以淀粉为模板多孔纳米氧化铈的制备及其催化性能研究
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摘要
为获得多孔纳米CeO_2(氧化铈),以淀粉为生物模板,以Ce(NO_3)_3·6H_2O为铈源,在温和条件下制备出海绵状的多孔纳米CeO_2,同时考察了焙烧温度、碱液、铈源投加量对样品形貌的影响.利用XRD (X射线衍射光谱)、SEM (扫描电镜)、N2吸附-脱附等表征手段对合成的多孔纳米CeO_2进行物相组成、微观形貌及孔径大小分布的分析.通过湿式催化过氧化试验,探究其对腈纶废水中有机物CODCr的催化降解性能.结果表明:(1)所制备的多孔纳米CeO_2具有多孔结构,孔径分布范围为2～4 nm,孔容为0. 225 cm3/g,BET比表面积为256. 426 m2/g;(2)多孔纳米CeO_2的最佳制备条件为1 g淀粉溶解于20 m L水中,加入0. 02 mol Ce(NO_3)_3·6H_2O,以5%的氨水调节前驱体混合液p H,以1℃/min升至400℃,焙烧4 h,得到海绵状的多孔纳米CeO_2.(3)以不同形貌的CeO_2作为湿式催化反应中的催化剂,催化降解腈纶废水中有机物,其中以制备的多孔纳米CeO_2催化性能最佳,CODCr去除率可达82. 5%.研究显示,焙烧温度、碱液、铈源投加量均可影响样品的形貌,在湿式催化过氧化处理腈纶废水试验中,多孔纳米CeO_2能显著提高废水CODCr的去除率.
In order to obtain porous nano CeO_2(cerium oxide),starch and Ce(NO_3)_3·6H_2O were employed as a biotemplate agent and cerium source,respectively. The porous nano CeO_2 was synthesized under mild conditions. Subsequently,the influence of calcination temperature and dosage of alkali and Ce( NO_3)_3·6H_2O on the morphology of the porous nano CeO_2 were investigated. The synthesized CeO_2 was characterized by X-ray diffraction( XRD),N2adsorption-desorption,and scanning electron microscopy( SEM). Furthermore,the catalytic performance was studied through the treatment of acrylic fiber wastewater by a catalytic wet peroxide oxidation method. The results indicated that:(1) The nano CeO_2 had a porous structure and with pore size between 2-4 nm,pore volume of 0. 225 cm3/g and BET surface area of 256. 426 m2/g.( 2) The optimum conditions for the preparation of the porous nano CeO_2were: dissolution of 1 g starch in 20 m L water followed by addition of 0. 02 mol Ce( NO_3)_3·6H_2O; p H adjustment of the precursor mixture using an aqueous solution of ammonia(5%); and calcination at 400 ℃ for 4 h with the heating rate of 1 ℃ /min in air. A nano CeO_2 with cavernous porous structure was obtained.(3) CeO_2 with different morphologies was used as catalyst in wet catalytic reactions for degrading refractory organic matters in acrylic wastewaters. The best catalytic efficiency was obtained with the prepared porous nano CeO_2,and the removal rate of CODCrreached 82. 5%. In conclusion,the morphology of the CeO_2 was affected by the calcination temperature and dosage of alkali and Ce( NO_3)_3·6H_2O. This porous nano CeO_2 can be used as an effective catalyst for treatment of acrylic wastewaters in wet catalyticperoxidation processes. The removal efficiency of CODCrcould be significantly improved.
