pn型Cu2O-WO3的制备及光催化性能

doi:10.16085/j.issn.1000-6613.2019-0421

摘要/Abstract

摘要：

采用高温水热法和共沉淀法制备了不同摩尔比的pn型Cu₂O-WO₃复合半导体材料。并利用扫描电子显微镜（SEM）、透射电子显微镜（TEM）和X射线衍射（XRD）对样品的形貌特征和晶格结构进行表征。表征结果显示，复合材料由立方相的Cu₂O和六方相的WO₃组成。与纯WO₃物质相比，Cu₂O-WO₃复合半导体材料的紫外吸收边界发生显著红移，在可见光波长范围内的光吸收明显增强，展示出优良的光电流响应性能。以罗丹明B（RhB）溶液的光降解表征材料的光催化性能的过程中，在可见光下光照8h后，相较于WO₃和Cu₂O仅为22.2%和45.2%的光降解率，摩尔比为1∶2的Cu₂O-WO₃复合物的降解效率达到了90.6%。

关键词: 氧化亚铜, 三氧化钨, 复合材料, 催化剂, 光催化反应

Abstract:

pn-Type Cu₂O-WO₃ composite semiconductor materials with different mole ratios were successfully prepared by high temperature hydrothermal method and coprecipitation method. The morphology and structure of the samples were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The result shows that the composite is composed of cubic phase Cu₂O and hexagonal phase WO₃. In comparison with pure WO₃, the ultraviolet absorption boundary of Cu₂O-WO₃ composite semiconductor material has a significant red shift which enhanced the optical absorption under visible light, showing the good photocurrent response. The photocatalytic activities of the materials were characterized by degradation of rhodamine B (RhB) solution under visible light, and the photodegradation rate of Cu₂O-WO₃ composite with 1∶2 mole ratio reached 90.6%, while those of 22.2% and 45.2% for WO₃ and Cu₂O respectively after 8h light irradiation were obtained.

Key words: cuprous oxide, tungsten trioxide, composites, catalyst, photocatalytic reaction

中图分类号:

O643

王宏智,李骏,姚素薇,张卫国. pn型Cu₂O-WO₃的制备及光催化性能[J]. 化工进展, 2019, 38(12): 5442-5448.

Hongzhi WANG,Jun LI,Suwei YAO,Weiguo ZHANG. Synthesis and photocatalytic properties of pn-type Cu₂O-WO₃[J]. Chemical Industry and Engineering Progress, 2019, 38(12): 5442-5448.

图/表 11

图1 系列Cu2O-WO3复合物的SEM图

图2 Cu2O-WO3-1∶2的TEM和HRTEM图

图3 WO3、Cu2O和Cu2O-WO3的XRD谱图

图4 Cu2O和WO3的Mott-Schottky曲线

图5 WO3和不同摩尔比Cu2O-WO3的光电流-电压曲线a—WO3; b—Cu2O-WO3-1∶4; c—Cu2O-WO3-1∶1; d—Cu2O-WO3-1∶2

图6 WO3和不同摩尔比例Cu2O-WO3复合物的紫外-可见吸收光谱a—WO3; b—Cu2O-WO3-1∶4; c—Cu2O-WO3-1∶1; d—Cu2O-WO3-1∶2

图7 无催化剂、WO3、Cu2O和Cu2O-WO3-1∶2的光降解性能曲线

图8 样品在可见光下降解RhB溶液的动力学曲线

表1 光降解RhB溶液的动力学常数和相关系数

催化材料	反应速率常数k/h^-1	线性相关系数R
Cu₂O	0.07722	0.99129
WO₃	0.03479	0.99651
Cu₂O-WO₃	0.22958	0.99198

