CN106268954B - 一种Au@MnPS催化剂及其制备方法和用途 - Google Patents
一种Au@MnPS催化剂及其制备方法和用途 Download PDFInfo
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Abstract
本发明公开了一种Au@MnPS催化剂及其制备方法和用途。本发明制备了MnPS并在其上负载了纳米金，形成Au@MnPS催化剂，其中MnPS用作催化剂的载体，Au和MnPS中的锰卟啉结构作为催化剂的主要活性成分，其负载效率较高，分散程度较好。本发明提供的催化剂对环己烯环氧化制备环氧环己烷具有活性高和选择性好的特点，符合工业生产的要求。
Description
技术领域
本发明涉及一种Au@MnPS3催化剂的制备方法及其在环己烯环氧化中的应用。
背景技术
环己烯选择性氧化是合成多种高附加值中间体环己烯醇，环己烯酮和环氧环己烷的重要工艺。由于环己烯分子中含有一个易发生氧化反应的不饱和C=C双键和多个活性α-H原子，导致发生氧化反应的选择性较差，产物复杂，学术界和工业界一直在寻求温和条件下具有高活性、高选择性的催化剂用于环己烯催化氧化反应。多相催化剂具有容易与产物分离和便于循环使用的优势，是绿色催化工艺的主要研究方向之一。
新型的多相催化剂涵盖诸多方向，对于选择性氧化来说，当下的研究热点之一便是纳米金催化剂。纳米金催化剂现在已经有用于多种选择性氧化的报道，CO氧化、丙烯环氧化、氢氧直接合成过氧化氢、环己烷氧化制KA油等，其中也包括在环己烯选择性氧化中的应用。而纳米金催化剂的载体一般为多孔材料，包括活性炭，分子筛等等。在多孔材料的方面，近年来，金属-有机骨架配合物(metal - organic frameworks，MOFs)逐渐走进人们的视野，但现在绝大多数MOF的相关研究工作都集中在该材料对气体的吸附，催化方面的应用研究也才刚开始崭露头角。MOFs作为载体具有比表面积大，可方便地调控其结构性质(如孔径的扩张或压缩)及表面功能基团，具有不饱和金属配位点等优点。由于MOFs能够有效的防止反应过程中颗粒的长大，有许多MOFs负载金属纳米催化剂在有机反应中表现出了优秀的催化性能，并且也有了Au@MOFs的报道。然而现在的Au@MOFs的研究基本上只集中在醇类氧化上，基本没有用于烯烃氧化的研究。
由于仿生催化剂一直在环己烯的选择性氧化中表现不俗，而金属卟啉可以形成构成MOFs的金属有机配体结构，因此MOFs 材料是实现仿生催化剂均相催化剂多相化手段之一。MOFs 的特殊结构使得仿生催化剂中有机配体的部分通过金属离子连接以单分子态存在，彼此互相分离，避免了二聚，可提高稳定性和催化活性。同时，其均匀的孔径和规整的孔道结构，又为催化反应提供良好的形状选择性。PIZA-3是由Suslick等最早报道的卟啉作为有机配体制备的MOFs 材料，有能力在亚碘酰苯为氧化剂的条件下催化烯烃环氧化，过氧化物产率可达20-74%。可以看出，金属卟啉MOFs在环己烯的选择性氧化方面具有巨大的潜力。
发明内容
为了克服现有技术的不足，本发明目的在于提供一种Au@MnPS催化剂及其制备方法和用途。
我们尝试将纳米金和金属卟啉MOFs相结合，合成了锰卟啉的金属有机框架MnPS，并将其作为载体制备了Au@MnPS催化剂用于环己烯氧化反应，对催化剂进行表征并考察不同反应条件对催化剂性能的影响。在文献中并没有将金属卟啉MOFs用作载体的先例，单独使用纳米金作为活性中心的催化剂在环己烯的氧化中并不能很好的获得环氧环己烷，另外金属卟啉MOFs用于催化氧化时所用的氧化剂多为亚碘酰苯和TBHP。本发明将纳米金引入金属卟啉MOFs后，纳米金可以活化分子氧提高反应的转化率，而金属卟啉MOFs则可以与此同时保证反应的选择性，两者的结合起到了比分别使用更好的技术效果。
一种Au@MnPS催化剂，它由Au和MnPS组成，其中Au和MnPS中的锰卟啉结构作为催化剂的主要活性成分，Au的质量百分含量为2.0%，MnPS用作催化剂的载体，其质量百分含量＞95%。
所述的Au为Au的金属、Au的金属氧化物或上述两者的混合物。
所述的MnPS为一种以锰卟啉结构为主的金属有机框架。
一种根据所述的Au@MnPS催化剂的制备方法，包括如下步骤：
1）将卟啉和十二水合醋酸锰溶于DMF之中，置于水热合成釜中，在180℃反应48h后，冷却至室温，抽滤，用去离子水洗涤，得到黑色块状的MnPS固体，研磨至粉末状；
2）上述步骤1）得到的黑色固体取0.5g，在三口烧瓶中加入尿素0.9g，氯金酸溶液2.5mL，用去离子水稀释至30mL，在80℃搅拌回流6h后，加入30mL甲醛溶液，50℃继续反应3h，待反应液冷却后，抽滤，用去离子水洗涤，110℃干燥2 h，得到块状固体，研磨得到Au@MnPS粉末。
