CN112808309B - 一种多孔催化微球的制备及其底物尺寸选择性催化应用 - Google Patents
一种多孔催化微球的制备及其底物尺寸选择性催化应用 Download PDFInfo
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Abstract
一种多孔催化微球的制备及其底物尺寸选择性催化应用。首先,以任意方式获得表面带负离子和/或环氧基团的交联聚合物纳球,通过静电作用和/或环氧‑氨基作用在纳球表面引入一层多胺聚合物;然后通过静电作用在多胺化纳球表面吸附一定量的阴离子表面活性剂,使纳球亲油化;其次,将所得粒子分散在油中,在强烈搅拌作用下溶胀一段时间后,向油中滴入含有聚乙二醇二甘油醚交联剂的水溶液,纳球粒子将在油水界面进行Pickering组装形成微球并被交联剂固定。同时水溶液还含有催化金属纳米颗粒,这些催化金属纳米粒子将被物理吸附在微球内壁。孵化后分出组装微球,依次以碱水洗涤去除外表面的阴离子表面活性剂、乙醇洗涤除去内部的水,得到亲水空心微球。
Description
技术领域
本发明属于选择性催化技术领域,具体涉及一种多孔空心微球催化材料的制备方法及其在底物尺寸选择催化上的应用。
背景
纳米催化剂又常称为可溶催化剂,特点是比表面大、催化效率高,但其回收常常是挑战。残留催化剂会降低产品质量,还可能污染环境。如果将纳米催化颗粒组装并固定下来形成微米颗粒,可能在较大程度上保持其高比表面和高催化效率,同时在又一定程度上便于回收。
生物学上一个常见的策略是将催化中心嵌入特定拓扑形态的孔穴中,使其只对特定底物发挥催化作用,而对那些拓扑不匹配的分子没有作用。人们已经能类似地制备一些选择性催化剂。比如将催化中心置于树枝状分子的中心,或包在交联壳层的核内,或无机多孔材料的内部。目前,这类选择性催化材料的孔都较小,主要针对次纳米级别的分子底物,同时其物质交换速率常会受到限制。目前的材料大多孔偏小,耐酸碱也常常不足。在许多反应中,常需要进行尺寸选择性反应或分离。例如,以活性染料进行织物染色,以颜料颗粒进行织物着色等,都会有残留的小分子或其小聚集体存在,会造成水污染。选择性还原能使染料或颜料变成无色,而其他大尺寸的物质不受影响,也不会反过来影响催化剂。
发明内容
针对现有技术中的不足,本发明的首要目的是设计一种具有介孔大孔尺寸的空心微球,且空心微球的内壁附有纳米催化剂。
本发明的第二个目的是制备空心微球催化材料。
本发明的第三个目的是利用上述材料选择性改性小尺寸的底物,或作为便于回收的催化材料使用。
为达到上述目的,本发明的解决方案是:
一种空心微球催化材料的制备方法,包括如下步骤:
(1)以任意方式获得表面带有负电荷和/或环氧基团的交联聚合物纳米球,并在pH7-9下通过静电作用和/或环氧-氨基作用在纳球表面引入一层多胺,清水洗涤除掉松散吸附的多胺。
(2)制备空心微球催化材料。将氨基化纳球和阴离子表面活性剂分散到油中,搅拌下纳球溶胀一段时间变软后,将含有聚乙二醇二甘油醚交联剂和纳米贵金属颗粒的水滴入油相,搅拌形成油包水性乳液并保持一定时间。蒸馏去掉油相后将所得空心微球进行洗涤纯化。
优选地,步骤(1)中,纳球内部交联度不超过15%。
优选地,步骤(1)中,多胺为聚烯丙基胺、线性或支化聚乙撑亚胺。
优选地,步骤(1)中,多胺分子量在2000以上。
优选地,步骤(2)中,阴离子表面活性剂的剂量一般大于氨基重复单元数的15mol%,便于形成油包水性乳液。
优选地,步骤(2)中,纳球的剂量为水相质量的0.5-3%。
