CN114700064B - 一种酸碱双功能金属/埃洛石杂化材料的制备方法与应用 - Google Patents
一种酸碱双功能金属/埃洛石杂化材料的制备方法与应用 Download PDFInfo
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Abstract
本发明公开一种酸碱双功能金属/埃洛石杂化材料的制备方法与应用，以具有特殊表面化学性质的埃洛石纳米管为配体，结合配位设计策略，将埃洛石纳米管与金属溶液依次进行超声、沉淀处理，有利于金属离子与埃洛石纳米管中表面结构的配位，再将其进行洗涤、干燥处理后得到金属/埃洛石杂化材料；本发明的原材料具有绿色环保、成本低廉、资源丰富的优势，本发明可以得到同时含有路易斯酸/路易斯碱位点的杂化材料，表现出高效的催化活性以及良好的稳定性，进一步提高了埃洛石纳米管的应用价值，实现了资源高值化利用。
Description
技术领域
本发明涉及酸碱功能化材料制备技术以及催化应用领域，具体涉及一种酸碱双功能金属/埃洛石杂化材料的制备方法与应用。
背景技术
催化转化可再生的生物质及其衍生化合物制备生物燃料和高附加值化学品，对人类社会的可持续发展具有重要影响。乙酰丙酸、糠醛、5-羟甲基糠醛等来源于生物质的平台分子，被认为是连接生物质和可再生化学品的桥梁。基于已建立的催化体系，均相催化剂的应用已十分成熟，无机酸是其中一种可实现高收率且具有成本效益的均相催化剂，但反应物和催化剂的分离成为工业应用中的主要障碍。然而，非均相催化剂具有易于从反应介质中去除的优点，有利于产品的纯化和重复利用。因此，人们将研究重点转向大量化学改性的固体载体衍生的各种固体酸催化剂。
埃洛石纳米管是具有中空纳米管结构的天然粘土矿物。由于其生物相容性和潜在应用，人们对这类性质的材料越来越感兴趣。埃洛石纳米管具有特殊的表面化学性质，由外表面的硅氧烷基团和内腔的铝醇基团构成，其内腔和外表面的靶向化学修饰是通用的。功能化的埃洛石纳米管成为催化剂的宝贵载体，促进了具有可调特性的催化应用。在催化路径中，埃洛石纳米管的特殊管状形状有利于具有活性的负载型金属纳米颗粒的分散和表面可用性。此外，由于局部浓度和限制的增加，空腔的存在为生产具有酸碱双功能协同催化作用的材料开辟了新的可能性，且自身含有的酸性位点可以更好地充当催化材料中的活性组分。
发明内容
本发明提供一种酸碱双功能金属/埃洛石杂化材料的制备方法与应用，制备工艺简单，生产成本低，绿色高效，催化性能稳定，可实现多次重复利用。
本发明通过以下技术方案实现：
一种酸碱双功能金属/埃洛石杂化材料的制备方法，具体步骤如下：
(1)将1g埃洛石纳米管分散在10-50mL金属溶液中；
(2)将步骤(1)的混合物进行超声处理；
(3)将步骤(2)的混合物在室温下静置沉淀；
(4)将步骤(3)的混合物过滤洗涤、干燥后得到金属/埃洛石杂化材料，其结构通式为M(x)@HNTs，其中M为金属，x为溶液浓度，HNTs为埃洛石纳米管。
步骤(1)金属溶液为HfCl4溶液、FeCl3溶液、NiCl2溶液中的至少一种。
步骤(1)金属溶液浓度为0.03-0.10mol/L。
步骤(2)超声处理时间为10-60min。
步骤(3)静置沉淀时间为4-12h。
步骤(4)洗涤是使用去离子水洗涤三次，再将其在80℃干燥12h。
本发明的技术方案中，埃洛石纳米管来自市售。
本发明还提供所述酸碱双功能金属/埃洛石杂化材料作为催化剂在羰基类化合物转移加氢反应中的应用，具体步骤如下：
