Cu2O/ZnO的形貌可控制备及光催化性能

doi:10.7503/cjcu20160502

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (2): 267.doi: 10.7503/cjcu20160502

Cu₂O/ZnO的形貌可控制备及光催化性能

李如^1,², 于良民¹, 闫雪峰¹(), 江涛³

1. 中国海洋大学海洋化学理论与工程技术教育部重点实验室, 青岛 266100
2. 纤维新材料与现代纺织国家重点实验室培育基地, 青岛 266071
3. 中国海洋大学医药学院, 青岛 266003

收稿日期:2016-07-13 出版日期:2017-02-10 发布日期:2017-01-16
作者简介:联系人简介: 闫雪峰, 男, 博士, 副教授, 主要从事环境友好型海洋防污涂料研究. E-mail: yanxuefeng@ouc.edu.cn
基金资助:
国家海洋公益性项目(批准号: 201005028-2)、国家自然科学基金(准批号: 51102219, 51342008)、国家重点科技支撑计划项目(批准号: 2012BAB15B02)、中央高校基本科研基金(批准号: 201113024, 201313042)、国家“八六三”计划项目(批准号: 2010AA09Z203, 2010AA065104)和青岛市博士后基金(批准号: 861605040072)资助

Morphology-controlled Preparation and Photocatalytic Properties of Cu₂O/ZnO Microstructures^†

LI Ru^1,², YU Liangmin¹, YAN Xuefeng^1,^*(), JIANG Tao³

1. Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education,Ocean University of China, Qingdao 266100, China
2. Growing Base for State Key Laboratory of Fiber Materials and Modern Textile, Qingdao 266071, China
3. School of Medicine and Pharmacy, Ocean University of China, Qingdao 266003, China

Received:2016-07-13 Online:2017-02-10 Published:2017-01-16
Contact: YAN Xuefeng E-mail:yanxuefeng@ouc.edu.cn
Supported by:
† Supported by the Nonprotit Research Project for the State Oceanic Administration, China(No.201005028-2), the National Natural Science Foundation of China(No.51102219, 51342008), the National Key Technology R & D Program, China(No.2012BAB15B02), the Fundamental Research Funds for the Central Universities, China(Nos.201113024, 201313042), the National High Technology Research and Development Program of China(Nos.2010AA09Z203, 2010AA065104), and the Research Fund for the Postdoctor of Qingdao, China(No.861605040072)

摘要/Abstract

摘要：

以CuSO₄和ZnCl₂为原料, 采用温和的液相还原法制备得到Cu₂O/ZnO微米结构高效光催化剂. 研究了不同[Cu²⁺]/[Zn²⁺]比条件下所得Cu₂O/ZnO复合物的形貌和光催化活性. 通过5.5 h的光照, Cu₂O/ZnO光催化剂对甲基橙染料的降解率为(77.5±0.1)%. 将多形貌Cu₂O/ZnO复合物作为阳极, 铂片作为对电极, 中间注入甲基橙溶液, 组装“三明治”结构拟电池, 研究了复合物的光降解机制.

关键词: 光催化剂, 多形貌, Cu₂O/ZnO微米结构, 甲基橙

Abstract:

The cuprous oxide/zinc oxide(Cu₂O/ZnO) microstructure were prepared by a mild solution strategy. The integration of polymorphic Cu₂O with wurtzite ZnO is a facile approach of elevating photocatalytic activity toward methyl orange degradation. The morphology and photocatalytic activity were investigated by adjusting Cu²⁺/Zn²⁺ ratio. Nearly 77.5% of methyl orange was photodegradated over Cu₂O/ZnO photocatalyst after 5.5 h light irradiation. The potential photodegradation mechanism was demonstrated by designing a pseudo cell comprised of polymorphic Cu₂O/ZnO anode, Pt counter electrode and sandwiched methyl orange solution.

Key words: Photocatalyst, Polymorphology, Cu₂O/ZnO microstructure, Methyl orange

中图分类号:

O644
O614.1

TrendMD:

李如, 于良民, 闫雪峰, 江涛. Cu₂O/ZnO的形貌可控制备及光催化性能. 高等学校化学学报, 2017, 38(2): 267.

LI Ru, YU Liangmin, YAN Xuefeng, JIANG Tao. Morphology-controlled Preparation and Photocatalytic Properties of Cu₂O/ZnO Microstructures^†. Chem. J. Chinese Universities, 2017, 38(2): 267.