优选地,步骤(2)中,水相体积占乳液总体积的20-25%。
优选地,步骤(2)中,交联剂的摩尔剂量一般不低于氨基重复单元数的40%。
优选地,步骤(2)中,当贵金属纳米颗粒小于微球孔穴时,贵金属纳米颗粒的配体应为与多胺有较强物理互补作用的大分子配体。
一种空心微球催化材料,其特征在于:其由上述制备方法得到。
一种如上所述的空心微球用于选择性还原小尺寸的分子或颗粒。
由于采用上述方案,本发明的有益效果是:
第一,本发明采用Pickering效应组装并获得空心微球催化材料,使催化材料在保持较高比表面时具有较大尺寸,便于分离回收。
第二,本发明制备的空心微球催化材料具有客体尺寸选择性。
由于表面多孔,尺寸较小的底物可以穿过空心微球的小孔进入内部与催化剂接触,从而被化学改性,而大尺寸的底物不受影响。这种大尺寸催化剂容易回收。
附图说明
图1.实施例1乳液基聚合物纳球的透射电镜图。
图2.实施例1超支化聚甘油醚调制的金纳米透射电镜图。
图3实施例2.4-硝基酚在硼氢化钠还原剂和空心微球催化剂存在下的紫外-可见光光谱随时间的变化。
以下结合实施例对本发明作进一步的说明。
实施例1(空心微球催化材料的制备)
(1)聚合物纳球制备。以十二烷基苯磺酸钠/OP-10(1:2)作为水包油型乳化剂,用量为油性单体质量的3%,加水溶解(水为单体质量的3倍),并加入加过硫酸铵(单体用量的0.6%)。油相由单体苯乙烯,二乙烯苯,甲基丙烯酸和甲基丙烯酸甘油醚酯构成,其中甲基丙烯酸4%,甲基丙烯酸甘油酯10%,二乙烯苯3%。强烈搅拌下,将油相滴入水相,形成乳液。乳液在75-80℃下加热8小时。离心收集,加清水振荡分散,离心收集,重复5次。经透射电镜统计分析表明粒径平均值为230钠米。(图1)
(2)聚合物纳球表面氨基功能化。取乳液粒子(1克),投入支化聚乙撑亚胺(PEI,分子量70000)水溶液(5%,20mL),以稀酸或稀碱调pH 9,温和搅拌半小时,离心收集并以依次以水和乙醇各洗涤一次。常温下真空干燥后进行元素分析,以氮含量(2.11%)可计算出PEI的负载量为6.5%。
(3)表面羟基化金纳米的合成。合成主要基于文献方法(Chem.Mater.2011,23,1461)。将超支化聚甘油醚(分子量22 000Dalton)配成水溶液(0.1mM),向其中加入氯金酸水溶液(30mM,金原子的含量为聚甘油醚的50摩尔当量),搅拌,然后将新配置的硼氢化钠水溶液(0.5M,金原子的3倍摩尔当量)加入,继续搅拌半小时。产物通过在离心收集。通过再次分散在水中并离心收集,并以大量丙酮洗涤纯化。TEM检测金纳米粒径在6.8纳米左右(图2)。
表面羧基化金纳米的合成。为便于金纳米颗粒吸附到带正电的多孔微球内表面,可将金纳米颗粒表面的羟基转化为带负电的羧基。将超支化聚甘油醚稳定的金纳米颗粒分散在二甲基甲酰胺中,向其中分批加入丁二酸酐(超支化甘油醚羟基的0.8摩尔当量),搅拌1小时,丙酮沉淀洗涤。所得的羧基化金纳米颗粒在pH大于4时能在水中良好分散,便于下一步步骤(4)负载到空心微球内表面。
(4)氨基化纳球的组装、固定和金纳米在组装体内壁的负载。取PEI功能化纳球(1克)和十二烷基苯磺酸钠(0.5克),投入到300毫升环己烷中,搅拌半小时。取水(100毫升),在其中加入聚乙二醇二甘油醚(0.8克,分子量500)和羧基化金纳米(0.1克),混匀后滴入不断搅拌的油相中,滴完后继续搅拌3小时。蒸馏去掉油和一部分水,向残留物中加0.1M的氢氧化钠水溶液,离心收集固体,并重复2次。残留固体以丙酮洗涤,干燥,得到内部装有金纳 米的空心微球。可做空心球催化剂应用。
