CN114100691B - 一种糖基介孔含锆复合材料及其制备方法和应用 - Google Patents
一种糖基介孔含锆复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供了一种糖基介孔含锆复合材料及其制备方法和应用，属于复合材料技术领域。本发明提供的制备方法，包括以下步骤：(1)将锆源的醇溶液、天然糖的水溶液、有机致孔剂混合，进行溶胶‑凝胶反应，得到前驱体凝胶；(2)对所述前驱体凝胶依次进行干燥和煅烧，得到糖基介孔含锆复合材料。本发明以天然糖为有机配体，其结构中富含的含氧官能团具有强大的金属配合能力，与锆离子具有良好的配合作用，能够增强锆的Lewis酸性。天然糖基有机配体能够充当保护剂，在溶胶‑凝胶过程中，有利于锆纳米颗粒的分散。本发明所得糖基介孔含锆复合材料的孔结构为介孔，能够增强催化点位的可及性，且利于传质。
Description
技术领域
本发明涉及复合材料技术领域，特别涉及一种糖基介孔含锆复合材料及其制备方法和应用。
背景技术
锆氧化物固体催化剂在选择性还原醛/羰基的Meerwein-Ponndorf-Verley反应中应用极其广泛。通过有机配体与含锆前驱物自组装，进而生成含锆复合材料，其催化活性相比单一的锆氧化物更加优异。现阶段，与锆进行组装的有机配体多以化石资源衍生得到的化合物为主，如对苯二甲酸、均苯三甲酸等，一般需要在有机溶剂中(常见如二甲基甲酰胺)进行自组装来制备。该方法制备的含锆复合材料的孔结构多以微孔为主，对于体积较大的底物分子具有一定的传质阻力。
发明内容
有鉴于此，本发明目的在于提供一种糖基介孔含锆复合材料及其制备方法和应用。本发明方法以天然糖作为有机配体，所得含锆复合材料的孔结构为介孔。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种糖基介孔含锆复合材料的制备方法，包括以下步骤：
(1)将锆源的醇溶液、天然糖的水溶液、有机致孔剂混合，进行溶胶-凝胶反应，得到前驱体凝胶；
(2)对所述前驱体凝胶依次进行干燥和煅烧，得到糖基介孔含锆复合材料。
优选的，所述有机致孔剂为聚氧乙烯-聚氧丙烯-聚氧乙烯共聚物。
优选的，所述锆源为ZrOCl2和/或ZrCl4；所述天然糖为葡萄糖、果糖、木糖和蔗糖中的一种或几种。
优选的，所述天然糖与锆源的质量比为1～2:1～15。
优选的，所述天然糖与有机致孔剂的质量比为1～2:2.5～15。
优选的，所述溶胶-凝胶反应的温度为15～35℃，时间为12～48h。
优选的，所述煅烧的温度为325～450℃，保温时间为3～5h。
本发明提供了上述制备方法制备得到的糖基介孔含锆复合材料，所述糖基介孔含锆复合材料的孔体积为0.04～0.06cm3/g，比表面积为25～56m2/g。
本发明提供了糖基介孔含锆复合材料作为Lewis酸催化剂的应用。
优选的，所述糖基介孔含锆复合材料用于催化糠醛还原为糠醇、催化乙酰丙酸/酯转化为γ-戊内酯、催化5-羟甲基糠醛转化为2,5-呋喃二甲醇、催化己醛转化为己醇、催化葡萄糖异构化或催化木糖异构化的应用。
本发明提供了一种糖基介孔含锆复合材料的制备方法，包括以下步骤：(1)将锆源的醇溶液、天然糖的水溶液、有机致孔剂混合，进行溶胶-凝胶反应，得到前驱体凝胶；(2)对所述前驱体凝胶依次进行干燥和煅烧，得到糖基介孔含锆复合材料。本发明以天然糖为有机配体，天然糖结构中富含的含氧官能团(羟基、醛基等)具有强大的金属配合能力，与锆离子具有良好的配合作用，能够增强锆的Lewis酸性。在本发明中，天然糖基有机配体能够充当保护剂，在溶胶-凝胶过程中，有利于锆纳米颗粒的分散。本发明所得糖基介孔含锆复合材料的孔结构为介孔，能够增强催化点位的可及性，且利于传质。实施例结果表明，本发明所得糖基介孔含锆复合材料作为Lewis酸催化剂催化糠醛转化为糠醇时，获得的最优糠醇产率93.4％，具有良好的催化活性。
