核壳结构CdS/CuS纳米复合材料的制备及光催化性能

doi:10.7503/cjcu20180596

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (3): 489-498.doi: 10.7503/cjcu20180596

核壳结构CdS/CuS纳米复合材料的制备及光催化性能

张克杰^1,²(), 李宇¹, 夏源¹, 韩烁¹, 曹静¹, 王瀚漾¹, 罗文韬¹, 周志萍³

1. 南京工程学院材料科学与工程学院, 南京211167
2. 江苏省先进结构材料与应用技术重点实验室, 南京 211167
3. 南京大学化学化工学院, 南京 210023

收稿日期:2019-08-27 出版日期:2019-01-24 发布日期:2019-01-24
作者简介:
联系人简介: 张克杰, 女, 博士, 副教授, 主要从事无机纳米复合材料研究. E-mail: zhangkejie2003@163.com
基金资助:
国家自然科学基金(批准号: 21603101)和南京工程学院创新基金(批准号: CKJA201303, TB201802035, TB201802038)资助.

Synthesis and Photocatalytic Performance of CdS/CuS Core-shell Nanocomposites^†

ZHANG Kejie^1,^2,^*(), LI Yu¹, XIA Yuan¹, HAN Shuo¹, CAO Jing¹, WANG Hanyang¹, LUO Wentao¹, ZHOU Zhiping³

1. School of Materials Science and Engineering, Nanjing Institute of Technology, Nanjing 211167, China
2. Jiangsu Key Laboratory of Advanced Structural Materials and Application Technology, Nanjing 211167, China
3. School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China

Received:2019-08-27 Online:2019-01-24 Published:2019-01-24
Contact: ZHANG Kejie E-mail:zhangkejie2003@163.com
Supported by:
† Supportted by the National Natural Science Foundation of China(No.21603101) and the Innovation Fund of Nanjing Institute of Technology, China(Nos.CKJA201303, TB201802035, TB201802038).

摘要/Abstract

摘要：

以乙酸镉、 2-巯基苯并噻唑、硫化钠和氯化铜为原料, 依次利用液相热分解与离子吸附法, 改变CdS晶化时间及含量, 制备了4种CdS/CuS纳米复合材料. 研究结果表明: CdS/CuS纳米复合材料呈类球形核壳结构, 改变CdS晶化时间可以控制CdS/CuS纳米复合材料粒径大小; CdS的晶化时间为10 min, CdS与CuS摩尔比为4∶1的纳米复合材料光催化活性最佳, 25 min内对RhB和MB的降解效率均达到99%.

关键词: 硫化镉/硫化铜, 纳米复合材料, 光催化, 降解效率

Abstract:

Four CdS/CuS core-shell nanocomposite samples with different molar ratios of CdS to CuS were synthesized via liquid-phase thermal decomposition and ion adsorption method under different crystallization time of CdS, using cadmium acetate, 2-mercaptobenzothiazole, sodium sulfide and cupric chloride as the raw materials. The experimental results indicated that the samples were spherical nucleus-like structures and their particle size was controllable with the crystallization time of CdS. The degradation efficiencies of rhodamine B(RhB) and methylene blue(MB) both reached about 99% when the molar ratio of CdS to CuS was 4∶1 and the crystallization time of CdS was 10 min. The method of ion adsorption makes CuS fully coat on the surface of CdS, forming effective core-shell structure and obviously improving the photocatalytic performance of CdS.

Key words: CdS/CuS, Nanocomposite, Photocatalysis, Degradation efficiency

中图分类号:

O644
O613.51

张克杰, 李宇, 夏源, 韩烁, 曹静, 王瀚漾, 罗文韬, 周志萍. 核壳结构CdS/CuS纳米复合材料的制备及光催化性能[J]. 高等学校化学学报, 2019, 40(3): 489-498.

ZHANG Kejie,LI Yu,XIA Yuan,HAN Shuo,CAO Jing,WANG Hanyang,LUO Wentao,ZHOU Zhiping. Synthesis and Photocatalytic Performance of CdS/CuS Core-shell Nanocomposites^†[J]. Chemical Journal of Chinese Universities, 2019, 40(3): 489-498.

图/表 12

Fig.1 XRD patterns of CdS/CuS samples(A) a. CdS(10 min)/CuS(3∶1); b. CdS(10 min)/CuS(4∶1); c. CdS(10 min)/CuS(5∶1);d. CdS(1 h)/CuS(4∶1). (B) CdS(10 min)/CuS(4∶1).

Fig.2 XPS spectra of CdS(10 min)/CuS(4∶1)(a), CdS(10 min)/CuS(3∶1)(b) and pure CdS(c)(A) Full spectrum; (B) Cd3d; (C) S2p; (D) Cu2p.

Fig.3 SEM images of different CdS/CuS samples(A) CdS(10 min)/CuS(4∶1); (B) CdS(1 h)/CuS(4∶1); (C) CdS(10 min)/CuS(5∶1); (D) CdS(10 min)/CuS(3∶1).

Fig.4 TEM(A) and HRTEM(B) images of CdS(10 min)/CuS(4∶1)

Fig.5 UV-Vis DRS spectra(A) and corresponding Tauc’s plots(B) of different samples

Fig.6 c/c0-t(A) and -ln(c/c0)-t(B) plots of RhB in the presence of different photocatalysts

Fig.7 c/c0-t(A) and -ln(c/c0)-t(B) plots of MB in the presence of different photocatalysts

Fig.8 c/c0-t(A) and -ln(c/c0)-t(B) plots of MO in the presence of CdS(10 min)/CuS(4∶1)

Fig.9 Degradation profiles of different dyes in the presence of different photocatalysts(A) and the photocatalytic efficiency of different photocatalysts for different dyes within 35 min(B)(A)CdS(1 h)/CuS(4∶1), MB;CdS(10 min)/CuS(3∶1), RhB; CdS(10 min)/CuS(5∶1), RhB;CdS(10 min)/CuS(4∶1), RhB;CdS(10 min)/CuS(4∶1), MB. (B) a. CdS(10 min)/CuS(3∶1), RhB; b. CdS(10 min)/CuS(5∶1), RhB; c. CdS(10 min)/CuS(4∶1), RhB; d. CdS(10 min)/CuS(4∶1), MB; e. CdS(1 h)/CuS(4∶1), MB.

Table 1 Kinetic equation of dyes degradation by different photocatalysts

Sample	Dye	First-order kinetic equation	R²
CdS(10 min)/CuS(3∶1)	RhB	-ln(c/c₀)=0.081t+1.437	0.878
CdS(10 min)/CuS(4∶1)	RhB	-ln(c/c₀)=0.157t+0.757	0.998
CdS(10 min)/CuS(5∶1)	RhB	-ln(c/c₀)=0.025t+2.489	0.995
CdS(10 min)/CuS(4∶1)	MB	-ln(c/c₀)=0.115t+1.871	0.954
CdS(1 h)/CuS(4∶1)	MB	-ln(c/c₀)=0.020t+0.488	0.947

Scheme 1 Preparation of CdS/CuS core-shell composites by using Cd(MBT)2 as the precursor

Fig.10 Schematic presentation of the photocatalytic mechanism in the CdS/CuS system under light illumination

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核壳结构CdS/CuS纳米复合材料的制备及光催化性能

Synthesis and Photocatalytic Performance of CdS/CuS Core-shell Nanocomposites^†

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核壳结构CdS/CuS纳米复合材料的制备及光催化性能

Synthesis and Photocatalytic Performance of CdS/CuS Core-shell Nanocomposites†

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Synthesis and Photocatalytic Performance of CdS/CuS Core-shell Nanocomposites^†