CN106311229A - 一种金凹凸棒土纳米负载催化剂及其制备方法和应用 - Google Patents
一种金凹凸棒土纳米负载催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种金凹凸棒土纳米负载催化剂及其制备方法和应用。所述催化剂载体为凹凸棒土,活性组分是金,其平均粒径约为3~8纳米,催化剂中金的质量分数为0.5~2%。本发明的金凹凸棒土纳米负载催化剂具有清洁环保而有方便的特点,并且本发明的金凹凸棒土纳米负载催化剂对硝基苯酚还原为氨基苯酚具有优异催化性能。
Description
技术领域
本发明涉及工业催化技术领域,尤其涉及一种金凹凸棒土纳米负载催化剂及其制备方法和应用。
背景技术
近几十年来,负载型纳米催化剂已得到广泛应用。关于金属和载体间的相互作用的研究报道日益增多。众所周知,金属和载体间特殊的相互作用会影响催化剂的表面性能,进而影响它的催化活性。比如,在Al2O3载体担载金属钴的过程中钴离子会迁移到Al2O3的晶格中形成CoAl2O4化合物。铁的氧化物和过渡金属氧化物或其碳酸盐发生固-固作用形成相应的铁氧体氧化物CoFe2O4。金纳米微粒具有高表面能,容易发生团聚。若将金纳米微粒负载在载体上可有效地阻止其团聚,从而提高催化剂的催化活性。
凹凸棒土是一种具纤维纹理层链状过渡结构的含水富镁硅酸盐为主的粘土矿,在矿物学上属于海泡石族,其化学式为:Mg5(H2O)4[Si4O10]2(OH)2·4H2O,在凹凸棒土晶体中,一部分的Si4+被Mg2+和Al3+所替代且缺少正电荷,表现出一定的电负性,它具有独特的链式结构,表现出不同寻常的吸附性能。
氨基苯酚是一种用途广泛的有机合成中间体,通常用于制备各种止痛药物(如扑热息痛、退热冰和非那西汀等),在染料行业中常被用作木材的着色剂和毛皮的染色剂,还可用于感光材料的显影剂、涂料的阻蚀剂、润滑油的防腐剂、尿素加成反应的抑制剂和丙烯腈二聚反应的催化剂等。在硝基苯还原中常常用到金属酸、雷尼镍等,这些使得反应比较复杂,后处理比较麻烦。
发明内容
为了解决现有的制备氨基苯酚催化剂的不足,本发明目的在于提供一种清洁环保而有方便的将硝基苯酚还原为氨基苯酚,并且具有优异催化性能的Au/ATP催化剂及其制备方法。
本发明采取的技术方案是:
本发明的金凹凸棒土纳米负载催化剂的载体为凹凸棒土,活性组分是金,其平均粒径约为3~8纳米,催化剂中金的质量分数为0.5~2%,优选为1%。
本发明的金凹凸棒土纳米负载催化剂的制备方法的具体步骤如下:
(1)载体的处理
用200~300目筛筛取粉碎后的凹凸棒土,加入酸溶液,加热回流4小时后,抽滤,清洗至pH为5~10,干燥至恒重,备用;
(2)Au溶胶的制备
向HAuCl4溶液加入15倍当量的稳定剂,搅拌均匀后滴加15倍当量的还原剂溶液,继续搅拌半小时制得稳定金溶胶;
(3)Au/ATP纳米催化剂的制备
将从步骤(1)中所得的载体加入由步骤(2)制得的金溶胶中,金属与载体质量比为1:72,磁力搅拌后静置,抽滤,烘干,得Au/ATP催化剂。
步骤(1)中,所述的酸溶液是盐酸、硫酸或磷酸,酸溶液的质量浓度为5%;优选为硫酸。
步骤(1)中,优选清洗至pH为6。
步骤(2)中,所述的还原剂为硼氢化钠、硼氢化钾或硼氢化锂。
步骤(2)中,所述的稳定剂为聚乙烯吡咯烷酮、聚乙二醇或聚乙烯醇。
本发明的金凹凸棒土纳米负载催化剂可以用于硝基苯酚制备氨基苯酚。
Au/ATP催化剂催化还原硝基苯酚具体步骤如下:
向三口瓶中加入对硝基苯酚的水溶液后,再加入一定量的Au/ATP催化剂,搅拌均匀后,加入还原剂溶液。反应结束后,离心,将催化剂与产物分离,催化剂留待循环使用。
本发明的积极效果如下:
本发明的金凹凸棒土纳米负载催化剂具有清洁、环保、可循环使用而又方便的特点,并且本发明的金凹凸棒土纳米负载催化剂对硝基苯酚还原为氨基苯酚的反应体系要求不高,并且具有优异的催化性能。
附图说明
图1是实施例1制备的Au/ATP的透射电镜照片。
具体实施方式
下面的实施例是对本发明的进一步详细描述。
实施例1
(1)凹凸棒土的预处理
把大块的凹凸棒土放入豆浆机中进行粉碎然后再用研钵研磨,并把研磨后的凹凸棒土用200目的目筛进行筛选。在150mL圆底烧瓶中加入5g筛选过的凹凸棒土,80mL 5%的稀硫酸溶液,在集热式恒温加热磁力搅拌器中搅拌加热至70℃回流,加热4h后,用去离子水进行清洗直至PH=6.0为止,清洗完后,将得到的产品在65℃下的真空干燥器中抽真空干燥,直至干燥到恒重为止,用于后续实验。
(2)金纳米溶胶的制备
