CN110252407B - 一种羧基功能化离子液体制备核-壳结构催化剂的方法 - Google Patents
一种羧基功能化离子液体制备核-壳结构催化剂的方法 Download PDFInfo
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Abstract
本发明提供了一种羧基功能化离子液体制备核‑壳结构催化剂的方法，属于复合材料技术领域。本发明通过结合金属有机骨架材料的形成原理及特点，利用羧基功能化离子液体与金属及金属簇之间的配位作用，以层层组装的方式将羧基功能化离子液体固载到颗粒载体上。使用该方法制备的离子液体多层负载的固体催化剂不仅具有离子液体固载稳定、固载量大的特点，而且通过调变羧基功能化离子液体的阴离子种类还能具备任意调控所制备催化剂的活性位种类和强度的性能。本发明制备的离子液体多层负载的固体催化剂用于各类醇酸酯化和模拟汽油脱硫反应，具有良好活性和稳定性。
Description
技术领域
本发明属于复合材料合成技术领域，具体涉及一种羧基功能化离子液体制备核-壳结构催化剂的方法。
背景技术
离子液体是指完全由阴阳离子组成的熔融盐，离子液体的阳离子是有机阳离子，其体积相对较大，而阴离子为无机阴离子，其体积相对较小，这种体积差异和对称性不匹配导致阴阳离子之间的静电势降低，从而具有了低熔点的特性，因此在室温下呈现液态。在实际应用研究中，离子液体已经表现出优异的性能，尤其是在催化方面。但是，离子液体作为催化剂往往是以均相体系或者液-液两相体系参与反应，从而给催化剂的回收、分离和重复使用过程带来了很多困难。为了解决这些问题，离子液体多相化是一种理想的方法。目前，实现离子液体多相化的方法主要是通过物理吸附和化学键锚定将离子液体负载在固体载体的表面上。
物理吸附负载离子液体主要是通过表面的静电作用或者物理吸附作用将离子液体束缚在载体的表面，这种复合材料在催化反应中离子液体容易流失，催化剂的稳定性较差。虽然化学键合固载离子液体复合材料表现出了较佳的催化效果和理想的稳定性，但是这是建立在催化剂用量极高的基础上的。因为这些载体（硅基材料、碳基材料和高分子聚合材料）主要是一些非孔或者不规则孔材料，其表面的固载位点分布随机，制备出来的离子液体活性组分不能均匀的分布在其表面或者孔道中，且普通的化学键合只能在载体表面单层连接一部分离子液体，造成单位质量复合材料的活性组分含量较低，因而需要加大催化剂用量，这些固载局限性将会直接影响催化剂的催化性能及固载化离子液体的工业化应用前景。因此，为从根本上解决离子液体化学键合固载量少的问题，开发一种离子液体多层负载制备非均相催化剂的方法具有很好的研究价值和应用前景。
发明内容
为了克服现有离子液体固载技术的缺点和不足，本发明的主要目的在于提供一种羧基功能化离子液体制备核-壳结构催化剂的方法。
为实现上述发明目的，本发明采用以下技术方案：
一种羧基功能化离子液体制备核-壳结构催化剂的方法：以羧基功能化纳米颗粒为核，以锆离子或者锆簇为连接点，利用锆离子或者锆簇与羧基的配位作用将羧基功能化离子液体层层组装到纳米颗粒上，形成离子液体多层负载的核-壳结构催化剂。
