CN112718008A - 一种基于金属有机框架材料为载体的异相光敏剂及其制备方法和应用 - Google Patents
一种基于金属有机框架材料为载体的异相光敏剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种基于金属有机框架材料为载体的异相光敏剂及其制备方法和应用，属于环境友好型功能复合材料制备技术领域。本发明中所述异相光敏剂是将在可见光区具有强吸收、且可高效产生单线态氧(1O2)的碘代‑BODIPY通过简单的“一锅煮”自组装方法负载到ZIF‑8金属有机框架材料孔道内制得碘代‑BODIPY@ZIF‑8复合材料，并将所制备异相光敏剂用于催化氧化苯甲硫醚，然后可通过简单的离心、洗涤、干燥回收催化剂，循环用于催化氧化苯甲硫醚。(1)本发明制备方法简单易操作，环保、廉价、重复性好，耗时短；(2)本发明中异相光敏剂在可见光区具有强吸收、且可高效产生1O2，在室温搅拌情况下即可将硫醚类化合物选择性氧化成亚砜，且转化率高、重复利用性好。
Description
技术领域
本发明涉及环境友好型功能复合材料制备技术领域，更具体地说，涉及一种在可见光照射下可高效催化氧化硫醚类化合物的异相光敏剂及其制法和用途。
背景技术
可见光作为一种安全、廉价、丰富的可持续能源，能够提供足够的能量从而可以有效地促进化学反应的进行。可见光驱动的光催化剂由于可高效利用太阳光而越来越受到研究者的关注。近年来，尽管钌、铱、铂和其他一些常见的铜、铬、铁等过渡金属配合物的发现极大地促进了有机合成的发展，但该类催化剂含有贵重稀有金属或者有毒重金属离子，不仅价格昂贵，而且从最终产品中分离脱除过渡金属光催化剂仍然存在着一些挑战，这将严重限制其在有机合成中应用。为了克服这些不足，不含金属的纯有机光敏剂作为环境友好型光催化剂引起了人们广泛的关注。近年来，已有许多研究报道了不含金属的纯有机染料，如氟硼-二吡咯(BODIPY)、曙红、亚甲基蓝、香豆素染料等作为光催化剂用于催化各种有机合成。在众多有机光催化剂中， BODIPY染料由于具有卓越的光物理性质而成为近年来的研究热点，如：(1) BODIPY在可见光区具有很强的摩尔吸光系数，使其可以有效吸收太阳光；(2)结构修饰能力强，通过不同的官能团修饰可实现不同的功用；(3)荧光量子产量高；(4)光稳定性强，这些优越的光物理性质极大地促进了该类荧光染料的发展。当在BODIPY的共轭核心区域引入重原子溴或碘时，由于重原子效应，三重态效率显著增加，进而高效产生1O2，其1O2产率远远高于目前广泛应用的孟加拉红。1O2具有很强的氧化活性，且选择性强，因此可以选择性的催化氧化多种有机反应。目前，已有多篇文献报道了溴或者碘原子取代的BODIPYs光敏剂用于催化有机合成。然而，均相BODIPY用于光催化剂时存在以下问题：(1)易聚集，导致活性物种产率降低；(2)光稳定性差；(2)不易分离回收循环利用。这些不足将严重限制其在更多领域的应用，而将其固定到各种载体上制成异相光敏剂则是克服上述缺陷的有效途径。其中，金属有机框架材料(MOFs)作为一种新型晶态多孔材料，因其具有高孔隙率、超大的比表面积、多孔且有序、孔道结构可调等优异的性质，使其在吸附、分离、催化、传感、离子导电等方面具有出色的性能和应用前景[28-31]。目前已有大量的文献报道MOFs用作载体来稳定和分散光敏剂或无机纳米粒子等客体分子制备主客体复合材料，并将其用于不同的领域。
近年来，将BODIPY固载到MOFs上制备异相光敏剂已有一些文献报道。Quan等将碘代-BODIPY嫁接到UIO-66MOFs骨架上制备异相光敏剂用于催化有机反应。Atilgan等通过后合成修饰的方法将碘代-BODIPY负载到 PCN-222MOFs孔道内，用于硫芥子气脱毒。这既可以保留碘代-BODIPY的光催化活性，又能实现催化剂的回收和循环利用。然而，上述复合材料的制备主要涉及到三个过程，如1)MOFs的合成；2)MOFs活化；3)MOF与客体分子结合。这不仅要求MOFs和客体分子同时都含有能够反应的功能基团，且MOFs的窗口和孔道尺寸要大于客体分子，否则客体分子很难封装到 MOFs孔道内。这一过程不仅条件苛刻，且繁琐耗时，又产生大量废物，而克服这些缺点的一个重要策略是将MOF合成和客体分子封装通过“一锅法”一步合成。然而，目前通过简单“一锅法”制备有机光敏剂@MOFs复合材料仍然具有一定的挑战。