In order to obtain porous nano CeO_2(cerium oxide),starch and Ce(NO_3)_3·6H_2O were employed as a biotemplate agent and cerium source,respectively. The porous nano CeO_2 was synthesized under mild conditions. Subsequently,the influence of calcination temperature and dosage of alkali and Ce( NO_3)_3·6H_2O on the morphology of the porous nano CeO_2 were investigated. The synthesized CeO_2 was characterized by X-ray diffraction( XRD),N2adsorption-desorption,and scanning electron microscopy( SEM). Furthermore,the catalytic performance was studied through the treatment of acrylic fiber wastewater by a catalytic wet peroxide oxidation method. The results indicated that:(1) The nano CeO_2 had a porous structure and with pore size between 2-4 nm,pore volume of 0. 225 cm3/g and BET surface area of 256. 426 m2/g.( 2) The optimum conditions for the preparation of the porous nano CeO_2were: dissolution of 1 g starch in 20 m L water followed by addition of 0. 02 mol Ce( NO_3)_3·6H_2O; p H adjustment of the precursor mixture using an aqueous solution of ammonia(5%); and calcination at 400 ℃ for 4 h with the heating rate of 1 ℃ /min in air. A nano CeO_2 with cavernous porous structure was obtained.(3) CeO_2 with different morphologies was used as catalyst in wet catalytic reactions for degrading refractory organic matters in acrylic wastewaters. The best catalytic efficiency was obtained with the prepared porous nano CeO_2,and the removal rate of CODCrreached 82. 5%. In conclusion,the morphology of the CeO_2 was affected by the calcination temperature and dosage of alkali and Ce( NO_3)_3·6H_2O. This porous nano CeO_2 can be used as an effective catalyst for treatment of acrylic wastewaters in wet catalyticperoxidation processes. The removal efficiency of CODCrcould be significantly improved.
引文
[1] ADIL L,JACQUELINE L,REN Guogang,et al. Simulation and experimental study of rheological properties of CeO2water nanofluid[J].Original Article,2015,5:1-7.
[2]张晓薇,甘国强.Fe3O4/CeO2复合材料催化降解橙黄G的效能及降解途径[J].环境科学研究,2017,30(9):1455-1463.ZHANG Xiaowei,GAN Guoqiang. OG degradation efficiency and pathway using Fe3O4/CeO2composite[J]. Research of Environmental Sciences,2017,30(9):1455-1463.
[3] HUANG Bingjie,YU Danqing,SHENG Zhongyi,et al. Novel CeO2@Ti O2core-shell nanostructure catalyst for selective catalytic reduction of NOxwith NH3[J].Journal of Environmental Sciences,2017,55:129-136.
[4] CHEN Feng,WANG Wei,CHEN Zhigang,et al.Biogenic synthesis and catalysis of porous CeO2hollow microspheres[J]. Journal of Rare Earths,2012,30(4):350-355.
[5] LIU Yiding,GOEBL J,YIN Yadong. Templated synthesis of nano structured materials[J]. Chemical Society Reviews,2013,42(7):2610-2653.
[6]黄鑫,周建飞,廖学品.生物模板法制备纳米材料[J].四川师范大学学报(自然科学版),2015,38(1):148-160.HUANG Xin,ZHOU Jianfei,LIAO Xuepin. Biotemplated synthesis of nanomaterials[J].Journal of Sichuan Normal University(Natural Science Edition),2015,38(1):148-160.
[7] RIJUTA G S,GANESH D S,HAN S S,et al.New insights on the green synthesis of metallic nanoparticles using plant and waste biomaterials:current knowledge, their agricultural and environmental applications[J]. Environmental Science&Pollution Research,2018,25:10164-10183.
[8] KOBRA A,ALI R,SAEID TF. A novel sol-gel synthesis and characterization of Mg Fe2O4@γ-Al2O3magnetic nanoparticles using tragacanth gel and its application as a magnetically separable photocatalyst for degradation of organic dyes under visible light[J].Journal of Materials Science,2018,29(8):6702-6710.
[9] PANG S C,CHEN L T,CHIN S F.Starch-based gel electrolyte thin films derived from native sago(Metroxylon sagu)starch[J].Original Paper,2014,20:1455-1462.
[10] VANESSA P,YASUAKI T. 3D hierarchical and porous layered double hydroxide structures:an overview of synthesis methods and applications[J]. Journal of Materials Science,2017,52:11229-11250.
[11] NARAYANAN T N,SAKTHI K D,YOSHIDA Y,et al. Strain induced anomalous red shift in mesoscopic iron oxide prepared by a novel technique[J].Bull Material Science,2008,31:759-766.
