磷钨酸/凹凸棒石复合催化剂光催化降解苯
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摘要
采用溶胶-凝胶法制备了凹凸棒石负载磷钨酸复合催化剂,利用XRD、SEM、BET对其进行表征,并探讨了该催化剂对气相苯的降解情况。考察了苯的初始浓度、光照时间以及外界气体对苯降解的影响。研究结果表明,PW/ATP复合催化剂具有良好的光催化活性,当PW/ATP复合催化剂用量为1 g,254 nm紫外光辐射4 h后对初始浓度为265.50 mg/m~3的苯的降解率可达到68.4%。PW/ATP复合催化剂对苯的降解过程中,凹凸棒石主要是为苯提供大量的吸附位点,主要降解机理是磷钨酸电子-空穴对的生成和生成具有氧化性的自由基。
Phosphotungstic acid/attapul gite(PW/ATP) composite photocatalysts were prepared by sol-gel method and characterized by X-ray diffraction(XRD) ,scanning electron microscope(SEM) and BET specific surface area methods.Photocatalytic performance and mechanism of composite catalysts were investigated with benzene as test compound.The effect such as benzene initial concentration and irradiation time on catalytic degradation of benzene was also discussed.The results indicated that the PW/ATP composite catalysts had excellent catalytic performance on gaseous benzene degradation.In the case of benzene concentration at 265.50 mg/m~3,the degradation efficiency,over PW/ATP composite with 1 g,reached 68.4% after 4 h under 254 nm UV light irradiation.PW/ATP composites photocatalytic degradation benzene was mainly caused by oxidizing property of electron-holes and oxidative free radicals synergy effect.
Phosphotungstic acid/attapul gite(PW/ATP) composite photocatalysts were prepared by sol-gel method and characterized by X-ray diffraction(XRD) ,scanning electron microscope(SEM) and BET specific surface area methods.Photocatalytic performance and mechanism of composite catalysts were investigated with benzene as test compound.The effect such as benzene initial concentration and irradiation time on catalytic degradation of benzene was also discussed.The results indicated that the PW/ATP composite catalysts had excellent catalytic performance on gaseous benzene degradation.In the case of benzene concentration at 265.50 mg/m~3,the degradation efficiency,over PW/ATP composite with 1 g,reached 68.4% after 4 h under 254 nm UV light irradiation.PW/ATP composites photocatalytic degradation benzene was mainly caused by oxidizing property of electron-holes and oxidative free radicals synergy effect.
引文
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[25]Yu Q Q,Tang Z R,Xu Y J.Synthesis of Bi VO4nanosheets-graphene composites toward improved visible light photoactivity[J].2014,23(5):564-574.
[26]Fu Y,Sun X,Xin W.Bi VO4-graphene catalyst and its high photocatalytic performance under visible light irradiation[J].Materials Chemistry&Physics,2011,131(1/2):325-330.
[27]Andrade L S,Rocha Filho R C,Bocchi N,et al.Degradation of phenol using Co and Co,F-doped Pb O2anodes in electrochemical filter-press cells[J].Journal of Hazardous Materials,2008,153(112):252-260.
[2]Bhorodwaj S K,Dutta D K.Activated clay supported het eropoly acid catalysts for esterication of acetic acid with butanol[J].Applied Clay Science,2011,53:347-352.
[3]马荣华,王佳奇,赵春燕.杂多酸/Ti O2复合光催化剂材料的制备及光催化性能[J].环境科学与技术,2011,34(5):35-38.Ma Ronghua,Wang Jiaqi,Zhao Chunyan.Preparation and photocatalytic properties of heteropoly Acids/Ti O2[J].Environmental Science&Technlogy,2011,34(5):35-38.(in Chinese)
[4]吕结,韩金玉,王华,等.水热法合成SBA-15负载杂多酸催化纤维素水解加氢[J].化学工业与工程,2016,33(2):1-6.Lyu Jie,Han Jinyu,Wang Hua,et al.Catalytic conversion of cellulose over SBA-15 supported heteropolyacids[J].Chemical Industry and Energineering,2016,33(2):1-6.(in Chinese)
[5]Kormali P,Troupis A,Triantis T,et al.Photocatalysis by polyoxometallates and Ti O2:A comparative study[J].Catal ysis Today,2007,124(3/4):149-155.
