番荔枝状聚苯胺-钒酸铋复合材料的制备及其光催化性能研究
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摘要
以Bi(NO_3)_3·5H_2O和NH_4VO_3为原料,通过水热法合成出直径为600～1 000 nm的番荔枝状单斜晶系白钨矿结构BiVO_4材料,并通过简单浸渍的方法将聚苯胺(PANI)负载到BiVO4微纳米材料上。运用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X-射线衍射光谱(XRD)和紫外-可见光谱(UV-vis)等一系列的表征手段对所制备材料进行形貌和物相分析。以广泛使用的染料罗丹明B(RhB)为降解对象,考察了复合材料的可见光催化性能。结果表明,PANI负载质量分数为5%的PANI-BiVO_4复合微纳米材料表现出良好的可见光催化性能,在300 min内使RhB溶液的脱色率达到99.1%;这是由于PANI和BiVO_4之间的协同效应促进光生电子-空穴对的分离。同时,活性物种实验发现,h~+和·OH是5%的PANI-BiVO_4复合微纳米材料光催化降解RhB的两种主要活性物种。
The diameter of 600～1 000 nmBiVO_4 with sweetsop-like monoclinic scheelite structure was synthesized based on Bi(NO_3)_3·5 H_2 O and NH_4 VO_3 via hydrothermal method. Polyaniline(PANI) was loaded onto the BiVO_4 micro-nano material by simple impregnation method. The morphology and phase of prepared material were analyzed by scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray powder diffraction(XRD), ultraviolet-visible spectroscopy(UV-Vis) and a series of characterization methods. The visible light catalytic performance of the composite was investigated by widely used dye rhodamine B(RhB).The results showed thatPANI-BiVO_4 composite micro-nano material with a PANI load mass fraction of 5% presented good visible light catalytic performance. The degradation rate of RhB solution reached 99.1% within 300 min, which is due to the synergistic effect between PANI and BiVO_4 to facilitate the separation of photo-generated electron-hole pairs. Meanwhile, the active species experiment found that h~+ and ·OH were the main active species of 5%PANI-BiVO_4 composite micro-nano material for the photocatalytic degradation of RhB.
The diameter of 600～1 000 nmBiVO_4 with sweetsop-like monoclinic scheelite structure was synthesized based on Bi(NO_3)_3·5 H_2 O and NH_4 VO_3 via hydrothermal method. Polyaniline(PANI) was loaded onto the BiVO_4 micro-nano material by simple impregnation method. The morphology and phase of prepared material were analyzed by scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray powder diffraction(XRD), ultraviolet-visible spectroscopy(UV-Vis) and a series of characterization methods. The visible light catalytic performance of the composite was investigated by widely used dye rhodamine B(RhB).The results showed thatPANI-BiVO_4 composite micro-nano material with a PANI load mass fraction of 5% presented good visible light catalytic performance. The degradation rate of RhB solution reached 99.1% within 300 min, which is due to the synergistic effect between PANI and BiVO_4 to facilitate the separation of photo-generated electron-hole pairs. Meanwhile, the active species experiment found that h~+ and ·OH were the main active species of 5%PANI-BiVO_4 composite micro-nano material for the photocatalytic degradation of RhB.
引文
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[2]WANG M G,HU Y M,HAN J T,et al.TiO2/NiO hybrid shells:p-n junction photocatalysts with enhanced activity under visible light[J].J.Mater.Chem.A,2015,3:20 727-20 735.
[3]TU W G,ZHOU Y,LIU Q,et al.Robust hollow spheres consisting of alternating titania nanosheets and graphene nanosheets with high photocatalytic activity for CO2conversion into renewable fuels[J].Adv.Funct.Mater.,2012,22:1 215-1 221.
[4]孙柳,王鹏.镧掺杂TiO2光催化降解酸性红B的研究[J].染整技术,2006,28(5):27-29.
[5]YANG HG,SUN C H,QIAO S Z,et al.Anatase TiO2 single crystals with a large percentage of reactive facets[J].Nature,2008,453:638-641.
