优化内浸式Ce掺杂ZnO光催化降解罗丹明B
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摘要
采用沉淀法优化制备了纳米级Ce掺杂ZnO,利用BET,XRD,SEM,ICP-AES,UV-VisDRS,FT-IR等手段对催化剂结构形态组成进行表征.提出内浸式光催化降解模式,考察液层厚度对透光率的影响,优化了Ce掺杂ZnO光催化降解罗丹明B实验条件,分析了其动力学和机理.结果表明,Ce掺杂比为3%(n:n),500℃热处理2h活性最高.催化剂呈球状,尺寸均匀,粒径80～100nm, BET比表面积12.9m~2/g,测定掺杂量和理论值一致, Ce掺杂增加了光吸收.悬浮液"遮挡效应"对光透过率衰减显著,催化剂浓度为0.1g/100mL时UV_(254)处光衰减率达到溶液的3倍.内浸式光催化降解1.0×10~(-5)mol/L罗丹明B溶液,在15W紫外灯,pH值为7,温度30℃,催化剂投加量0.1g/250mL条件下,70min降解率达到92.5%,6次套用降解率保持在80%以上,降解过程符合一级动力学,反应速率常数0.05min~(-1).
Cerium doped zinc oxide nano-scale particles was prepared by precipitation method, the properties including structure,morphology and composition were characterized by BET, XRD, SEM, ICP-AES, UV-Vis DRS and FT-IR. A new type of internal immersed irradiation photocatalytic degradation mode was proposed, relationship between liquid layer thickness and light transmittance was investigated. Finally, The conditions of photocatalytic degradation of rhodamine B were optimized, and the kinetics and mechanism were studied. Results showed that the optimum doped ratio and calcination temperature were 3%(n:n) and 500℃ for 2 h, respectively. Catalyst particles was sphere appearance with an average diameter distribution of 80～100 nm, and with BET specific surface area of 12.9 m~2/g, the content of doped cerium determined by ICP-AES accorded with theoretical value. The enhancement of catalytic activity was mainly due to the increase of light absorption after cerium doping. The shielding effect of suspension suggested a significant attenuation on light transmittance, light attenuation rate of UV_(254) was twice more than that of homogeneous solution when the catalyst concentration was 0.1 g/100 mL. It was applied to rhodamine B with concentration of 1.0×10~(-5) mol/L, the degradation rate reached to 92.5% in 70 min when UV lamp power was 15 W, pH value was 7, 30℃ and catalyst dosage was 0.1 g/250 mL, and the degradation rate was up to 80% even after 6 recycle, it followed first-order kinetic equation and the reaction rate constant was 0.05 min~(-1).
Cerium doped zinc oxide nano-scale particles was prepared by precipitation method, the properties including structure,morphology and composition were characterized by BET, XRD, SEM, ICP-AES, UV-Vis DRS and FT-IR. A new type of internal immersed irradiation photocatalytic degradation mode was proposed, relationship between liquid layer thickness and light transmittance was investigated. Finally, The conditions of photocatalytic degradation of rhodamine B were optimized, and the kinetics and mechanism were studied. Results showed that the optimum doped ratio and calcination temperature were 3%(n:n) and 500℃ for 2 h, respectively. Catalyst particles was sphere appearance with an average diameter distribution of 80～100 nm, and with BET specific surface area of 12.9 m~2/g, the content of doped cerium determined by ICP-AES accorded with theoretical value. The enhancement of catalytic activity was mainly due to the increase of light absorption after cerium doping. The shielding effect of suspension suggested a significant attenuation on light transmittance, light attenuation rate of UV_(254) was twice more than that of homogeneous solution when the catalyst concentration was 0.1 g/100 mL. It was applied to rhodamine B with concentration of 1.0×10~(-5) mol/L, the degradation rate reached to 92.5% in 70 min when UV lamp power was 15 W, pH value was 7, 30℃ and catalyst dosage was 0.1 g/250 mL, and the degradation rate was up to 80% even after 6 recycle, it followed first-order kinetic equation and the reaction rate constant was 0.05 min~(-1).