[6]李红跃,王雷,张曼,等.负载型杂多酸脱除焦化蜡油中碱性氮化物[J].化工进展,2016,35(3):826-830.Li Hongyao,Wang Lie,Zhang Man,et al.Removal of basic nitrogen compounds in coker gas oil by supported het eropoly acid[J].Chemical progress,2016,35(3):826-830.(in Chinese)
[7]路莹,鲁楠,赵雅辉,等.磺胺甲唑在磷钨酸/二氧化钛复合膜上的光催化降解[J].环境化学,2014,33(4):649-655.Lu Ying,Lu Nan,Zhao Yahui,et al.Photocatlytic degrada tion sulfamethoxazole of using H3PW12O4/Ti O2composite film[J].Environmental Chemistry,2014,33(4):649-655.(in Chinese)
[8]Shi Y,Yang Z,Wang B,et al.Adsorption and photocatalyt ic degradation of tetracycline hydrochloride using a paly gorskite-supported Cu2O-Ti O2composite[J].Applied Clay Science,2016,119:311-320.
[9]Chen T H,Liu H B,Li J H,et al.Effect of thermal treatment on adsorption-desorption of ammonia and sulfur dioxide on palygorskite:Change of surface acid-alkali properties[J].Chemical Engineering Journal,2011,166(3):1017-1021.
[10]He X,Tang A,Yang H,et al.Synthesis and catalytic activi ty of doped Ti O2-palygorskite composites[J].Applied Clay Science,2011,53(1):80-84.
[11]Juan J C,Zhang J,Yarmo M A.12-Tungstophosphoric acid supported on MCM-41 for esterification of fatty acid under solvent-free condition[J].Journal of Molecular Catalysis A:Chemical,2007,267(1/2):265-271.
[12]Bouna L,Rhouta B,Amjoud M,et al.Synthesis,characteri zation and photocatalytic activity of Ti O2supported natural palygorskite microfibers[J].Applied Clay Science,2011,52(3):301-311.
[13]Wu D,Huo P,Lu Z,et al.Preparation of heteropolyacid/Ti O2/fly-ash-cenosphere photocatalyst for the degradation of ciprofloxacin from aqueous solutions[J].Applied Surface Science,2012,258(18):7008-7015.
[14]李湘祁,汤德平,翁国坚,等.煅烧对Ti O2柱撑粘土光催化性能的影响[J].硅酸盐通报,2004(2):25-27.Li Xiangqi,Tang Deping,Weng Guojian,et al.Effect of calcination on the photocatlytic properties of Ti O2-pillared clays[J].Bulletin of the Chinese Ceramic Society,2004(2):25-27.(in Chinese)
[15]Chala S,Wetchakun K,Phanichphant S,et al.Enhanced visible-light-response photocatalytic degradation of methylene blue on Fe-loaded Bi VO4photocatalyst[J].Journal of Alloys&Compounds,2014,597(10):129-135.
[16]潘钢华,夏艺,王然良,等.煅烧凹凸棒石粘土对干粉砂浆性能的影响[J].东南大学学报:自然科学版,2006,36(1):129-133.
[17]Lee J,Dong X,Dong X.Ultrasonic synthesis and photo catalytic characterization of H3PW12O40/Ti O2(anatase)[J].Ultrasonics Sonochemistry,2010,17(4):649-653.
[18]Ma J Z,Zhu C,Lu J,et al.Catalytic degradation of gaseous benzene by using Ti O2/goethite immobilized on palygorskite:preparation,characterization and mechanism[J].Solid State Sciences,2015,49:1-9.
[19]李云霞,李冬妮,朱承驻,等.复合催化剂磷钨酸/Ti O2光催化降解苯[J].环境科学与技术,2014,37(S2):77-81.Li Yunxia,Li Dongni,Zhu Chengzhu,et al.Photodegradation of benzene with PW/Ti O2composite catalysts[J].Environmental Science&Technology,2014,37(S2):77-81.(in Chinese)
[20]刘洋,杨海燕.Ti O2光催化降解苯和甲苯的动力学研究[J].化学通报,2007,70(3):222-227.Liu Yang,Yang Haiyan.Kinetic study on photocatalytic degradation of benzene and toluene by Ti O2[J].Chemistry Bulletin,2007.70(3):222-227.(in Chinese)
[21]And R R O,Ferry J L.Kinetic probes of the mechanism of polyoxometalate-mediated[J].Applied Catalysis B Environmental,2011,110(45):286-295.
[24]邓谦,吕晓萌,蔡铁军,等.磷钨酸表面修饰Ti O2光催化降解空气污染物[J].中国环境科学,2005,25(3):375-379.
[25]Yu Q Q,Tang Z R,Xu Y J.Synthesis of Bi VO4nanosheets-graphene composites toward improved visible light photoactivity[J].2014,23(5):564-574.
[26]Fu Y,Sun X,Xin W.Bi VO4-graphene catalyst and its high photocatalytic performance under visible light irradiation[J].Materials Chemistry&Physics,2011,131(1/2):325-330.
[27]Andrade L S,Rocha Filho R C,Bocchi N,et al.Degradation of phenol using Co and Co,F-doped Pb O2anodes in electrochemical filter-press cells[J].Journal of Hazardous Materials,2008,153(112):252-260.