进一步的，本发明以天然糖作为有机配体，具有可再生、成本低廉的优势，相比于以化石资源衍生得到的化合物，更有利于资源持续化发展。本发明使用天然糖作为有机配体，以醇-水分散体系代替有机溶剂，在溶胶-凝胶过程中不需要添加酸/或碱催化剂，可极大提高含锆复合材料制备过程的环境友好性和可操作性。
附图说明
图1为糖基介孔含锆复合材料催化剂的N2吸脱附等温线；
图2为糖基介孔含锆复合材料催化剂的小角XRD谱图；
图3为糖基介孔含锆复合材料催化剂的广角XRD谱图；
图4为糖基介孔含锆复合材料催化剂的高分辨透射电镜谱图；
图5为二氧化锆与糖基介孔含锆复合材料催化剂中锆元素化学形态的XPS谱图。
具体实施方式
本发明提供了一种糖基介孔含锆复合材料的制备方法，包括以下步骤：
(1)将锆源的醇溶液、天然糖的水溶液、有机致孔剂混合，进行溶胶-凝胶反应，得到前驱体凝胶；
(2)对所述前驱体凝胶依次进行干燥和煅烧，得到糖基介孔含锆复合材料。
本发明将锆源的醇溶液、天然糖的水溶液、有机致孔剂混合，进行溶胶-凝胶反应，得到前驱体凝胶。在本发明中，所述锆源优选为ZrOCl2和/或ZrCl4，所述锆源的醇溶液优选为锆源的乙醇溶液。在本发明中，所述ZrOCl2优选为ZrOCl2·8H2O。在本发明中，所述锆源的醇溶液的浓度优选为25～150g/L，更优选为50～100g/L。
在本发明中，所述锆源的醇溶液的制备方法，优选包括以下步骤：
将锆源、醇溶剂搅拌混合，得到锆源的醇溶液。
在本发明中，所述搅拌混合的温度优选为15～35℃，更优选为20～30℃；时间优选为12～24h，更优选为16～20h。在本发明中，所述搅拌混合优选为磁力搅拌混合，所述磁力搅拌混合的转速优选为800～1500r/min，更优选为1000～1200r/min。
在本发明中，所述天然糖优选为葡萄糖；所述天然糖的水溶液的浓度优选为30～100g/L，更优选为50～80g/L。
在本发明中，所述有机致孔剂优选为聚氧乙烯-聚氧丙烯-聚氧乙烯共聚物。在本发明中，所述聚氧乙烯-聚氧丙烯-聚氧乙烯共聚物优选为的型号优选为F127(EO106PO70EO106)、P123(EO20PO70EO20)、P103(EO17PO60EO17)或P85(EO26PO40EO26)。
在本发明中，所述天然糖与锆源的质量比优选为1～2:1～15，更优选为1～2:5～10；所述天然糖与有机致孔剂的质量比优选为1～2:2.5～15，更优选为1～2:5～10。
在本发明中，所述混合的温度优选为15～35℃，更优选为20～30℃；时间优选为30～90min，更优选为40～60min。在本发明中，所述混合的方式优选为搅拌混合，所述搅拌混合的转速优选为400r/min。在本发明中，所述混合的过程中，锆源、天然糖与有机致孔剂形成溶胶。
在本发明中，所述溶胶-凝胶反应的温度优选为15～35℃，更优选为20～30℃；时间优选为24～48h，更优选为30～40h。在本发明中，所述溶胶-凝胶反应的过程中，聚氧乙烯-聚氧丙烯-聚氧乙烯共聚物形成胶束，与含锆醇盐、葡萄糖发生自组装，随着含锆醇盐水解、聚合最终形成凝胶，胶束和天然糖有机配体则包覆在其内部。
本发明在溶胶-凝胶过程中，无须添加酸或碱、在室温条件(15～35℃)下进行24h即能完成，反应时间短，条件温和，可极大提高制备过程的环境友好性和量产能力。
得到所述前驱体凝胶后，本发明对所述前驱体凝胶依次进行干燥和煅烧，得到糖基介孔含锆复合材料。在本发明中，所述干燥的温度优选为80℃，时间优选为12h。
在本发明中，所述煅烧优选为N2条件下进行。在本发明中，所述煅烧的温度优选为325～450℃，更优选为350℃；保温时间为3～5h，更优选为4h。在本发明中，升温至所述煅烧温度的升温速率优选为1℃/min。在本发明中，所述煅烧能够去除有机致孔剂形成介孔，同时使材料发生不完全炭化。
本发明提供了上述制备方法制备得到的糖基介孔含锆复合材料，所述糖基介孔含锆复合材料的孔体积为0.04～0.06cm3/g，优选为0.05cm3/g；比表面积为25～56m2/g，优选为35～50m2/g。
本发明提供了所述糖基介孔含锆复合材料作为Lewis酸催化剂的应用。
