CN113546687A - 一种超薄钛基MOFs纳米片的可见光催化剂的制备方法及应用 - Google Patents
一种超薄钛基MOFs纳米片的可见光催化剂的制备方法及应用 Download PDFInfo
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Abstract
本发明公开一种超薄钛基MOFs纳米片的可见光催化剂的制备方法包括以下步骤:(1)称取2‑氨基对苯二甲酸置于聚乙烯四氟衬里的高压釜中,先向衬中滴加无水N,N‑二甲基甲酰胺,再向衬里加入无水甲醇;(2)将经过步骤(1)获得的混合液放入电热恒温干燥箱中160℃的条件下晶化反应4天,离心分离后将产物置于烘箱中60℃干燥制得超薄钛基MOFs纳米片前驱物;(3)将超薄钛基MOFs纳米片前驱物分散在甲醇溶剂里并置于沉积瓶中,向沉积瓶中通入氮气,加入硝酸钯溶液,打开氙灯光照反应,光照反应结束后加入无水乙醇洗涤产物,并将产物置于烘箱中60℃干燥,制得负载有Pb的超薄钛基MOFs纳米片。
Description
技术领域
本发明涉及一种超薄钛基MOFs纳米片的可见光催化剂的制备方法及应用,属于光催化剂制备技术领域。
背景技术
近年来,金属有机框架材料(MOFs)吸引了人们的广泛关注,MOFs材料在清洁能源生产以及太阳能利用等方面的拥有广泛的应用前景。其中,二维(2D)金属有机框架材料(MOFs)是一类由金属离子或无机簇单元和有机配体之间通过配位键作用形成的配位聚合物。在众多MOFs材料中,NH2-MIL-125(Ti)具有诸多优良的性质,例如多孔性和大的比表面积、骨架结构具有多变性和可调控性以及丰富的不抱和金属配位点等。MIL-125(Ti)以Ti8O8(OH)4-(BDC)6基本单元,边缘或角上的八面体钛单元构成的环八聚体,这些八聚体依次与其它12个循环八聚体相结合,形成多孔的三维准立方正方结构,通过将BDC胺功能化(BDC-NH2)合成NH2-MIL-125(Ti)。NH2-MIL-125(Ti)是一种棕黄色具有可见光响应的光催化材料,按照前线轨道理论NH2-MIL-125(Ti)中的HOMO主要是靠苯环上共轭的π键来构成的,因此配体中苯环上取代基的不同直接影响着MOF中电子的激发。NH2-MIL-125(Ti)中氨基(-NH2)的存在,使其具有可见光吸收响应的同时,其未占用的p电子与苯环中的π键形成了更强的共轭效应,从而产生电子离域,致使光照激发电子所需能量降低,提高了催化的效率。此外,NH2-MIL-125(Ti)表面/晶格中存在多种包含氢键、配位键、共价键等多种键的功能位点;体相的NH2-MIL-125(Ti)还具有{001}、{110}、{100}和{111}面等不同的晶面结构,以上独特的性质使NH2-MIL-125(Ti)成为一种具有较大应用潜力的光催化基础材料。但是,体相材料的可见光响应和光量子利用效率还处于较低的水平,如何修饰改性该材料使其能够发挥其最好的效果是目前光催化材料研究的重点之一。与三维体相材料相比,二维MOFs材料具有比表面积大、活性中心暴露充分等优点,在光催化反应中不仅能够充分地与反应分子化学结合,而且其在光催化动力学中有利于光生载流子快速迁移到表面,能够有效抑制光生电子-空穴的复合使其成为最具有应用前景的光催化材料之一,也成为构筑,设计和组装性能优异的复合结构光催化材料的基石。
公开号为CN112316982A的中国专利具体公开了一种制备钛基金属有机框架同源异质结光催化剂的方法,其中公开了采用两步水热法,制备Ti基MOFs同源异质结光催化剂以及NH2-MIL-125@NTU-9异质结光催化剂备,实现具有吸附-光催化双功能Ti-MOFs基二维范德华异质结复合材料。但是,上述发明公开的复合材料较厚,缺少氧空位,应用受到局限,同时利用钛酸异丙酯作为钛源容易快速分解和蒸发,影响产物产率。
