乙烯基化二氧化铈表面改性研究
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摘要
为了提高CeO_2的表面性能,采用乙烯基三甲氧基硅烷(VTMOS)作为表面改性剂,冰乙酸、氨水作pH值调节剂,对CeO_2粉末进行表面改性。通过沉降实验、TG和FTIR等测试手段分析了溶液体系、改性时间、改性温度对CeO_2表面性能的影响,并且研究了改性后CeO_2与聚苯胺(PANI)形成复合材料的电化学性能。结果表明,在60℃醇水体系中改性2 h对CeO_2表面改性效果最好,其疏水性和热稳定性均得到提高;在65 g/L Zn~(2+)、150 g/L H_2SO_4电解液中,PANI、PANI/CeO_2、PANI/改性CeO_2复合材料的析氧过电位分别为0.659 V、0.679 V、0.652 V,说明改性CeO_2表现出更好的电催化活性,从而扩展了CeO_2在导电高分子材料领域的应用。
In order to improve the surface properties of CeO_2, CeO_2 powers were modified by using VTMOS as modifier, glacial acetic acid and ammonia as pH adjuster. The effects of solution system, modification time and modification temperature on the properties of modified CeO_2 were analyzed by sedimentation experiments, TG and FTIR. Meanwhile, the electrochemical properties of PANI/modified CeO_2 composites were also studied. The results showed that the modification of CeO_2 at 60 ℃ for 2 h in alcohol-water system was the best, and its hydrophobicity and the thermal stability were improved. In the electrolyte of 65 g/L Zn~(2+), 150 g/L H_2SO_4, the oxygen evolution over-potential of PANI, PANI/CeO_2, PANI/modified CeO_2 were respectively 0.659 V, 0.679 V and 0.652 V, indicating that the modified CeO_2 showed better electrocatalytic activity, and expanding the application of CeO_2 in the conductive polymer materials.
In order to improve the surface properties of CeO_2, CeO_2 powers were modified by using VTMOS as modifier, glacial acetic acid and ammonia as pH adjuster. The effects of solution system, modification time and modification temperature on the properties of modified CeO_2 were analyzed by sedimentation experiments, TG and FTIR. Meanwhile, the electrochemical properties of PANI/modified CeO_2 composites were also studied. The results showed that the modification of CeO_2 at 60 ℃ for 2 h in alcohol-water system was the best, and its hydrophobicity and the thermal stability were improved. In the electrolyte of 65 g/L Zn~(2+), 150 g/L H_2SO_4, the oxygen evolution over-potential of PANI, PANI/CeO_2, PANI/modified CeO_2 were respectively 0.659 V, 0.679 V and 0.652 V, indicating that the modified CeO_2 showed better electrocatalytic activity, and expanding the application of CeO_2 in the conductive polymer materials.
引文
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[13] 李梅, 付海, 柳召刚, 胡艳红, 李岩峰, 吴锦绣. 硬脂酸改性氧化铈的效果表征与机理研究[J]. 稀土, 2010, 31(3):11-14.Li M, Fu H, Liu Z G, Hu Y H, Li Y F, Wu J X. Characterization of CeO2 modified by stearic acid and the modification mechanism[J]. Chinese Rare Earths, 2010, 31(3):11-14.
[14] 林志远, 胡孝勇, 柯勇. 功能型LED CeO2/苯基硅橡胶封装材料[J]. 复合材料学报, 2016, 33(11):2454-2460.Lin Z Y, Hu X Y, Ke Y. CeO2/phenyl-silicone rubber composites for functional LED packaging materials[J]. Acta Materiae Compositae Sinica, 2016, 33(11):2454-2460.
[15] 刘振东, 李运领, 张海龙. 表面改性CeO2基抛光粉在水介质中的悬浮稳定性[J]. 稀土, 2015, 36(4):67-74.Liu Z D, Li Y L, Zhang H L. Suspension ability of modified ceria powder in water[J]. Chinese Rare Earths, 2015,36 (4):67-74.
