ZnTiO_3-TiO_2复合光催化剂的制备及光催化降解有机污染物机制分析
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摘要
TiO_2光催化剂因无毒无害而在光催化降解污染物领域有巨大潜力.但由于TiO_2的光生电子空穴复合较快,量子效率较低,限制了它的广泛使用.在本研究中,通过溶胶-凝胶(Sol-Gel)法制备了ZnTiO_3-TiO_2异质结复合光催化剂,分析了配比和煅烧温度对材料光催化性能的影响,以甲基橙(MO)溶液为模拟污染物进行光催化降解,探讨了其催化效果及效率提升的机制.结果表明,在紫外光照射下,ZnTiO_3与TiO_2比值为0. 3时,在600℃下煅烧3 h后,其催化效果最佳且表现出良好的化学稳定性.通过光电流测试和电子自旋共振波谱仪的检测结果,证明复合光催化剂的光生电子和空穴复合率降低,从而提高了光催化活性.
TiO_2 is a promising photocatalysis for degradation of organic pollutants due to its innocuity. However,its widespread practical application was hindered by the fast combination speed of photogenerated electron-hole pairs and low quantum efficiency. In this study, we prepared ZnTiO_3-TiO_2 using the Sol-Gel method to get heterojunctions, which exhibit efficient separation of photogenerated electron-hole pairs. The photocatalytic performances of various ZnTiO_3-TiO_2 were evaluated by the removal efficiency of Methyl orange. The experimental results showed that the ZnTiO_3-TiO_2( ZnTiO_3∶ TiO_2= 0. 3),which was calcinated under 600℃,had the best photocatalytic activity under ultraviolet light. The photocatalyst was stable under a wide range of p H( 2. 5-12. 5). The photocurrent and ESR analysis verified the superior photocatalysis of ZnTiO_3-TiO_2,which was attributed to the efficient separation of electron-hole pairs induced by the heterojunctions.
TiO_2 is a promising photocatalysis for degradation of organic pollutants due to its innocuity. However,its widespread practical application was hindered by the fast combination speed of photogenerated electron-hole pairs and low quantum efficiency. In this study, we prepared ZnTiO_3-TiO_2 using the Sol-Gel method to get heterojunctions, which exhibit efficient separation of photogenerated electron-hole pairs. The photocatalytic performances of various ZnTiO_3-TiO_2 were evaluated by the removal efficiency of Methyl orange. The experimental results showed that the ZnTiO_3-TiO_2( ZnTiO_3∶ TiO_2= 0. 3),which was calcinated under 600℃,had the best photocatalytic activity under ultraviolet light. The photocatalyst was stable under a wide range of p H( 2. 5-12. 5). The photocurrent and ESR analysis verified the superior photocatalysis of ZnTiO_3-TiO_2,which was attributed to the efficient separation of electron-hole pairs induced by the heterojunctions.
引文
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[25] Morozov I G,Belousova O V,Ortega D,et al. Structural,optical,XPS and magnetic properties of Zn particles capped by ZnO nanoparticles[J]. Journal of Alloys and Compounds,2015,633:237-245.
[26]张鹏.钛基复合纳米纤维材料的制备及光催化性质研究[D].长春:东北师范大学,2014.
[27] Wang C C, Ying J Y. Sol-gel synthesis and hydrothermal processing of anatase and rutile titania nanocrystals[J].Chemistry of Materials,1999,11(11):3113-3120.
[28] Zhang Y C,Zhang Q,Shi Q W,et al. Acid-treated g-C3N4with improved photocatalytic performance in the reduction of aqueous Cr(Ⅵ)under visible-light[J]. Separation and Purification Technology,2015,142:251-257.
[29] Lu L Y,Wang G H,Zou M,et al. Effects of calcining temperature on formation of hierarchical Ti O2/g-C3N4hybrids as an effective Z-scheme heterojunction photocatalyst[J]. Applied Surface Science,2018,441:1012-1023.
[30]张雪,刘建新,王雅文,等.异质结型Ag Br/CuO光催化剂的合成、光催化活性及再生[J].高等学校化学学报,2016,37(1):88-93.Zhang X,Liu J X,Wang Y W,et al. Synthesis,photocatalytic activity and regeneration of Ag Br/CuO heterojunction photocatalyst[J]. Chemical Journal of Chinese Universities,2016,37(1):88-93.
[31] Zhang C Q,Li X Y,Zheng S Z,et al. Construction of Ti O2nanobelts-Bi2O4heterojunction with enhanced visible light photocatalytic activity[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2018,548:150-157.