发明内容
为了克服上述有机光敏剂@MOFs复合材料制备方法繁琐、条件苛刻、污染性强的不足，本发明提供一种在水相中通过简单的“一锅煮”一步自组装的方法将碘代-BODIPY有机光敏剂负载到ZIF-8金属有机框架材料内，与目前所报道的有机光敏剂@MOFs异相光敏剂的制备方法相比，本发明提供的制备工艺不仅操作简单方便、环保、快捷，且普适性强，多种不同结构的碘代 -BODIPY都可通过该方法将其负载到ZIF-8。通过该方法制备得到的碘代 -BODIPY@ZIF-8异相光敏剂集合了碘代-BODIPY的可见光吸收能力强，单线态产率高和ZIF-8稳定性强、比表面积大、孔隙率高的优点，在绿色LED灯照射、室温条件下可循环用于硫醚类化合物催化氧化，且转化率高、选择性强。因此，本发明无论在有机光敏剂@MOFs复合材料的制备，还是在硫醚类化合物选择性亚砜化反应方面都具有重要的应用价值。
为了实现上述实验目的，本发明的技术方案如下：
(1)将以下任意一种碘代-BODIPY与非离子型表面活性剂PVP复合得到碘代-BODIPY@PVP复合材料，其中碘代-BODIPY结构如下所示，本发明所用的碘代-BODIPY结构包含以下结构，但不限于以下结构；
(2)将以上制备所得到的碘代-BODIPY@PVP复合材料溶于水，然后加入制备ZIF-8所需的金属离子(Zn2+)水溶液和有机配体(2-甲基咪唑)水溶液，室温搅拌10min即可得到目标光敏剂碘代-BODIPY@ZIF-8，然后通过离心、洗涤、干燥得到最终碘代-BODIPY@ZIF-8异相光敏剂。
以上所述的在可见光区具有强吸收、且可高效产生单线态氧的碘代 -BODIPY@ZIF-8异相光敏剂的应用，所述的异相光敏剂用于硫醚类化合物的催化氧化。
所述的碘代-BODIPY@ZIF-8异相光敏剂催化氧化硫醚类化合物过程如下：在装有磁力搅拌子的10mL玻璃小瓶中加入10mg碘代-BODIPY@ZIF-8 催化剂、硫醚类化合物(0.5mmol)和甲醇溶剂(2mL)，超声混合均匀，避光条件下空气鼓泡10分钟。然后，室温条件下搅拌、采用绿色LED灯照射一定的时间，取少量的混合物进行1H NMR分析，利用底物与产物的1H NMR峰积分面积之比计算转化率。
有益效果：
本发明的显著优点：(1)首次通过简单“一锅煮”一步自组装的方法在水相、室温搅拌条件下即可快速大量合成碘代-BODIPY@ZIF-8复合材料。与目前所报道的碘代-BODIPY@MOFs异相光敏剂的制备方法相比，本发明提供的制备工艺不仅操作简单方便、环保、快捷，且普适性强。(2)通过该方法制得的碘代-BODIPY@ZIF-8集合了碘代-BODIPY和ZIF-8的优点，不仅可高效吸收可见光，单线态氧产率高，且稳定性强、比表面积大、孔隙率高，在硫醚类化合物的催化氧化方面，转化率高、选择性强。(3)本发明制备的碘代-BODIPY@ZIF-8稳定性强，通过简单的离心、洗涤、干燥可循环用于催化氧化硫醚，且催化活性并没有明显降低。
本发明中所述异相光敏剂是将在可见光区具有强吸收、且可高效产生单线态氧(1O2)的碘代-BODIPY通过简单的“一锅煮”自组装方法负载到ZIF-8 金属有机框架材料孔道内制得碘代-BODIPY@ZIF-8复合材料，并将所制备异相光敏剂用于催化氧化苯甲硫醚，然后可通过简单的离心、洗涤、干燥回收催化剂，循环用于催化氧化苯甲硫醚。本发明与现有技术相比，其显著优点体系在以下方面：本发明提供的异相光敏剂是在水相、室温搅拌下快速合成，因此该制备方法简单易操作，环保、廉价、重复性好，耗时短；本发明中异相光敏剂在可见光区具有强吸收、且可高效产生1O2，在室温搅拌情况下即可将硫醚类化合物选择性氧化成亚砜，且转化率高、重复利用性好。因此，本发明中无论是异相光敏剂的制备还是在硫醚类化合物的催化氧化应用方面都更加环保。
附图说明
