AgVO_3/BiVO_4复合光催化剂的制备及可见光催化性能
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摘要
通过水热法制备了不同复合比例的AgVO_3/BiVO_4复合型光催化剂,以有机染料甲基橙作为目标降解物评价了其光催化活性,并通过X射线衍射、扫描电子显微镜、X射线能谱、X射线光电子能谱和紫外–可见漫反射光谱对其进行了表征。结果表明:制备的样品纯度很高,复合AgVO3后,BiVO_4的晶体结构未发生改变,但形貌由石笼状变为分散的粒状混合体,光吸收性能增强,同时,二者形成了异质结结构,进一步促进了光生电子-空穴的分离,从而提高了光催化活性。当AgVO_3与BiVO_4的摩尔比为70%时,光催化活性最高且稳定性良好,光照50min对甲基橙降解率高达96.7%,较纯BiVO_4提高约86.5%,且该体系中的主要活性氧物质为空穴。
AgVO_3/BiVO_4 composite photocatalysts were prepared by a hydrothermal method. The photocatalytic activities of the synthesized samples were evaluated by the degradation of methyl orange. And the samples were analyzed by X-ray diffraction, scanning electron microscopy, X-ray energy spectroscopy, X-ray photoelectron spectroscopy and UV-visible diffuse reflectance spectroscopy. The results exhibited that the AgVO3/BiVO_4 samples were of good purity. After compounding AgVO_3, the crystal structure of BiVO_4 did not change, but the morphology changed from a stone cage to a single irregular stone, and had a enhanced light absorption performance. At the same time, the formation of a heterojunction structure further promoted the separation of photo electron-holes, then improving the photocatalytic activity. When the mass ratio of AgVO3/BiVO_4 was 70%, the composite showed the highest photocatalytic activity, and the degradation rate of methyl orange was 96.7%, 86.5% higher than pure BiVO_4. Recycling experiments presented that heterojunctions retained excellent photo-stability after five-time recycles. And the holes were the main active species in the process of photocatalytic degradation.
AgVO_3/BiVO_4 composite photocatalysts were prepared by a hydrothermal method. The photocatalytic activities of the synthesized samples were evaluated by the degradation of methyl orange. And the samples were analyzed by X-ray diffraction, scanning electron microscopy, X-ray energy spectroscopy, X-ray photoelectron spectroscopy and UV-visible diffuse reflectance spectroscopy. The results exhibited that the AgVO3/BiVO_4 samples were of good purity. After compounding AgVO_3, the crystal structure of BiVO_4 did not change, but the morphology changed from a stone cage to a single irregular stone, and had a enhanced light absorption performance. At the same time, the formation of a heterojunction structure further promoted the separation of photo electron-holes, then improving the photocatalytic activity. When the mass ratio of AgVO3/BiVO_4 was 70%, the composite showed the highest photocatalytic activity, and the degradation rate of methyl orange was 96.7%, 86.5% higher than pure BiVO_4. Recycling experiments presented that heterojunctions retained excellent photo-stability after five-time recycles. And the holes were the main active species in the process of photocatalytic degradation.
引文
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[2]CHEN F,YANG Q,WANG Y L,et al.Novel ternary heterojunction photcocatalyst of Ag nanoparticles and g-C3N4 nanosheets co-modified BiVO4 for wider spectrum visible-light photocatalytic degradation of refractory pollutant[J].Appl Catal B:Environ,2017,205:133?147.
[3]ZHANG A P,ZHANG J Z.Effects of europium doping on the photocatalytic behavior of BiVO4[J].J Hazard Mater,2010,173:265?272.
[4]王敏,郑浩岩,杨长秀,等.pH值对乙二醇溶胶-凝胶法制备BiVO4光催化性能的影响[J].材料工程,2015,43(9):6?11.WANG Min,ZHENG Haoyan,YANG Changxiu,et al.J Mater Eng(in Chinese),2015,43(9):6?11.
[5]LI H B,ZHANG J,HUANG G Y.Hydrothermal synthesis and enhanced photocatalytic activity of hierarchical flower-like Fe-doped BiVO4[J].T Nonferr Metal Soc,2017,27(4):868?875.
[6]WANG M,YANG G J,YOU M Y,et al.Effects of Ni doping contents on photocatalytic activity of B-BiVO4 synthesized through sol-gel and impregnation two-step method[J].T Nonferr Metal Soc,2017,27:2022?2030.