[6]段芳,张琴,魏取福,等.铋系半导体光催化剂的光催化性能调控[J].化学进展,2014,26(1):30-40.
[7]CHEN L,WANG J X,MENG D W,et al.Enhanced photocatalytic activity of hierarchically structured BiVO4 oriented along{040}facets with different morphologies[J].Mater.Lett.,2015,147:1-3.
[8]HUANG H W,HAN X,LI X W,et al.Fabrication of multiple heterojunctions with tunable visible-light-active photocatalytic reactivity in BiOBr-BiOI fullrange composites based on microstructure modulation and band structures[J].ACS Appl.Mater.,Interfaces,2015,7:482-492.
[9]LI Z Q,CHEN X T,XUE Z L,et al.Bi2MoO6 microstructures:controllable synthesis,growth mechanism,and visible-light-driven photocatalytic activities[J].Cryst.Eng.Comm.,2013,15(15):498-508.
[10]PAYNE D J,ROBINSON MDM,EGDELL RG,et al.The nature of electron lone pairs in BiVO4[J].Appl.Phys.Lett.,2011,98(21):37.
[11]SAISON T,CHEMIN N,CHANéAC C,et al.New insights into BiVO4 properties as visible light photocatalyst[J].J.Phys.Chem.C,2015,119(23):12 967-12 977.
[12]KIM Y,SHIN D,CHANG W J,et al.Hybrid Z-scheme using photosystem I and BiVO4 for hydrogen production[J].Adv.Funct.Mater.,2015,25(16):2 369-2 377.
[13]PEREZ U M G,GUZMAN S S,CRUZ A M L et al.Photocatalytic activity of BiVO4 nanospheres obtained by solution combustion synthesis using sodium carboxymethylcellulose[J].J.Mol.Catal.A:Chem.,2011,335(1-2):169-175.
[14]GE L.Novel visible-light-driven Pt/BiVO4 photocatalyst for efficient degradation of methyl orange[J].J.Mol.Catal.A:Chem.,2008,282(1-2):62-66.
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[17]GHOSH S,KOUAMéNA,RAMOS L,et al.Conducting polymer nanostructures for photocatalysis under visible light[J].Nat.Mater.,2015,14:505-511.
[18]DU J,PEI S,MA L,et al.25th anniversary article:carbon nanotubeand graphene-based transparent conductive films for optoelectronic devices[J].Adv.Mater.,2014,26:1 958-1 991.
[19]MACDIARMID A G,CHIANG J C,HUANG W,et al.Protonic acid doping to the metallic regime[J].Mol.Cryst.Liq.Cryst.,1985,125(6):309-318.
[20]WAN M X.A template-free method towards conducting polymer nanostructures[J].Adv.Mater.,2008,20:2 926-2 932.
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[30]刘秀萍.钒酸铋光催化剂的制备、表征及其作用机理研究[D].福州:福建师范大学,2009.
[31]Hu R P,XIAO X,TU S H,et al.Synthesis of flower-like heterostructuredβ-Bi2O3/Bi2O2CO3 microspheres using Bi2O2CO3 self-sacrifice precursor and its visible-light-induced photocatalytic degradation of o-phenylphenol[J].Appl.Catal.,B:Environ.,2015,163:510-519.
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[33]XU T G,ZHANG L W,CHENG H Y,et al.Significantly enhanced photocatalytic performance of ZnO via graphene hybridization and the mechanism study[J].Appl.Catal.,B:Environ.,2011,101(3-4):382-387.
[34]MANGESH G,VISWANATHAN B,VISWANATH RP,et al.Photocatalytic behavior of CeO2-TiO2 system for the degradation of methylene blue[J].Indian J.Chem.,2009,48A:480-488.
[35]JIANG H Q,ENDO H,NATORI H,et al.Fabrication and efficient photocatalytic degradation of methylene blue over CuO/BiVO4 composite under visible-light irradiation[J].Mater.Res.Bull.,2009,44(3):700-706.
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