相关研究表明,与三维体相材料相比,超薄无机二维纳米片由于其独特的二维平面结构、纳米级的厚度通常会具有如下几个特性:①大比表面积、活性位增多:超薄二维纳米片的表面原子是充分暴露的,这必然引起比表面积增大;同时,由于催化活性位通常分布在催化剂表面,催化剂比表面积增大、活性位也增多;②胶体性质、量子尺寸效应:超薄二维纳米片的厚度仅有几个纳米甚至零点几个纳米,能够充分分散在溶剂中能够形成胶体,并且纳米级的厚度甚至能够引起材料的能级***而出现量子尺寸效应;③表面原子新颖的化学特性:由于三维静电场的消失或者在纳米片制备过程中容易出现结构缺陷,纳米片表面原子的配位情况会发生变化而诱导新的化学特性;④准分子级别的异相催化反应:二维纳米片表面发生的异相催化反应可以看成准分子与分子的化学反应,为分子水平上认识异相催化反应提供平台。
发明内容
为了解决现有技术所存在的上述问题,本发明提供一种超薄钛基MOFs纳米片的可见光催化剂的制备方法,制成反应活性好、稳定性好且氧空位充足的超薄钛基MOFs纳米片,并将其应用在苄胺氧化偶联反应中。
本发明的技术方案如下:
本发明公开一种超薄钛基MOFs纳米片的可见光催化剂的制备方法,包括以下步骤:
(1)称取2-氨基对苯二甲酸置于聚乙烯四氟衬里的高压釜中,先向衬中滴加无水N,N-二甲基甲酰胺,再向衬里加入无水甲醇;
(2)将经过步骤(1)获得的混合液放入电热恒温干燥箱中160℃的条件下晶化反应4天,离心分离后将产物置于烘箱中60℃干燥制得超薄钛基MOFs纳米片前驱物;
(3)将超薄钛基MOFs纳米片前驱物分散在甲醇溶剂里并置于沉积瓶中,向沉积瓶中通入氮气,加入硝酸钯溶液,打开氙灯光照反应,光照反应结束后加入无水乙醇洗涤产物,并将产物置于烘箱中60℃干燥,制得负载有Pb的超薄钛基MOFs纳米片。
进一步的,所述步骤(1)中无水N,N-二甲基甲酰胺与无水甲醇的体积比为9:1。
本发明还公开一种根据上述制备方法制得的超薄钛基MOFs纳米片,所述超薄钛基MOFs纳米片的厚度为8~10nm,长度为1.2~1.5μm,宽度为0.8~1.1μm。
本发明还公开一种超薄钛基MOFs纳米片作为非均相光催化剂在光催化苄胺氧化制备亚胺反应中的应用。
本发明的有益效果在于:
1、本发明制得的钛基MOFs纳米片材料厚度为8~10nm,为超薄材料,超薄纳米片的比表面积大于普通纳米片,本发明中采用一步合成制备超薄钛基MOFs纳米片前驱物,实验操作方法简单,选择使用二硫化钛作为钛源,不易引入副产物,反应后生成硫化氢气体实现气液分离;利用光沉积还原法在超薄钛基MOFs纳米片前驱物上负载金属Pb制得超薄钛基MOFs纳米片,使得Pb负载在材料表面,在不影响材料超薄的性质,同时提高了超薄钛基MOFs纳米片作为光催化剂的光催化活性和反应稳定性。
2、本发明制得的超薄钛基MOFs纳米片的氧空位多于普通纳米片,将超薄钛基MOFs纳米片作为非均相光催化剂应用在光催化苄胺氧化制备亚胺反应中,有利于氧化偶联反应的进行,具有高效的光催化活性和反应稳定性,其中苄胺的转化率以及得到的产物亚胺的选择性都高达95%以上;且利用本发明制得的超薄钛基MOFs纳米片对其它的光催化反应如光催化清洁能源制备、光催化环境污染物治理以及光催化有机合成等都具有较大的应用场景。
附图说明
图1为本发明提供的超薄钛基MOFs纳米片前驱物、负载Pb后的超薄钛基MOFs纳米片以及根据现有技术制备的三维MOFs的X射线衍射(XRD)图;
图2为本发明提供的超薄钛基MOFs纳米片前驱物的透射电子显微镜(TEM)图和负载Pb后的超薄钛基MOFs纳米片的高分辨透射电子显微镜(HRTEM)图;
图3为本发明提供的超薄钛基MOFs纳米片前驱物的原子力显微镜测试图和紫外-可见漫反射图;
图4为本发明提供的超薄钛基MOFs纳米片前驱物的氮气吸脱附等温曲线图;
图5为本发明提供的以超薄钛基MOFs纳米片前驱物、负载Pd后的超薄钛基MOFs纳米片和根据现有技术制备的三维MOFs为催化剂在常温常压光照条件下催化苄胺氧化的产物图。