图1为本发明中碘代-BODIPY-1@ZIF-8、合成的ZIF-8、模拟ZIF-8和碘代-BODIPY-1的粉末X-射线衍射图；
图2为本发明中碘代-BODIPY-1@ZIF-8的扫描电镜图；
图3为本发明中碘代-BODIPY-1(在二氯甲烷溶剂中)、ZIF-8和碘代 -BODIPY-1@ZIF-8固态粉末吸收光谱；
图4a为本发明中碘代-BODIPY-1@ZIF-8与DPBF混合后光照情况下引起DPBF吸收光谱变化情况；b为碘代-BODIPY-1@ZIF-8+DPBF、 ZIF-8+DPBF和单独DPBF在光照情况下DPBF吸收光谱变化图
图5为本发明中碘代-BODIPY-1@ZIF-8光催化氧化苯甲硫醚情况；
图6为本发明中碘代-BODIPY-1@ZIF-8稳定性和循环利用性。
具体实施方式
下面将结合实施例进一步阐明本发明的内容，但这些实施例并不限制本发明的保护范围，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种有机光敏剂修饰仍在本发明的保护范围内。
实施例1.碘代-BODIPY@PVP的制备
根据参考文献制备碘代-BODIPY-1、碘代-BODIPY-2和碘代-BODIPY-3 (HarrisJ.,Optical limiting properties of 3,5-dithienylenevinylene BODIPY dyes at532nm.Chem.Eur.J.2017,23,14507-14514)。分别称取20.0mg碘代 -BODIPY-1、碘代-BODIPY-2和碘代-BODIPY-3溶于5.0mL四氢呋喃，称取250.0mg聚乙烯吡咯烷酮溶于5.0mL氯仿，将碘代-BODIPY溶液和聚乙烯吡咯烷酮溶液混合，室温搅拌24小时，反应结束时加入正己烷析出碘代 -BODIPY@PVP沉淀，抽滤，用正己烷淋洗，然后直接用于下一步反应。
实施例2.碘代-BODIPY@ZIF-8的制备
将上述所制备的碘代-BODIPY@PVP溶于5.0mL的蒸馏水。称取0.5g Zn(NO3).6H2O溶于1.0mL蒸馏水。称取1g 2-甲基咪唑溶于4mL蒸馏水。将碘代-BODIPY@PVP水溶液和2-甲基咪唑溶液充分混合均匀，然后缓慢滴加Zn(NO3).6H2O溶液，很快会有沉淀析出，室温搅拌10分钟停止反应，离心分离，用蒸馏水、氮氮-二甲基甲酰胺和乙醇依次洗涤数次，直到上清液变成无色，然后真空干燥，得到最终的目标产物碘代-BODIPY@ZIF-8。
实施例3.应用
选用苯甲硫醚为反应底物，碘代-BODIPY-1@ZIF-8为催化剂，研究上述所制备的碘代-BODIPY@ZIF-8的催化性能、稳定性、循环利用性等。具体实验过程如下：在装有磁力搅拌子的10mL玻璃小瓶中分别加入10.0mg 碘代-BODIPY-1@ZIF-8催化剂、苯甲硫醚(0.5mmol)和甲醇溶剂(2mL)，超声混合均匀，避光条件下空气鼓泡10分钟。然后，室温条件下搅拌、采用绿色LED灯照射，每间隔2个小时取少量的混合物进行1H NMR分析，利用底物与产物的1HNMR峰积分面积之比计算转化率。
催化完成后，通过离心，乙醇洗涤干燥回收碘代-BODIPY-1@ZIF-8催化剂，采用上述同样的实验操作催化氧化苯硫醚，实验结果如附图5所示。经过五次重复使用后，苯甲硫醚的转化率仍然很高，表明碘代-BODIPY-1@ZIF-8 仍具有很高的催化活性。五次循环使用后，测定碘代-BODIPY-1@ZIF-8的 PXRD，通过与催化前碘代-BODIPY@ZIF-8的PXRD进行对比，实验结果表明，循环使用后，PXRD峰型没有发生变化，这也说明2I-BODIPY@ZIF-8结构稳定，循环后仍能保持其完整晶型。最后，我们通过改变底物研究碘代 -BODIPY-1@ZIF-8对其他硫醚类化合物的催化效果，结果如表1所示。从实验结果可以看出，碘代-BODIPY-1@ZIF-8对多种硫醚都具有很好的催化氧化效果。碘代-BODIPY-2@ZIF-8，碘代-BODIPY-3@ZIF-8也可以基本达到碘代-BODIPY-1@ZIF-8的效果。
Claims (6)