[12] RAMALINGAM K,KAMATCHI T,SUMOD P A. Synthesis,spectral,thermal and CO2absorption studies on birnessites type layered Mn O6oxide[J].Transition Metal Chemistry,2006,31:429-433.
[13] KOCHKAR H,TRIKI M,JABOU K,et al.Novel synthesis route to titanium oxides nanomaterials using soluble starch[J]. Journal of Sol-Gel Science Technology,2007,42:27-33.
[14] IWASAKI M,DAVIS S A,MANN S.Spongelike macroporous Ti O2monoliths prepared from starch gel template[J]. Journal of Sol-Gel Science Technology,2004,32:99-105.
[15] CHEN Qing,YU Haojie,WANG Li,et al. Recent progress in chemical modification of starch and its applications[J]. RSC Advances,2015,5:67459-67474.
[16] EMIL I M,NICANOR C,ALEXANDRA B.Effect of the template on the textural properties of the macrospherical trimodal metallosilicate materials[J]. Journal of Inorganic&Organometallic Polymers,2015,25(5):1-9.
[17] HOSSEINI S A. Low-cost and eco-friendly viable approach for synthesis of thulium doped copper ferrite nanoparticles using starch[J].Journal of Materials Science Materials in Electronics,2016,27(7):7433-7437.
[18] JURRIAAN B,GADI R. Sustainable selective oxidations using ceria-based materials[J].Green Chemistry,2010,12:939-948.
[19]张永利,韦朝海,王庆雨,等.制备工艺对La改性湿式氧化催化剂活性和稳定性的影响[J].环境科学研究,2014,27(2):210-217.ZHANG Yongli,WEI Chaohai,WANG Qingyu,et al. Influence of preparation conditions on activity and stability of CWAO catalyst Cu-Fe-La/FSC modified by La[J]. Research of Environmental Sciences,2014,27(2):210-217.
[20] SAIDA M G,FRINI S N.Catalytic wet peroxide oxidation of phenol over Ce-Zr-modified clays:effect of the pillaring method[J].Korean Journal of Chemical Engineering,2015,32(1):68-73.
[21] RALUCA P C,COSMIN C L,ANDRADA M. Preparation,characterization,and testing of metal-doped carbon xerogels as catalyst for phenol CWAO[J].Environmental Science and Pollution Research,2017,24(3):2980-2986.
[22]王晓叶,郑斌,冯志海.X射线衍射全谱拟合定量分析方法研究[J].宇航材料工艺,2012,42(2):108-110.WANG Xiaoye,ZHENG Bin,FENG Zhihai. Quantitive phase analysis of Si-TiO2by rietveld refinement of XRD patterns[J].Aerospace Materals&Technology,2012,42(2):108-110.
[23]王中平.表面物理化学[M].上海:同济大学出版社,2015:172-173.
[24]王栋,张信莉,彭建升,等.煅烧温度对γ-Fe2O3催化剂结构及其脱硝活性的影响[J].环境科学研究,2015,28(5):808-815.WANG Dong,ZHANG Xinli,PENG Jiansheng,et al. Effects of calcination temperature on selective catalytic reduction of NO,overγ-Fe2O3catalysts prepared with microwave assistance[J].Research of Environmental Sciences,2015,28(5):808-815.
[25] TAHEREH T,MOHSEN H,BABAK R. Effect of sintering temperature on the microstructure,roughness and electrochemical impedance of electrophoretically deposited YSZ electrolyte for SOFCs[J]. International Journal of Hydrogen Energy,2010,35(17):9420-9426.
[26] LEE S M,JUN Y W,CHO S N,et al.Single-crystalline star-shaped nanocrystals and their evolution:programming the geometry of nanobuilding blocks[J]. Journal of American Chemical Society,2002,124:11244-11245.
[27]吴庆银.现代无机合成与制备化学[M].北京:化学工业出版社,2010:5-16.