引文
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[27]吴春红,方艳芬,赵萍,等.Ag-BiVO4复合光催化剂的制备及其可见光光催化机理的研究[J].分子催化,2015,29(04):369-381.Wu C H,Fang Y F,Zhao P,et al.Preparation of Ag-BiVO4 composite and its photocatalytic oxidation mechanism[J].Journal of Molecular Catalysis(China),2015,29(4):369-381.
[28]Kumar R,Umar A,Kumar G,et al.Ce-doped ZnO nanoparticles for efficient photocatalytic degradation of direct red-23dye[J].Ceramics International,2015,41(2):7773-7782.
[29]Rasalingam S,Peng R,Koodali R T.An insight into the adsorption and photocatalytic degradation of rhodamine B in periodic mesoporous materials[J].Applied Catalysis B:Environmental,2015,174-175:49-59.
[2]雷佳妮,李晓良,袁孟孟,等.脉冲电化学氧化降解亚甲基蓝[J].中国环境科学,2018,38(5):1767-1773.Lei J N,Li X L,Yuan M M,et al.Pulse-electrochemical oxidation for methylene blue[J].China Environmental Science,2018,38(5):1767-1773.
[3]Katheresan V,Kansedo J,Lau S Y.Efficiency of various recent wastewater dye removal methods:A review[J].Journal of Environmental Chemical Engineering,2018,6(4):4676-4697.
[4]Duan W Y,Meng F P,Cui H W,et al.Ecotoxicity of phenol and cresols to aquatic organisms:A review[J].Ecotoxicology and Environmental Safety,2018,157:441-456.
[5]Huang Z H,Li Y Z,Chen W J,et al.Modified bentonite adsorption of organic pollutants of dye wastewater[J].Materials Chemistry and Physics,2017,202:266-276.
[6]Wang X H,Jiang C L,Hou B X,et al.Carbon composite lignin-based adsorbents for the adsorption of dyes[J].Chemosphere,2018,206:587-596.
[7]Shi X G,Tian A,You J H,et al.Degradation of organic dyes by a new heterogeneous Fenton reagent-Fe2Ge S4nanoparticle[J].Journal of Hazardous Materials,2018,353:182-189.
[8]Dutta S,Saha R,Kalita H,et al.Rapid reductive degradation of azo and anthraquinone dyes by nanoscale zero-valent iron[J].Environmental Technology&Innovation,2016,5:176-187.
[9]Lin Y T,Weng C H,Chen F Y.Effective removal of AB24dye by nano/micro-size zero-valent iron[J].Separation and Purification Technology,2008,64(1):26-30.
[10]Han Y H,Li H,Liu M L,et al.Purification treatment of dyes wastewater with a novel micro-electrolysis reactor[J].Separation and Purification Technology,2016,170:241-247.
[11]Meerbergen K,Crauwels S,Willems K A,et al.Decolorization of reactive azo dyes using a sequential chemical and activated sludge treatment[J].Journal of Bioscience and Bioengineering,2017,142(6):668-673.
[12]Tan L,He M Y,Song L,et al.Aerobic decolorization,degradation and detoxification of azo dyes by a newly isolated salt-tolerant yeast Scheffersomyces spartinae TLHS-SF1[J].Bioresource Technology,2016,23:287-294.
[13]Garcia-Segura S,Brillas E.Applied photoelectrocatalysis on the degradation of organic pollutants in wastewaters[J].Journal of Photochemistry and Photobiology C:Photochemistry Reviews,2017,31:1-35.
[14]Byrne C,Subramanian G,Pillai S C.Recent advances in photocatalysis for environmental applications[J].Journal of Environmental Chemical Engineering,2018,6(3):3531-3555.
[15]苏营营,于艳卿,杨沛珊,等.纳米Ti O2/硅藻土光催化降解蒽醌染料废水的研究[J].中国环境科学,2009,29(11):1171-1176.Su Y Y,Yu Y Q,Yang P S,et al.Photocatalytic degradation of anthraquinone dye wastewater with nano-Ti O2/diatomite[J].China Environmental Science,2009,29(11):1171-1176.
