Bi_2S_3/TiO_2复合光催化剂的制备及光催化还原Cr(Ⅵ)性能研究
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摘要
环境中污染物的低耗能绿色处理方法,特别是环境中重金属Cr(Ⅵ)的绿色处理方法,是近年来的热点研究领域。本文首先制备了TiO_2单晶颗粒,之后与不同量的Bi2S3进行复合,制备了Bi_2S_3/TiO_2复合光催化材料。研究了不同的Bi_2S_3复合量对所制备样品的组成、形貌、结构和光催化还原Cr(Ⅵ)性能的影响。通过XRD、SEM、TEM、DRS、SPV等方法对样品进行了表征。研究结果表明,TiO_2表面复合有棒状的Bi_2S_3,复合样品对Cr(Ⅵ)的可见光光催化还原效率明显高于纯TiO_2,其中0. 02 mol/L的Bi(NO_3)_3反应液制备的复合样品具有最高光催化还原效率。对样品催化机理研究表明,Bi_2S_3/TiO_2复合材料的带隙随着Bi2S3含量的增加而变窄,对可见光的吸收和利用效率明显提高;并且TiO_2与Bi_2S_3的复合,可以减弱光生电子和空穴的复合,从而有效地利用了光生电子,提高了样品对Cr(Ⅵ)的光催化还原效率。
Green and low energy consumption treatment of environmental pollutants,such as Cr( Ⅵ),has been a research hotspot in recent years. In this study,single crystal particle of TiO_2 was prepared,and then it was composed with different amounts of Bi_2S_3. The effect of the Bi_2S_3 amount on the Bi_2S_3/TiO_2 composed sample,such as composition,morphological structure and photocatalytic properties,were investigated. The XRD,SEM,TEM,DRS and SPV were used to characterize the sample. The test results show that the Bi_2S_3 in the composed sample was rodlike. The Bi_2S_3/TiO_2 composed sample has much higher photocatalysis efficiency than that of pure TiO_2 in the reduction of Cr( Ⅵ),especially the sample prepared with 0. 02 mol/L Bi( NO3)3 solution. The band gap of Bi_2S_3/TiO_2 composite is narrowed by the adding of Bi_2S_3,therefore,its utilization of visible light is improved. The Bi_2S_3 can recede the recombination of photogenerated electrons and holes,and this is the reason for its high photocatalysis efficiency in Cr( Ⅵ) reduction.
Green and low energy consumption treatment of environmental pollutants,such as Cr( Ⅵ),has been a research hotspot in recent years. In this study,single crystal particle of TiO_2 was prepared,and then it was composed with different amounts of Bi_2S_3. The effect of the Bi_2S_3 amount on the Bi_2S_3/TiO_2 composed sample,such as composition,morphological structure and photocatalytic properties,were investigated. The XRD,SEM,TEM,DRS and SPV were used to characterize the sample. The test results show that the Bi_2S_3 in the composed sample was rodlike. The Bi_2S_3/TiO_2 composed sample has much higher photocatalysis efficiency than that of pure TiO_2 in the reduction of Cr( Ⅵ),especially the sample prepared with 0. 02 mol/L Bi( NO3)3 solution. The band gap of Bi_2S_3/TiO_2 composite is narrowed by the adding of Bi_2S_3,therefore,its utilization of visible light is improved. The Bi_2S_3 can recede the recombination of photogenerated electrons and holes,and this is the reason for its high photocatalysis efficiency in Cr( Ⅵ) reduction.
引文
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[31]Lu J,Han Q,Wang Z.Synthesis of Ti O2/Bi2S3,Heterojunction with a Nuclear-shell Structure and Its High Photocatalytic Activity[J].Materials Research Bulletin,2012,47(7):1621-1624.
[2]Mills A,Hunte S L.An Overview of Semiconductor Photocatalysis[J].Journal of Photochemistry and Photobiology A Chemistry,1997,108(1):1-35.
[3]Hoffmann M R,Martin S T,Choi W,et al.Environmental Applications of Semiconductor Photocatalysis[J].Chemical Reviews,1995,95(1):69-96.
[4]高铁,钱朝勇.Ti O2光催化氧化水中有机污染物进展[J].工业水处理,2000,(4):10-13.
[5]黄文娅,余颖.可见光化的半导体光催化剂[J].化学进展,2005,(2):242-247.
[6]Ni M,Leung M K H,Leung D Y C,et al.A Review and Recent Developments in Photocatalytic Water-splitting Using Ti O2for Hydrogen Production[J].Renewable and Sustainable Energy Reviews,2007,11(3):401-425.
[7]Zhu K,Neale NR,Miedaner A,et al.Enhanced Charge-collection Efficiencies and Light Scattering in Dye-sensitized Solar Cells Using Oriented Ti O2Nanotubes Arrays[J].Nano Letters,2007,7(1):69-74.
[8]李田,陈正夫.城市自来水光催化氧化深度净化效果[J].环境科学学报,1998,10(2):167-171.
[9]姚清照,刘正宝.光电催化降解塑料废水[J].工业水处理,1999,19(6):15-16.