[16] 侯杰. 氨基功能化铈基氧化物制备、表征及可见光催化性能研究[D]. 金华:浙江师范大学, 2015. 12.Hou J. Preparation, characterization and visible light drived catalytic performance of amino-functionalized cerium-based oxides[D]. Jinhua: Zhejiang Normal University, 2015. 12.
[17] 彭华湘, 陈彦模, 朱美芳, 张瑜, 邢强, 蒋翀, 孙宾. 纳米CeO2的表面改性及其在聚丙烯中的分散性研究[J]. 中国稀土学报, 2004, 22(6):791-794.Peng H X, Chen Y M, Zhu M F, Zhang Y, Xing Q, Jiang C, Sun B. Surface modification of cerium oxide nanoparticles and its dispersion in polypropylene[J]. Journal of The Chinese Society of Rare Earths, 2004, 22(6):791-794.
[18] 王晓艳, 黄玉玲, 刘文波, 胡威, 张怀斌. 乙烯基化的中空二氧化硅球的制备与表征[J]. 分子科学学报, 2013, 29(4):320-323.Wang X Y, Huang Y L, Liu W B, Hu W, Zhang H B. Preparation and characterization of vinyl functionalized hollow silica sphere[J]. Jouranl of Molecular Science, 2013, 29(4):320-323.
[19] 刘业翔, 吴良蕙. 锌电解节能惰性阳极的研究——惰性阳极上的析氧超电压[J]. 有色金属(冶炼部分), 1984, (4):30-33.Liu Y X, Wu L H. Study on zinc electrolytic energy-saving inert anodes——the oxygen evolution overvoltage on inert anode[J]. Nonferrous Metals(Extractive Metallurgy), 1984, (4):30-33.
[2] Lipińska Chwa?ek M, Schulze Küppers F, Malzbender J. Mechanical properties of pure and doped cerium oxide[J]. Journal of the European Ceramic Society, 2015, 35(5):1539-1547.
[3] He L Y, Su Y M, Jiang L H, Shi S K. Recent advances of cerium oxide nanoparticles in synthesis, luminescence and biomedical studies:A review[J]. Journal of Rare Earths, 2015, 33(8):791-799.
[4] Noriya I, Matsubara I, Toshio I, Woosuck S. Performance of a carbon monoxide sensor based on zirconia-doped ceria[J]. Journal of Asian Ceramic Societies, 2016, 4(2):205-208.
[5] Li Y Z, Sun Q, Kong M, Shi W Q. Coupling oxygen ion conduction to photocatalysis in mesoporous nanorod-like ceria significantly improves photocatalytic efficiency[J]. Journal of Physical Chemistry C, 2011, 115(29):14050-14057.
[6] 侯扶林, 李红欣, 杨阳, 董寒, 崔立峰, 张晓东. 特定形貌和多孔纳米CeO2的制备及其CO催化氧化研究进展[J]. 化工进展, 2017, 36(7):2481-2487.Hou F L, Li H X, Yang Y, Dong H, Cui L F, Zhang X D. Preparation and catalytic oxidation of CO with specific morphology and porous nano CeO2[J]. Chemical Industry and Engineering Progress, 2017, 36(7):2481-2487.
[7] Harth?j A, Holt T, M?ller P. Oxidation behaviour and electrical properties of cobalt/cerium oxide composite coatings for solid oxide fuel cell interconnects[J]. Journal of Power Sources, 2015, 281:227-237.
[8] 徐丹, 李柯慧, 高阳, 周永军, 徐世峰. CeO2基中温复合电解质材料的研究进展[J]. 电源技术, 2017, 41(4):647-650.Xu D, Li K H, Gao Y, Zhou Y J, Xu S F. Recent development of ceria-based middle temperature composite electrolyte materials[J]. Chinese Journal of Power Sources, 2017, 41(4):647-650.