1.一种基于金属有机框架材料为载体的异相光敏剂，其特征在于：所述异相光敏剂可将硫醚类化合物高转化率、高选择性催化氧化成亚砜类化合物的可见光响应型异相光敏剂，所述异相光敏剂具体制备方法：将在可见光区具有强吸收、且可高效产生1O2的碘代-氟硼二吡咯(BODIPY)通过简单的“一锅煮”自组装方法负载到具有稳定性强、比表面积大的ZIF-8金属有机框架材料内。
2.根据权利要求1所述的基于金属有机框架材料为载体的异相光敏剂的制备方法，其特征在于：包括如下步骤：
(1)将碘代-BODIPY类化合物与非离子型表面活性剂PVP复合得到碘代-BODIPY@PVP复合材料；
(2)将碘代-BODIPY@PVP复合材料溶于水，然后加入制备ZIF-8所需的金属离子水溶液(Zn2+)和有机配体水溶液(2-甲基咪唑)，室温搅拌10min即可得到目标光敏剂碘代-BODIPY@ZIF-8，然后通过离心、洗涤、干燥得到最终碘代-BODIPY@ZIF-8异相光敏剂。
3.根据权利要求2所述的基于金属有机框架材料为载体的异相光敏剂的制备方法，其特征在于：其中碘代-BODIPY结构为如下任一所示:
4.根据权利要求1所述的基于金属有机框架材料为载体的异相光敏剂的应用，其特征在于：所述的异相光敏剂用于高选择性、高转换率的催化氧化硫醚类化合物。
5.根据权利要求1所述的基于金属有机框架材料为载体的异相光敏剂的应用，其特征在于：在可见光的激发下，所述的异相光敏剂可以高效产生1O2，在可见光照射下即可催化氧化苯甲硫醚。
6.根据权利要求5所述的在基于金属有机框架材料为载体异相光敏剂的应用，其特征在于：所述的异相光敏剂催化氧化硫醚类化合物的过程如下：在装有磁力搅拌子的10mL玻璃小瓶中加入10mg碘代-BODIPY@ZIF-8催化剂、硫醚类化合物0.5mmol和甲醇溶剂2mL，超声混合均匀，避光条件下空气鼓泡10分钟；然后，室温条件下搅拌、采用绿色LED灯照射一定的时间，取少量的混合物进行1H NMR分析，利用底物与产物的1H NMR峰积分面积之比计算转化率。
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| CN113940998A (zh) * | 2021-08-31 | 2022-01-18 | 深圳大学 | 一种纳米载氧颗粒及其制备方法与应用 |
| CN114835733A (zh) * | 2022-05-27 | 2022-08-02 | 南昌大学 | 一种sp2-C金属有机框架的制备方法和解毒芥子气模拟物应用 |
| CN116651512A (zh) * | 2023-08-02 | 2023-08-29 | 北京理工大学 | 一种强可见光吸收的Ru-Fe环状光催化剂及其制备方法 |
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| CN113940998A (zh) * | 2021-08-31 | 2022-01-18 | 深圳大学 | 一种纳米载氧颗粒及其制备方法与应用 |
| CN113940998B (zh) * | 2021-08-31 | 2023-07-18 | 深圳大学 | 一种纳米载氧颗粒及其制备方法与应用 |
| CN114835733A (zh) * | 2022-05-27 | 2022-08-02 | 南昌大学 | 一种sp2-C金属有机框架的制备方法和解毒芥子气模拟物应用 |
| CN114835733B (zh) * | 2022-05-27 | 2023-10-03 | 南昌大学 | 一种sp2-C金属有机框架的制备方法和解毒芥子气模拟物应用 |
| CN116651512A (zh) * | 2023-08-02 | 2023-08-29 | 北京理工大学 | 一种强可见光吸收的Ru-Fe环状光催化剂及其制备方法 |
| CN116651512B (zh) * | 2023-08-02 | 2023-10-24 | 北京理工大学 | 一种强可见光吸收的Ru-Fe环状光催化剂及其制备方法 |
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