CN106268886B - 一种碳掺杂介孔磷酸铝及其制备方法和应用 - Google Patents
一种碳掺杂介孔磷酸铝及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于新材料技术领域，具体涉及一种碳掺杂介孔磷酸铝及其制备和应用，本发明通过溶剂挥发自主装合成含有表面活性剂的有机‑无机杂合的膦酸铝固体颗粒，并在氮气保护下通过焙烧膦酸铝固体，得到的材料具有丰富的介孔的碳掺杂孔磷酸铝，其介孔孔径为1.5～3.0nm，比表面积为200～600m2/g。该碳掺杂介孔磷酸铝用于CO2和1‑乙基‑2‑苯基氮杂丙叮环加成反应，表现出非常好的催化活性，催化反应在低压的条件下顺利进行，且催化剂可循环使用，是绿色合成噁唑烷酮类化合物的一条新途径。
Description
技术领域
本发明属于新材料技术领域，具体涉及一种碳掺杂介孔磷酸铝及其制备方法；这种新型的介孔磷酸铝材料作为固体催化剂用于CO2和1-乙基-2-苯基氮杂丙叮的环加成反应。
背景技术
CO2是主要的温室气体，同时也是一种廉价、丰富C1资源，因此将CO2转化为高附加值化学品具有重要意义。到目前为止，有各种各样的方法用于转变CO2为有用的化学物质，其中利用小环化合物譬如环氧乙烷和氮杂丙叮类衍生物与CO2反应是一种可行的路径。因为氮杂丙叮类衍生物是一种高度活性的物质，可以和相对惰性的CO2反应，同时得到的产物噁唑烷酮作为重要的手性助剂、中间体以及一类新型抗菌剂已引起世界范围内科学界的高度重视。目前各种各样的催化剂已被发展起来催化此类反应，包括均相催化剂，譬如碱土金属卤化物、碘化物、α-氨基酸和四烷基季铵盐体系；虽然它们中的部分催化剂体系表现出相当好的活性，然而在反应中往往需要添加有毒的有机溶剂、共催化剂以及苛刻的反应条件和产物净化繁杂的操作手续，使其实际应用受到极大限制。从催化剂分离角度而言，固体催化剂作为另一种选择也已得到应用。另外，从绿色化学和工业生产角度而言，固体催化剂比液体催化剂更有优势。目前有溴化季铵盐功能化的聚乙二醇和ZrOCl2作为固体催化剂可以催化一系列的氮杂丙叮衍生物与CO2的反应，不过此类催化剂中含有环境不友好的卤素元素，另外催化反应条件相对比较苛刻(反应压力高)。因此发展具有高效催化活性、温和反应条件和环境友好的固体催化剂仍然是个挑战。
发明内容
为了解决上述问题，本发明的目的之一在于提供一种碳掺杂介孔磷酸铝；本发明的目的之二是提供了所述碳掺杂介孔磷酸铝的制备方法；本发明的目的之三是提供了所述碳掺杂介孔磷酸铝的应用。
本发明是通过以下技术方案来实现的：
一种碳掺杂介孔磷酸铝，所述碳掺杂介孔磷酸铝的介孔孔径为1.5～3.0nm，比表面积为200～600m2/g。
制备所述碳掺杂介孔磷酸铝的方法，包括如下步骤：
1)、将氯化铝(AlCl3·6H2O)、羟基亚乙基二膦酸(HEDP)和十六烷基三甲基溴化铵(CTAB)，于乙醇/水溶液中溶解，形成澄清溶液；
2)、将步骤1)中所得澄清溶液搅拌0.5～48小时，所得混合物倒入培养皿中，静置挥发，直至溶剂挥发干，得到固体颗粒；
3)、将步骤2)中所得固体颗粒在氮气保护下焙烧，得到所述碳掺杂介孔磷酸铝。
较佳地，步骤1)中所述氯化铝、羟基亚乙基二膦酸、十六烷基三甲溴化铵、乙醇和水之间的摩尔比为(1～2):(0.5～2.5):(0.5～3):(15～50):(20～60)。
较佳地，步骤2)中所述澄清溶液静置挥发温度为5～30℃。
较佳地，步骤3)中所述焙烧温度为250～500℃。
所述碳掺杂介孔磷酸铝的应用，所述碳掺杂介孔磷酸铝用于CO2和1-乙基-2-苯基氮杂丙叮的环加成反应。表现出非常好的催化活性，催化反应在低压的条件下顺利进行，且催化剂可循环使用。
碳掺杂介孔磷酸铝的应用具体为：0.05～0.2g催化剂和1mmol 1-乙基-2-苯基氮杂丙叮放入25ml的高压反应釜中，然后在釜中冲入CO2气体，接着在指定的温度预热5min，将釜中的CO2压力调到1～5MPa，温度升至80～120℃，继续搅拌2～6h。