实施例2
向4-硝基苯酚(0.06mM)的水溶液(20mL)中加入NaBH4(0.5g),通氮气,随后加入实施例1制备获得的空心球催化剂(0.1g),搅拌,红色溶液以UV/vis光谱计监测400纳米左右的光谱吸附变化。大约40分钟后吸收完全消失,溶液变为无色(图3)。
实施例3
对实施例2参与催化的空心球催化剂以亲水化多孔特氟龙膜(0.45微米孔)过滤、收集。可以直接再次使用。参照实施例2重复使用5次,仍能在40分钟内保持催化还原的能力。
实施例4(尺寸选择性催化)
(1)活性染料处理棉纤维。取脱脂棉纤维少许,和活性染料KGR(脱脂棉的1%)一起加入水中(水量至少浸没纤维),60-80C加热并温和搅拌6小时。取出脱脂棉并多次清洗,直至洗出水由蓝色变为无色,同时可发行脱脂棉保持蓝色。
类似地,以黄色的K6G代替KGR进行操作,得到黄色脱脂棉。
(2)选择性催化还原。在步骤(1)的加热后的后处理中,如果在水中加入0.2M的新配置硼氢化钠水溶液,则水中的蓝色在数小时内大部分缓慢褪去,而棉纤维的蓝色则需要数十小时褪去。如果同时加入硼氢化钠和载有金纳米的空心微球(来源于实施例1方法制备),则水中的蓝色会快速退去,而面纤维的蓝色与无催化剂相比几乎无差别。这说明催化剂对棉纤维上的染料没有作用。
对K6G的情形,情况差不多,不过自由的K6G在催化剂存在下褪色更快。
实施例5在实施例1步骤(3)中,以氯亚铂酸代替氯金酸,同样获得选择性催化空心微球。
实施例6
在实施例1步骤(3)中,以羧乙基化的超支化聚甘油醚代替超支化聚甘油醚类似操作,同样获得选择性催化空心微球,且耐用性更持久。
羧乙基化超支化聚甘油醚的合成如下。将超支化聚甘油醚(5克)溶于二甲基亚砜(20毫升)中,另取溴乙酸钾(12克)和氢氧化钾(15克)研磨成粉后加入,形成固液混合体系,在50-70C下搅拌8小时。减压下蒸馏除去大部分二甲亚砜。残留固体加酸性水调至中性,以透析膜(切断分子量1000)在水中进行透析。透析袋中的液体经蒸馏除水或丙酮沉淀后得到产物,即催化空心微球。
实施例7
在实施例1步骤(3)中,以柠檬酸代替超支化聚甘油醚进行类似操作,同样获得尺寸选择性空心球催化材料。
Claims (2)
1.一种空心微球催化材料的制备方法,其特征在于,其制备包括如下步骤:
(1)以任意方式获得表面带有负电荷和/或环氧基团的交联聚合物纳米球,并在pH 7-9下通过静电作用和/或环氧-氨基作用在纳米球表面引入一层多胺,清水洗涤除掉松散吸附的多胺;
(2)将氨基化纳米球和阴离子表面活性剂分散到油中,搅拌下纳米球溶胀一段时间后,将含有聚乙二醇二甘油醚交联剂和含有配体的纳米贵金属颗粒的水滴入油相,搅拌形成油包水性乳液并保持一定时间;蒸馏去掉油相后将所得空心微球进行洗涤纯化;
步骤(1)中:
纳米球内部交联度不超过15%;
多胺为聚烯丙基胺、线性或支化聚乙撑亚胺;
多胺分子量在2000以上;
步骤(2)中:
阴离子表面活性剂的剂量大于氨基重复单元数的15 mol%,便于形成油包水性乳液;
纳米球的剂量为水相质量的0.5-3%;
水相体积占乳液总体积的20-25%;
交联剂的摩尔剂量不低于氨基重复单元数的40%;
当贵金属纳米颗粒小于微球孔穴时,贵金属纳米颗粒的配体为与多胺有较强物理互补作用的大分子配体。
2.一种如权利要求1方法制备获得的空心微球催化材料作为易回收催化剂,或作为底物尺寸选择性催化材料。
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