表2 比较不同材料的光降解RhB性能

材料	光源	光降解率/%	参考文献
Cu₂O-WO₃	500W Xe灯	90.6	本文
15%g-C₃N₄/LaFeO₃	200W Xe灯	58.4	[29]
g-C₃N₄/Fe₃O₄/NiWO₄	50W LED灯	87	[30]
N-doped KTiNbO₅/g-C₃N₄	500W Xe灯	89.9	[31]
Ag₂CO₃/Ag/WO₃	300W Xe 灯	89.3	[32]
TiO₂ NTs/Cu₂O	500W Xe灯	61.83	[33]

图9 Cu2O-WO3复合材料电荷转移过程示意图

参考文献 35

1	FU L, CAI W, WANG A, et al. Photocatalytic hydrogenation of nitrobenzene to aniline over tungsten oxide-silver nanowires[J]. Materials Letters, 2015, 142: 201-203.
2	LI S, SHELAR D P, HOU C C, et al. WO₃ nanospheres with improved catalytic activity for visible light induced cross dehydrogenative coupling reactions[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2018, 363: 44-50.
3	廖永进, 张亚平, 朱一闻, 等. WO₃掺杂对V₂O₅/TiO₂-SnO₂催化剂NH₃选择性催化还原NO_x的影响[J]. 化工进展, 2017, 36(3): 951-956.
	LIAO Y J, ZHANG Y P, ZHU Y W, et al. Influence of WO₃ doping on properties of V₂O₅/TiO₂-SnO₂ catalysts for selective catalytic reduction of NO_x by NH₃[J]. Chemical Industry and Engineering Progress, 2017, 36(3): 951-956.
4	MOON H G, SHIM Y S, KIM D H, et al. Self-activated ultrahigh chemosensitivity of oxide thin film nanostructures for transparent sensors[J]. Scientific Reports, 2012, 2: 588.
5	KAVITHA V S, SURESH S, CHALANA S R, et al. Luminescent Ta doped WO₃ thin films as a probable candidate for excitonic solar cell applications[J]. Applied Surface Science, 2019, 466: 289-300.
6	WANG S, FAN W, LIU Z, et al. Advances on tungsten oxide based photochromic materials: strategies to improve their photochromic properties[J]. Journal of Materials Chemistry C, 2018, 6(2): 191-212.
7	LOU Z Z, ZHU M S, YANG X G, et al. Continual injection of photoinduced electrons stabilizing surface plasmon resonance of non-elemental-metal plasmonic photocatalyst CdS/WO_3-_x for efficient hydrogen generation[J]. Applied Catalysis B: Environmental, 2018, 226: 10-15.
8	WANG J, CHEN Z, ZHAI G, et al. Boosting photocatalytic activity of WO₃ nanorods with tailored surface oxygen vacancies for selective alcohol oxidations[J]. Applied Surface Science, 2018, 462: 760-771.
9	ZHANG Q, DONG R, WU Y, et al. Light-driven Au-WO₃@C janus micromotors for rapid photodegradation of dye pollutants[J]. ACS Applied Materials & Interfaces, 2017, 9(5): 4674-4683.
10	ZHOU H, WEN Z, LIU J, et al. Z-scheme plasmonic Ag decorated WO₃/Bi₂WO₆ hybrids for enhanced photocatalytic abatement of chlorinated-VOCs under solar light irradiation[J]. Applied Catalysis B: Environmental, 2019, 242: 76-84.
11	TORABI M M, NASIRI M, ABEDINI E, et al. Enhanced gas-phase photocatalytic oxidation of n-pentane using high visible-light-driven Fe-doped WO₃ nanostructures[J]. Journal of Environmental Chemical Engineering, 2018, 6(5): 6741-6748.
12	AN X, YU J C, WANG Y, et al. WO₃ nanorods/graphene nanocomposites for high-efficiency visible-light-driven photocatalysis and NO₂ gas sensing[J]. Journal of Materials Chemistry, 2012, 22(17): 8525.
13	TIE L, YU C, ZHAO Y, et al. Fabrication of WO₃ nanorods on reduced graphene oxide sheets with augmented visible light photocatalytic activity for efficient mineralization of dye[J]. Journal of Alloys and Compounds, 2018, 769: 83-91.
14	XIAO T, TANG Z, YANG Y, et al. In situ construction of hierarchical WO₃/g-C₃N₄ composite hollow microspheres as a Z-scheme photocatalyst for the degradation of antibiotics[J]. Applied Catalysis B: Environmental, 2018, 220: 417-428.
15	MART NEZ-GARC A A, VENDRA V K, SUNKARA S, et al. Tungsten oxide-coated copper oxide nanowire arrays for enhanced activity and durability with photoelectrochemical water splitting[J]. Journal of Materials Chemistry A, 2013, 1(48): 15235.
16	SHARMA K, MAITI K, KIM N H,et al. Green synthesis of glucose-reduced graphene oxide supported Ag-Cu₂O nanocomposites for the enhanced visible-light photocatalytic activity[J]. Composites Part B: Engineering, 2018, 138: 35-44.
17	HUANG H, ZHANG J, JIANG L, et al. Preparation of cubic Cu₂O nanoparticles wrapped by reduced graphene oxide for the efficient removal of rhodamine B[J]. Journal of Alloys and Compounds, 2017, 718: 112-115.