一种羧基功能化离子液体制备核-壳结构催化剂的方法，包括以下具体步骤：（1）将作为核的纳米颗粒表面羧基化，获得羧基功能化纳米颗粒，然后将羧基功能化纳米颗粒分散在溶剂DMF中形成浑浊液，将氯化锆和冰醋酸按一定的质量比加入到浑浊液中，经超声分散后获得分布均匀的悬浮液，然后将所得的悬浮液转移至水热合成釜中，并于高温下反应一定的时间，所得产物经DMF和乙醇洗涤、干燥后得固体粉末，将固体粉末继续分散在溶剂DMF中，加入与氯化锆等物质的量的双羧基离子液体并在水热合成釜中高温反应一定的时间，即得一层离子液体负载的核-壳结构催化剂，重复多次上述操作，得离子液体多层负载的核-壳结构催化剂；
（2）将上述所得的离子液体多层负载的核-壳结构催化剂置于含有硫酸或者氯化铁的乙醇或乙腈溶液中进行置换，经洗涤得含有特定基团的离子液体多层负载的核-壳结构催化剂，离子液体负载量为40~45wt%。
上述步骤（1）中所述的羧基功能化纳米颗粒为羧基化二氧化硅。
上述步骤（1）中所述的氯化锆和冰醋酸的质量比介于1 ~ 20之间。
上述步骤（1）中所述的高温为70~140℃，反应时间为2~24 h。
上述步骤（1）中所述的双羧基离子液体为1,3-二羧乙基咪唑氯盐、1,3-二羧丙基咪唑氯盐、1,3-二羧丁基咪唑氯盐、1,3-二羧乙基咪唑溴盐、1,3-二羧丙基咪唑溴盐、1,3-二羧丁基咪唑溴盐、1,3-二羧乙基咪唑硫酸氢盐、1,3-二羧丙基咪唑硫酸氢盐、1,3-二羧丁基咪唑硫酸氢盐中的一种。
上述步骤（1）中所述的重复次数为5~20次。
一种上述方法制备获得的离子液体多层负载的核-壳结构催化剂。
上述方法制备的离子液体多层负载的核-壳结构催化剂在各类醇酸酯化和模拟汽油脱硫反应中的应用。
本发明的有益效果在于：
本发明通过利用羧基与金属离子及金属簇的配位作用，以羧基功能化纳米颗粒为核，锆离子或者锆簇为连接点，将羧基功能化离子液体层层组装到纳米颗粒上，形成以多层离子液体为壳的核-壳结构催化剂。该催化剂除具有很强的物理和化学稳定性外，通过调变羧基功能化离子液体的阴离子种类还能达到定向功能化的目的；另外，通过该方法制备的催化剂除了能从根本上解决离子液体化学键合固载量少的问题外，还具有形貌可设计性强、性能易调控、工业化应用前景广阔等特点。本发明制备的离子液体多层负载的核-壳结构催化剂用于各类醇酸酯化和模拟汽油脱硫反应中取得了很好的效果。
附图说明
图1是所制核壳材料的制备机理及结构图。
图2是所制材料的X射线衍射图。
图3是所制材料的红外光谱图。
具体实施方法
通过以下具体的实施例对本发明作进一步的阐述。但本发明的保护范围并不限于下列实施例。
实施例1
（1）SiO2的表面羧基化
准确称取2 g经120℃活化过的亲水性气相SiO2分散在50 mL的无水乙醇中，在磁力搅拌下逐滴加入3 mL的3-氨丙基三乙氧基硅烷，在80 ℃条件下回流6 h，冷却至室温，经乙醇（50 mL×3）洗涤，并真空干燥后，所得产物重新分散在30 mL的无水乙醇中，在磁力搅拌情况下，逐滴加入6 g戊二酸酐，在缓慢搅拌条件下，37℃回流3 h，用无水乙醇（10 mL×3）洗涤，并真空干燥，即得羧基功能化的SiO2。
（2）HSO4-IL@ZrCl4@SiO2的制备
