly ascribed to the matched bandgap configurations of TiO₂, Cu₂O and InVO₄, and the formations of two p-n junctions by the p-type semiconductor Cu₂O with the n-type semiconductors TiO₂ and InVO₄, all of which favor spatial photogenerated charge carrier separation. The X-ray photoelectron spectroscopy (XPS) characterization for the used 10%InVO₄-40%Cu₂O-50%TiO₂ reveals that only a small shakeup satellite peak appears for Cu(II) species, implying bearable photocorrosion of Cu₂O. This work could provide new insight into the design and preparation of novel visible-light-responding semiconductor composites.

Key words: Indium orthovanadate, Cuprous oxide, Titanium dioxide, Nanoheterostructure, Visible light, Photocatalytic degradation, Methyl orange

冯海波, 李亚萍, 罗冬明, 谭功荣, 蒋剑波, 袁惠敏, 彭三军, 钱东. 新型可见光响应的InVO₄-Cu₂O-TiO₂三元纳米异质结:制备及其光催化性能[J]. 催化学报, 2016, 37(6): 855-862.

Haibo Feng, Yaping Li, Dongming Luo, Gongrong Tan, Jianbo Jiang, Huimin Yuan, Sanjun Peng, Dong Qian. Novel visible-light-responding InVO₄-Cu₂O-TiO₂ ternary nanoheterostructure: Preparation and photocatalytic characteristics[J]. Chinese Journal of Catalysis, 2016, 37(6): 855-862.

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新型可见光响应的InVO₄-Cu₂O-TiO₂三元纳米异质结:制备及其光催化性能

Novel visible-light-responding InVO₄-Cu₂O-TiO₂ ternary nanoheterostructure: Preparation and photocatalytic characteristics

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