图/表 12

Fig.1 Experimental setup used for photocatalytic experiments1. Cooling water nozzle; 2. snorkel; 3. reactor; 4. magnetic force stirrer; 5. insert type long Hg lamp; 6. quartz cool trap; 7. condensation tube; 8. sample tap; 9. reactor stand.

Fig.2 SEM images of Cu2O/ZnO photocatalysts synthesized at various [Cu2+]/[Zn2+] ratios[Cu2+]/[Zn2+]: (A) 1:0.025; (B) 1:0.05; (C) 1:0.15; (D) 1:0.18; (E) 1:0.25; (F) 1:0.30; (G) 1:0.40;(H) 1:0.50; (I) 1:1.00.

Fig.3 HRTEM image(A) and the corresponding FFT pattern(B) of Cu2O/ZnO microstructure synthesized at [Cu2+]/[Zn2+]=1:0.50

Fig.4 XRD patterns of the pristine Cu2O and various Cu2O/ZnOa. Zn2O; b. Cu2O; c. Cu2O/ZnO-1:0.025; d. Cu2O/ZnO-1:0.05; e. Cu2O/ZnO-1:0.015; f. Cu2O/ZnO-1:0.25; g. Cu2O/ZnO-1:0.50; h. Cu2O/ZnO-1:1.10.

Table 1 Structural parameters extracted from XRD patterns and photocatalytic results of different photocatalysts

Sample	β	2θ/(°)	Crystallite size/nm	Δd/d	S_BET/(m²·g^-1)	Degradation rate(%)	R²
Cu₂O	0.0029	36.46	49.82	0.0022		37.3±0.1	0.989
ZnO						38.0±0.2	0.955
Cu₂O/ZnO-1:0.025	0.0025	36.48	57.79	0.0019	2.12	33.2±0.1	0.969
Cu₂O/ZnO-1:0.05	0.0027	36.48	53.51	0.0020	7.61
Cu₂O/ZnO-1:0.15	0.0028	36.55	51.61	0.0021
Cu₂O/ZnO-1:0.25	0.0032	36.56	45.16	0.0024		41.4±0.1	0.936
Cu₂O/ZnO-1:0.30	0.0033	36.55	43.79	0.0025	6.66	41.6±0.1	0.990
Cu₂O/ZnO-1:0.40	0.0034	36.54	42.50	0.0026	43.61	55.0±0.2	0.831
Cu₂O/ZnO-1:0.50	0.0037	36.53	39.05	0.0028	62.11	77.5±0.1	0.806
Cu₂O/ZnO-1:0.80	0.0035	36.51	41.28	0.0027
Cu₂O/ZnO-1:1.00	0.0025	36.48	57.79	0.0019	61.54	30.5±0.2	0.911

Fig.5 XPS survey spectra(A) and Cu2p XPS spectra(B) for bare Cu2O(a) and Cu2O/ZnO-1:0.50(b)

Fig.6 UV-Vis diffuse reflectance spectra of bare Cu2O particles(a) and Cu2O/ZnO-1:0.50(b)

Fig.7 Determination of the band gap energy of pure ZnO(A), pure Cu2O(B), and Cu2O/ZnO synthesized at [Cu2+]/[Zn2+]=1:0.05(C), 1:0.15(D), 1:0.30(E), 1:0.50(F), 1:1.0(G)

Fig.8 A-t(A) and -ln(c/c0)-t(B) plots for the photodegradation of MO over different photocatalysts

Fig.9 Schematic diagram for the potential photocatalytic mechanism by Cu2O/ZnO

Fig.10 Schematic of a pseudo cell for MO degradation by Cu2O/ZnO photocatalyst

Fig.11 Transient photocurrent responses(A) and Bode EIS plots(B) of pseudo cells with different Cu2O/ZnO photoanodes a. Cu2O/ZnO-1:0.25; b. Cu2O/ZnO-1:0.30; c. Cu2O/ZnO-1:0.40; d. Cu2O/ZnO-1:0.50; e. Cu2O/ZnO-1:0.80; f. Cu2O/ZnO-1:1.00.