将0.2 g羧基功能化的SiO2和0.05 g 氯化锆分散于50 mL的DMF中，然后加入1 mL醋酸并超声分散30 min获得分布均匀的悬浮液，然后将悬浮液倒入100 mL聚四氟乙烯内衬的水热合成釜中，120℃条件下晶化10 h，离心分离，分别使用DMF 和乙醇清洗两遍，烘干得固体粉末备用；将得到的固体粉末和0.05g 1,3-二羧乙基咪唑氯盐均匀分散在50 mL的DMF中，并于100 mL聚四氟乙烯内衬的水热合成釜中120℃条件下晶化8 h，经洗涤、烘干即得1层羧基离子液体和氯化锆负载的IL@ZrCl4@SiO2核-壳结构催化剂，重复上述操作八次，即得8层羧基离子液体和氯化锆负载的IL@ZrCl4@SiO2核-壳结构催化剂；将上述所得IL@ZrCl4@SiO2复合材料加入到50 mL 含0.05 mol.L-1硫酸的乙醇溶液中，室温搅拌5 h，经乙醇洗涤，即得HSO4-IL@ZrCl4@SiO2核-壳结构催化剂，复合材料经元素分析可得其N元素含量为0.038g/g，由此计算可得离子液体的负载量为0.418g/g，即41.8%。
图1是本实施例所制核壳材料的制备机理及结构图。
图2是本实施例所制核壳材料的X射线衍射图。由图2知在SiO2上生长了一定的类晶体材料，从出峰位置可判断合成的核-壳结构催化剂与UiO-66（一种氯化锆与对苯二甲酸配位合成的晶体材料）具有一定的结构类似性。
图3是本实施例所制核壳材料的红外光谱图。由图3知相比于SiO2,羧基功能化的COOH-SiO2具有明显的羧基振动峰（1710 cm-1附近），证明对SiO2进行了成功的表面羧基化；在IL@ZrCl4@SiO2的红外谱图上可以清晰的发现羧基振动峰由1710 cm-1转移至了1630 cm-1附近，这是由于羧基与氯化锆的配位所致，另外，结合780 cm-1附近的C-N峰可进一步说明离子液体和氯化锆的成功配位与固载。
实施例2
Fe2Cl7-IL@ZrCl4@SiO2的制备
将0.2 g实施例1制备的羧基功能化的SiO2和0.05 g 氯化锆分散于50 mL的DMF中，然后加入1 mL 醋酸并超声分散30 min，获得分布均匀的悬浮液，然后将悬浮液浑浊液倒入100 mL聚四氟乙烯内衬的水热合成釜中，120℃条件下晶化10 h，离心分离，分别使用DMF 和乙醇清洗两遍，烘干得固体粉末备用；将得到的固体粉末和0.05 g1,3-二羧乙基咪唑氯盐均匀分散在50 mL的DMF中，并于100 mL聚四氟乙烯内衬的水热合成釜中120℃条件下晶化8 h，经洗涤、烘干即得1层羧基离子液体和氯化锆负载的IL@ZrCl4@Fe3O4核-壳结构催化剂，重复上述操作八次，即得8层羧基离子液体和氯化锆负载的IL@ZrCl4@SiO2核-壳结构催化剂；将上述所得IL@ZrCl4@SiO2复合材料和0.5 g无水氯化铁置于100 mL的圆底烧瓶内，加入50 mL 乙腈，于83℃下搅拌24 h，经乙腈洗涤，即得 Fe2Cl7-IL@ZrCl4@SiO2核-壳结构催化剂，复合材料经元素分析可得其N元素含量为0.022g/g，由此计算可得离子液体的负载量为0.449g/g，即44.9%。
应用实施例1
将1.2 g HSO4-IL@ZrCl4@SiO2复合催化剂、0.2 mol乙酸和0.2 mol乙醇加入到100mL圆底烧瓶中，加入一定量的带水剂，在100 ℃条件下，反应2 h，冷却至室温后，离心分离，滴定检测乙酸转化率为95.8%。
应用实施例2
将1.2 g HSO4-IL@ZrCl4@SiO2复合催化剂、0.2 mol丙酸和0.2 mol正丙醇加入到100 mL圆底烧瓶中，加入一定量的带水剂，在100 ℃条件下，反应2 h，冷却至室温后，离心分离，滴定检测丙酸转化率为93.9%。
应用实施例3
将1.2 g HSO4-IL@ZrCl4@SiO2复合催化剂、0.05 mol油酸和0.5 mol乙醇加入到50mL圆底烧瓶中，在80 ℃条件下，反应2 h，冷却至室温后，离心分离，气相色谱检测油酸甲酯收率为92.7%。