[9] Efendi A F, Nurhasanah I. UV-light absorption and photocatalytic properties of Zn-doped CeO2 nanopowders prepared by ultrasound irradiation[J]. Materials Science Forum, 2015, 827:56-61.
[10] Caputo F, De N M, Sienkiewicz A, Giovanetti A, Bejarano I, Licoccia S, Traversa E, Ghibelli L. Cerium oxide nanoparticles, combining antioxidant and UV shielding properties, prevent UV-induced cell damage and mutagenesis[J]. Nanoscale, 2015, 7(38):15643.
[11] Vassie J A, Whitelock J M, Lord M S. Endocytosis of cerium oxide nanoparticles and modulation of reactive oxygen species in human ovarian and colon cancer cells[J]. Acta biomaterialia, 2016, 50:127-141.
[12] Walkey C, Das S, Seal S, Erlichman J, Heckman K, Ghibelli L, Traversa E, McGinnis J F, Self W T. Catalytic properties and biomedical applications of cerium oxide nanoparticles[J]. Environmental Science Nano, 2015, 2(1):33-53.
[13] 李梅, 付海, 柳召刚, 胡艳红, 李岩峰, 吴锦绣. 硬脂酸改性氧化铈的效果表征与机理研究[J]. 稀土, 2010, 31(3):11-14.Li M, Fu H, Liu Z G, Hu Y H, Li Y F, Wu J X. Characterization of CeO2 modified by stearic acid and the modification mechanism[J]. Chinese Rare Earths, 2010, 31(3):11-14.
[14] 林志远, 胡孝勇, 柯勇. 功能型LED CeO2/苯基硅橡胶封装材料[J]. 复合材料学报, 2016, 33(11):2454-2460.Lin Z Y, Hu X Y, Ke Y. CeO2/phenyl-silicone rubber composites for functional LED packaging materials[J]. Acta Materiae Compositae Sinica, 2016, 33(11):2454-2460.
[15] 刘振东, 李运领, 张海龙. 表面改性CeO2基抛光粉在水介质中的悬浮稳定性[J]. 稀土, 2015, 36(4):67-74.Liu Z D, Li Y L, Zhang H L. Suspension ability of modified ceria powder in water[J]. Chinese Rare Earths, 2015,36 (4):67-74.
[16] 侯杰. 氨基功能化铈基氧化物制备、表征及可见光催化性能研究[D]. 金华:浙江师范大学, 2015. 12.Hou J. Preparation, characterization and visible light drived catalytic performance of amino-functionalized cerium-based oxides[D]. Jinhua: Zhejiang Normal University, 2015. 12.
[17] 彭华湘, 陈彦模, 朱美芳, 张瑜, 邢强, 蒋翀, 孙宾. 纳米CeO2的表面改性及其在聚丙烯中的分散性研究[J]. 中国稀土学报, 2004, 22(6):791-794.Peng H X, Chen Y M, Zhu M F, Zhang Y, Xing Q, Jiang C, Sun B. Surface modification of cerium oxide nanoparticles and its dispersion in polypropylene[J]. Journal of The Chinese Society of Rare Earths, 2004, 22(6):791-794.
[18] 王晓艳, 黄玉玲, 刘文波, 胡威, 张怀斌. 乙烯基化的中空二氧化硅球的制备与表征[J]. 分子科学学报, 2013, 29(4):320-323.Wang X Y, Huang Y L, Liu W B, Hu W, Zhang H B. Preparation and characterization of vinyl functionalized hollow silica sphere[J]. Jouranl of Molecular Science, 2013, 29(4):320-323.
[19] 刘业翔, 吴良蕙. 锌电解节能惰性阳极的研究——惰性阳极上的析氧超电压[J]. 有色金属(冶炼部分), 1984, (4):30-33.Liu Y X, Wu L H. Study on zinc electrolytic energy-saving inert anodes——the oxygen evolution overvoltage on inert anode[J]. Nonferrous Metals(Extractive Metallurgy), 1984, (4):30-33.
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