参考文献 35

[1]	Schüler E., Gustavsson A. K., Hertenberger S., Sattler K., Sol. Energy,2013, 96, 220—226
[2]	Li X. H., Chen G. Y., Yang L. B., Jin Z., Liu J. H., Adv. Funct. Mater., 2010, 20, 2815—2824
[3]	Luo Z. W., Jiang H., Li D., Hu L. Z., Geng W. H., Wei P., Ouyang P. K., RSC Adv., 2014, 4, 17797—17804
[4]	Diab M., Moshofsky B., Plante I. J. L., Mokari T., J. Mater. Chem., 2011, 21, 11626—11630
[5]	Zhao H. Y., Wang Y. F., Zeng J. H., Cryst. Growth Des., 2008, 8, 3731—3734
[6]	Younsi M., Aider A., Bouguelia A., Trari M., Sol. Energy,2005, 78, 574—580
[7]	Siegfried M. J., Choi K. S., Adv. Mater., 2004, 16, 1743—1746
[8]	Xu H., Wang W., Zhu W., J. Phys. Chem. B,2006, 110, 13829—13834
[9]	White B., Yin M., Hall A., Le D., Stolbov S., Rahman T., Turro N., O’Brien S., Nano Lett., 2006, 6, 2095—2098
[10]	Sui Y. M., Zeng Y., Fu L. L., Zheng W. T., Li D. M., Liu B. B., Zou B., RSC Adv., 2013, 3, 18651—18660
[11]	Zhang H., Zhu Q., Zhang Y., Wang Y., Zhao L., Yu B., Adv. Funct. Mater., 2007, 17, 2766—2771
[12]	Paracchino A., Laporte V., Sivula K., Grätzel M., Thimsen E., Nat. Mater., 2011, 10, 456—461
[13]	Sivagami K., Krishna R. R., Swaminathan T., Sol. Energy,2014, 103, 488—493
[14]	Wu S. X., Yin Z. Y., He Q. Y., Lu G., Zhou X. Z., Zhang H., J. Mater. Chem., 2011, 21, 3467—3470
[15]	Han Z. Z., Ren L. L, Cui Z. H., Chen C. Q., Pan H. B., Chen J. Z., Appl. Catal. B,2012, 126, 298—305
[16]	Morales-Flores N., Pal U., Mora E. S., Appl. Catal. A,2011, 394, 269—275
[17]	Jing L. Q., Wang B. Q., Xin B. F., Li S. D., Shi K. Y., Cai W. M., Fu H. G., J. Solid State Chem., 2004, 177, 4221—4227
[18]	Forzani E. S., Lu D. L., Leright M. J., Aguilar A. D., Tsow F., Iglesias R. A., Zhang Q., Lu J., Li J. H., Tao N. J., J. Am. Chem. Soc., 2009, 131, 1390—1391
[19]	Li Q. H., Jin X., Yang X. W., Chen C. Y., Chen Z. H., Qin Y. C., Wei T. H, Sun W. F., Appl. Catal., B,2015, 162, 524—531
[20]	Jin X., Sun W. F., Chen Z. H., Wei T. H., Chen C. Y., He X. D., Yuan Y. B., Li Y., Li Q. H., ACS Appl. Mater. Interfaces,2014, 6, 8771—8781
[21]	Li R., Yu L. M., Yan X. F., Tang Q. W., RSC Adv., 2015, 5, 11917—11924
[22]	Jing L. Q., Sun X. J., Xin B. F., Wang B. Q., Cai W. M., Fu H. G., J. Solid State Chem., 2004, 177, 3375—3382
[23]	Zhang Q. H., Gao L., Guo J. K., Appl. Catal. B-Environ., 2000, 26, 207—215
[24]	Lin L., Chai Y. C., Yang Y. C., Wang X. He D. N., Tang Q. W., Ghoshroy S., Int. J. Hydrogen Energy,2013, 38, 2634—2640
[25]	Kortum G. Reflectance Spectroscopy; Springer-Verlag: Berlin, 1969, 15—21
[26]	Zhang W.G., Halasyamani P. S., Cryst. Growth Des., 2012, 12, 2127—2132
[27]	Wodka D., Bielanska E., Socha R.P., Elzbeciak-Wodka M., Gurgul J., Nowak P., Warszyński P., Kumakiri I., ACS Appl. Mater. Interfaces, 2010, 2, 1945—1955
[28]	Xu C., Cao L. X., Su G., Liu W., Liu H., Yu Y. Q., Qu X. F., J. Hazard. Mater., 2010, 176, 807—813
[29]	Li R., Yan X. F., Yu L. M., Zhang Z. M., Tang Q. W., Pan Y. P., Cryst. Eng. Comm., 2013, 15, 10049—10058
[30]	Huang L., Peng F., Wang H. J., Yu H., Li Z., Catal. Commun., 2009, 10, 1839—1843
[31]	Ullah R., Dutta J., J. Hazard. Mater., 2008, 156, 194—200
[32]	Li D. P., Dai K., Lv J. L., Lu L. H., Liang C. H., Zhu G. P., Materials Letters,2015, 150, 48—51
[33]	Suib S. L., Segal S. R., Chem. Mater., 1997, 9, 2526—2532
[34]	Cai H. Y., Chen X. X., Li Q. H., He B. L., Tang Q. W., Appl. Surf. Sci., 2013, 284, 837—842
[35]	Lin L., Yang Y. C., Men L., Wang X. He D. N., Chai Y. C., Zhao B., Ghoshroy S., Tang Q. W., Nanoscale,2013, 5, 588—593

