Catalytic properties of CeO2-TiO2/attapulgite nanocomposites prepared by sol-gel method

doi:10.3969/j.issn.0438-1157.2013.07.050

Abstract

Abstract: CeO₂-TiO₂/attapulgite (ATP)nanocomposites were prepared by the sol-gel method using ATP as support,cerium nitrate hexahydrate and tetrabutyl titanate as raw materials,glacial acetic acid as complexing agent.The microstructures of the as-prepared composites were characterized by thermogravimetric-differential scanning caloricity (TG-DSC)analysis,transmission electron microscopy (TEM),X-ray diffraction (XRD),and nitrogen adsorption-desorption measurements.The effects of Ce/Ti molar ratio on catalytic properties of the as-prepared composites for decomposing Rhodamine B solutions were investigated.The results indicated that when Ce/Ti was more than or equal to 5/5,CeO₂-TiO₂ solid solution oxide particles with cubic fluorite structure were uniformly coated on the surface of ATP with particle size of 5—10 nm.With the increase of Ti⁴⁺ content,CeO₂ nanoparticles tended to form a defective crystalline phase and existed as amorphous phase.When Ce/Ti was less than 3/7,a separated anatase TiO₂ was observed in the composites.A suitable amount of Ti⁴⁺ doping could promote the formation of structure defects,which contributed to increasing the content of oxygen vacancies and improving the catalytic activity.The catalytic efficiency of CeO₂-TiO₂/ATP (Ce/Ti=5/5)nanocomposite on Rhodamine B solution was higher than that of others,and the removal rate of chemical oxygen demand (COD)could reach over 96%.

Key words: attapulgite, CeO₂-TiO₂, catalytic property

摘要： 以凹凸棒石(ATP)为载体,Ce(NO₃)₃·6H₂O和Ti(OBu)₄为原料,冰醋酸为抑制剂,采用溶胶-凝胶法制备CeO₂-TiO₂/ATP纳米复合材料。利用TG-DSC、TEM、XRD和N₂吸附/脱附仪对复合材料进行表征,考察铈钛摩尔比对所制备样品催化降解罗丹明B溶液性能的影响。结果表明,当Ce/Ti≥5/5时,具有立方萤石结构的氧化物颗粒以固溶体形式均匀分布在ATP表面,颗粒尺寸约5~10 nm;随Ti⁴⁺的进一步增加,样品中的CeO₂结晶不完全;当Ce/Ti<3/7时,样品中出现锐钛矿型TiO₂的分离相。适量的Ti⁴⁺掺杂能促进CeO₂产生较多的结构缺陷,有利于增加晶格氧空位的浓度,提高样品的催化活性。对罗丹明B的催化降解实验表明,当Ce/Ti=5/5时,样品的催化性能较好,对罗丹明B溶液的化学需氧量(COD)去除率可达96%以上。

关键词: 凹凸棒石, CeO₂-TiO₂, 催化性能

CLC Number:

TB332
TB383

MENG Yingqin, ZHAO Xiaobing, LI Xiazhang. Catalytic properties of CeO₂-TiO₂/attapulgite nanocomposites prepared by sol-gel method[J]. CIESC Journal, 2013, 64(7): 2679-2686.

孟英芹, 赵晓兵, 李霞章. sol-gel法制备CeO₂-TiO₂/凹凸棒石复合材料的催化性能[J]. 化工学报, 2013, 64(7): 2679-2686.