将0.1g金属/埃洛石杂化材料、0.2g羰基类化合物和20mL异丙醇溶剂混合置于密封高压反应釜中，在140-180℃，反应1-4h，制备得到羰基类化合物转移加氢产物，将金属/埃洛石杂化材料催化剂过滤，并用无水乙醇和去离子水分别洗涤三次，在80℃干燥12h后回收循环利用。
本发明的有益效果：
1、本发明结合配位设计策略得到以带有空轨道的金属离子为路易斯酸位中心，氧负离子为路易斯碱位中心的杂化材料，作为催化剂使用，催化活性好且稳定性高。
2、本发明工艺简单，原材料丰富，成本低，有利于工业化推广和使用。
3、本发明催化材料具有良好的普遍适用性，可应用于各类生物质基和石油基羰基化合物的转移加氢反应，条件温和，催化效果显著。
附图说明
图1是埃洛石纳米管的透射电子显微镜图；
图2是埃洛石纳米管的HAADF-STEM图和相应元素(Al，Si，O)mapping图；
图3是实施例1得到的铪/埃洛石杂化材料的HAADF-STEM和相应元素(Hf，Al，Si，O)mapping图。
具体实施方式
下面结合具体实施方式对本发明作进一步说明，但是本发明的保护范围不限于所述内容。
实施例1
一种酸碱双功能铪/埃洛石杂化材料的制备方法，具体步骤如下：
(1)称取1g埃洛石纳米管分散在50mL浓度为0.05mol/L的HfCl4溶液；
(2)将步骤(1)的混合物进行超声处理60min；
(3)将步骤(2)的混合物在室温下静置沉淀12h；
(4)将步骤(3)的混合物过滤后，用去离子水洗涤三次、80℃干燥12h后得到Hf(0.05)@HNTs-1杂化材料。
实施例2
一种酸碱双功能铁/埃洛石杂化材料的制备方法，具体步骤如下：
(1)称取1g埃洛石纳米管分散在50mL浓度为0.05mol/L的FeCl3溶液；
(2)将步骤(1)的混合物进行超声处理60min；
(3)将步骤(2)的混合物在室温下静置沉淀12h；
(4)将步骤(3)的混合物过滤后，用去离子水洗涤三次、80℃干燥12h后得到Fe(0.05)@HNTs杂化材料。
实施例3
一种酸碱双功能镍/埃洛石杂化材料的制备方法，具体步骤如下：
(1)称取1g埃洛石纳米管分散在50mL浓度为0.05mol/L的NiCl2溶液；
(2)将步骤(1)的混合物进行超声处理60min；
(3)将步骤(2)的混合物在室温下静置沉淀12h；
(4)将步骤(3)的混合物过滤后，用去离子水洗涤三次、80℃干燥12h后得到Ni(0.05)@HNTs杂化催化材料。
实施例4
一种酸碱双功能铪/埃洛石杂化材料的制备方法，具体步骤如下：
(1)称取1g埃洛石纳米管分散在50mL浓度为0.03mol/L的HfCl4溶液；
(2)将步骤(1)的混合物进行超声处理60min；
(3)将步骤(2)的混合物在室温下静置沉淀12h；
(4)将步骤(3)的混合物过滤后，用去离子水洗涤三次、80℃干燥12h后得到Hf(0.03)@HNTs杂化材料。
实施例5
一种酸碱双功能铪/埃洛石杂化材料的制备方法，具体步骤如下：
(1)称取1g埃洛石纳米管分散在50mL浓度为0.10mol/L的HfCl4溶液；
(2)将步骤(1)的混合物进行超声处理60min；
(3)将步骤(2)的混合物在室温下静置沉淀12h；
(4)将步骤(3)的混合物过滤后，用去离子水洗涤三次、80℃干燥12h后得到Hf(0.10)@HNTs杂化材料。
实施例6
一种酸碱双功能铪/埃洛石杂化材料的制备方法，具体步骤如下：
(1)称取1g埃洛石纳米管分散在20mL浓度为0.05mol/L的HfCl4溶液；
(2)将步骤(1)的混合物进行超声处理10min；
(3)将步骤(2)的混合物在室温下静置沉淀4h；
(4)将步骤(3)的混合物过滤后，用去离子水洗涤三次、80℃干燥12h后得到Hf(0.05)@HNTs-2杂化材料。
