Fe掺杂对水热合成In_2O_3结构与光催化性能的影响
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摘要
通过水热合成法制备了不同Fe掺杂浓度的Fe-In_2O_3复合材料,采用扫描电镜、元素能谱、X射线衍射、X射线光电子能谱、红外光谱、紫外-可见漫反射光谱等技术分析了样品的形貌与微观结构,并以罗丹明B为目标降解物测试了其光催化性能.结果表明,随Fe掺杂量的增加,In_2O_3晶粒的形貌由短纤维构成的不规则厚片状向纤细的薄片状变化,最终呈现花朵状.表面形貌的改变使样品的吸附性增强,并导致OH键(H_2O)的振动加强,样品形成了新的化学键Fe—O—In,使晶体衍射峰的峰位发生偏移.Fe掺杂也抑制了In_2O_3晶粒的长大,同时随Fe含量的增加,In_2O_3的光吸收范围逐渐向可见光方向移动.最终发现Fe掺杂可以明显提高In_2O_3的光催化性能,在紫外光照射下其对罗丹明B的降解率可达96%.光催化降解罗丹明B的过程符合一级反应动力学方程,活性物种捕获实验证明空穴和超氧自由基是光催化体系中的主要活性物种.
In this work,Fe-In_2O_3 composites with different Fe-doping concentrations were prepared by hydrothermal synthesis.The morphology and structure of the materials were characterized by SEM,EDS,XRD,XPS,FT-IR and UV-Vis DRS,then the Rhodamine-B(RhB) was used as the target to test their photocatalytic performance.The results showed that as the increase of Fe content,the morphology of Fe-In_2O_3 grains can be changed from thick flakes which consist of short fibers to thin flakes,finally,it forms a flower-like shape.The refinement of the surface morphology leads to the enhancement of the adsorption properties which has been evidenced by the increase of OH groups and a new chemical bond Fe—O—In is formed in the composites,which leads to the peak position of the crystal diffraction shifts.The crystal growth of In_2O_3 has been hindered by the doping of Fe,while the light absorption range is also gradually shifted toward the visible light as the Fe content increases in the composie.It is found that the photocatalytic performance of In_2O_3 has been obviously improved by Fe-doping,and the degradation rate of RhB can reach to 96% under the ultraviolet light irradiation.The degradation of RhB can be described by the first-order kinetics equation.Meanwhile,the capture test of active species proves that holes and superoxide radicals play a major role in the photocatalytic degradation.
In this work,Fe-In_2O_3 composites with different Fe-doping concentrations were prepared by hydrothermal synthesis.The morphology and structure of the materials were characterized by SEM,EDS,XRD,XPS,FT-IR and UV-Vis DRS,then the Rhodamine-B(RhB) was used as the target to test their photocatalytic performance.The results showed that as the increase of Fe content,the morphology of Fe-In_2O_3 grains can be changed from thick flakes which consist of short fibers to thin flakes,finally,it forms a flower-like shape.The refinement of the surface morphology leads to the enhancement of the adsorption properties which has been evidenced by the increase of OH groups and a new chemical bond Fe—O—In is formed in the composites,which leads to the peak position of the crystal diffraction shifts.The crystal growth of In_2O_3 has been hindered by the doping of Fe,while the light absorption range is also gradually shifted toward the visible light as the Fe content increases in the composie.It is found that the photocatalytic performance of In_2O_3 has been obviously improved by Fe-doping,and the degradation rate of RhB can reach to 96% under the ultraviolet light irradiation.The degradation of RhB can be described by the first-order kinetics equation.Meanwhile,the capture test of active species proves that holes and superoxide radicals play a major role in the photocatalytic degradation.
引文
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[2] GHAYEB Y,MOMENI M M,MOZAFARI A.Effect of silver sulfide decorating on structural,optical and photo catalytic properties of iron-doped titanium dioxide nanotubes films[J].Journal of Materials Science:Materials in Electronics,2016,27(11):11804.
[3] YU K F,LING M Q,LIANG J C,et al.Formation of TiO2 hollow spheres thtough nanoscale Kirkendall effect and their lithium storage and photocatalytic properties [J].Chemical Physics,2019,517:222.
[4] LI W X,BZK T,ATANACIO A,et al.Photocatalytic properties of TiO2:effect of niobium and oxygen activity on partial water oxidation [J].Applied Catalysis B:Environmental,2016,198:243.
[5] MAEDA K,DOMEN K.Solid solution of GaN and ZnO as a stable photocatalyst for overall water splitting under visible light[J].Chemistry of Materials,2010,22(3):612.
[6] WANG L,ZHANG R,ZHOU T,et al.P-type octahedral Cu2O particles with exposed {111} facets and superior CO sensing properties[J].Sensors and actuators B-Chemical,2017,239:211.
[7] SHAO M L,CHEN H T,SHEN M,et al.Synthesis and photocatalytic properties of In2O3 micro/nanostructures with different morphologies [J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2017,529:503.