References 28

[1]	Zou Jianguo (邹建国),Zhong Qin (钟秦).Purifying diesel exhaust gas with rare earth modified attapulgite clay[J].Journal of the Chinese Ceramic Society(硅酸盐学报),2005,33(8):1028-1031
[2]	Khaodee W,Jongsomjit B,Assabumrungrat S,Praserthdam P,Goto S.Investigation of isosynthesis via CO hydrogenation over ZrO2 and CeO2 catalysts:effects of crystallite size,phase composition and acid-base sites[J].Catal.Commun.,2007,8(3):548-556
[3]	Zhao Xiaobing (赵晓兵),You Jing (游静),Lu Xiaowang (陆晓旺),Chen Zhigang(陈志刚).Hydrothermal synthesis,characterization and property of CeO2 nanotube[J].Journal of Inorganic Materials(无机材料学报),2011,26(2):159-164
[4]	Lin S S,Chen C L,Chang D J,Chen C C.Catalytic wet air oxidation of phenol by various CeO2 catalysts[J].Water Res.,2002,36(12):3009-3014
[5]	Bueno-López A,Krishna K,Makkee M,Moulijn J A.Enhanced soot oxidation by lattice oxygen via La3+-doped CeO2[J].J.Catal.,2005,230:237-248
[6]	Bueno-López A,Krishna K,van der Linden B,Mul G,Moulijn J A,Makkee M.On the mechanism of model diesel soot-O2 reaction catalyzed by Pt-containing La3+-doped CeO2 A TAP study with isotopic O2[J].Catal.Today,2007,121:237-245
[7]	Li H F,Lu G Z,Dai Q G,Wang Y Q,Guo Y,Guo Y L.Efficient low-temperature catalytic combustion of trichloroethylene over flower-like mesoporous Mn-doped CeO2 microspheres[J].Appl.Catal.B:Environ.,2011,102(3/4):475-483
[8]	Yuan Wenhui (袁文辉),Zhou Chenchen (周辰辰),Li Li (李莉).Study on catalytic properties of nano-CeO2-ZrO2 mixed oxides prepared by modified sol-gel method[J].Journal of Inorganic Materials(无机材料学报),2010,25(8):820-824
[9]	Nakagama K,Murata Y,Kishida M,Adachi M,Hiro M,Susa K.Formation and reaction activity of CeO2 nanoparticles of cubic structure and various shaped CeO2-TiO2 composite nanostructures[J].Mater.Chem.Phys.,2007,104(1):30-39
[10]	Baidya T,Gayen A,Hegde M S,Ravishankar N,Dupont L.Enhanced reducibility of Ce1-xTixO2 compared to that of CeO2 and higher redox catalytic activity of Ce1-x-yTixPtyO2-δ compared to that of Ce1-xPtxO2-δ[J].J.Phys.Chem.B,2006,110(11):5262-5272
[11]	Dutta G,Waghmare U V,Baidya T,Hegde M S,Priolkar K R,Sarode P R.Origin of enhanced reducibility/oxygen storage capacity of Ce1-xTixO2 compared to CeO2 or TiO2[J].Chem.Mater.,2006,18(14):3249-3256
[12]	Tryba B,Tsumura T,Janus M,Morawski,Inagaki M.Carbon-coated anatase:adsorption and decomposition of phenol in water[J].Appl.Catal.B:Environ.,2004,50(3):177-183
[13]	Chen M L,Zhang F J,Oh W C.Synthesis,characterization,and photocatalytic analysis of CNT/TiO2 composites derived from MWCNTs and titanium sources[J].New Carbon Mater.,2009,24(2):159-166
[14]	Kamegawa T,Yamahana D,Yamashita H.Graphene coating of TiO2 nanoparticles loaded on mesoporous silica for enhancement of photocatalytic activity[J].J. Phys. Chem.C,2010,114(35):15049-15053
[15]	Hu Yuhai (胡玉海),Gao Jian(高健),Wang Jun(王军),Dong Lin(董林),Ding Weiping (丁维平),Chen Yi (陈懿).Surface interaction and Denox properties of CuO/CeO2/γ-Al2O3 catalysis[J].Chemical Journal of Chinese Universities(高等学校化学学报),2001,22(10):1735-1737