一种根据所述的Au@MnPS催化剂的用途，用于环己烯直接选择性环氧化生成环氧环己烷。
本发明与现有技术相比具有的有益效果：
1）环己烯环氧化的转化率和选择性较好；
2）条件温和；
3）可以用绿色的分子氧为氧化剂。
附图说明
图1是Au@MnPS的TEM图；
图2是Au@MnPS的XRD谱图；
图3是Au@MnPS的SEM图；
图4 是Au@MnPS的EDS谱图。
具体实施方式
以下结合附图和实施例对本发明做进一步的说明。
实施例1
Au@MnPS催化剂的制备：
3.8625g香草醛溶于50 mL丙酸中，141℃冷凝回流，缓慢滴加1.3 mL吡咯后，反应45min。冷却至室温，抽滤，并用无水甲醇洗涤数次。得到的紫红色固体在110℃干燥2h；将制得的卟啉0.2415g和醋酸锰1.2255g溶于DMF之中，放入水热合成釜中。在180℃反应48h后，冷却至室温，抽滤，用去离子水洗涤，得到黑色块状的MnPS固体，研磨至粉末状。取上述步骤得到的黑色固体0.5g，在三口烧瓶中加入尿素0.9g，根据金负载量不同加入不同量的氯金酸溶液（HAuCl4·4H2O，浓度为0.1g/L），用去离子水稀释至30mL。在80℃搅拌回流6h后，加入30mL市售甲醛溶液（国药集团化学试剂有限公司），50℃继续反应3h。待反应液冷却后，抽滤，用去离子水洗涤，110℃干燥2 h，得到块状固体，研磨得到不同金含量Au@MnPS粉末。其中得到的金含量2%Au@MnPS的催化剂XRD如图2所示，TEM图如图1所示，SEM图如图3所示，EDS图如图4所示。
催化剂活性评价中产物采用气相色谱分析，毛细管柱为SE-54 (30 m×0.32mm×0.5μm)，检测器为火焰离子化检测器(FID)。正己烷作为内标物。
以分子氧为氧化剂，采用DP法制备的锰分子筛负载纳米金催化剂对于环己烷选择性氧化，在80 ℃、0.5 MPa、24 h、无溶剂反应条件下，环己烯氧化转化率为39.9%，环氧环己烷选择性仅为2.52%；采用CZJ-1-Mn（一种锰卟啉MOFs）作为催化剂时，在乙腈溶剂，室温反应6h条件下，虽然环己烯转化率和环氧环己烷选择性都有99%，但是所用的氧化剂为亚碘酰苯，和分子氧相比不够绿色。
实施例2
催化剂活性评价。金含量2%Au@MnPS催化剂0.10 g置于一个PTFE-lined高压釜(容积= 20mL)中，0.8215g的环己烯，溶剂乙腈10mL，TBHP引发剂5滴，和作为氧化剂的分子氧在1 MPa的压力下在80°C搅拌反应20小时。得到环己烯氧化的转化率为45.047%，环氧环己烷的选择性为68.406%，环己烯醇的选择性为12.502%，环己烯酮的选择性为12.675%，邻环己二醇的选择性为6.416%。
实施例3
催化剂活性评价。金含量2% Au@MnPS催化剂0.10 g用于反应。0.8215g的环己烯，溶剂乙腈10mL，TBHP引发剂5滴，和作为氧化剂的分子氧在1 MPa的压力下在80°C搅拌反应5小时。得到环己烯氧化的转化率为39.667%，环氧环己烷的选择性为52.966%，环己烯醇的选择性为9.566%，环己烯酮的选择性为10.827%，邻环己二醇的选择性为26.641%。
实施例4
催化剂活性评价。金含量2% Au@MnPS催化剂0.10 g用于反应。0.8215g的环己烯，溶剂乙腈10mL，TBHP引发剂5滴，和作为氧化剂的分子氧在1 MPa的压力下在80°C反应搅拌15小时。得到环己烯氧化的转化率为71.942%，环氧环己烷的选择性为76.585%，环己烯醇的选择性为7.013%，环己烯酮的选择性为11.302%，邻环己二醇的选择性为5.101%。
实施例5
催化剂活性评价。金含量2% Au@MnPS催化剂0.10 g用于反应。0.8215g的环己烯，溶剂乙腈10mL，TBHP引发剂5滴，和作为氧化剂的分子氧在1 MPa的压力下在120°C搅拌反应20小时。得到环己烯氧化的转化率为77.904%，环氧环己烷的选择性为71.722%，环己烯醇的选择性为2.439%，环己烯酮的选择性为6.628%，邻环己二醇的选择性为19.211%。
实施例6
催化剂活性评价。金含量0.25% Au@MnPS催化剂0.10 g用于反应。0.8215g的环己烯，溶剂乙腈10mL，TBHP引发剂5滴，和作为氧化剂的分子氧在1 MPa的压力下在80°C搅拌反应20小时。得到环己烯氧化的转化率为88.439%，环氧环己烷的选择性为82.967%，环己烯醇的选择性为1.924%，环己烯酮的选择性为1.209%，邻环己二醇的选择性为13.900%。