在100mL烧杯中,量取6mL 5.886×10-3mol/L HAuCl4水溶液,加入0.06g PVP水溶液和20mL去离子水,然后在磁力搅拌器上搅拌,再称取0.02g NaBH4溶于少量水,滴入溶液中,溶液瞬间由橙黄色变成灰色,继续滴加搅拌,溶液渐渐变成酒红色[8],即制得由离子液体包裹的稳定金胶体。
(3)Au/ATP纳米催化剂的制备
在上述制得的金溶胶中,加入处理过的0.5g凹凸棒土,磁力搅拌3-4h后静置,抽滤,将所得的固体于60℃恒温箱下烘干,即制得由ATP负载的纳米金催化剂。
图1是Au/ATP的透射电镜照片,由图1可以看出层链棒状为凹凸棒土,分布比较均匀、粒径范围大多为3~8nm的为负载的纳米Au,互相之间并没有发生团聚的现象。而且作为载体的凹凸棒土的形态基本上没有发生很大的变化。
Au/ATP催化剂催化还原对硝基苯酚为对氨基苯酚
于250mL三口烧瓶中加入186mL 1.25×10-4mol/L的対硝基苯酚的水溶液,并控制体系的温度为40℃,然后加入0.1956g Au/ATP(含金量为1.0%)催化剂,磁力搅拌30min后加入10mL 0.2mol/L新鲜的NaBH4溶液,当NaBH4加入时可明显观察到体系的颜色由淡黄色变为黄绿色。反应30min,体系的颜色逐渐褪去。离心,将催化剂与产物分离,留待循环使用。
対硝基苯酚的转化率约为99%
催化剂循环使用六次
表1
循环次数 | 1 | 2 | 3 | 4 | 5 | 6 |
转化率(%) | 99.72 | 99.01 | 98.80 | 96.88 | 94.50 | 92.05 |
实施例2
(1)载体的处理
用300目筛筛取粉碎后的凹凸棒土,加入酸溶液,加热回流数小时后,抽滤,清洗至pH为5,干燥至恒重,备用;
(2)Au溶胶的制备
向HAuCl4溶液加入稳定剂,搅拌均匀后滴加还原剂溶液,继续搅拌一定时间,制得稳定金溶胶;
(3)Au/ATP纳米催化剂的制备
将从步骤(1)中所得的载体加入由步骤(2)制得的金溶胶中,磁力搅拌后静置,抽滤,烘干,得Au/ATP催化剂。
步骤(1)中,所述的酸溶液是盐酸,酸溶液的质量浓度为5%。
步骤(2)中,所述的还原剂为硼氢化钾。
步骤(2)中,所述的稳定剂为聚乙二醇。
实施例3
(1)载体的处理
用200目筛筛取粉碎后的凹凸棒土,加入酸溶液,加热回流数小时后,抽滤,清洗至pH为10,干燥至恒重,备用;
(2)Au溶胶的制备
向HAuCl4溶液加入稳定剂,搅拌均匀后滴加还原剂溶液,继续搅拌一定时间,制得稳定金溶胶;
(3)Au/ATP纳米催化剂的制备
将从步骤(1)中所得的载体加入由步骤(2)制得的金溶胶中,磁力搅拌后静置,抽滤,烘干,得Au/ATP催化剂。
步骤(1)中,所述的酸溶液是磷酸,酸溶液的质量浓度为5%。
步骤(2)中,所述的还原剂为硼氢化锂。
步骤(2)中,所述的稳定剂为聚乙烯醇。
实施例2和3制备的催化剂的性能与实施例1制备的催化剂的性能相似。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (8)
1.一种金凹凸棒土纳米负载催化剂,其特征在于:所述催化剂载体为凹凸棒土,活性组分是金,其平均粒径约为3~8纳米,催化剂中金的质量分数为0.5~2%。
2.一种制备如权利要求1所述的金凹凸棒土纳米负载催化剂的方法,其特征在于:所述方法的具体步骤如下:
(1)载体的处理
用200~300目筛筛取粉碎后的凹凸棒土,加入酸溶液,加热回流4小时后,抽滤,清洗至pH为5~10,干燥至恒重,备用;
(2)Au溶胶的制备
向HAuCl4溶液加入15倍当量的稳定剂,搅拌均匀后滴加15倍当量的还原剂溶液,继续搅拌半小时制得稳定金溶胶;
(3)Au/ATP纳米催化剂的制备
将从步骤(1)中所得的载体加入由步骤(2)制得的金溶胶中,金属与载体质量比为1:72,磁力搅拌后静置,抽滤,烘干,得Au/ATP催化剂。
3.如权利要求2所述的制备方法,其特征在于:步骤(1)中,所述的酸溶液是盐酸、硫酸或磷酸,酸溶液的质量浓度为5%。
4.如权利要求2所述的制备方法,其特征在于:步骤(1)中,所述的酸溶液是硫酸。
5.如权利要求2所述的制备方法,其特征在于:步骤(1)中,清洗至pH为6。
6.如权利要求2所述的制备方法,其特征在于:步骤(2)中,所述的还原剂为硼氢化钠、硼氢化钾或硼氢化锂。
7.如权利要求2所述的制备方法,其特征在于:步骤(2)中,所述的稳定剂为聚乙烯吡咯烷酮、聚乙二醇或聚乙烯醇。
8.如权利要求1所述的金凹凸棒土纳米负载催化剂用于硝基苯酚制备氨基苯酚的应用。
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