[16]	Wang Lijian (王利剑),Zheng Shuilin (郑水林),Shu Feng (舒峰).Preparation and photocatalytic activity of titania/diatomite composite[J].Journal of the Chinese Ceramic Society(硅酸盐学报),2006,34(7):823-826
[17]	Zhao D F,Zhou J,Liu N.Preparation and characterization of Mingguang palygorskite supported with silver and copper for antibacterial behavior[J].Appl.Clay Sci.,2006,33(3/4):161-170
[18]	Stathatos E,Papoulis D,Aggelopoulos C,Panagiotaras D,Nikolopoulou A.TiO2/palygorskite composite nanocrystalline films prepared by surfactant templating route:synergistic effect to the photocatalytic degradation of an azo-dye in water[J].J.Hazard.Mater.,2012,211/212:68-76
[19]	Lu Zhenxiang (陆振翔),Huang Zhenghong (黄正宏)Kang Feiyu (康飞宇).SO2 removal by nano-sized ZnO and attapulgite compounds at room temperature[J].CIESC Journal(化工学报),2011,62(1):243-247
[20]	Chen Zhigang(陈志刚),Guo Tingting(郭亭亭),Li Xiazhang(李霞章),Chen Feng (陈丰),Lu Xiaowang (陆晓旺),Zhang Yue(张跃).Catalytic oxidation process of methylene blue dyestuff by cerium coated attapulgite[J].Journal of Functional Material(功能材料),2009,10(40):1709-1712
[21]	Chen Feng (陈丰),Li Xiazhang (李霞章),Lu Xiaowang (陆晓旺),Wang Jianmei (王健美),Ni Chaoying (倪超英),Chen Zhigang(陈志刚).Preparation and characterization of palygorskite/CeO2 nano-composite material and its catalytic performance[J].Journal of the Chinese Ceramic Society(硅酸盐学报),2009,37(1):52-56
[22]	Li X Z,Ni C Y,Yao C,Chen Z G.Development of attapulgite/Ce1-xZrxO2 nanocomposite as catalyst for the degradation of methylene blue[J].Appl.Catal.B:Environ.,2012,117/118:118-124
[23]	Zhao Xiaobing (赵晓兵),Jin Chao (靳超),Zhang Yue (张跃),Chen Zhigang (陈志刚).Preparation and catalytic properties of Ce1-xMnxO2-δ-attapulgite nanocomposite materials[J].The Chinese Journal of Nonferrous Metals(中国有色金属学报),2011,21(7):1580-1586
[24]	Chen Tianhu (陈天虎),Xu Xiaochun (徐晓春),Yue Shucang (岳书仓).Nanometer Mineralogy and Geochemistry of Palygorskite Clays in the Border of Jiangsu and Anhui Provinces (苏皖凹凸棒石黏土纳米矿物学及地球化学)[M].Beijing:Science Press,2004:85-162
[25]	Zhu Chuangao (朱传高),Wang Fengwu (王凤武).Electro-catalytic activity and preparation of nano-crystalline TiO2/ZrO2 modified electrode in organic system[J].Chinese Journal of Inorganic Chemistry(无机化学学报),2008,24(5):813-817
[26]	Cao J L,Shao G S,Wang Y,Liu Y P,Yuan Z Y.CuO catalysts supported on attapulgite clay for low-temperature CO oxidation[J].Catal.Commun.,2008,9(15):2555-2559
[27]	Yang S X,Zhu W P,Jiang Z P,Chen Z P,Wang J B.The surface properties and the activities in catalytic wet air oxidation over CeO2-TiO2 catalysts[J].Appl. Surf.Sci.,2006,252(24):8499-8505
[28]	Zhao Lei (赵雷),Sun Zhizhong (孙志忠),Ma Jun(马军).Mechanism of heterogenous surface in catalytic ozonation for degradation of nitrobenzene in aqueous solution[J].Journal of Harbin Institute of Technology(哈尔滨工业大学学报),2009,41(2):71-75