[28]赵国峥,颜廷广,戚益,等.微波辅助湿式催化氧化处理腈纶废水的研究[J].工业水处理,2015,35(11):22-25.ZHAO Guozheng,YAN Tingguang,QI Yi,et al. Study on microwave-assisted CWAO for treating acrylic fiber wastewater[J].Industrial Water Treatment,2015,35(11):22-25.
[29] SAIDA M G,FRINI-SRASRA N.Catalytic wet peroxide oxidation of phenol over Ce-Zr-modified clays:effect of the pillaring method[J].Korean Journal of Chemical Engineering,2015,32(1):68-73.
[30] VALENTIN V,LUBOMIRA T. Porous nanosized particles:preparation,properties,and applications[J]. Chemical Reviews,2013,113(8):6734-6760.
[2]张晓薇,甘国强.Fe3O4/CeO2复合材料催化降解橙黄G的效能及降解途径[J].环境科学研究,2017,30(9):1455-1463.ZHANG Xiaowei,GAN Guoqiang. OG degradation efficiency and pathway using Fe3O4/CeO2composite[J]. Research of Environmental Sciences,2017,30(9):1455-1463.
[3] HUANG Bingjie,YU Danqing,SHENG Zhongyi,et al. Novel CeO2@Ti O2core-shell nanostructure catalyst for selective catalytic reduction of NOxwith NH3[J].Journal of Environmental Sciences,2017,55:129-136.
[4] CHEN Feng,WANG Wei,CHEN Zhigang,et al.Biogenic synthesis and catalysis of porous CeO2hollow microspheres[J]. Journal of Rare Earths,2012,30(4):350-355.
[5] LIU Yiding,GOEBL J,YIN Yadong. Templated synthesis of nano structured materials[J]. Chemical Society Reviews,2013,42(7):2610-2653.
[6]黄鑫,周建飞,廖学品.生物模板法制备纳米材料[J].四川师范大学学报(自然科学版),2015,38(1):148-160.HUANG Xin,ZHOU Jianfei,LIAO Xuepin. Biotemplated synthesis of nanomaterials[J].Journal of Sichuan Normal University(Natural Science Edition),2015,38(1):148-160.
[7] RIJUTA G S,GANESH D S,HAN S S,et al.New insights on the green synthesis of metallic nanoparticles using plant and waste biomaterials:current knowledge, their agricultural and environmental applications[J]. Environmental Science&Pollution Research,2018,25:10164-10183.
[8] KOBRA A,ALI R,SAEID TF. A novel sol-gel synthesis and characterization of Mg Fe2O4@γ-Al2O3magnetic nanoparticles using tragacanth gel and its application as a magnetically separable photocatalyst for degradation of organic dyes under visible light[J].Journal of Materials Science,2018,29(8):6702-6710.
[9] PANG S C,CHEN L T,CHIN S F.Starch-based gel electrolyte thin films derived from native sago(Metroxylon sagu)starch[J].Original Paper,2014,20:1455-1462.
[10] VANESSA P,YASUAKI T. 3D hierarchical and porous layered double hydroxide structures:an overview of synthesis methods and applications[J]. Journal of Materials Science,2017,52:11229-11250.
[11] NARAYANAN T N,SAKTHI K D,YOSHIDA Y,et al. Strain induced anomalous red shift in mesoscopic iron oxide prepared by a novel technique[J].Bull Material Science,2008,31:759-766.
[12] RAMALINGAM K,KAMATCHI T,SUMOD P A. Synthesis,spectral,thermal and CO2absorption studies on birnessites type layered Mn O6oxide[J].Transition Metal Chemistry,2006,31:429-433.
[13] KOCHKAR H,TRIKI M,JABOU K,et al.Novel synthesis route to titanium oxides nanomaterials using soluble starch[J]. Journal of Sol-Gel Science Technology,2007,42:27-33.
[14] IWASAKI M,DAVIS S A,MANN S.Spongelike macroporous Ti O2monoliths prepared from starch gel template[J]. Journal of Sol-Gel Science Technology,2004,32:99-105.