实施例7
催化剂活性评价。金含量2% Au@MnPS催化剂0.10 g用于反应。0.8215g的环己烯，溶剂乙腈10mL，TBHP引发剂5滴，和作为氧化剂的分子氧在1 MPa的压力下在80°C无搅拌反应20小时。得到环己烯氧化的转化率为37.095%，环氧环己烷的选择性为75.617%，环己烯醇的选择性为3.921%，环己烯酮的选择性为6.017%，邻环己二醇的选择性为14.444%。
Claims (3)
1.一种Au@MnPS催化剂，其特征在于，它由Au和MnPS组成，其中Au和MnPS中的锰卟啉结构作为催化剂的主要活性成分，Au的质量百分含量为2.0%，MnPS用作催化剂的载体，其质量百分含量＞95%；
所述的Au@MnPS催化剂的制备方法，包括如下步骤：
1）将卟啉和十二水合醋酸锰溶于DMF之中，置于水热合成釜中，在180℃反应48h后，冷却至室温，抽滤，用去离子水洗涤，得到黑色块状的MnPS固体，研磨至粉末状；
2）上述步骤1）得到的黑色固体取0.5g，在三口烧瓶中加入尿素0.9g，氯金酸溶液2.5mL，用去离子水稀释至30mL，在80℃搅拌回流6h后，加入30mL甲醛溶液，50℃继续反应3h，待反应液冷却后，抽滤，用去离子水洗涤，110℃干燥2 h，得到块状固体，研磨得到Au@MnPS粉末。
2.一种根据权利要求1所述的Au@MnPS催化剂的制备方法，其特征在于，包括如下步骤：
1）将卟啉和十二水合醋酸锰溶于DMF之中，置于水热合成釜中，在180℃反应48h后，冷却至室温，抽滤，用去离子水洗涤，得到黑色块状的MnPS固体，研磨至粉末状；
2）上述步骤1）得到的黑色固体取0.5g，在三口烧瓶中加入尿素0.9g，氯金酸溶液2.5mL，用去离子水稀释至30mL，在80℃搅拌回流6h后，加入30mL甲醛溶液，50℃继续反应3h，待反应液冷却后，抽滤，用去离子水洗涤，110℃干燥2 h，得到块状固体，研磨得到Au@MnPS粉末。
3.一种根据权利要求1所述的Au@MnPS催化剂的用途，其特征在于，用于环己烯直接选择性环氧化生成环氧环己烷。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966464A (zh) * | 2010-09-07 | 2011-02-09 | 浙江大学 | 一种用于环己烯氧化的负载型纳米金催化剂及其制备方法 |
| JP2011212614A (ja) * | 2010-03-31 | 2011-10-27 | Nippon Shokubai Co Ltd | エチレンオキシド製造用触媒およびエチレンオキシドの製造方法 |
| CN105585541A (zh) * | 2016-03-10 | 2016-05-18 | 中山大学惠州研究院 | 一种环氧环己烷的制备方法 |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011212614A (ja) * | 2010-03-31 | 2011-10-27 | Nippon Shokubai Co Ltd | エチレンオキシド製造用触媒およびエチレンオキシドの製造方法 |
| CN101966464A (zh) * | 2010-09-07 | 2011-02-09 | 浙江大学 | 一种用于环己烯氧化的负载型纳米金催化剂及其制备方法 |
| CN105585541A (zh) * | 2016-03-10 | 2016-05-18 | 中山大学惠州研究院 | 一种环氧环己烷的制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| Manganese porphyrin in solution and heterogenized in differentmaterials mediates oxidation of hydrocarbons by iodosylbenzeneGabriel;Gabriel Kaetan Baio Ferreira等;《Journal of Molecular Catalysis A: Chemical》;20130708;第378卷;第263-272页 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126889A (zh) * | 2018-08-03 | 2019-01-04 | 湖南大学 | 一种适于电催化水氧化的锰氧化物/金属卟啉复合层状夹心纳米材料 |
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