CN115466402A - 一种金属-有机骨架材料UiO-66及其超声合成方法和应用 - Google Patents
一种金属-有机骨架材料UiO-66及其超声合成方法和应用 Download PDFInfo
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Abstract
本发明涉及一种金属‑有机骨架材料UiO‑66及其超声合成方法和应用。本发明的金属‑有机骨架材料UiO‑66，以Zr4+、Al3+、Fe3+、Cr3+或Zn2+为金属离子，以对苯二甲酸为刚性有机配体，金属离子与刚性有机配体之间通过配位键形成微孔材料，外形尺寸为20～200nm，具有立方体状的规整几何外形，其制备方法是按比例将金属离子和刚性有机配体溶于溶剂中，在一定温度下，通过超声作用合成金属‑有机骨架材料UiO‑66，超声输出功率为100W，超声时间为30～150min，反应时间短、产率高、产物尺寸可控。本发明的金属–有机骨架材料UiO‑66进一步装载Cu2O纳米晶形成的金属‑有机骨架复合材料UiO‑66@Cu2O能够作为光催化剂，应用于可见光下降解环境废水中的有机污染物。
Description
技术领域
本发明涉及光催化应用领域，特别涉及一种金属-有机骨架材料UiO-66及其超声合成 方法，并研究了该材料的在光催化领域的应用。
背景技术
金属有机骨架(MOF)由于具有高比表面积和巨大的比表面积的多孔材料，在气体吸 附/分离，在催化或生物等方面具有较好的应用前景。Guillerm V等报道了以四氯化锆和对 苯二甲酸为原料，在N,N-二甲基甲酰胺(DMF)溶液中，150℃下，水热反应24h，通过Zr6节点与对苯二甲酸构筑具有八面体结构的多孔材料，该材料具有比表面积大(>900 m2g-1)，耐热性高(>250℃)在中性或酸性溶液中稳定等特点。
金属-有机骨架材料的合成方法中，通常采用溶剂热法、沉淀法、扩散法等。另外快速 合成金属-有机骨架材料，具有时间短、节能，科研获得尺寸可控纳米晶，符合绿色化学的 理念。例如，Li等采用超声法常压合成了形貌可控的Cu3(BTC)2纳米晶和Zn3(BTC)2纳米晶。在UiO-66系里材料的合成方法中，Huang等采用球磨法合成了UiO-66等材料；Wu 等利用家用微波炉，材料微波法快速合成了UiO-66-NH2复合材料；Wei等采用电化学法合 成了UiO-66-NH2。
发明内容
本发明的目的在于提供一种金属-有机骨架材料UiO-66，具有规整的几何外形，外形 尺寸为20～200nm，而且在可见光下具有较好的光催化性能，其装载Cu2O纳米晶形成的复合材料UiO-66@Cu2O可作为光催化剂，应用于环境废水中有机污染物的降解。
为实现上述目的，本发明提供了一种金属-有机骨架材料UiO-66，包含至少一种金属 离子和至少一种刚性有机配体，金属离子与刚性有机配体之间通过配位键形成微孔材料， 外形尺寸为20～200nm，且具有规整的几何外形；所述的金属离子是Zr4+、Al3+、Fe3+、Cr3+或Zn2+；所述的刚性有机配体是对苯二甲酸。
为解决上述技术问题，本发明还提供了这种金属-有机骨架材料UiO-66的超声合成方 法，具体为：将金属离子和刚性有机配体按比例溶于溶剂中，通过超声作用合成外形尺寸 在50～400nm的金属-有机骨架材料UiO-66，超声输出功率为100W，超声时间为30～150 min；所述金属离子是Zr4+、Al3+、Fe3+、Cr3+或Zn2+；所述的刚性配体是对苯二甲酸。所 述溶剂是水、碱性有机溶剂、醇类有机溶剂或它们中任意两种的混合物；所述的碱性有机 溶剂是N,N–二甲基甲酰胺、N,N–二乙基甲酰胺、N,N–二甲基乙酰胺、N,N–二甲基乙醇胺、 三乙醇胺、三乙胺；所述的醇类有机溶剂是甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁 醇、苯甲醇、乙二醇、丙三醇或二甘醇。
本发明的金属-有机骨架材料UiO-66的制备方法，优选的技术方案为：将金属盐和刚 性有机配体分别溶于碱性有机溶剂中，混合均匀，将混合物置于一定额定功率的细胞破碎 仪中，调节超声输出功率为100W，超声反应时间为10～150min；反应完毕后，利用常 用分离方式对产物进行分离，例如固液分离、离心分离、抽滤或萃取等方式，优选方式为 抽滤分离；分离后的固体用至少一种洗涤溶剂洗涤至少三次，优选洗涤溶剂为水、乙醇、 三氯甲烷或丙酮；洗涤后产物的干燥方式选择真空干燥或在空气中烘干，优选真空干燥， 即可获得金属–有机骨架纳米晶材料。
本发明采用超声法一步合成具有立方体状规整几何外形、晶体尺寸在20～200nm的 金属–有机骨架材料UiO-66，具有反应时间短、产率高、能耗低、反应条件易控等特点，产物尺寸可以通过控制超声时间实现。