[7]向礼.铋基复合光催化剂的制备及其性能研究[D].济南:山东大学,2014.XIANG Li.Synthesis and photocatalytic activity of Bi-based composite photocatalyst(in Chinese,dissertation).Jinan:Shandong University,2014.
[8]桑艳.钒酸盐及其复合光催化剂的制备及其性能研究[D].合肥:安徽师范大学,2015.SANG Yan.Preparation and properties of vanadate and their composite photocatalyst(in Chinese,dissertation).Hefei:Anhui Normal University,2015.
[9]刘仁月,吴榛,白羽,等.Ag2CO3/BiVO4复合微米片光催化剂的制备、表征及光催化机理[J].无机化学学报,2017,33(3):519?527.LIU Renyue,WU Zhen,BAI Yu,et al.Chin J Inorg Chem(in Chinese),2017,33(3):519?527.
[10]WANG R,CAO L.Facile synthesis of a novel visible-light-driven AgVO3/BiVO4 heterojunction photocatalyst and mechanism insight[J].J Alloy Compd,2017,722:445?451.
[11]YANG Y,LIU Y,HUANG B.Enhanced visible photocatalytic activity of a BiVO4@b-AgVO3 composite synthesized by an in situ growth method[J].Rsc Adv,2014,4(39):20058?20061.
[12]WANG M,HAN J,GUO P Y,et al.Hydrothermal synthesis of B-doped Bi2MoO6 and its high photocatalytic performance for the degradation of Rhodamine B[J].J Phys Chem Solids,2018,113:86?93.
[13]WANG M,NIU C,LIU Q,et al.Enhanced photo-degradation methyl orange by N-F co-doped BiVO4 synthesized by sol-gel method[J].Mater Sci Semicond Proc,2014,25(18):271?278.
[14]GUAN M L,MA D K,HU S W,et al.From hollow olive-shaped BiVO4 to n-p core-shell BiVO4@Bi2O3 microspheres:Controlled synthesis and enhanced visible-light-responsive photocatalytic properties[J].Inorg Chem,2010,50:800?805.
[15]ZHAO J,YAN J H,JIA H J,et al.Bi VO4/g-C3N4 composite visible-light photocatalyst for effective elimination of aqueous organic pollutants[J].J Mol Catal A:Chem,2016,424:162?170.
[16]WANG M,YOU M Y,GUO P Y,et al.Hydrothermal synthesis of Sm-doped Bi2MoO6 and its high photocatalytic performance for the degradation of Rhodamine B[J].J Alloy Compd,2017,728:739?746.
[17]CHEN F,YANG Q,LI X,et al.Hierarchical assembly of graphene-bridged Ag3PO4/Ag/BiVO4(040)Z-scheme photocatalyst:An efficient,sustainable and heterogeneous catalyst with enhanced visible-light photoactivity towards tetracycline degradation under visible light irradiation[J].Appl Catal B:Environ,2017,200:330?342.
[18]王敏,刘琼,孙亚杰,等.溶胶-凝胶法制备Eu3+掺杂BiVO4及其可见光光催化性能[J].无机材料学报,2013,28(2):153?158.WANG Min,LIU Qiong,SUN Yajie,et al.J Inorg Mater(in Chinese),2013,44(2):153?158.
[19]YIN J Z,HUANG S B,JIAN Z C,et al.Fabrication of heterojunction SnO2/BiVO4 composites having enhanced visible light photocatalystic activity[J].Mater Sci Semicond Proc,2015,34(2):198?204.
[20]WANG M,GUO P Y,YANG G J,et al.The honeycomb-like Eu3+,Fe3+doping bismuth molybdate photocatalyst with enhanced performance prepared by a citric acid complex process[J].Mater Lett,2017,192:96?100.
[21]CHANG X,WANG T,ZHANG P,et al.Enhanced surface reaction kinetics and charge separation of p-n heterojunction Co3O4/BiVO4photoanodes[J].J Am Chem Soc,2015,137(26):8356?8359.
[22]GE M,TAN M M,CUI G H.Synthesis of Ag3PO4/BiVO4 composite photocatalyst and its photocatalytic degradation of dyes under visible light irradiation[J].Acta Phys-Chim Sin,2014,30(11):2107?2112.
[23]WANG Y,NIU C G,ZHANG L,et al.High-efficiency visible-light AgI/Ag/Bi2MoO6 as a z-scheme photocatalyst for environmental applications[J].Rsc Adv,2016,6(13):10221?10228.