Cu₂O/ZnO的形貌可控制备及光催化性能

Morphology-controlled Preparation and Photocatalytic Properties of Cu₂O/ZnO Microstructures^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 35

相关文章 15

编辑推荐

Metrics

本文评价

[1]	杨晓梅, 吴强, 郭茹, 叶凯波, 薛屏, 王晓中, 赖小勇 . 超薄骨架有序介孔CdS/NiS的制备及光催化产氢性能[J]. 高等学校化学学报, 2021, 42(5): 1581.
[2]	李闪闪, 赵文娟, 李辉, 方千荣. 偶氮苯功能化的光响应共价有机框架材料[J]. 高等学校化学学报, 2020, 41(6): 1384.
[3]	赵孟欣, 孟哲, 李和平, 马宗琴, 詹海鹃, 刘万毅. 氧化石墨烯调控钼酸铋在可见光下选择性光催化降解环境水中的抗生素[J]. 高等学校化学学报, 2020, 41(11): 2479.
[4]	何鹏琛, 周健, 周阿武, 豆义波, 李建荣. MOFs基材料在光催化CO₂还原中的应用[J]. 高等学校化学学报, 2019, 40(5): 855.
[5]	甘露,董永春. 不同结构二元羧酸改性棉纤维铁配合物的制备和光催化性能[J]. 高等学校化学学报, 2019, 40(10): 2205.
[6]	张晶, 董玉明, 刘湘, 李和兴. Z型光催化剂Sb₂WO₆/g-C₃N₄的制备及光催化性能[J]. 高等学校化学学报, 2019, 40(1): 123.
[7]	丛日敏, 于怀清, 罗运军, 李蛟, 王卫伟, 李秋红, 孙武珠, 司维蒙, 张华. Bi₂₅FeO₄₀/α-Fe₂O₃复合纳米颗粒光催化剂的制备与性能[J]. 高等学校化学学报, 2018, 39(4): 629.
[8]	高晓明, 代源, 费娇, 张裕, 付峰. n-p异质结型CdS/BiOBr复合光催化剂的制备及性能[J]. 高等学校化学学报, 2017, 38(7): 1249.
[9]	张春磊, 黄丹娅, 孙明慧, 欧阳逸挺, 王超, 李小云, 陈丽华, 苏宝连. 非金属元素掺杂及三维花状多级结构对介孔TiO₂可见光催化性能的促进作用[J]. 高等学校化学学报, 2017, 38(3): 471.
[10]	陈颖, 赵宇, 李静, 韩星月. 共模板法一步合成绣球状BiOCl/Br固溶体光催化剂[J]. 高等学校化学学报, 2017, 38(11): 2045.
[11]	安会琴, 于育才, 闫琳, 吴婷婷, 李晓峰, 贺晓凌, 赵莉芝, 黄唯平. 赖氨酸辅助高分散金粒子修饰氮掺杂TiO₂纳米管催化剂的合成及光催化性能[J]. 高等学校化学学报, 2016, 37(11): 2034.
[12]	孙代红, 刘华荣, 李睿哲. 空心锌铬铁氧体/二氧化钛复合物的制备及去污性能[J]. 高等学校化学学报, 2016, 37(11): 2050.
[13]	卢勇宏, 吴平霄, 黄俊毅, 陈理想, 朱能武, 党志. 碱化辅助水热法制备高活性CdZnS可见光催化剂[J]. 高等学校化学学报, 2015, 36(8): 1563.
[14]	李星星, 黄在银, 范高超, 吴烨楠, 谭学才. 光量热法初探甲基橙光催化原位降解过程[J]. 高等学校化学学报, 2014, 35(7): 1480.
[15]	揣宏媛, 周德凤, 朱晓飞, 杨国程, 李朝辉. MoO₃/V₂O₅异质结构材料的静电纺丝法制备及光催化性能[J]. 高等学校化学学报, 2014, 35(5): 941.