具体实施方式
下面结合较佳实施例和附图对本发明做进一步的说明。
实施例1超薄钛基MOFs纳米片的制备
一种超薄钛基MOFs纳米片的可见光催化剂的制备方法,包括以下步骤:
(1)用天平称取2.24g的2-氨基对苯二甲酸置于50mL聚乙烯四氟衬里的高压釜中,先向衬中滴加27mL的无水N,N-二甲基甲酰胺,再向衬里加入3mL的无水甲醇;
(2)将经过步骤(1)获得的混合液放入电热恒温干燥箱中160℃的条件下晶化反应4天,再分别用DMF和甲醇洗涤多次后离心分离,将得到的亮黄的产物置于烘箱中60℃干燥,研磨处理后制得超薄钛基MOFs纳米片前驱物;
(3)将超薄钛基MOFs纳米片前驱物分散在甲醇溶剂里并置于沉积瓶中,向沉积瓶中通入氮气,通30min,加入浓度为10mg/L的硝酸钯溶液,打开氙灯光照反应,光照反应1h结束后加入无水乙醇洗涤多次产物,并将产物置于烘箱中60℃干燥,制得负载有Pb的超薄钛基MOFs纳米片。
实施例2超薄钛基MOFs纳米片在光照条件下催化氧化苄胺的应用
将经过实施例1制得的负载有Pb的超薄钛基MOFs纳米片用作催化剂在光照条件下催化氧化苄胺;称取5mg负载有Pb的超薄钛基MOFs纳米片置于Schlenk管中,加入2mL乙腈之后再加入10.92μL苄胺,在常温下搅拌,然后开启光源进行光催化反应,产物使用GC-2014气相色谱检测;实验使用的光源为300W氙灯;参见图5为以超薄钛基MOFs纳米片前驱物、负载Pd后的超薄钛基MOFs纳米片和根据现有技术制备的三维MOFs为催化剂在常温常压光照条件下催化苄胺氧化的产物图,从图中可以看出负载有Pb的超薄钛基MOFs纳米片对光催化苄胺氧化的活性远远高于现有技术三维机构的MOFs的活性,同时本发明的负载Pd后的超薄钛基MOFs纳米片对产生的产物亚胺的选择性达到95%以上,进而说明本发明提供的超薄钛基MOFs纳米片具有较高的苄胺氧化活性和较高的合成亚胺的选择性。
对比实施例
三维NH2-MIL-125(Ti)的制备:
1.用天平称取0.628g的2-氨基对苯二甲酸(H2ATA),并将其在磁力搅拌的情况下加入到15mL无水甲醇(MeOH)和15mL N,N-二甲基甲酰胺(DMF)的混合液中,在室温的条件下剧烈搅拌至H2ATA完全溶解,然后用微量进样器吸取0.531mL的钛酸四异丙酯(Ti(C3H7O)4)在搅拌的情况下缓慢加入到上述混合液中。
2.剧烈搅拌30min并得到均匀的澄清混合溶液后,将该混合溶液转移至以聚四氟乙烯为内衬的50mL高压反应釜中,密封放入到恒温干燥箱中并在150℃的条件下晶化反应。
3.待晶化反应完成后,自然冷却至室温。将反应釜中的产物倒出并分别用DMF和MeOH溶剂洗涤两次。
4.洗涤完成后,将所得黄色产物在真空烘箱60℃的条件下干燥6h,干燥完成后取出,并在石英研钵中研磨成粉末,备用。
参见图1为根据实施例制得的超薄钛基MOFs纳米片前驱物与负载有Pb的超薄钛基MOFs纳米片以及根据现有技术制得的三维MOFs的X射线衍射(XRD)图,从图中可以看出负载有Pb的超薄钛基MOFs纳米片与负载有Pb的超薄钛基MOFs纳米片几乎相同,其二维结构在负载前后并没有发生变化,本发明制得的二维结构的超薄钛基MOFs材料与现有的三维结构的MOFs材料组份相近,在2θ角等于15.5°左右为纳米片的(001)晶面;
参见图2为根据实施例制得的超薄钛基MOFs纳米片前驱物的透射电子显微镜(TEM)图和负载Pb后的超薄钛基MOFs纳米片的高分辨透射电子显微镜(HRTEM)图;从图中可以看出,超薄钛基MOFs纳米片前驱物和负载Pb后的超薄钛基MOFs纳米片的形貌为片状材料,长度约为1.2~1.5μm,宽度约为0.8~1.1μm,从负载Pb后的超薄钛基MOFs纳米片的HRTEM图上可以看到许多粒径在2nm左右的Pd纳米晶体;