[10]Xu J,Xiao X,Ren F,et al.Enhanced Photocatalysis by Coupling of Anatase Ti O2Film to Triangular Ag Nanoparticle Island[J].Nanoscale Research Letters,2012,7(1):239-244.
[11]马龙涛,余小红,鲁灿,等.Fe掺杂纳米ZnO的制备及其光催化性能研究[J].人工晶体学报,2014,43(1):58-63.
[12]Asahi R,Morikawa T,Ohwaki T,et al.Visible-light Photocatalysis in Nitrogen-doped Titanium Oxides[J].Science,2001,293(5528):269-271.
[13]Zhang N,Liu S,Fu X,et al.Synthesis of M@Ti O2(M=Au,Pd,Pt)Core-shell Nanocomposites with Tunable Photoreactivity[J].Journal of Physical Chemistry C,2011,115(18):9136-9145.
[14]周建伟,王储备,褚亮亮,等.Ti O2/石墨烯纳米复合材料制备及其光催化性能研究[J].人工晶体学报,2013,42(4):762-767.
[15]李向清,康诗钊,唐韵秋,等.碳掺杂的二氧化钛纳米管的制备及其可见光催化性能[J].应用化学,2013,(2):178-184.
[16]Guan K.Relationship between Photocatalytic Activity,Hydrophilicity and Self-cleaning Effect of Ti O2/SiO2Films[J].Surface and Coatings Technology,2005,191(2):155-160.
[17]Li C,Yuan J,Han B,et al.Ti O2Nanotubes Incorporated with CdS for Photocatalytic Hydrogen Production from Splitting Water under Visible Light Irradiation[J].International Journal of Hydrogen Energy,2010,35(13):7073-7079.
[18]王婉妮,章富,张传玲,等.内嵌硫化镉与上转换纳米颗粒的二氧化钛复合纳米管用于近红外光驱动光催化[J].催化学报,2017,(11):1851-1859.
[19]李玥,宋育泽,陶雁忠,等.CdS/Ti O2复合纳米网的制备及光催化性能研究[J].影像科学与光化学,2018,(3):275-282.
[20]Franco A,Neves M C,Carrott M M,et al.Photocatalytic Decolorization of Methylene Blue in the Presence of Ti O2/ZnS Nanocomposites[J].Journal of Hazardous Materials,2009,161(1):545-550.
[21]Kumar S,Sharma S,Sood S,et al.Bismuth Sulphide(Bi2S3)nanotubes Decorated Ti O2Nanoparticles Heterojunction Assembly for Enhanced Solar Light Driven Photocatalytic Activity[J].Ceramics International,2016,42(15):17551-17557.
[22]Li C X,Zhao Z Y,Lomboleni Hamukwaya Shindume.Enhanced Visible Photocatalytic Activity of Nitrogen Doped Single-crystal-like Ti O2by Synergistic Treatment with Urea and Mixed Nitrates[J].Journal of Materials Research,2017,7(32):737-747.
[23]Zhao Z Y,Feng M C,Peng Z J.Molten-salt Fabrication of(N,F)-codoped single-crystal-like Titania with High Exposure of(001)crystal Facet for Highly Efficient Degradation of Methylene Blue under Visible Light Irradiation[J].Journal of Materials Research,2018,10(33):1411-1421.
[24]Zhou C Y,Lai C,Xu P,et al.In Situ Grown Agl/Bi12O17Cl2Heterojunction Photocatalysts for Visible Light Degradation of Sulfamethazine:Efficiency,Pathway,and Mechanism[J].ACS Sustainable Chemistry&Engineering,2018,6(3):4174-4184.
[25]Lu J,Han Q,Wang Z.Synthesis of Ti O2/Bi2S3,Heterojunction with a Nuclear-shell Structure and Its High Photocatalytic Activity[J].Materials Research Bulletin,2012,47(7):1621-1624.
[26]Selvam K,Balachandran S,Velmurugan R,et al.Mesoporous Nitrogen Doped Nano Titania-a Green Photocatalyst for the Effective Reductive Cleavage of Azoxybenzenes to Amines or 2-phenyl Indazoles in Methano[J].Journal of the American Chemical Society,2012,413:213-222.
[27]康俊龙,姚兰芳,杨松林,等.Ce掺杂Ti O2纳米复合薄膜的制备及光催化活性[J].人工晶体学报,2013,42(4):671-676.
[28]唐洁,展红全,江向平,等不同酸性助剂水热合成钨酸铋的制备及光催化性能研究[J].人工晶体学报,2013,42(6):1092-1097.
[29]Yang J,Dai J,Li J.Visible-light-induced Photocatalytic Reduction of Cr(VI)with Coupled Bi2O3/Ti O2Photocatalyst and the Synergistic Bisphenol a Oxidation[J].Environmental Science and Pollution Research,2013,20(4):2435-2447.
[30]姜三营,许红亮,李勇辉,等.高岭土/纳米Ti O2复合光催化材料制备及性能研究[J].人工晶体学报,2013,42(11):2322-2327.
[31]Lu J,Han Q,Wang Z.Synthesis of Ti O2/Bi2S3,Heterojunction with a Nuclear-shell Structure and Its High Photocatalytic Activity[J].Materials Research Bulletin,2012,47(7):1621-1624.