生物质改性纳米TiO_2的制备及其结构表征
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摘要
采用溶胶-凝胶法制备了系列生物质改性复合纳米TiO_2。以亚甲基蓝溶液为模拟污染物,考察了其可见光催化活性,并确定了最佳制备工艺。通过X射线光电子能谱(XPS)、X射线衍射(XRD)、场发射扫描电镜(FESEM)、紫外-可见漫反射光谱(UV-Vis-DRS)、荧光光谱(PL)等手段对催化剂样品进行了表征。实验结果表明,催化剂对亚甲基蓝的光催化降解适应一级反应动力学,复合TiO_2和纯TiO_2的反应速率常数分别为0.4990 h-1和0.0305h-1,且复合催化剂实现了C、N、S、P、K等多元素的共掺杂。相比纯TiO_2,复合TiO_2的比表面积增大,结晶度升高,光生载流子复合率降低,吸收边带红移,禁带宽度窄化了0.09 e V。
A series of biomass modified composite nano TiO_2 were prepared by sol-gel method. The visible photocatalytic activity was investigated and the optimum preparation process was determined,using methylene blue solution as a simulated pollutant. The catalysts were characterized by X-ray photoelectron spectroscopy( XPS),X-ray diffraction( XRD),field emission scanning electron microscopy( FESEM),ultraviolet-visible diffuse reflectance spectroscopy( UV-Vis-DRS) and fluorescence spectroscopy( PL).The experimental results show that the photocatalytic degradation of methylene blue is adapted to the firstorder reaction kinetics,and the reaction rate constants of composite titanium dioxide and pure titanium dioxide are 0. 4990 h-1 and 0. 0305 h-1,respectively. The composite catalyst realizes the simultaneous doping of C,N,S,P,K and other elements. Compared with pure titanium dioxide,the specific surface area of composite titanium dioxide increases, the crystallinity increases, the recombination rate of photogenerated carriers decreases,the absorption sideband redshifts,and the band gap narrows by0. 09 e V.
A series of biomass modified composite nano TiO_2 were prepared by sol-gel method. The visible photocatalytic activity was investigated and the optimum preparation process was determined,using methylene blue solution as a simulated pollutant. The catalysts were characterized by X-ray photoelectron spectroscopy( XPS),X-ray diffraction( XRD),field emission scanning electron microscopy( FESEM),ultraviolet-visible diffuse reflectance spectroscopy( UV-Vis-DRS) and fluorescence spectroscopy( PL).The experimental results show that the photocatalytic degradation of methylene blue is adapted to the firstorder reaction kinetics,and the reaction rate constants of composite titanium dioxide and pure titanium dioxide are 0. 4990 h-1 and 0. 0305 h-1,respectively. The composite catalyst realizes the simultaneous doping of C,N,S,P,K and other elements. Compared with pure titanium dioxide,the specific surface area of composite titanium dioxide increases, the crystallinity increases, the recombination rate of photogenerated carriers decreases,the absorption sideband redshifts,and the band gap narrows by0. 09 e V.
引文
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[24]邹隽,孙小华,徐晓飞,等.K掺杂PST薄膜的制备与介电调谐性能[J].三峡大学学报(自然科学版),2009,31(04):76-79.
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[26]程修文,于秀娟.C-N-S-Ti O2光催化剂的制备、表征及其性能[J].应用化学,2012,29(3):291-296.
[27]姜洪泉,王巧凤,李井申,等.N-P-Ti O2纳米粒子的溶胶-水热制备及太阳光下光催化降解4-氯酚性能[J].化学学报,2012,70(20):2173-2178.
[28]王磊,夏璐,金帅,等.硫掺杂二氧化钛光催化降解曙红Y溶液的研究[J].太阳能学报,2013,34(01):131-136.
[29]于洋洋,于美燕,张玥,等.氮掺杂二氧化钛粉体的制备及掺杂机理研究[J].无机化学学报,2013,29(8):1657-1662.
[30]郭薇,王开,沈艺花,等.简易模板剂法制备多级介孔Ti O2微球及其在染料敏化太阳能电池中的性能[J].物理化学学报,2013(01):82-88.
[2]Reddy K R,Hassan M,Gomes V G.Hybrid Nanostructures Based on Titanium Dioxide for Enhanced Photocatalysis[J].Applied Catalysis A General,2015,489:1-16.
[3]Tseng L T,Luo X,Bao N,et al.Structures and Properties of Transition-metal-doped Ti O2Nanorods[J].Materials Letters,2016,170:142-146.
[4]He P,Tao J,Huang X,et al.Preparation and Photocatalytic Antibacterial Property of Nitrogen Doped Ti O2Nanoparticles[J].Journal of Sol-gel Science Technology,2013,68(2):213-218.
[5]Nasirian M,Lin Y P,Bustillo-Lecompte C F,et al.Enhancement of Photocatalytic Activity of Titanium Dioxide Using Non-metal Doping Methods under Visible Light:A Review[J].International Journal of Environmental Science Technology,2017,15(9):2009-2032.