参见图3为根据实施例制得的超薄钛基MOFs纳米片前驱物的原子力显微镜和紫外可见漫反射光谱图,从图中可以看出该材料的厚度平均为10nm左右,此外该材料在负载Pd后具有更好的光吸收性能;
图4为根据实施例制得的超薄钛基MOFs纳米片前驱物的N2脱吸附等温曲线图,该材料的平均比表面积约为1379.97m2/g,其比表面积是远远高于现有技术三维结构的MOFs材料。
除上述实施例之外,本发明制得的超薄钛基MOFs纳米片还可以作为光催化剂,应用于除光照条件下催化氧化苄胺的其它有机催化反应中,还可以应用于光催化清洁能源制备、光催化环境污染物治理以及光催化有机合成等领域。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (4)
1.一种超薄钛基MOFs纳米片的可见光催化剂的制备方法,其特征在于,包括以下步骤:
(1)称取2-氨基对苯二甲酸置于聚乙烯四氟衬里的高压釜中,先向衬中滴加无水N,N-二甲基甲酰胺,再向衬里加入无水甲醇;
(2)将经过步骤(1)获得的混合液放入电热恒温干燥箱中160℃的条件下晶化反应4天,离心分离后将产物置于烘箱中60℃干燥制得超薄钛基MOFs纳米片前驱物;
(3)将超薄钛基MOFs纳米片前驱物分散在甲醇溶剂里并置于沉积瓶中,向沉积瓶中通入氮气,加入硝酸钯溶液,打开氙灯光照反应,光照反应结束后加入无水乙醇洗涤产物,并将产物置于烘箱中60℃干燥,制得负载有Pb的超薄钛基MOFs纳米片。
2.根据权利要求1所述的一种超薄钛基MOFs纳米片的可见光催化剂的制备方法,其特征在于:所述步骤(1)中无水N,N-二甲基甲酰胺与无水甲醇的体积比为9:1。
3.一种根据权利要求1所述的制备方法制得的超薄钛基MOFs纳米片,其特征在于:所述超薄钛基MOFs纳米片的厚度为8~10nm,长度为1.2~1.5μm,宽度为0.8~1.1μm。
4.如权利要求3所述的一种超薄钛基MOFs纳米片作为非均相光催化剂在光催化苄胺氧化制备亚胺反应中的应用。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115090326A (zh) * | 2022-05-30 | 2022-09-23 | 安徽中医药大学 | 一种高活性立方体Ti-MOF光催化剂、制备方法及应用 |
CN115785459A (zh) * | 2022-07-22 | 2023-03-14 | 扬州大学 | 一种2D ZnBDC MOFs纳米润滑材料的制备方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103493266A (zh) * | 2010-11-12 | 2014-01-01 | 安德斯·帕姆奎斯特 | 具有在其上含有大环金属螯合物的多孔质碳芯的燃料电池电极 |
CN104624160A (zh) * | 2015-01-21 | 2015-05-20 | 北京科技大学 | 一种导热增强型金属有机框架气体存储材料的制备方法 |
CN106166495A (zh) * | 2016-07-06 | 2016-11-30 | 陕西科技大学 | 一种硫掺杂缺氧型TiO2光催化剂的制备方法 |
CN106986776A (zh) * | 2017-03-29 | 2017-07-28 | 中国科学院化学研究所 | 一种利用光催化实现胺类化合物n‑甲基化的方法 |
CN107837820A (zh) * | 2017-11-21 | 2018-03-27 | 南京工业大学 | 一种二维MOFs材料负载纳米粒子的制备方法 |
CN110194730A (zh) * | 2019-07-04 | 2019-09-03 | 福州大学 | DUT-67(Zr)在光催化氧化甲基苯基硫醚制备甲基苯基亚砜中的应用 |