在本发明中，所述糖基介孔含锆复合材料优选用于催化糠醛还原为糠醇、催化乙酰丙酸/酯转化为γ-戊内酯、催化5-羟甲基糠醛转化为2,5-呋喃二甲醇、催化己醛转化为己醇、催化葡萄糖异构化或催化木糖异构化的应用。
在本发明中，当所述糖基介孔含锆复合材料用于催化糠醛还原为糠醇反应时，糠醛与糖基介孔含锆复合材料的质量比优选为4:1。在本发明中，当所述糖基介孔含锆复合材料用于催化糠醛还原为糠醇反应时，反应温度优选为160～200℃，更优选为170～180℃；反应时间优选为45～300min，更优选为120～180min。
下面结合实施例对本发明提供的糖基介孔含锆复合材料及其制备方法和应用进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。
实施例1
(1)锆溶液的制备：取10g ZrOCl2·8H2O(>98％)置于100mL无水乙醇中，室温下磁力搅拌12h形成均一溶液，转速为800r/min。
(2)葡萄糖溶液的制备：取1.05g葡萄糖于室温下溶解于20mL去离子水中。
(3)溶胶的制备：软模板分子F127三嵌段共聚物作为致孔剂。将10gF127和(2)中制备的20mL葡萄糖溶液同时加入(1)中制备的100mL锆溶液中。于室温下磁力搅拌30min形成溶胶，转速为400r/min。
(4)凝胶化：将(3)中的溶胶直接于室温下静置陈化24h即得到凝胶，无须外加酸或碱为催化剂。
(5)首先将(4)中得到的凝胶于80℃烘干12h；烘干后的样品在N2氛围中于350℃煅烧4h，升温速率为1℃/min，最终得到糖基介孔含锆复合材料催化剂。
所得糖基介孔含锆复合材料催化剂的N2吸脱附等温线如图1所示。由图1可以看出，本发明制备的糖基介孔含锆复合材料催化剂含有介孔结构，计算孔体积为0.05cm3/g，比表面积为37m2/g。
所得糖基介孔含锆复合材料催化剂的小角XRD谱图如图2所示。由图2可以看出，本发明所得糖基介孔含锆复合材料中的介孔具有无序性。
所得糖基介孔含锆复合材料催化剂的广角XRD谱图如图3所示。由图3可以看出，本发明所得糖基介孔含锆复合材料属于无定型态。
本发明所得糖基介孔含锆复合材料的高分辨透射电镜(HRTEM)谱图如图4所示，由图4可以看出，本发明所得糖基介孔含锆复合材料中锆颗粒分散均匀，尺寸为6～7nm。
本发明所得糖基介孔含锆复合材料与二氧化锆的XPS图谱如图5所示。由图5可以看出，相比单一二氧化锆，本发明所得糖基介孔含锆复合材料催化剂的活性中心锆元素的电正性更强，说明其Lewis酸性更强。
应用例1
(一)糖基介孔含锆复合材料催化剂催化糠醛还原为糠醇的Meerwein-Ponndorf-Verley反应
试验步骤如下：在容积为30mL的聚四氟乙烯内衬管中加入10mL异丙醇作为溶剂和还原剂，加入2mmol糠醛和50mg糖基介孔含锆复合材料催化剂。密闭后置于加热搅拌仪中，磁力搅拌转速为1000r/min，反应温度为160～200℃，反应时间为45～300min。反应液经过滤后由气相色谱测定，外标法定量，糠醛转化率、糠醇产率、糠醇选择性的计算公式如下：
所得结果见表1。
表1糖基介孔含锆复合材料催化剂催化糠醛还原为糠醇的试验结果
由表1可以看出，在180℃下反应180min，糠醇最高产率为93.4％，糠醇选择性和糠醛转化率分别为94.2％和99.1％。说明本发明的糖基介孔含锆复合材料催化剂对于探针反应糠醛还原为糠醇催化效果优异。
(二)糖基介孔含锆复合材料催化剂的循环利用
试验步骤如下：在容积为30mL的聚四氟乙烯内衬管中加入10mL异丙醇作为溶剂和还原剂，加入2mmol糠醛和50mg糖基介孔含锆复合材料催化剂。密闭后置于加热搅拌仪中，磁力搅拌转速为1000r/min，反应温度180℃，反应180min。反应结束后反应液高速离心(5000r/min)5min，分离得到使用后的催化剂；将使用后的催化剂在10mL无水乙醇中清洗5min，共进行3次；清洗后的催化剂在60℃烘干4h后重复利用，一共进行5次。
所得结果见表2。