[8] 张爱平,张进治.Cu、Ag、Au掺杂BiVO4可见光催化剂的制备及性能研究[J].分子催化,2010,24(1):51.
[9] 胡志刚,段满益,徐明,等.Fe和Ni共掺杂ZnO的电子结构和光学性质[J].物理学报,2009,58(2):1166.
[10] 闫共芹,蒋安邦,何强.Zn掺杂In2O3的水热法制备及其光催化与电化学性能研究[J].广西科技大学学报,2017,28(1):6.
[11] SHANMUGA P B,SHANTHI M,MANOHARAN C,et al.Hydro-thermal synthesis of Ga-doped In2O3 nanostructure and its structural,optical and photo-catalytic properties[J].Materials Science in Semiconductor Processing,2017,71:357.
[12] 赵平歌,张格红,周孝德,等.氧化铟的铋掺杂改性及其光催化性能[J].安全与环境学报,2016,16(6):224.
[13] VALERO-ROMERO M J,SANTACLARA J G,OAR-ARTETA L,et al.Photocatalytic properties of TiO2 and Fe-doped TiO2 prepared by metal organic framework-mediated synthesis[J].Chemical Engineering Journal,2019,360:75.
[14] YAN Y,SUN S,YANG S.Microwave-assisted in situ synthesis of reduced graphene oxide-BiVO4 composite photo-catalysts and their enhanced photo-catalytic performance for the degradation of ciprofloxacin[J].Journal of Hazardous Materials,2013,205/251:106.
[15] ZHANG G,GUAN W,SHEN H.Organic additives-free hydro-thermal synthesis and visible-light-driven photo-degradation of tetracycline of WO3 nanosheets[J].Industrial & Engineering Chemistry Research,2014,53(13):5443.
[16] DONG R,NA C,ZHANG H.TiO2/SiO2 mesoporous micro-spheres with intelligently controlled texture[J].Materials and Design,2016,89:830.
[17] WANG J,FAN Z,WANG Y,et al.Preparation of In(OH)3 and In2O3 nanorods through a novel hydrothermal method and the effect of Sn dopant on crystal structures[J].Industrial & Engineering Chemistry Research,2018,57(8):):2282.
[18] XU J,DONG Z,HU T,et al.Construction of TiO2-Fe-C3N4 compound:promotion of interfacial charge transfer effect through facile energy level alignment[J].Journal of Alloys and Compounds,2018,781:140.
[19] LIU L,CHEN Y,GUO L,et al.Gallium-doped indium oxide nanoleaves:structural characterization,growth mechanism and optical properties[J].Applied Surface Science,2011,258(2):923.
[20] REGOUTZ A,EGDELL R G,MORGAN D J,et al.Electronic and surface properties of Ga-doped In2O3 ceramics[J].Applied Surface Science,2015,349:970.
[21] KUMAR Y,SHARMA A,SEHGAL R,et al.Distribution trends of salmonella serovars in india[J].Transactions of the Royal Society of Tropical Medicine and Hygiene,2009,103(4):390.
[22] ZHAO J,YANG T,LIU Y.Enhancement of NO2 gas sensing response based on ordered mesoporous Fe-doped In2O3[J].Sensors and Actuators B:Chemical,2014,191:806.
[23] ZHANG T,GU F,HAN D.Synthesis,characterization and alcohol-sensing properties of rare earth doped In2O3 hollow spheres[J].Sensors and Actuators B:Chemical,2013,177:1180.
[24] ZULUGA S,LIU L H,SHAFIAL N.Structural band-gap tuning in g-C3N4[J].Physical Chemistry Chemical Physics,2015,17(2):957.
[25] AN Y K,REN Y,YANG D Y,et al.Oxygen vacancy-induced room temperature ferromagnetism and magnetoresistance in Fe-doped In2O3 films[J].Journal of Physical Chemistry C,2015,119(8):4414.
[26] SUN X K,MA K,LI C E,et al.Formation of Fe-doped In2O3 nanowires and influence evolution of Fe ions on its photoluminescence property[J].Journal of Alloys and Compounds,2018,764:861.
[27] 王超,敬和民.铁掺杂二氧化钛光催化性能研究[J].化工时刊,2018,32(8):4.
[28] LI J H,LIU Y Y,ZHOU Y,etal.Enhanced visible-light photocatalytic activity of Bi2O2CO3nanoplates by Fe-doping in the degradation of Rhodamine B[J].Materials Research Bulletin,2018,107:438.
[29] LIU S Q,ZHANG N,TANG Z R,et al.Synthesis of one-dimensional CdS@TiO2 core-shell nanocomposites photocatalyst for selective redox:the dual role of TiO2 shell[J].ACS Applied Materials & Interfaces,2012,4(11):6378.
[30] CHAI B,YAN J T,WANG C L,et al.Enhanced visible light photocatalytic degradation of Rhodamine B over phosphorus doped graphitic carbon nitride[J].Applied Surface Science,2016,391:376.