Z型复合催化剂g-C3N4/Vo-ZnO光催化活性的研究

doi:10.1016/S1872-2067(15)60985-8

催化学报 ›› 2015, Vol. 36 ›› Issue (12): 2135-2144.DOI: 10.1016/S1872-2067(15)60985-8

Z型复合催化剂g-C₃N₄/V_o-ZnO光催化活性的研究

刘亚男^a, 王瑞霞^b, 杨正坤^a, 杜虹^a, 姜一帆^a, 申丛丛^a, 梁况^a, 徐安武^a

a 中国科学技术大学合肥微尺度物质科学国家实验室, 安徽合肥 230026;
b 池州学院材料与化学工程系, 安徽池州 247100

收稿日期:2015-08-16 修回日期:2015-09-25 出版日期:2015-12-02 发布日期:2015-12-07
通讯作者: 徐安武
基金资助:
国家重点基础研究发展计划(2011CB933700);国家自然科学基金(21271165).

Enhanced visible-light photocatalytic activity of Z-scheme graphitic carbon nitride/oxygen vacancy-rich zinc oxide hybrid photocatalysts

Yanan Liu^a, Ruixia Wang^b, Zhengkun Yang^a, Hong Du^a, Yifan Jiang^a, Congcong Shen^a, Kuang Liang^a, Anwu Xu^a

a Division of Nanomaterials and Chemistry, Hefei National Laboratory for Physical Sciences at Microscale, University of Science and Technology of China, Hefei 230026, Anhui, China;
b Department of Materials and Chemical Engineering, College of Chi Zhou, Chizhou 247100, Anhui, China

Received:2015-08-16 Revised:2015-09-25 Online:2015-12-02 Published:2015-12-07
Supported by:
This work was supported by the National Basic Research Program of China (2011CB933700) and the National Natural Science Foundation of China (21271165).

摘要/Abstract

摘要：

随着科学技术的不断进步和经济的快速发展,人类对自然资源的需求量越来越大,在开发利用自然资源的同时,大量的有机污染物也随之进入自然环境.这些物质不仅污染环境、破坏生态,更对人类的生活和健康带来了巨大的威胁.研究证实,半导体光催化剂在光照条件下可以破坏有机污染物的分子结构,最终将其氧化降解成CO₂、H₂O或其它不会对环境产生二次污染的小分子,从而净化水质.近年来,有关光催化降解有机污染物的报道日益增多.ZnO作为一种广泛研究的光催化降解材料,因其无毒、低成本和高效等特点而具有一定的应用前景.但是ZnO较大的禁带宽度(3.24eV)导致其只能吸收紫外光部分,而对可见光的吸收效率很小,极大地制约了其实际应用.除此之外,ZnO受光激发产生的电子-空穴分离效率较低、光催化过程中的光腐蚀严重也是制约其实际应用的重要因素.为了提高ZnO的光催化活性和稳定性,本文合成了用g-C₃N₄修饰的氧空位型ZnO(g-C₃N₄/V_o-ZnO)复合催化剂,在有效调控ZnO半导体能带结构的同时,通过负载一定量的g-C₃N₄以降低光生电子-空穴对的复合速率和反应过程中ZnO的光腐蚀,增强催化剂的光催化活性和稳定性.
本文首先合成前驱体Zn(OH)F,然后焙烧三聚氰胺和Zn(OH)F的混合物得到g-C₃N₄/V_o-ZnO复合催化剂,并采用电子顺磁共振波谱(EPR)、紫外-可见光谱(UV-vis)、高分辨透射电镜(HRTEM)和傅里叶变换红外光谱(FT-IR)等表征了它们的结构及其性质. EPR结果表明,ZnO焙烧后具有一定浓度的氧空位,导致其禁带宽度由3.24eV降至3.09eV,因而提高了ZnO对可见光的吸收效率.UV-vis结果显示,V_o-ZnO复合g-C₃N₄后对可见光的吸收显著增强.HRTEM和FT-IR结果均表明,g-C₃N₄纳米片和V_o-ZnO颗粒之间通过共价键形成了强耦合,这对g-C₃N₄/V_o-ZnO复合催化剂中光生载流子的传送和光生电子-空穴对的有效分离起到重要作用.可见光催化降解甲基橙(MO)和腐殖酸(HA)的实验进一步证明,g-C₃N₄/V_o-ZnO复合材料具有较好的光催化活性,优于单一的g-C₃N₄或V_o-ZnO材料.同时还发现,g-C₃N₄的负载量对光催化活性有显著影响,当氮化碳的负载量为1wt%时,所制材料具有最高的光催化活性:可见光照射60min后,MO降解率可达到93%,HA降解率为80%.复合材料光催化活性的增强一方面是因为氧空位的形成减小了ZnO的禁带宽度,使得ZnO对可见光的吸收能力大大增强;另一方面,g-C₃N₄和V_o-ZnO的能带符合了Z型催化机理所需的有效能带匹配,使得光生电子-空穴对得到了有效的分离,从而提高了光催化活性.
降解MO的循环实验表明,g-C₃N₄/V_o-ZnO催化剂具有很好的稳定性且不容易发生光腐蚀.与此同时,我们对比了用不同方法制备的g-C₃N₄/ZnO材料的催化性能.结果显示,本文制备的g-C₃N₄/V_o-ZnO复合材料具有更好的降解效率.总体而言,对于降解有机污染物,g-C₃N₄/V_o-ZnO可能是一个更为有效可行的催化体系.此外,本文也为设计与制备其他新型光催化剂提供了一条新的思路.