[15] CHEN Qing,YU Haojie,WANG Li,et al. Recent progress in chemical modification of starch and its applications[J]. RSC Advances,2015,5:67459-67474.
[16] EMIL I M,NICANOR C,ALEXANDRA B.Effect of the template on the textural properties of the macrospherical trimodal metallosilicate materials[J]. Journal of Inorganic&Organometallic Polymers,2015,25(5):1-9.
[17] HOSSEINI S A. Low-cost and eco-friendly viable approach for synthesis of thulium doped copper ferrite nanoparticles using starch[J].Journal of Materials Science Materials in Electronics,2016,27(7):7433-7437.
[18] JURRIAAN B,GADI R. Sustainable selective oxidations using ceria-based materials[J].Green Chemistry,2010,12:939-948.
[19]张永利,韦朝海,王庆雨,等.制备工艺对La改性湿式氧化催化剂活性和稳定性的影响[J].环境科学研究,2014,27(2):210-217.ZHANG Yongli,WEI Chaohai,WANG Qingyu,et al. Influence of preparation conditions on activity and stability of CWAO catalyst Cu-Fe-La/FSC modified by La[J]. Research of Environmental Sciences,2014,27(2):210-217.
[20] SAIDA M G,FRINI S N.Catalytic wet peroxide oxidation of phenol over Ce-Zr-modified clays:effect of the pillaring method[J].Korean Journal of Chemical Engineering,2015,32(1):68-73.
[21] RALUCA P C,COSMIN C L,ANDRADA M. Preparation,characterization,and testing of metal-doped carbon xerogels as catalyst for phenol CWAO[J].Environmental Science and Pollution Research,2017,24(3):2980-2986.
[22]王晓叶,郑斌,冯志海.X射线衍射全谱拟合定量分析方法研究[J].宇航材料工艺,2012,42(2):108-110.WANG Xiaoye,ZHENG Bin,FENG Zhihai. Quantitive phase analysis of Si-TiO2by rietveld refinement of XRD patterns[J].Aerospace Materals&Technology,2012,42(2):108-110.
[23]王中平.表面物理化学[M].上海:同济大学出版社,2015:172-173.
[24]王栋,张信莉,彭建升,等.煅烧温度对γ-Fe2O3催化剂结构及其脱硝活性的影响[J].环境科学研究,2015,28(5):808-815.WANG Dong,ZHANG Xinli,PENG Jiansheng,et al. Effects of calcination temperature on selective catalytic reduction of NO,overγ-Fe2O3catalysts prepared with microwave assistance[J].Research of Environmental Sciences,2015,28(5):808-815.
[25] TAHEREH T,MOHSEN H,BABAK R. Effect of sintering temperature on the microstructure,roughness and electrochemical impedance of electrophoretically deposited YSZ electrolyte for SOFCs[J]. International Journal of Hydrogen Energy,2010,35(17):9420-9426.
[26] LEE S M,JUN Y W,CHO S N,et al.Single-crystalline star-shaped nanocrystals and their evolution:programming the geometry of nanobuilding blocks[J]. Journal of American Chemical Society,2002,124:11244-11245.
[27]吴庆银.现代无机合成与制备化学[M].北京:化学工业出版社,2010:5-16.
[28]赵国峥,颜廷广,戚益,等.微波辅助湿式催化氧化处理腈纶废水的研究[J].工业水处理,2015,35(11):22-25.ZHAO Guozheng,YAN Tingguang,QI Yi,et al. Study on microwave-assisted CWAO for treating acrylic fiber wastewater[J].Industrial Water Treatment,2015,35(11):22-25.
[29] SAIDA M G,FRINI-SRASRA N.Catalytic wet peroxide oxidation of phenol over Ce-Zr-modified clays:effect of the pillaring method[J].Korean Journal of Chemical Engineering,2015,32(1):68-73.
[30] VALENTIN V,LUBOMIRA T. Porous nanosized particles:preparation,properties,and applications[J]. Chemical Reviews,2013,113(8):6734-6760.