[32] Wang Y J,Shi R,Lin J,et al. Enhancement of photocurrent and photocatalytic activity of Zn O hybridized with graphite-like C3N4[J]. Energy&Environmental Science,2011,4(8):2922-2929.
[33]闫俊青.基于Ti O2半导体光生载流子分离、可见光范畴拓展策略探究[D].天津:南开大学,2015.Yan J Q. Study of Ti O2-based semiconductors:Photo-generated carriers'separation and visible light response[D]. Tianjin:Nankai University,2015.
[2] Han F,Kambala V S R,Srinivasan M,et al. Tailored titanium dioxide photocatalysts for the degradation of organic dyes in wastewater treatment:A review[J]. Applied Catalysis A:General,2009,359(1-2):25-40.
[3] Fujishima A,Honda K. Electrochemical photolysis of water at a semiconductor electrode[J]. Nature,1972,238(5358):37-38.
[4]于艳辉,哈日巴拉,徐传友,等.纳米二氧化钛光催化剂研究进展[J].材料导报,2008,22(S1):54-57.Yu Y H,Hari B,Xu C Y,et al. Research progress in Nano Ti O2photocatalyst[J]. Materials Review,2008,22(S1):54-57.
[5] Singh R, Dutta S. A review on H2production through photocatalytic reactions using Ti O2/Ti O2-assisted catalysts[J].Fuel,2018,220:607-620.
[6] Kumar S G,Devi L G. Review on modified Ti O2photocatalysis under UV/visible light:selected results and related mechanisms on interfacial charge carrier transfer dynamics[J]. The Journal of Physical Chemistry A,2011,115(46):13211-13241.
[7] Liu Y,Wei J H,Xiong R,et al. Enhanced visible light photocatalytic properties of Fe-doped Ti O2nanorod clusters and monodispersed nanoparticles[J]. Applied Surface Science,2011,257(18):8121-8126.
[8] Nishiyama N,Yamazaki S. Effect of mixed valence states of platinum ion dopants on the photocatalytic activity of titanium dioxide under visible light irradiation[J]. ACS Omega,2017,2(12):9033-9039.
[9] Xiong Y L,Yang L,Xiao P,et al. Enhanced charge separation and oxidation kinetics by loading Pt nanoparticles with hydrogenated Ti O2nanotubes[J]. Journal of Materials Science,2018,53(10):7703-7714.
[10]刘晴,喻泽斌,张睿涵,等.钯掺Ti O2光催化降解全氟辛酸[J].环境科学,2015,36(6):2138-2146.Liu Q,Yu Z B,Zhang R H,et al. Photocatalytic degradation of perfluorooctanoic acid by Pd-TiO2photocatalyst[J].Environmental Science,2015,36(6):2138-2146.
[11] Sun C X,He P,Pan G F,et al. Study on preparation and visible-light activity of Ag-TiO2supported by artificial zeolite[J].Research on Chemical Intermediates,2018,44(4):2607-2620.
[12]倪冰楠,陆婷,刘心娟,等.纳米Au/Ti O2复合物光催化降解亚甲基蓝[J].环境工程学报,2014,8(12):5372-5376.Ni B N,Lu T,Liu X J,et al. UV photocatalytic reduction of methylene blue by Nano Au/Ti O2composites[J]. Chinese Journal of Environmental Engineering,2014,8(12):5372-5376.
[13] Chen Q,Tong R F,Chen X J,et al. Ultrafine ZnO quantum dot-modified Ti O2composite photocatalysts:the role of the quantum size effect in heterojunction-enhanced photocatalytic hydrogen evolution[J]. Catalysis Science&Technology,2018,8(5):1296-1303.
[14] Liao D L,Badour C A,Liao B Q. Preparation of nanosized Ti O2/ZnO composite catalyst and its photocatalytic activity for degradation of methyl orange[J]. Journal of Photochemistry and Photobiology A:Chemistry,2008,194(1):11-19.
[15] Su E C,Huang B S,Wey M Y. Enhanced optical and electronic properties of a solar light-responsive photocatalyst for efficient hydrogen evolution by SrTiO3/Ti O2nanotube combination[J].Solar Energy,2016,134:52-63.
[16] Gao K,Li S D. Multi-modal Ti O2-La Fe O3composite films with high photocatalytic activity and hydrophilicity[J]. Applied Surface Science,2012,258(17):6460-6464.
[17]苏碧桃,朱平武,许晶晶,等. ZnTiO3-Ti O2纳米复合材料的光催化性能[J].应用化学,2011,28(1):33-38.Su B T,Zhu P W,Xu J J,et al. Photocatalytic property of ZnTiO3-Ti O2Nano-composite materials[J]. Chinese Journal of Applied Chemistry,2011,28(1):33-38.
