CN101786002B - 铈锆纳米棒、纳米方块或纳米管担载铜基的催化剂及其制法 - Google Patents
铈锆纳米棒、纳米方块或纳米管担载铜基的催化剂及其制法 Download PDFInfo
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Abstract
一种铈锆纳米棒、纳米方块或纳米管担载铜基的催化剂,其特征是:它是以铈锆纳米棒、纳米方块或纳米管为载体,担载氧化铜的铈锆纳米棒、纳米方块或纳米管担载铜基的催化剂,其中铈与锆的摩尔比为8∶2,氧化铜的质量百分含量为2.4%,该催化剂表现出良好的催化还原NO的活性。本发明公开了其制法。
Description
技术领域
本发明涉及一类铈锆复合氧化物纳米棒、纳米方块、纳米管担载铜催化剂及其制备方法。
背景技术
铈锆复合氧化物在催化、燃料电池、陶瓷、气体传感、固态电极等领域有着广泛的应用,特别在三效催化剂中起到非常重要的作用,常用于催化消除机动车尾气(CO,NOx,CxHy)。这与其良好的储释氧性能、高温稳定性和氧化还原性质是密切相关的。掺杂Zr可以显著提高其储/释氧性能和热稳定性,这是由于锆周围亚晶格氧被取代从而促进了氧迁移性和体相氧的还原。显然,这些结构性质受固溶体的制备方法、比例、焙烧温度、助剂等因素影响。此外,铜基催化剂也表现出良好的CO氧化和NO还原活性以及抗水抗硫效果。研究发现,纳米材料由于其独特的形貌效应、尺寸效应、量子效应而表现出独特的结构和性质。例如,CeO2纳米棒{110}{100})比普通粉末CeO2({111})的活性要高很多。对于含铈纳米材料,目前主要集中在制备纯CeO2纳米管、纳米棒、纳米线、纳米多面体等,而对于合成具有规整形貌和小尺寸的掺杂型纳米铈锆复合物并以其为载体负载氧化铜的催化剂却鲜见报道。传统的模板法、共沉淀法、溶胶-凝胶法、微乳法制备的铈锆固溶体是无规则的小粒子,并没有制备出较规整的铈锆纳米棒等。因此,巧妙的设计构筑有可控尺寸、形貌和组成的负载型纳米铈锆复合催化剂依然是个挑战。
目前合成纳米铈锆复合材料的方法主要是水热法和模板法,主要的形貌是单分散小球、纳米管、有序介孔固溶体。如2008年JACS报道了Li课题组通过Kerkendall效应,以乙二醇为分散剂,采用水热法在180℃制备了铈锆固溶体纳米笼(J.AM.CHEM.SOC.2008,130,2736-2737);Fuentes等人采用多孔聚碳酸酯为模板合成了铈锆复合物的纳米管(Chem.Mater.2008,20,7356-7363);Yuan等人通过P123模板合成了不同比例的有序结构的介孔铈锆固溶体(J.AM.CHEM.SOC.2007,129,6698-6699)。这些方法也存在些不足,如需要分散剂、表面活性剂。同时只是强调了铈锆材料的合成机理,并没有引入活性组分和相关性质研究。我们通过Kerkendall效应,利用不同锆盐在不同溶剂体系中扩散系数的差异(选择性改变锆盐前驱物和反应体系溶剂),采用较简单的方法(不需要分散剂和表面活性剂)成功地合成了铈锆纳米棒、纳米方块、纳米管,并且以其为载体采用简单的浸渍法制备负载型纳米铜基催化剂用于NO的消除。
发明内容
本发明的目的:提供一种新的制备方法,合成铈锆复合物纳米棒、纳米管或纳米方块,并以其为载体制备铜基催化剂。
本发明的原理如下:首先在强碱条件下水热控制合成二氧化铈纳米棒或纳米管,以其为母体,再加入不同的锆盐前驱物,改变反应体系的溶剂。在强碱性条件下,通过晶核的成型、生长以及氢氧化物之间的相互作用,形成复合物。洗涤去除碱液,干燥,焙烧以后得到不同形貌的铈锆材料。利用活性组分和载体相互作用,在载体表明均匀分散制备负载型铜基催化剂。
本发明的目的是这样实现的:
一种铈锆纳米棒、纳米方块或纳米管担载铜基的催化剂,它是以铈锆纳米棒、纳米方块或纳米管为载体,担载氧化铜的铈锆纳米棒、纳米方块或纳米管担载铜基的催化剂,其中铈与锆的摩尔比为8∶2,铜的负载量为0.3mmol/g载体(质量百分比2.4%),该催化剂表现出良好的催化还原NO的活性。
一种制备上述的铈锆纳米棒、纳米方块或纳米管担载铜基的催化剂的方法,它是将Ce(NO3)3·6H2O溶于去离子水中,再加入5mol·L-1的NaOH溶液,其用量为:每1mmolCe(NO3)3用去离子水2ml,用5mol·L-1的NaOH溶液18ml,室温搅拌1h,转移至高压釜中置于140℃下保持24小时,得到Ce(OH)3纳米棒;然后取出上层澄清液,每投料1mmol Ce(NO3)3取出上层清夜10ml,加入丙三醇、乙醇、甲醇或水10mL,再加入硝酸锆、氧氯化锆、硫酸锆或二氧化锆,加入锆的量使Ce∶Zr=8∶2,继续搅拌1h,140℃反应24h;产物经分离、洗涤、干燥后,于空气气氛下400~500℃焙烧3小时,后降至室温得到纳米棒、纳米方块或纳米管状的纳米铈锆材料,然后采用浸渍法,加入Cu(NO3)2溶液,搅拌,蒸干,干燥,450℃焙烧得到铈锆纳米棒、纳米方块或纳米管担载铜基的催化剂。
