磁控溅射制备Cu2O和Cu2O/TiO2复合膜及其光催化活性

doi:10.3724/SP.J.1077.2012.00395

无机材料学报 ›› 2012, Vol. 27 ›› Issue (4): 395-399.DOI: 10.3724/SP.J.1077.2012.00395 CSTR: 32189.14.SP.J.1077.2012.00395

磁控溅射制备Cu₂O和Cu₂O/TiO₂复合膜及其光催化活性

刘灿, 魏子栋, 张骞, 胡宝山, 齐学强, 陈四国, 丁炜

(重庆大学输配电装备及系统安全与新技术国家重点实验室, 化学化工学院, 重庆 400044)

收稿日期:2011-06-11 修回日期:2011-10-03 出版日期:2012-04-10 网络出版日期:2012-03-12
作者简介:刘灿(1988-), 男, 硕士研究生. E-mail: liucan111@yahoo.com.cn
基金资助:
国家自然科学基金(20806096);国家重点实验室项目(2007DA10512711211);中央高校基本科研业务费专项基金(CDJXS10221141和11132229)

Photocatalytic Activity of Cu₂O and Bilayer Cu₂O/TiO₂ Films Prepared by Magnetron Sputtering

LIU Can, WEI Zi-Dong, ZHANG Qian, HU Bao-Shan, QI Xue-Qiang, CHEN Si-Guo, DING Wei

(State Key Laboratory of Power Transmission Equipment & System Security and New Technology, School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China)

Received:2011-06-11 Revised:2011-10-03 Published:2012-04-10 Online:2012-03-12
About author:LIU Can. E-mail: liucan111@yahoo.com.cn
Supported by:
National Natural Science Foundation of China (20806096);The Program of State Key Laboratory (2007DA10512711211);Fundamental Research Funds for the Central Universities (Nos;CDJXS10221141 and 11132229)

摘要/Abstract

摘要：

采用直流反应磁控溅射的方法在普通玻璃上沉积得到Cu₂O、TiO₂和Cu₂O/TiO₂复合薄膜. 用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和X射线能谱仪(EDS)对薄膜的晶体结构、表面形态和薄膜元素组成进行了分析. XRD结果表明, 当反应溅射时间为5 min时, Cu₂O薄膜由单一的(111)晶面组成; 反应时间的延长促进了Cu₂O(110)和(220)晶面的生长. 通过计算得出Cu₂O(111)更有利于对O₂的吸附. 进一步使用氙灯作为光源, 用薄膜对亚甲基蓝(MB)的降解率来表征光催化活性. 结果表明, Cu₂O/TiO₂复合薄膜的光催化效果随着Cu₂O含量的增加升高而后降低, 当Cu₂O含量为2.6mol%时, 光催化活性最高. 光催化效率的提高主要归因于Cu₂O的加入引起光生电子-空穴的分离, 而过量的Cu₂O会延长光生电子迁移到Cu₂O/TiO₂界面和空穴迁移至表面所需要的时间, 使电子和空穴复合的几率增大, 从而降低了量子效率.

关键词: 磁控溅射, 氧化亚铜, 复合薄膜, 光催化

Abstract:

Cu₂O, TiO₂ and composite Cu₂O/TiO₂ films were deposited on slide glass by direct current (DC) reactive magnetron sputtering. X-ray diffraction (XRD), scanning electron microscope (SEM) and energy-dispersive spectrometry (EDS) were applied to characterize crystal structure, morphology and composition of the films, respectively. Photocatalytic activity was evaluated by the degradation of methylene blue (MB) with Xenon lamp. XRD results show that besides the initial (111) crystal plane at sputtering time of 5 min, (110) and (220) crystal planes gradually develop on the Cu₂O film with the increase of sputtering time. Our calculation result indicates that (111) crystal plane is more beneficial to absorption of O₂than other crystal planes. The photocatalytic activity of the Cu₂O/TiO₂ composite films first increases with increasing Cu₂O-deposited content, and then reaches the highest value when the deposited content of Cu₂O is 2.6mol%, and successively undergoes a drop. The enhancement of the photocatalytic activity is mainly attributed to alleviate the recombination of electron-hole pairs. Excessive Cu₂O will prolong the time for transferring of electrons to Cu₂O/TiO₂interface and holes to surface, which increases the recombination probability of electrons and holes, and thus reduces the quantum efficiency.

Key words: magnetron sputtering, cuprous oxide, composite films, photocatalytic

中图分类号:

O643

刘灿, 魏子栋, 张骞, 胡宝山, 齐学强, 陈四国, 丁炜. 磁控溅射制备Cu₂O和Cu₂O/TiO₂复合膜及其光催化活性[J]. 无机材料学报, 2012, 27(4): 395-399.

LIU Can, WEI Zi-Dong, ZHANG Qian, HU Bao-Shan, QI Xue-Qiang, CHEN Si-Guo, DING Wei. Photocatalytic Activity of Cu₂O and Bilayer Cu₂O/TiO₂ Films Prepared by Magnetron Sputtering[J]. Journal of Inorganic Materials, 2012, 27(4): 395-399.

图/表 8

图1 不同溅射时间获得的Cu2O的XRD图谱

Fig. 1 XRD patterns of Cu2O after sputtened for different time

图2 不同溅射时间获得的Cu2O薄膜的光催化活性

Fig. 2 Photocatalytic activity of Cu2O film after deposited for different time

图3 Cu2O(110)晶面(a)和(111)晶面(b)表面结构模型图

Fig. 3 Structural models for Cu2O (110) (a) and (111) (b) surface

图4 Cu2O(110)晶面(a)和(111)晶面(b)吸附O2后的结构模型

Fig. 4 Structural model for Cu2O (110) (a) and (111) (b) surface after O2 adsorption

Table 1 Adsorption parameter of O2 on different crystal planes of Cu2O

	E_abs/(kJ?mol^-1)	d_Cu—O/nm	d_O—O/nm
O₂/Cu₂O(110)	-44.78	0.2383	0.1225
O₂/Cu₂O(111)	-157.45	0.1821	0.1225

图5 TiO2和Cu2O/TiO2复合薄膜的XRD图谱

Fig. 5 XRD patterns of TiO2 and Cu2O/TiO2 composite film Sputtering Cu2O for 6 s

图6 TiO2(a)和Cu2O/TiO2(b)复合薄膜的SEM照片

Fig. 6 SEM images of TiO2 (a) and Cu2O/TiO2 composite films (b)

图7 Cu2O/TiO2复合薄膜中Cu2O含量对亚甲基蓝(MB)降解率的影响

Fig. 7 Dependence of MB degradation rate on Cu2O content in Cu2O/TiO2 composite film

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磁控溅射制备Cu₂O和Cu₂O/TiO₂复合膜及其光催化活性

Photocatalytic Activity of Cu₂O and Bilayer Cu₂O/TiO₂ Films Prepared by Magnetron Sputtering

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