[18]王爱民,白妮,王金玺,等. ZnTiO3/Ti O2异质复合材料的制备及光催化性能[J].人工晶体学报,2018,47(2):382-388.Wang A M, Bai N, Wang J X, et al. Preparation and photocatalytic property of ZnTiO3/Ti O2heterogeneous composite material[J]. Journal of Synthetic Crystals,2018,47(2):382-388.
[19]郑红娟,赵志伟,张琳琪,等. ZnO-TiO2纳米复合材料的制备及光催化性能研究[J].功能材料,2010,41(12):2120-2123.Zheng H J,Zhao Z W,Zhang L Q,et al. Preparation and photocatalytic property of ZnO-TiO2nanocomposites[J]. Journal of Functional Materials,2010,41(12):2120-2123.
[20]程刚,周孝德,李艳,等.纳米ZnO-TiO2复合半导体的La3+改性及其光催化活性[J].催化学报,2007,28(10):885-889.Cheng G,Zhou X D,Li Y,et al. La3+modification of Zn OTi O2coupled semiconductors and their photocatalytic activity[J]. Chinese Journal of Catalysis,2007,28(10):885-889.
[21]邱明艳,张天永,李彬,等. La-TiO2/ZnO异质结纳米复合材料的光催化性能[J].人工晶体学报,2014,43(7):1809-1814,1822.Qiu M Y,Zhang T Y,Li B,et al. Photocatalytic properties of La-TiO2/ZnO heterojunction nanocomposites[J]. Journal of Synthetic Crystals,2014,43(7):1809-1814,1822.
[22] Salavati-Niasari M, Soofivand F, Sobhani-Nasab A, et al.Synthesis,characterization,and morphological control of ZnTiO3nanoparticles through sol-gel processes and its photocatalyst application[J]. Advanced Powder Technology,2016,27(5):2066-2075.
[23]陈小泉,古国榜.以钛氧有机物为前驱物制备具有高光催化活性的纳米二氧化钛晶体[J].催化学报,2002,23(4):312-316.Chen X Q,Gu G B. Preparation of nanometer crystal Ti O2of high photocatalytic activity with titanyl organic compound as precursor[J]. Chinese Journal of Catalysis,2002,23(4):312-316.
[24] Mofokeng S J,Kumar V,Kroon R E,et al. Structure and optical properties of Dy3+activated sol-gel ZnO-TiO2nanocomposites[J]. Journal of Alloys and Compounds,2017,711:121-131.
[25] Morozov I G,Belousova O V,Ortega D,et al. Structural,optical,XPS and magnetic properties of Zn particles capped by ZnO nanoparticles[J]. Journal of Alloys and Compounds,2015,633:237-245.
[26]张鹏.钛基复合纳米纤维材料的制备及光催化性质研究[D].长春:东北师范大学,2014.
[27] Wang C C, Ying J Y. Sol-gel synthesis and hydrothermal processing of anatase and rutile titania nanocrystals[J].Chemistry of Materials,1999,11(11):3113-3120.
[28] Zhang Y C,Zhang Q,Shi Q W,et al. Acid-treated g-C3N4with improved photocatalytic performance in the reduction of aqueous Cr(Ⅵ)under visible-light[J]. Separation and Purification Technology,2015,142:251-257.
[29] Lu L Y,Wang G H,Zou M,et al. Effects of calcining temperature on formation of hierarchical Ti O2/g-C3N4hybrids as an effective Z-scheme heterojunction photocatalyst[J]. Applied Surface Science,2018,441:1012-1023.
[30]张雪,刘建新,王雅文,等.异质结型Ag Br/CuO光催化剂的合成、光催化活性及再生[J].高等学校化学学报,2016,37(1):88-93.Zhang X,Liu J X,Wang Y W,et al. Synthesis,photocatalytic activity and regeneration of Ag Br/CuO heterojunction photocatalyst[J]. Chemical Journal of Chinese Universities,2016,37(1):88-93.
[31] Zhang C Q,Li X Y,Zheng S Z,et al. Construction of Ti O2nanobelts-Bi2O4heterojunction with enhanced visible light photocatalytic activity[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2018,548:150-157.
[32] Wang Y J,Shi R,Lin J,et al. Enhancement of photocurrent and photocatalytic activity of Zn O hybridized with graphite-like C3N4[J]. Energy&Environmental Science,2011,4(8):2922-2929.
[33]闫俊青.基于Ti O2半导体光生载流子分离、可见光范畴拓展策略探究[D].天津:南开大学,2015.Yan J Q. Study of Ti O2-based semiconductors:Photo-generated carriers'separation and visible light response[D]. Tianjin:Nankai University,2015.
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