[16]Ong C B,Ng L Y,Mohammad A W.A review of ZnO nanoparticles as solar photocatalysts:Synthesis,mechanisms and applications[J].Renewable and Sustainable Energy Reviews,2018,81:536-551.
[17]Samadi M,Zirak M,Naseri A,et al.Recent progress on doped Zn Onanostructures for visible-light photocatalysis[J].Thin Solid Films,2016,605:2-19.
[18]袁敏,徐仁扣,封亚辉.微波辅助光催化降解兽药环丙氨嗪[J].中国环境科学,2012,32(4):603-608.Yuan M,Xu R K,Feng Y H.Microwave assisted photocatalytic degradation of cyromazine in aqueous solutions[J].China Environmental Science,2012,32(4):603-608.
[19]Valadés-Pelayo P J,Guayaquil S F,Serrano B,et al.Eight-lamp externally irradiated bench-scale photocatalytic reactor:Scale-up and performance prediction[J].Chemical Engineering Journal,2015,282:142-151.
[20]殷晓梅,王欣,雷磊,等.有机磷农药纳米Ti O2光催化降解反应器的优化设计[J].农业工程学报,2012,28(12):251-256.Yin X M,Wang X,Lei L,et al.Optimization design of nano-Ti O2photocatalytic degradation reactor for organic phosphorus pesticide[J].Transactions of the Chinese Society of Agricultural Engineering,2012,28(12):251-256.
[21]朱文庆,许磊,马瑾,等.粒径可控纳米Ce O2的微乳液法合成[J].物理化学学报,2010,26(5):1284-1290.Zhu W Q,Xu L,Ma J,et al.Size controlled synthesis of Ce O2nanoparticles by a microemulsion method[J].Acta Physico-Chimica Sinica,2010,26(5):1284-1290.
[22]余长林,杨凯,舒庆,等.WO3/ZnO复合光催化剂的制备及其光催化性能[J].催化学报,2011,32(4):555-565.Yu C L,Yang K,Shu Q,et al.Preparation of WO3/ZnO Composite Photocatalyst and Its Photocatalytic Performance[J].Chinese Journal of Catalysis,2011,32(4):555-565.
[23]陈沾,朱雷,汪恂.钇掺杂纳米氧化锌的光催化性能[J].环境工程学报,2016,10(11):6290-6294.Chen Z,Zhu L,Wang X.Photocatalysis of yttrium doped ZnOnanoparticles[J].Chinese Journal of Environmental Engineering,2016,10(11):6290-6294.
[24]余长林,杨凯,余济美,等.稀土Ce掺杂对ZnO结构和光催化性能的影响[J].物理化学学报,2011,27(2):505-512.Yu C L,Yang K,Yu J C,et al.Effects of rare earth Ce doping on the structure and photocatalytic performance of Zn O[J].Acta PhysicoChimica Sinica,2011,27(2):505-512.
[25]武志富,李素娟.氢氧化锌和氧化锌的红外光谱特征[J].光谱实验室,2012,29(4):2172-2175.Wu Z F,Li S J.Infrared spectra characteristics of zinc hydroxide and zinc oxide[J].Chinese Journal of Spectroscopy Laboratory,2012,29(4):2172-2175.
[26]刘恩科.半导体物理学[M],北京:电子工业出版社,2017:145-149.Liu E K.The physics of semiconductors(7th edition)[M].Beijing:publishing house of electronics industry,2017:145-149.
[27]吴春红,方艳芬,赵萍,等.Ag-BiVO4复合光催化剂的制备及其可见光光催化机理的研究[J].分子催化,2015,29(04):369-381.Wu C H,Fang Y F,Zhao P,et al.Preparation of Ag-BiVO4 composite and its photocatalytic oxidation mechanism[J].Journal of Molecular Catalysis(China),2015,29(4):369-381.
[28]Kumar R,Umar A,Kumar G,et al.Ce-doped ZnO nanoparticles for efficient photocatalytic degradation of direct red-23dye[J].Ceramics International,2015,41(2):7773-7782.
[29]Rasalingam S,Peng R,Koodali R T.An insight into the adsorption and photocatalytic degradation of rhodamine B in periodic mesoporous materials[J].Applied Catalysis B:Environmental,2015,174-175:49-59.