实施例7
一种酸碱双功能铪/埃洛石杂化材料的制备方法，具体步骤如下：
(1)称取1g埃洛石纳米管分散在10mL浓度为0.05mol/L的HfCl4溶液；
(2)将步骤(1)的混合物进行超声处理30min；
(3)将步骤(2)的混合物在室温下静置沉淀8h；
(4)将步骤(3)的混合物过滤后，用去离子水洗涤三次、80℃干燥12h后得到Hf(0.05)@HNTs-3杂化材料。
图1是埃洛石纳米管的透射电子显微镜图，从图中可以看出其具有中空管状结构，外径和孔径分别在60-75nm和10-20nm之间。
图2是埃洛石纳米管的HAADF-STEM图和相应元素(Al，Si，O)mapping图，从图中可以观察到Al、O元素主要存在于纳米管的内腔，Si元素主要分布于外表面。
图3是实施例1得到的Hf(0.05)@HNTs-1杂化材料的HAADF-STEM和相应元素(Hf，Al，Si，O)mapping图，与图2对比可以看出，Hf元素均匀地分布于材料的内腔和外表面，进一步验证了Hf的存在，使其易于与反应底物接触，从而实现反应底物的高效转化。
将实施例1-7制备的金属/埃洛石杂化材料作为催化剂在乙酰丙酸转移加氢制备γ-戊内酯中的应用，具体步骤如下：
将0.1g实施例1-7制备的金属/埃洛石杂化材料、0.2g乙酰丙酸作为底物和20mL异丙醇溶剂混合置于密封高压反应釜中，在160℃，反应4h制备得到γ-戊内酯，将金属/埃洛石杂化材料催化剂过滤，并用无水乙醇和去离子水分别洗涤三次，在80℃干燥12h后回收循环利用。
实施例制备的金属/埃洛石杂化材料的路易斯酸/路易斯碱位点含量及催化乙酰丙酸合成γ-戊内酯相应的转化率和得率分别详见表1，从表中可知，实施例1-7制备的杂化材料均可以作为乙酰丙酸转移加氢制备γ-戊内酯的催化剂使用，实施例1的催化材料具有最高的酸碱含量，催化效果最佳，且分别循环2次和5次后，依旧表现出良好的稳定性，可多次重复使用。
表1
将实施例1制备的Hf(0.05)@HNTs-1杂化材料作为催化剂应用于羰基类化合物转移加氢制备相应醇的反应中，具体步骤如下：
将0.1g实施例1制备的Hf(0.05)@HNTs-1杂化材料、0.2g羰基类化合物作为底物和20mL异丙醇溶剂混合置于密封高压反应釜中，在一定的条件下转移加氢制备醇。
本发明实施例1制备的Hf(0.05)@HNTs-1杂化材料催化多种羰基类化合物合成相应醇的转化率和得率详见表2，可以观察到，生物质基羰基类化合物(序号1-5)和石油基羰基类化合物(序号6-16)均可在该催化材料的作用下转化为相应的醇，转化率和得率分别高达93.8％和91.7％，说明其具有优异的催化活性和普遍适用性。
表2
以上对本发明的具体实施方式作了详细说明，但是本发明并不限于上述实施方式，在本领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下做出各种变化。
Claims (1)
1.一种酸碱双功能金属/埃洛石杂化材料在催化乙酰丙酸转移加氢制备γ-戊内酯中的应用，所述酸碱双功能金属/埃洛石杂化材料的制备步骤如下：
（1）称取1g埃洛石纳米管分散在50mL浓度为0.05mol/L的HfCl4溶液；
（2）将步骤（1）的混合物进行超声处理60min；
（3）将步骤（2）的混合物在室温下静置沉淀12h；
（4）将步骤（3）的混合物过滤后，用去离子水洗涤三次，80℃干燥12h后得到酸碱双功能金属/埃洛石杂化材料。
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