本发明通过溶剂挥发自主装合成含有表面活性剂的有机-无机杂合的膦酸铝固体颗粒，该颗粒在氮气保护下通过焙烧，得到的碳掺杂磷酸铝具有丰富的介 孔结构。该碳掺杂介孔磷酸铝用于CO2和1-乙基-2-苯基氮杂丙叮环加成反应，表现出非常好的催化活性，催化反应在低压的条件下顺利进行，且催化剂可循环使用，是绿色合成噁唑烷酮类化合物的一条新途径。
本发明可通过调节实验中原料配比、改变晶化温度、焙烧温度等实验条件调变孔径分布和比表面；具有高机械稳定性和水热稳定性；催化剂易回收和循环使用，适用于连续化生产。总之，本发明合成设备简单、操作方便、条件宽松、原料简单易得、成本低廉，其中催化剂很容易地从反应体系中过滤分离，且可循环使用，催化反应在低压的条件下进行，同时简化了产品的分离、纯化过程，提高了产品纯度、降低了生产成本。
具体的实施方式
下面结合具体实施方式对本发明作进一步的详细说明，以助于本领域技术人员理解本发明。
实施例中所用到的试剂除了特别说明的以外，均为化学纯试剂。在实施例中，样品比表面积、孔容、孔径由低温氮气吸附-脱附法测定。
实施例1
一种碳掺杂介孔磷酸铝的制备：将0.010mol CTAB溶于醇/水(25mL/15mL)溶液中，接着将0.03mol HEDP加入上述溶液，等搅拌溶解后，继续加入0.03molAlCl3。在室温下搅拌30min后，将得到的澄清溶液导入培养皿中，让溶剂自然挥发，然后将得到的固体放入50℃的烘箱进一步的干燥。紧接着将固体样品在氮气保护下进行焙烧，具体步骤为：在氮气保护下以20/min的升温速率先升到350℃恒温4h，然后接着升到400℃保持2h。样品经XRD、TG-DSC、N2吸附/脱附、SEM、TEM、XPS、FT-IR光谱、31P、27Al和13C MAS NMR表征证实为具有介孔结构的碳掺杂的磷酸铝材料。氮气吸附-脱附等温线及其相应的孔径分布图表明该材料具有典型的介孔结构，BET比表面积为420m2/g；孔容为0.29cm3/g；介孔孔径大小为2.2nm。
实施例2
一种碳掺杂介孔磷酸铝的制备：采用实施例1的制备过程，将0.015molCTAB溶于醇/水(25mL/15mL)溶液中，接着将0.025mol HEDP加入上述溶液，等搅拌溶解后，继续加入0.03mol AlCl3。在室温下搅拌30min后，将得到的澄清溶液导入培养皿中，让溶剂自然挥发，然后将得到的固体放入50℃的烘箱进一步的干燥。紧接着将固体样品在氮气保护下进行焙烧。氮气吸附-脱附测试表明该材料BET比表面积为380m2/g；孔容为0.31cm3/g；介孔孔径大小为2.5nm。
实施例3
一种碳掺杂介孔磷酸铝的制备：采用实施例2的制备过程，将样品在氮气保护下以20/min的升温速率先升到250℃恒温4h，然后接着升到350℃保持2h。所得材料BET比表面积为350m2/g；孔容为0.28cm3/g；介孔孔径大小为2.0nm。实施例4
一种碳掺杂介孔磷酸铝的制备：采用实施例2的制备过程，将样品在氮气保护下以20/min的升温速率先升到250℃恒温4h，然后接着升到450℃保持2h。所得材料BET比表面积为262m2/g；孔容为0.33cm3/g；介孔孔径大小为2.3nm。应用例1
取实施例1中所得碳掺杂介孔磷酸铝0.1g，和1-乙基-2-苯基氮杂丙叮(1mmol)放入25ml的高压反应釜中，然后在釜中冲入CO2气体，接着在指定的温度预热5min，将釜中的CO2压力调到3MPa，温度升至120℃，继续搅拌6h。反应方程式如下式所示。当反应结束后，等反应釜冷却，先将CO2气体慢慢的释放，从釜中取出一滴反应液，加入CH2Cl2和内标联苯，用气相色谱分析产物。所得产物的转化率>99％，产率为95％，区域选择性为2a:3a＝97:3。
应用例2