Catalytic properties of CeO₂-TiO₂/attapulgite nanocomposites prepared by sol-gel method

sol-gel法制备CeO₂-TiO₂/凹凸棒石复合材料的催化性能

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References 28

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	ZHEN Wenyuan, LI Qing. Preparation of TiO₂/attapulgite composite photocatalyst by supercritical fluid drying method [J]. CIESC Journal, 2018, 69(5): 2290-2298.
[2]	ZHANG Ao, YANG Haicun, MA Wenzhong, LI Yuxue, GONG Fanghong, TAO Guoliang, LIU Chunlin. Preparation of attapulgite/polystyrene hybrid particles via simultaneous reverse and normal initiation atom transfer radical polymerization [J]. CIESC Journal, 2018, 69(5): 2299-2308.
[3]	ZHOU Shouyong, XUE Ailian, ZHANG Yan, WANG Qiwei, LI Meisheng, CHU Xiaozhong, ZHAO Yijiang, XING Weihong. Selective adsorption of Pb²⁺, Ni²⁺ and Cr³⁺ by polyacrylic acid/attapulgite composite adsorbents [J]. CIESC Journal, 2015, 66(2): 618-625.
[4]	WU Jie, DING Shijie, CHEN Jing, JIANG Jinlong, WANG Junjun. Preparation and sustained release properties of acidified-attapulgite/alginate composite material [J]. CIESC Journal, 2014, 65(11): 4627-4632.
[5]	LI Shan1，2，DAI Hongqi2，KONG Yong1，JIANG Xingmao1. Research progress of attapulgite’s application [J]. Chemical Industry and Engineering Progree, 2013, 32(12): 2934-2939.
[6]	SHAO Hui1，YAO Pengfei1，LI Jin1，ZHONG Jin1，JIANG Jinlong2. Control of membrane fouling and regeneration in microfiltration separating of attapulgite by ceramics membranes [J]. Chemical Industry and Engineering Progree, 2013, 32(05): 1168-1171.
[7]	WANG Qingning, ZHANG Zhengcai, XIE Zhenping, WU Yingqin, LI Lan, JIAO Linhong. Thiol and thioether removal from RFCC gasoline with attapulgite clay [J]. CIESC Journal, 2012, 63(1): 292-300.
[8]	SU Xiuxia1，LI Yiyang1，LI Zhongjin1，LI Mingjie1，ZHAO Yan1，HAO Mingde2. Preparation and characterization of XG-g-P(AA-co-AM)/AC composite super absorbent resin [J]. , 2011, 30(7): 1556-.
[9]	LI Guixian1，SONG Weiwei1，MA Jianjun1，2，GAO Yunyan1，WANG Guang1，LI Yazhen1. Heteropolyacid salts catalysts supported on silylated attapulgite for cyclohexane oxidation [J]. , 2011, 30(7): 1494-.
[10]	WANG Jun，ZHANG Peng，LI Cuiqin，LI Jie. Synthesis，characterization and properties of dendritic transition metal catalysts [J]. , 2011, 30(2): 322-.
[11]	WANG Wenjuan，YAO Chao，DING Yonghong，LIU Jianping. Preparation and structural characterization of polypyrrole/attapulgite nanocomposites [J]. , 2009, 28(9): 1613-.
[12]	ZONG Xuwei，WANG Qingning，JIANG Ruiyu，YE Yetong，LI Lan. Decolorization of C₉ fraction with attapulgite clay decolorant [J]. , 2009, 28(11): 1969-.
[13]	ZHANG Ting，YU Shurong，FENG Huixia，WANG Yi. Preparation of compound desulphurization agent and study on its removal of SO2 [J]. , 2009, 28(1): 159-.
[14]	FAN Guodong，SHEN Mao. Advances in research and application of attapulgite [J]. , 2009, 28(1): 99-.
[15]	YUAN Jiacheng，LU Weiping，ZHOU Zhuang. Study on Pd-catalyst used for hydrogenation of fluorine-containing aromatic nitro-compounds [J]. , 2008, 27(2): 241-.