关键词: 氧空位氧化锌, 石墨化氮化碳, 复合光催化剂, 光降解, Z型

Abstract:

With the objectives of enhancing the stability, optical properties and visible-light photocatalytic activity of photocatalysts, we modified oxygen vacancy-rich zinc oxide (V_o-ZnO) with graphitic carbon nitride (g-C₃N₄). The resulting g-C₃N₄/V_o-ZnO hybrid photocatalysts showed higher visible-light photocatalytic activity than pure V_o-ZnO and g-C₃N₄. The hybrid photocatalyst with a g-C₃N₄ content of 1 wt% exhibited the highest photocatalytic degradation activity under visible-light irradiation (λ ≥ 400 nm). In addition, the g-C₃N₄/V_o-ZnO photocatalyst was not deactivated after five cycles of methyl orange degradation, indicating that it is stable under light irradiation. Finally, a Z-scheme mechanism for the enhanced photocatalytic activity and stability of the g-C₃N₄/V_o-ZnO hybrid photocatalyst was proposed. The fast charge separation and transport within the g-C₃N₄/V_o-ZnO hybrid photocatalyst were attributed as the origins of its enhanced photocatalytic performance.

Key words: Oxygen deficient zinc oxide, Graphitic carbon nitride, Hybrid photocatalysts, Photodegradation, Z-scheme

刘亚男, 王瑞霞, 杨正坤, 杜虹, 姜一帆, 申丛丛, 梁况, 徐安武. Z型复合催化剂g-C₃N₄/V_o-ZnO光催化活性的研究[J]. 催化学报, 2015, 36(12): 2135-2144.

Yanan Liu, Ruixia Wang, Zhengkun Yang, Hong Du, Yifan Jiang, Congcong Shen, Kuang Liang, Anwu Xu. Enhanced visible-light photocatalytic activity of Z-scheme graphitic carbon nitride/oxygen vacancy-rich zinc oxide hybrid photocatalysts[J]. Chinese Journal of Catalysis, 2015, 36(12): 2135-2144.

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Z型复合催化剂g-C₃N₄/V_o-ZnO光催化活性的研究

Enhanced visible-light photocatalytic activity of Z-scheme graphitic carbon nitride/oxygen vacancy-rich zinc oxide hybrid photocatalysts

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