采用实施例5的催化过程，将釜中的CO2压力调到2MPa，温度100℃，继续搅拌6h。所得产物的转化率>99％，产率为99％，区域选择性为98:2。
上述实施例，只是本发明的较佳实施例，并非用来限制本发明实施范围，故凡以本发明权利要求所述的特征及原理所做的等效变化或修饰，均应包括在本发明权利要求范围之内。
催化结果：
为了考察催化剂的循环使用，首先将实施例1中制备的催化剂从反应液中过滤回收，再用大量的CH2Cl2洗提，真空60℃干燥6h。回收得到的催化剂的催化降至使用过程和应用例2中的使用过程一样。催化结果见表1。
表1
| 催化次数 | 转化率 | 产率 | 区域选择性(2a:3a) |
| 1 | >99％ | 98％ | 98:2 |
| 2 | >99％ | 99％ | 98:2 |
| 3 | >99％ | 97％ | 97:3 |
| 4 | >99％ | 96％ | 95:5 |
由表1可以看出，本发明所述的碳掺杂介孔磷酸铝用于CO2和1-乙基-2-苯基氮杂丙叮的环加成反应。表现出非常好的循环使用效果。
Claims (2)
1.一种碳掺杂介孔磷酸铝的应用，其特征在于，所述碳掺杂介孔磷酸铝用于CO2和1-乙基-2-苯基氮杂丙叮的环加成反应，比表面积为200～600m2/g，所述碳掺杂介孔磷酸铝的制备方法包括如下步骤：
1)、将氯化铝、羟基亚乙基二膦酸和十六烷基三甲基溴化铵，于乙醇和水溶液中溶解，形成澄清溶液；
2)、将步骤1)中所得澄清溶液搅拌0.5～48小时，所得混合物倒入培养皿中，静置挥发，直至溶剂挥发干，得到固体颗粒；
3)、将步骤2)中所得固体颗粒在氮气保护下焙烧，得到所述碳掺杂介孔磷酸铝；
步骤1)中所述氯化铝、羟基亚乙基二膦酸、十六烷基三甲溴化铵、乙醇和水之间的摩尔比为1～2:0.5～2.5:0.5～3:15～50:20～60；
步骤2)中所述静置挥发温度为5～30℃；
步骤3)中所述焙烧温度为250～500℃。
2.如权利要求1中所述碳掺杂介孔磷酸铝的应用，其特征在于，具体为0.05～0.2g催化剂和1mmol 1-乙基-2-苯基氮杂丙叮放入25ml的高压反应釜中，然后在釜中冲入CO2气体，接着在指定的温度预热5min，将釜中的CO2压力调到1～5MPa，温度升至80～120℃，继续搅拌2～6h。
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| WO2013077989A1 (en) * | 2011-11-22 | 2013-05-30 | Icl-Ip America Inc. | Process for preparation of aluminum salt of phosphonic acid ester |
| CN104174417A (zh) * | 2014-09-02 | 2014-12-03 | 西华师范大学 | 磷酸铝催化剂及其制备和应用 |
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| CN103003289A (zh) * | 2010-06-24 | 2013-03-27 | Icl-Ip美国公司 | 金属膦酸酯盐阻燃剂及其制造方法 |
| WO2013077989A1 (en) * | 2011-11-22 | 2013-05-30 | Icl-Ip America Inc. | Process for preparation of aluminum salt of phosphonic acid ester |
| CN104174417A (zh) * | 2014-09-02 | 2014-12-03 | 西华师范大学 | 磷酸铝催化剂及其制备和应用 |
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