水热法制备Nd~(3+)掺杂WO_3粉体及其光致变色性质
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摘要
以钨酸钠为钨源,硝酸钕为钕源,加入硫酸钾作为矿化剂,在120℃条件下通过水热法成功合成了六方相钕掺杂三氧化钨纳米粉.采用X射线衍射、扫描电镜和X射线光电子能谱分别对掺杂纳米粉的物相、形貌和掺杂成分进行了研究.结果表明,钕离子成功掺杂进入三氧化钨晶格当中,使一部分钨离子转为+5价,从而使电子从价带激发到导带并且增加了光生电子-空穴对的数量,导致其对激发光具有更大的吸收能力,光致变色性能也得到了较大的增强.在钕离子掺杂浓度为5.63%时,材料的光致变色性能最好,其色差值为纯三氧化钨色差值的13倍.
The synthesis of neodymium-doped hexagonal tungsten oxide nanopowder was reported by using sodium tungstate as the tungsten source,neodymium nitrate as the neodymium source,and potassium sulfate as the mineralizing agent.Phase composition,micro-morphology and doping content of the obtained nanopowder were studied by using X-ray diffraction analysis,scanning electronic microscopyand X-ray photoelectron spectroscopy.The result shows that only neodymium-doped hexagonal tungsten oxide was obtained in the synthesized product and no impurity was found.Due to successfully intruding Nd3+ion into the host lattice,partial tungsten ions were reduced to be pentavalent,which further resulted exciting electrons from valence band to conducting band and formation of additional photogenerated electron-hole pairs.Then the photochromic performance of nanoowder was found highly improved contributing to the increased absorbance of excitation light.The nanopowder with best photochromic property was obtained in the sample with a optimized trivalent neodymium ion concentration of 5.63%.Its change of color was estimated to be 13 times of that observed in the pure WO3.
The synthesis of neodymium-doped hexagonal tungsten oxide nanopowder was reported by using sodium tungstate as the tungsten source,neodymium nitrate as the neodymium source,and potassium sulfate as the mineralizing agent.Phase composition,micro-morphology and doping content of the obtained nanopowder were studied by using X-ray diffraction analysis,scanning electronic microscopyand X-ray photoelectron spectroscopy.The result shows that only neodymium-doped hexagonal tungsten oxide was obtained in the synthesized product and no impurity was found.Due to successfully intruding Nd3+ion into the host lattice,partial tungsten ions were reduced to be pentavalent,which further resulted exciting electrons from valence band to conducting band and formation of additional photogenerated electron-hole pairs.Then the photochromic performance of nanoowder was found highly improved contributing to the increased absorbance of excitation light.The nanopowder with best photochromic property was obtained in the sample with a optimized trivalent neodymium ion concentration of 5.63%.Its change of color was estimated to be 13 times of that observed in the pure WO3.
引文
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[3]DEB S K.Optical and photoelectric properties and colour centres in thin films of tungsten oxide[J].Philosophical Magazine,2012,27(4):801-822.
[4]CHEN Wei-long,SHEN Hong-jie,ZHU Xiao-rong,et al.Effect of citric acid on structure and photochromic properties of WO3-TiO2-ZnO composite films prepared by a sol-gel method[J].Ceramics International,2015,41(10):12638-12643.
[5]PAN Li,SHEN Yi,LI Zhen.Hydrothermal synthesis of WO3,films on the TiO2,substrates and their photochromic properties[J].Materials Science in Semiconductor Processing,2015,40:479-483.
[6]CHU Wen-jing,LIN Jun-liang,ZHENG You-wei,et al.Electrochromic properties of WO3films prepared by polymer precursor method[J].Acta Optica Sinica,2018,38(2):0216002-1.初文静,林俊良,郑友伟,等.聚合物前驱体法制备WO3薄膜的电致变色性能[J].光学学报,2018,38(2):0216002-1.
[7]YAN Min-yan.Organic induced synthesis and photochromic properties of MoO3powders[D].China University of Geosciences(Wuhan),2011.闫敏艳.MoO3粉体的有机诱导合成与光致变色性质研究[D].中国地质大学(武汉),2011.
[8]ZHOU Yan,ZHANG Ran,WANG Dong-sheng,et al.Hydrothermal synthesis and photochromic characterization of Mo doped WO3nanomaterial[J].Journal of Materials Engineering,2012,10:73-79.周妍,张然,王东生,等.水热法制备Mo掺杂WO3纳米材料及其光致变色性质的研究[J].材料工程,2012,10:73-79.
[9]SHEN Yi,YAN Peng,YANG Ya-li,et al.Hydrothermal synthesis and studies on photochromic properties of Al doped WO3,powder[J].Journal of Alloys&Compounds,2015,629:27-31.
[10]LU Yuan-yuan,LIU Guo,ZHANG Jing,et al.Fabrication of a monoclinic/hexagonal junction in WO3and its enhanced photocatalytic degradation of rhodamine B[J].Chinese Journal of Catalysis,2016,37(3):349-358.卢圆圆,刘果,张静,等.WO3中单斜相/六方相异相结的构建及提高光催化降解罗丹明B活性[J].催化学报,2016,37(3):349-358.
[11]YAN Song,HAN Ke-ke,ZHAO Lin,et al.WO3with different crystal structure prepared by thermo-decomposition method and its photocatalysis activity[J].Journal of Synthetic Crystals,2017,46(10):1959-1964.阎松,韩可可,赵琳,等.不同晶相WO3的热分解法制备及其光催化性能[J].人工晶体学报,2017,46(10):1959-1964.
[12]MANCERIU L M,ROUGEIR A,DUTA A.Comparative investigation of the Ti and Mo additives influence on the opto-electronic properties of the spray deposited WO3,thin films[J].Journal of Alloys&Compounds,2015,630:133-145.
[13]LIU Bao-shun,WANG Xue-lai,CAI Guo-fa,et al.Low temperature fabrication of V-doped TiO2 nanoparticles,structure and photocatalytic studies.[J].Journal of Hazardous Materials,2009,169(1):1112-1118.
[14]SONG Jing-jing,WANG Ping-ping,YAN Hui,et al.Influence of malic acid dosage on structure and photochromic properties of WO3nanopowders[J].Journal of the Chinese Ceramic Society,2016,44(7):976-980.宋敬敬,王萍萍,严回,等.苹果酸用量对WO3粉体结构及光致变色性能的影响[J].硅酸盐学报,2016,44(7):976-980.
[15]GU De-en,Yang Bang-chao,Hu Yong-da.V and N co-doped nanocrystal anatase TiO2 photocatalysts with enhanced photocatalytic activity under visible light irradiation[J].Catalysis Communications,2008,9(6):1472-1476.