采用磁控溅射法在玻璃基底上制备了非化学计量比的WO3-x薄膜,并进一步在WO3-x表面负载了不同含量的银(Ag)纳米粒子。采用扫描电镜、原子力显微镜、X射线衍射仪、X射线光电子能谱仪、紫外-可见光谱仪、荧光分光光度计等分析方法对样品进行了表征。可见光条件下以催化降解亚甲基蓝为探针反应考察了Ag含量对薄膜光催化性能的影响。结果表明:室温下制备的样品表面粗糙度较大,呈非晶态。负载适量Ag后,薄膜吸收可见光能力显著增强,光生电子-空穴对更加稳定。Ag修饰量为6.2%时,WO3-x/Ag薄膜对亚甲基蓝的降解率最高,反应2h后催化剂对亚甲基蓝的降解率达到93.6%,比纯WO3-x降解率提高23%,反应常数k为1.249h-1,是纯WO3-x反应速率的2.04倍。
Non-stoichiometric WO3-x thin films were prepared on the glass substrate by magnetron sputtering method.Furthermore,different amounts of Ag nanoparticles were loaded on the surface of WO3-x.SEM,AFM,XRD,XPS,UV-Vis and PL were used to characterize the samples.The results shown that all samples were amorphous and had large surface roughness.Loading Ag significantly increased the ability of the films to absorb visible light,and enhanced the separation of the photogenerated electron-hole pairs.Visible-light driven degradation of methylene blue was conducted to investigate effect of different Ag amounts on the photocatalytic performance of the film.When amount of Ag was 6.2%,the degradation rate of methylene blue by WO3-x/Ag was the highest.After 2h of reaction,the degradation rate of methylene blue by WO3-x/Ag was 93.6%,which was 23% higher than that of pure WO3-x.The reaction rate constant k of WO3-x/Ag was 1.249h-1 which was 2.04 times higher than pure WO3-x.
[1] 刘广涵,张斌.半导体光催化材料研究进展[J].现代盐化工,2019,46(2):43-44.
[2] 谢立进,马峻峰,赵忠强,等.半导体光催化剂的研究现状及展望[J].硅酸盐通报,2005,24(6):80-84.
[3] Lv Y,Liu Y,Zhu Y,et al.Surface oxygen vacancy induced photocatalytic performance enhancement of a BiPO4 nanorod[J].Journal of Materials Chemistry A,2014,2(4):1174-1182.
[4] Li J,Xu X,Liu X,et al.Sn doped TiO2 nanotube with oxygen vacancy for highly efficient visible light photocatalysis[J].Journal of Alloys and Compounds,2016,679:454-462.
[5] Shen Z,Zhao Z,Qian J,et al.Synthesis of WO3-x nanomaterials with controlled morphology and composition for highly efficient photocatalysis[J].Journal of Materials Research,2016,31(8):1065-1076.
[6] Chen S H,Yang X,Wu Y H,et al.A facile approach to prepare black TiO2 with oxygen vacancy for enhancing photocatalytic activity[J].Nanomaterials,2018,8(4):245-253.
[7] Li Y,Wang C,Zheng H,et al.Surface oxygen vacancies on WO3 contributed to enhanced photothermo-synergistic effect[J].Applied Surface Science,2016,391:654-661.
[8] Yu J,Wen H,Shafiei M,et al.A hydrogen/methane sensor based on niobium tungsten oxide nanorods synthesised by hydrothermal method[J].Sensors and Actuators B:Chemical,2013,184:118-129.
[9] Chen D C,Fu Z Y,Zhen J S,et al.Preparation and H+ response mechanism of W/WO3 pH electrode by sol-gel method[J].Transactions of Nonferrous Metals Society of China,2005(4):855-862.
[10] Chiang C T L D,Chiu P K,Chu N N.Effect of Ag layer on the optical and electrical properties of WO3/Ag/WO3 films by magnetron sputtering[C].Kwei-Shan Tao-Yuan,Taiwan:2014 International Symposium on Next-Generation Electronics (ISNE),IEEE,2014.
[11] Xiao X,Zhou X,Ma J,et al.Rational synthesis and gas sensing performance of ordered mesoporous semiconducting WO3/NiO composites[J].ACS Applied Materials & Interfaces,2019,11(29):26268-26276.
[12] 李渊,赵青南,张泽华,等.磁控溅射功率对WOx薄膜结构和光催化活性的影响[J].硅酸盐通报,2019,38(2):207-211.
[13] Huang W,Wang J,Bian L,et al.Oxygen vacancy induced self-doping effect and metalloid LSPR in non-stoichiometric tungsten suboxide synergistically contributing to the enhanced photoelectrocatalytic performance of WO3-x/TiO2-x heterojunction[J].Physical Chemistry Chemical Physics Pccp,2018,20(25):17268-17278.
[14] Ramzan M,Brydson R.Characterization of sub-stoichiometric tungsten trioxide (WO3-x) using impedance spectroscopy[J].Sensors and Actuators A (Physical),2005,118(2):322-331.
[15] Li Q L,Li S,Ajouyed O,et al.Room temperature plasma enriching oxygen vacancies of WO3 nanoflakes for photoelectrochemical water oxidation[J].Journal of Alloys and Compounds,2020,816:152610.
[16] 朱晓东,王尘茜,裴玲秀,等.Ag修饰TiO2的制备及其在模拟太阳光下的光催化性能研究[J].人工晶体学报,2018,47(6):1136-1141.
[17] Johansson M B,Zietz B,Niklasson G A,et al.Optical properties of nanocrystalline WO3 and WO3-x thin films prepared by DC magnetron sputtering[J].Journal of Applied Physics,2014,115(21):213510.1-213510.7.
[18] 柯银环,曾敏,姜宏,等.N掺杂TiO2纳米纤维高可见光催化CO2合成甲醇[J].无机材料学报,2018,33(8):839-844.
[19] 葛金龙,高洪成,崔世亮,等.铜掺杂TiO2光催化剂的制备及光催化亚甲基蓝研究[J].化工新型材料,2016,44(7):219-221.
[20] Dani N A B,Rosi O,Risti R,et al.Amorphous content on the photocatalytic performance of micrometer-sized tungsten trioxide particles[J].Arabian Journal of Chemistry,2020,13(1):2912-2924.
[21] Zhao Z,Ping N,Di J,et al.Highly selective adsorption of organic dyes onto tungsten trioxide nanowires[J].Research on Chemical Intermediates,2016,42(6):5639-5651.
[22] 李胜英,陈慧文,苏惠,等.碳点/TiO2的制备及对亚甲基蓝的光催化性能[J].化工新型材料,2019,47(5):204-208.