18	JAMALI S, MOSHAII A. Improving photo-stability and charge transport properties of Cu₂O/CuO for photo-electrochemical water splitting using alternate layers of WO₃ or CuWO₄ produced by the same route[J]. Applied Surface Science, 2017, 419: 269-276.
19	龙丹, 周俊伶, 时洪民, 等. 氧化亚铜光催化剂性能提升及增强机制的研究进展[J]. 化工进展, 2019, 38(6): 2756-2767.
	LONG D, ZHOU J L, SHI H M, et al. Research progress on the improved performance of cuprous oxide photocatalyst and its enhancement mechanism[J]. Chemical Industry and Engineering Progress, 2019, 38(6): 2756-2767.
20	付星晨, 颜德健, 刘冀锴. 基于氧化亚铜光电极的制备及其光电化学性能的研究进展[J]. 化工进展, 2018, 37(1): 140-148.
	FU X C, YAN D J, LIU J K. Research progress of fabrication and photoelectrochemical properties based on Cu₂O photoelectrodes[J]. Chemical Industry and Engineering Progress, 2018, 37(1): 140-148.
21	GONG H, ZHANG Y, CAO Y, et al. Pt@Cu₂O/WO₃ composite photocatalyst for enhanced photocatalytic water oxidation performance[J]. Applied Catalysis B: Environmental, 2018, 237: 309-317.
22	SHI W, GUO X, CUI C, et al. Controllable synthesis of Cu₂O decorated WO₃ nanosheets with dominant (001) facets for photocatalytic CO₂ reduction under visible-light irradiation[J]. Applied Catalysis B: Environmental, 2019, 243: 236-242.
23	HU C C, NIAN J N, TENG H. Electrodeposited p-type Cu₂O as photocatalyst for H₂ evolution from water reduction in the presence of WO₃[J]. Solar Energy Materials and Solar Cells, 2008, 92(9): 1071-1076.
24	黄颖, 闫常峰, 郭常青, 等. 半导体Z反应光解水制氢的光能转换效率及研究进展[J]. 化工进展, 2014, 33(12): 3221-3229.
	HUANG Y, YANG C F, GUO C Q, et al. Photo conversion efficiency of and research advance in semiconductor Z-scheme photocatalytic water splitting for hydrogen production[J]. Chemical Industry and Engineering Progress, 2014, 33(12): 3221-3229.
25	庄朋强, 肖占文, 朱向东, 等. 钽阳极氧化膜的半导体性研究[J]. 电子元件与材料, 2011, 30(8): 35-39.
	ZHUANG P Q, XIAO Z W, ZHU X D, et al. Study on semiconductor properties of anodic oxide films on tantalum[J]. Electronic Components & Materials, 2011, 30(8): 35-39.
26	ZHANG J, MA H, LIU Z. Highly efficient photocatalyst based on all oxides WO₃/Cu₂O heterojunction for photoelectrochemical water splitting[J]. Applied Catalysis B: Environmental, 2017, 201: 84-91.
27	ZHOU Z, WU Z, XU Q, et al. A solar-charged photoelectrochemical wastewater fuel cell for efficient and sustainable hydrogen production[J]. Journal of Materials Chemistry A, 2017, 5(48): 25450-25459.
28	FANG H, CAO X, YU J, et al. Preparation of the all-solid-state Z-scheme WO₃/Ag/AgCl film on glass accelerating the photodegradation of pollutants under visible light[J]. Journal of Materials Science, 2018, 54(1): 286-301.
29	YE Y, YANG H, WANG X, et al. Photocatalytic, Fenton and photo-Fenton degradation of RhB over Z-scheme g-C₃N₄/LaFeO₃ heterojunction photocatalysts[J]. Materials Science in Semiconductor Processing, 2018, 82: 14-24.
30	MOUSAVI M, HABIBI-YANGJEH A. Integration of NiWO₄ and Fe₃O₄ with graphitic carbon nitride to fabricate novel magnetically recoverable visible-light-driven photocatalysts[J]. Journal of Materials Science, 2018, 53(12): 9046-9063.
31	LIU C, ZHU H, ZHU Y, et al. Ordered layered N-doped KTiNbO₅/g-C₃N₄ heterojunction with enhanced visible light photocatalytic activity[J]. Applied Catalysis B: Environmental, 2018, 228: 54-63.
32	YUAN X, JIANG L, CHEN X, et al. Highly efficient visible-light-induced photoactivity of Z-scheme Ag₂CO₃/Ag/WO₃ photocatalysts for organic pollutant degradation[J]. Environmental Science: Nano, 2017, 4(11): 2175-2185.
33	WANG Q, SUN C, LIU Z, et al. Ultrasound-assisted successive ionic layer adsorption and reaction synthesis of Cu₂O cubes sensitized TiO₂ nanotube arrays for the enhanced photoelectrochemical performance[J]. Materials Research Bulletin, 2019, 111: 277-283.
34	MINGGU L J, NG K H, KADIR H A, et al. Bilayer n-WO₃/p-Cu₂O photoelectrode with photocurrent enhancement in aqueous electrolyte photoelectrochemical reaction[J]. Ceramics International, 2014, 40(10): 16015-16021.
35	WEI S, MA Y, CHEN Y, et al. Fabrication of WO₃/Cu₂O composite films and their photocatalytic activity[J]. Journal of Hazardous Materials, 2011, 194: 243-249.