CN111848974A (zh) * | 2020-08-24 | 2020-10-30 | 河南大学 | 多酸基金属有机框架材料及其合成方法和在光催化氧化苄胺偶联中的应用 |
CN112521618A (zh) * | 2020-10-30 | 2021-03-19 | 山东大学 | 一种铋基金属有机框架材料及其制备方法和应用 |
-
2021
- 2021-07-21 CN CN202110824321.3A patent/CN113546687A/zh active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103493266A (zh) * | 2010-11-12 | 2014-01-01 | 安德斯·帕姆奎斯特 | 具有在其上含有大环金属螯合物的多孔质碳芯的燃料电池电极 |
CN104624160A (zh) * | 2015-01-21 | 2015-05-20 | 北京科技大学 | 一种导热增强型金属有机框架气体存储材料的制备方法 |
CN106166495A (zh) * | 2016-07-06 | 2016-11-30 | 陕西科技大学 | 一种硫掺杂缺氧型TiO2光催化剂的制备方法 |
CN106986776A (zh) * | 2017-03-29 | 2017-07-28 | 中国科学院化学研究所 | 一种利用光催化实现胺类化合物n‑甲基化的方法 |
CN107837820A (zh) * | 2017-11-21 | 2018-03-27 | 南京工业大学 | 一种二维MOFs材料负载纳米粒子的制备方法 |
CN110194730A (zh) * | 2019-07-04 | 2019-09-03 | 福州大学 | DUT-67(Zr)在光催化氧化甲基苯基硫醚制备甲基苯基亚砜中的应用 |
CN111848974A (zh) * | 2020-08-24 | 2020-10-30 | 河南大学 | 多酸基金属有机框架材料及其合成方法和在光催化氧化苄胺偶联中的应用 |
CN112521618A (zh) * | 2020-10-30 | 2021-03-19 | 山东大学 | 一种铋基金属有机框架材料及其制备方法和应用 |
Non-Patent Citations (3)
Title |
---|
TING WANG ET AL: ""Charge separation and molecule activation promoted by Pd/MIL-125-NH2 hybrid structures for selective oxidation reactions"", 《CATALYSIS SCIENCE & TECHNOLOGY》 * |
YANWEI SUN ET AL: ""Two-dimensional transition metal dichalcogenides as metal sources of metal-organic frameworks"", 《CHEMICAL COMMUNICATIONS》 * |
沈丽娟: ""含Zr、Ti等具有光催化活性的金属有机骨架材料(MOFs)的合成、改性及调变"", 《中国优秀博硕士学位论文全文数据库(博士)工程科技Ⅰ辑》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115090326A (zh) * | 2022-05-30 | 2022-09-23 | 安徽中医药大学 | 一种高活性立方体Ti-MOF光催化剂、制备方法及应用 |
CN115785459A (zh) * | 2022-07-22 | 2023-03-14 | 扬州大学 | 一种2D ZnBDC MOFs纳米润滑材料的制备方法 |
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