[6]Feng W,Lin L,Li H,et al.Hydrogenated Ti O2/Zn O Heterojunction Nanorod Arrays with Enhanced Performance for Photoelectrochemical Water Splitting[J].International Journal of Hydrogen Energy,2016,42(7):3938-3946.
[7]Peng C,Yao B H,Zhang W,et al.Synthesis of Cu APTPP-TDI-Ti O2Conjugated Microspheres and its Photocatalytic Activity[J].Chinese Journal of Chemical Physics,2014,27(2):200-208.
[8]Sushma C,Kumar S G.C-N-S Tridoping into Ti O2Matrix for Photocatalytic Applications:Observations,Speculations and Contradictions in the Codoping Process[J].Inorganic Chemistry Frontiers,2017,4(8):1250-1267.
[9]Zhang D,Yang M.Band Structure Engineering of Ti O2Nanowires by n-p Codoping for Enhanced Visible-light Photoelectrochemical Watersplitting[J].Physical Chemistry Chemical Physics,2013,15(42):18523-18529.
[10]江鸿,陈志武,卢振亚,等.铁、氮共掺杂二氧化钛的水热法合成及其光催化性能研究[J].人工晶体学报,2015,44(11):3292-3296.
[11]Di Valentin C,Pacchioni G,Selloni A.Theory of carbon doping of titanium dioxide[J].Chemistry of materials,2005,17(26):6656-6665.
[12]Ren W,Ai Z,Jia F,et al.Low temperature preparation and visible light photocatalytic activity of mesoporous carbon-doped crystalline Ti O2[J].Applied Catalysis B:Environmental,2007,69(3):138-144.
[13]彭婧娅,杜利成.大米洗涤水成分及功效的分析[J].食品与发酵科技,2013,49(01):76-78.
[14]乔金锁,刘冷,曹亚荣.淘米水中营养物质与矿物质的定性检测[J].化学教学,2013(08):47-49.
[15]Hoffmann M R,Martin S T,Choi W,et al.Environmental applications of semiconductor photocatalysis[J].Chemical reviews,1995,95(1):69-96.
[16]沈俊,罗妮,张明俊,等.介孔Ti O2-SO2-4的合成及表征[J].催化学报,2007,28(03):264-268.
[17]Qian J,Cui G,Jing M,et al.Hydrothermal synthesis of nitrogen-doped titanium dioxide and evaluation of its visible light photocatalytic activity[J].International Journal of Photoenergy,2012.
[18]Sato S,Nakamura R,Abe S.Visible-light sensitization of Ti O2photocatalysts by wet-method N doping[J].Applied Catalysis A:General,2005,284(1):131-137.
[19]秦好丽,古国榜,柳松,等.溶胶凝胶法制备氮掺杂二氧化钛及其可见光活性的研究[J].太阳能学报,2007,28(04):363-367.
[20]Lim J,Murugan P,Lakshminarasimhan N,et al.Synergic photocatalytic effects of nitrogen and niobium co-doping in Ti O2for the redox conversion of aquatic pollutants under visible light[J].Journal of Catalysis,2014,310:91-99.
[21]于新娈,王岩,孟祥江,等.钯氮共掺杂Ti O2的制备与表征及其可见光催化活性[J].催化学报,2013,34(07):1418-1428.
[22]Chen X,Zhang X,Su Y,et al.Preparation of visible-light responsive PF-codoped Ti O2nanotubes[J].Applied Surface Science,2008,254(20):6693-6696.
[23]张振兴,张海军,廖梦舟,等.溶胶-凝胶法制备K-N共掺Zn O薄膜的结构及光学特性[J].功能材料,2013,44(22):3301-3304.
[24]邹隽,孙小华,徐晓飞,等.K掺杂PST薄膜的制备与介电调谐性能[J].三峡大学学报(自然科学版),2009,31(04):76-79.
[25]孙大贵,杜军,刘作华,等.离子液体辅助N,S,F共掺杂纳米Ti O2的制备与表征[J].光谱学与光谱分析,2011,31(02):525-529.
[26]程修文,于秀娟.C-N-S-Ti O2光催化剂的制备、表征及其性能[J].应用化学,2012,29(3):291-296.
[27]姜洪泉,王巧凤,李井申,等.N-P-Ti O2纳米粒子的溶胶-水热制备及太阳光下光催化降解4-氯酚性能[J].化学学报,2012,70(20):2173-2178.
[28]王磊,夏璐,金帅,等.硫掺杂二氧化钛光催化降解曙红Y溶液的研究[J].太阳能学报,2013,34(01):131-136.
[29]于洋洋,于美燕,张玥,等.氮掺杂二氧化钛粉体的制备及掺杂机理研究[J].无机化学学报,2013,29(8):1657-1662.
[30]郭薇,王开,沈艺花,等.简易模板剂法制备多级介孔Ti O2微球及其在染料敏化太阳能电池中的性能[J].物理化学学报,2013(01):82-88.