编辑推荐 0

Metrics

阅读次数

全文

489

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	13	4	0	472

来源	本网站	其他网站

次数	317	172
比例	65%	35%

摘要

296

最新录用	在线预览	正式出版

15	0	281

来源	本网站	其他网站

次数	186	110
比例	63%	37%

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	胡喜, 王明珊, 李恩智, 黄思鸣, 陈俊臣, 郭秉淑, 于博, 马志远, 李星. 二硫化钨复合材料制备与储钠性能研究进展[J]. 化工进展, 2023, 42(S1): 344-355.
[6]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[7]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[8]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[9]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[10]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[11]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[12]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[13]	林晓鹏, 肖友华, 管奕琛, 鲁晓东, 宗文杰, 傅深渊. 离子聚合物-金属复合材料（IPMC）柔性电极的研究进展[J]. 化工进展, 2023, 42(9): 4770-4782.
[14]	吴海波, 王希仑, 方岩雄, 纪红兵. 3D打印催化材料开发与应用进展[J]. 化工进展, 2023, 42(8): 3956-3964.
[15]	向阳, 黄寻, 魏子栋. 电催化有机合成反应的活性和选择性调控研究进展[J]. 化工进展, 2023, 42(8): 4005-4014.

pn型Cu₂O-WO₃的制备及光催化性能

Synthesis and photocatalytic properties of pn-type Cu₂O-WO₃

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 35

相关文章 15

编辑推荐 0

Metrics

本文评价