本发明的铈锆纳米棒、纳米方块或纳米管担载铜基的催化剂的优点是:
1.原料易得,制备过程简单,只要改变锆盐前驱物和反应体系的溶剂,即可以控制合成特定形貌的铈锆固溶体材料。
2.本发明的催化剂NO转换活性高。
附图说明
图1:分别以氧氯化锆(a)、二氧化锆(b)、硫酸锆(c)和硝酸锆(d)为前驱物,以丙三醇为助溶剂制备的铈锆纳米棒、纳米方块担载氧化铜催化剂的透射电镜(TEM)结果
图2:以氧氯化锆前驱物,分别以乙醇(a-c)、甲醇(d-f)为助溶剂制备的铈锆纳米棒、纳米方块和纳米管担载氧化铜催化剂的透射电镜(TEM)及高分辨(HRTEM)结果。
图3:制得含铜催化剂的NO转换活性结果,(a)改变不同锆的前驱物所制的催化剂的转换活性,(b)以氧氯化锆为前驱物改变不同的反应溶剂制得的催化剂的转换活性,其中:Cu/CZ-Cl采用的是氧氯化锆;Cu/CZ-N采用的是硝酸锆;Cu/CZ-S采用的是硫酸锆;Cu/CZ-O采用的是二氧化锆;Cu/CZ-H是采用水为溶剂;Cu/CZ-I是采用丙醇为溶剂;Cu/CZ-M是采用甲醇为溶剂;Cu/CZ-E是采用乙醇为溶剂。
具体实施方式
实施例1.铈锆纳米棒、纳米方块或纳米管担载铜基的催化剂的制备
(1)将2.21g Ce(NO3)3·6H2O融化10mL去离子水,加入90mL 5mol·L-1的NaOH溶液,室温搅拌1h,转移至高压釜中置于140℃下保持24小时,得到暗灰色的Ce(OH)3纳米棒。
(2)铈锆纳米棒、纳米方块的制备
将(1)中上层澄清液取出50mL,加入50ml的丙三醇,并加入硝酸锆、氧氯化锆、硫酸锆或二氧化锆(Ce∶Zr=8∶2);继续搅拌1h,140℃反应24h;产物经分离、去离子水和乙醇洗涤(至中性),100℃干燥24h,于空气气氛下450℃焙烧3小时,后降至室温得到相应的铈锆纳米棒或纳米方块。
(3)铈锆纳米管、纳米方块的制备
将(1)中上层澄清液取出50mL,加入50ml的乙醇、甲醇或水,并加入氧氯化锆(Ce∶Zr=8∶2);继续搅拌1h,140℃反应24h;产物经分离、去离子水和乙醇洗涤(至中性),100℃干燥24h,于空气气氛下450℃焙烧3小时,后降至室温得到铈锆纳米管(加入甲醇为溶剂)或纳米方块(以乙醇或甲醇为溶剂)。
(4)含氧化铜催化剂的制备
将(2)或(3)得到纳米铈锆材料称取1.0g,加入Cu(NO3)2溶液,加入Cu(NO3)2溶液的量为0.3mmol CuO/g载体,再加入去离子水(50-100mL)室温搅拌3h,80-100℃蒸干,然后110℃干燥过夜,取出研磨,在马弗炉中空气气氛450℃焙烧4-5h,得到铈锆纳米棒、纳米方块或纳米管担载铜基的催化剂。
实施例2.本发明的催化剂的NO转化活性的测试
催化剂的活性评价采用微反应固定床,反应物的浓度为NO(5%体积),CO(10%体积),He(85%体积)气为平衡气,反应的空速为12,000g·mL-1·h-1。首先催化剂在100℃氮气气氛中活化30分钟,然后切换到反应气,。每隔25℃,反应15分钟后采集数据。反应物检测采用热导检测器,分离采用5A和13X分子筛(40-60M)分离NO、CO、N2,采用Paropak Q分离N2O和CO2。
Claims (2)
1.一种铈锆纳米棒、纳米方块或纳米管担载铜基的催化剂,其特征是:它是以铈锆纳米棒、纳米方块或纳米管为载体,在载体上担载氧化铜的催化剂,其中铈与锆的摩尔比为8∶2,氧化铜的质量百分含量为2.4%,该催化剂表现出良好的催化还原NO的活性。
2.一种制备权利要求1所述的铈锆纳米棒、纳米方块或纳米管担载铜基的催化剂的方法,其特征是:它是将Ce(NO3)3·6H2O溶于去离子水中,再加入5mol·L-1的NaOH溶液,其用量为:每1mmol Ce(NO3)3用去离子水2ml,用5mol·L-1的NaOH溶液18ml,室温搅拌1h,转移至高压釜中置于140℃下保持24小时,得到Ce(OH)3纳米棒;然后取出上层澄清液,每投料1mmol Ce(NO3)3取出上层清液10ml,加入丙三醇、乙醇、甲醇或水10mL,再加入硝酸锆、氧氯化锆、硫酸锆或二氧化锆,加入锆的量使Ce∶Zr=8∶2,继续搅拌1h,140℃反应24h;产物经分离、洗涤、干燥后,于空气气氛下400~500℃焙烧3小时,后降至室温得到纳米棒、纳米方块或纳米管状的纳米铈锆材料,然后采用浸渍法,加入Cu(NO3)2溶液,搅拌,蒸干,干燥,450℃焙烧得到铈锆纳米棒、纳米方块或纳米管担载铜基的催化剂。
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