本发明的金属–有机骨架材料UiO-66进一步装载Cu2O、N4C3、TiO2或贵金属单质(如Pt、Pd等)形成金属–有机骨架复合材料，其中装载Cu2O纳米晶形成的复合材料 UiO-66@Cu2O可作为光催化剂，应用于可见光下降解环境废水中的有机污染物，所述有机 污染物指有色染料类污染物，所述的有色染料为次甲基蓝、罗丹明B或甲基橙。
本发明利用超声法合成金属–有机骨架材料UiO-66，具有反应速度快、节能等特点， 获得金属–有机骨架材料UiO-66具有规整额的几何外形，外形尺寸为20～200nm。装载Cu2O纳米晶形成的复合材料UiO-66@Cu2O，具有良好的光催化性能，在环境领域有一定 的应用前景。
附图说明
图1是不同时间合成的金属–有机骨架材料UiO-66的X射线衍射图谱。
图2是实施例2制备的金属–有机骨架复合材料UiO-66@Cu2O的X射线衍射图谱。
图3是实施例1和2超声合成的金属–有机骨架材料UiO-66(60min)及金属–有机骨架复合材料UiO-66@Cu2O的投射电镜照片。
图4是10mg金属–有机骨架复合材料UiO-66@Cu2O光催化剂的光催化性能。
图5是不同用量金属–有机骨架复合材料UiO-66@Cu2O光催化剂的光催化性能。
具体实施方式
以下结合具体实施例对本发明作进一步描述。
实施例1
金属-有机骨架UiO-66的超声合成：
称取氯化锆0.782g，对苯二甲酸(H2BDC)0.468g于碘量瓶中，加入32mL N,N- 二甲基甲酰胺(DMF)，再滴入0.3mL甲酸，油浴，130℃。使用超声波细胞粉碎机，设 置参数功率100W，工作总时间30min，超声开时间2s，超声关时间2s，超声时间分别 为45min、60min、90min，反应完毕，关闭仪器，清洗超声探头，将盛装溶液的碘量瓶 水浴冷却，将溶液离心，把上清液倒入废水池，再用DMF和乙醇进行交替离心洗涤三次， 最后在70℃下干燥6h，得到白色块状固体金属-有机骨架UiO-66。
图1为超声合成的金属-有机骨架材料UiO-66的X射线衍射图谱，X射线对样品进行扫描的角度范围是2θ＝5-80°。从图1中不同超声时间合成的样品与标准谱图(a)(CCDC 晶体号：733458)基本一致。其中，2θ角为7.42°，8.53°，对应晶面指数为(1,1,1)面和 (2,0,0)面，表明采用超声法成功获得了目标产物UiO-66。
实施例2
金属-有机骨架复合材料UiO-66@Cu2O的合成：
取0.1g超声60min合成的金属-有机骨架UiO-66和0.03g Cu(NO3)2·6H2O加入烧瓶中， 再倒入50mL DMF溶液，放入超声波清洗器中，超声40min，再取出放在磁力搅拌器上，连续搅拌12h后取出，架在100℃的油浴集热式加热搅拌器上，配制体积比为5:1的DMF 水溶液，加入0.1g KOH，将配好的KOH的DMF水溶液预热后在100℃倒入混合，将油 浴温度调整为110℃，启动油浴锅的磁力搅拌功能，搅拌30min，得到褐色溶液。待溶液 冷却后，称取0.04g的L-抗坏血酸加入其中，将溶液放在磁力搅拌器上搅拌10min，然后 将溶液离心，把上清液倒入废液池，再用去离子水、乙醇交替离心洗涤三次，最后把纳米 晶放在真空干燥箱中70℃干燥6h，得到黄褐色固体金属-有机骨架复合材料 UiO-66@Cu2O。
图2为超声合成的金属-有机骨架复合材料UiO-66@Cu2O的X射线衍射图谱，图2是在实施例1的条件下，在UiO-66悬浮液中，通过维生素C还原法，装载立方晶系的Cu2O 纳米晶。从图2中可以看出，UiO-66的骨架结构没有发生明显的变化，同时，在骨架材料 中成功装载了Cu2O，通过与PDF卡号05-0667比对，在2θ分别为29.7°、36.59°、42.50°、 61.68°、73.90°，对应晶面指数分别为(110)、(111)、(200)、(220)、(311)，由于装载情 况良好，同时部分UiO-66骨架的衍射峰与Cu2O的衍射峰重合，图2中可以发现Cu2O的 衍射峰不明显。
实施例3
金属-有机骨架复合材料UiO-66@Cu2O的光催化性能研究：
量取100mL亚甲基蓝溶液于250mL烧杯中，分别称取5mg、10mg、15mg、20mg 金属-有机骨架复合材料UiO-66@Cu2O粉末加入其中。以350W氙灯，放置420nm滤光 片作为可见光源。磁力搅拌，距离氙灯光源15cm，光照5、15、30、40、50、60min时 取样离心，离心机设置为9000r/min，离心时间为3min，每次将离心后的上清液留样测量 吸光度，下层残留倒回烧杯。
结果分析：