表2糖基介孔含锆复合材料催化剂催化的循环利用试验结果
由表2可以看出，循环利用5次之后，糠醇的产率和选择性仍可达到77.6％和88.7％，说明本发明的糖基介孔含锆复合材料催化剂性能非常稳定。
(三)糖基介孔含锆复合材料催化剂的重生
试验步骤如下：将应用例(二)中循环利用5次的糖基介孔含锆复合材料催化剂在10mL 0.5mmol/L的NaOH溶液中室温搅拌60min，转速为300r/min。经高速离心(5000r/min,5min)分离后，用50mL去离子水清洗，共进行3次，至清洗液的pH至中性。清洗后的催化剂在60℃烘干12h，按照上文(二)糖基介孔含锆复合材料催化剂的循环利用的步骤再进行一次利用。
所得结果见表3。
表3重生的糖基介孔含锆复合材料催化剂与新制材料的催化活性比对
由表3可以看出，重生后的糖基介孔含锆复合材料催化剂作用下，糠醇的产率重新恢复到92.8％，糠醇选择性和糠醛转化率分别恢复到94.1％和98.6％，这与新制催化剂的催化效果相当，这说明本发明的糖基介孔含锆复合材料催化剂非常容易实现催化活性的重生，利于提高催化剂的使用寿命。
实施例2
将葡萄糖加入量改为2.1g，其余制备方法与实施例1一致，得到糖基介孔含锆复合材料催化剂。
实施例3
将葡萄糖加入量改为0.6g，其余制备方法与实施例1一致，得到糖基介孔含锆复合材料催化剂。
实施例4
将煅烧温度改为400℃，其余制备方法与实施例1一致，得到糖基介孔含锆复合材料催化剂。
实施例5
将煅烧温度改为450℃，其余制备方法与实施例1一致，得到糖基介孔含锆复合材料催化剂。
实施例6
将天然糖改为果糖，其余制备方法与实施例1一致，得到糖基介孔含锆复合材料催化剂。
实施例7
将天然糖改为蔗糖，其余制备方法与实施例1一致，得到糖基介孔含锆复合材料催化剂。
对比例1
不加入任何有机致孔剂，其余制备方法与实施例1一致，得到无孔含锆复合材料催化剂。
对实施例2～7制备的糖基介孔含锆复合材料催化剂和对比例1中制备的无孔含锆复合材料催化剂进行催化糠醛转化为糠醇的性能测试，测试条件为：在容积为30mL的聚四氟乙烯内衬管中加入10mL异丙醇作为溶剂和还原剂，加入2mmol糠醛和50mg含锆复合材料催化剂。密闭后置于加热搅拌仪中，磁力搅拌转速为1000r/min，反应温度180℃，反应180min。
所得结果见表4。
表4实施例2～7和对比例1的催化活性结果
实施例1～7和对比例1的结果表明，糖基介孔含锆复合材料催化剂相比无孔含锆复合材料催化剂的催化性能明显提高。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (5)
1.一种糖基介孔含锆复合材料的制备方法，包括以下步骤：
（1）将锆源的醇溶液、天然糖的水溶液、有机致孔剂混合，进行溶胶-凝胶反应，得到前驱体凝胶；
（2）对所述前驱体凝胶依次进行干燥和煅烧，得到糖基介孔含锆复合材料；
所述有机致孔剂为聚氧乙烯-聚氧丙烯-聚氧乙烯共聚物；
所述锆源为ZrOCl2和/或ZrCl4；所述天然糖为葡萄糖、果糖、木糖和蔗糖中的一种或几种；
所述天然糖与锆源的质量比为1~2:1~15；
所述天然糖与有机致孔剂的质量比为1~2:2.5~15；
所述煅烧的温度为325~450 ℃，保温时间为3~5 h。
2.根据权利要求1所述的制备方法，其特征在于，所述溶胶-凝胶反应的温度为15~35℃，时间为12~48 h。
3.权利要求1或2所述制备方法制备得到的糖基介孔含锆复合材料，所述糖基介孔含锆复合材料的孔体积为0.04~0.06 cm3/g，比表面积为25~56 m2/g。
4.权利要求3所述糖基介孔含锆复合材料作为Lewis酸催化剂的应用。
5.根据权利要求4所述的应用，其特征在于，所述糖基介孔含锆复合材料用于催化糠醛还原为糠醇、催化乙酰丙酸或乙酰丙酯转化为γ-戊内酯、催化5-羟甲基糠醛转化为2,5-呋喃二甲醇、催化己醛转化为己醇、催化葡萄糖异构化或催化木糖异构化的应用。
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