应用实施例4
以应用实施例1中的乙酸和乙醇酯化反应作为探针反应，做 HSO4-IL@ZrCl4@SiO2催化剂的活性重复性试验，重复使用5次，乙酸的转化率如表1所示：
表1 HSO4-IL@ZrCl4@SiO2催化剂活性重复性试验中乙酸的转化率
表1结果表明：层层组装制备的HSO4-IL@ZrCl4@SiO2核壳结构催化剂经五次重复使用，活性基本不变，展现了其优良的催化稳定性。
应用实施例5
以加氢脱硫中较难脱除的苯并噻吩为目标硫化物，以正辛烷为溶剂，配制硫含量为1000 pm的模拟汽油，在50 mL单口烧瓶中加入20 ml 模拟汽油、1 g的Fe2Cl7-IL@ZrCl4@SiO2复合催化剂和0.85 g的双氧水，于40℃下反应20 min，模拟气油中苯并噻吩的脱除率可达93.8%。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (8)
1.一种羧基功能化离子液体制备核-壳结构催化剂的方法，其特征在于：以羧基功能化纳米颗粒为核，以锆离子或者锆簇为连接点，利用锆离子或者锆簇与羧基的配位作用将羧基功能化离子液体层层组装到纳米颗粒上，形成离子液体多层负载的核-壳结构催化剂；
包括以下具体步骤：
（1）将作为核的纳米颗粒表面羧基化，获得羧基功能化纳米颗粒，然后将羧基功能化纳米颗粒分散在溶剂DMF中形成浑浊液，将氯化锆和冰醋酸按一定的质量比加入到浑浊液中，经超声分散后获得分布均匀的悬浮液，然后将所得的悬浮液转移至水热合成釜中，并于高温下反应一定的时间，所得产物经DMF和乙醇洗涤、干燥后得固体粉末，将固体粉末继续分散在溶剂DMF中，加入与氯化锆等物质的量的双羧基离子液体并在水热合成釜中高温反应一定的时间，即得一层离子液体负载的核-壳结构催化剂，多次重复上述操作，得离子液体多层负载的核-壳结构催化剂；
（2）将上述所得的离子液体多层负载的核-壳结构催化剂置于含有硫酸或者氯化铁的乙醇或乙腈溶液中进行置换，经洗涤得含有特定基团的离子液体多层负载的核-壳结构催化剂，离子液体负载量为40~45wt%。
2.根据权利要求1所述的方法，其特征在于：所述步骤（1）中的羧基功能化纳米颗粒为羧基化二氧化硅、羧基化四氧化三铁和羧基化氧化铝中的一种。
3.根据权利要求1所述的方法，其特征在于：所述步骤（1）中的氯化锆和冰醋酸质量比介于1~20之间。
4. 根据权利要求1所述的方法，其特征在于：所述步骤（1）中的高温为70~140℃，反应时间为2~24 h。
5.根据权利要求1所述的方法，其特征在于：所述步骤（1）中的双羧基离子液体为1,3-二羧乙基咪唑氯盐、1,3-二羧丙基咪唑氯盐、1,3-二羧丁基咪唑氯盐、1,3-二羧乙基咪唑溴盐、1,3-二羧丙基咪唑溴盐、1,3-二羧丁基咪唑溴盐、1,3-二羧乙基咪唑硫酸氢盐、1,3-二羧丙基咪唑硫酸氢盐、1,3-二羧丁基咪唑硫酸氢盐中的一种。
6.根据权利要求1所述的方法，其特征在于：所述步骤（1）中的重复次数为5~20次。
7.一种如权利要求1-6任一所述方法制备获得的离子液体多层负载的核-壳结构催化剂。
8.如权利要求7所述的离子液体多层负载的核-壳结构催化剂在各类醇酸酯化和模拟汽油脱硫反应中的应用。
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