通过透射电镜图像分析，从图3中可以看到，采用超声法60min合成的金属-有机骨架材 料UiO-66纳米晶尺寸大小为50nm左右；通过实施例2装载Cu2O纳米晶获得的UiO-66@Cu2O 复合材料的尺寸在60-80nm，比原UiO-66纳米晶的尺寸略大，估计这是在后续合成过程了， 晶体进行了进一步生长，导致尺寸增加。另外，在图3中还可以发现，UiO-66装载Cu2O纳 米晶情况良好，Cu2O纳米晶主要装载在UiO-66的孔道内部。
以350w氙灯加载420nm的滤光片，模拟太阳光源，考察复合材料UiO-66@Cu2O的 光催化性能。光催化剂UiO-66@Cu2O的用量为10mg，以次甲基蓝为模拟污染物，从图4 可以看出，复合材料UiO-66@Cu2O的光催化性能良好，光催化60min，对目标污染物的 降解率达到97.64％。
考察不同用量的光催化剂UiO-66@Cu2O对目标污染物的光催化性能，可以发现，在相同的光催化条件下，光催化剂UiO-66@Cu2O的用量对其光催化性能有一定的影响，从 图5可以看出，光催化剂UiO-66@Cu2O的用量10mg效果最好，用量增加到20mg时效 果反而降低，主要原因是由于光催化剂的用量较多，对光线有了一定的遮挡，光线难以进 入溶液内部进行光催化反应。
本发明利用超声法合成金属–有机骨架材料UiO-66，具有反应速度快、节能等特点， 获得金属–有机骨架材料UiO-66具有规整额的几何外形，外形尺寸为20～200nm。装载Cu2O纳米晶形成的复合材料UiO-66@Cu2O，具有良好的光催化性能，光催化60min，对 目标污染物(次甲基蓝)的降解率达到97.64％，在环境领域有一定的应用前景。
Claims (6)
1.一种金属-有机骨架材料UiO-66，其特征在于：包含至少一种金属离子和至少一种刚性有机配体，金属离子与刚性有机配体之间通过配位键形成微孔材料，外形尺寸为20～200nm，具有立方体状的规整几何外形；
所述的金属离子是Zr4+、Al3+、Fe3+、Cr3+或Zn2+；
所述的刚性有机配体是对苯二甲酸。
2.权利要求1所述的金属-有机骨架材料UiO-66的超声合成方法，其特征在于，具体为：将金属离子和刚性有机配体按比例溶于溶剂中，滴加甲酸，120～140℃下超声作用合成外形尺寸为20～200nm，具有立方体状的规整几何外形的金属-有机骨架材料UiO-66，超声输出功率为100W，超声时间为10～90min；
所述金属离子是Zr4+、Al3+、Fe3+、Cr3+或Zn2+；
所述的刚性配体是对苯二甲酸；
所述的溶剂是水、碱性有机溶剂、醇类有机溶剂或它们中任意两种的混合物。
3.如权利要求2所述的金属-有机骨架材料UiO-66的超声合成方法，其特征在于：所述的碱性有机溶剂是N,N–二甲基甲酰胺、N,N–二乙基甲酰胺、N,N–二甲基乙酰胺、N,N–二甲基乙醇胺、三乙醇胺、三乙胺；
所述的醇类有机溶剂是甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、苯甲醇、乙二醇、丙三醇或二甘醇。
4.权利要求1所述金属-有机骨架材料UiO-66的应用，其特征在于：装载Cu2O纳米晶形成的金属-有机骨架复合材料UiO-66@Cu2O作为光催化剂，应用于可见光下降解环境废水中的有机污染物。
5.如权利要求4所述的金属-有机骨架材料UiO-66的应用，其特征在于：所述有机污染物指有色染料类污染物。
6.如权利要求5所述的金属-有机骨架材料UiO-66的应用，其特征在于：所述的有色染料为次甲基蓝、罗丹明B或甲基橙。
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163258A (zh) * | 2017-05-31 | 2017-09-15 | 同济大学 | 一种乙醇相中金属有机骨架材料UiO‑66的制备方法 |
| CN108084453A (zh) * | 2018-01-10 | 2018-05-29 | 蚌埠学院 | UiO-66金属有机骨架材料的孔径拓展方法及应用 |
| EP3381924A1 (en) * | 2017-03-31 | 2018-10-03 | Toyota Jidosha Kabushiki Kaisha | Metal-organic framework and method of manufacturing the same |
| CN109400890A (zh) * | 2017-08-18 | 2019-03-01 | 中国石化扬子石油化工有限公司 | 一种多级孔金属有机骨架材料的制备方法 |
| CN111019152A (zh) * | 2019-12-17 | 2020-04-17 | 浙江大学 | 一种超声辅助合成锆基金属有机骨架材料的方法及其产品 |
| CN113058659A (zh) * | 2021-03-19 | 2021-07-02 | 东南大学 | 一种纳米TiO2/UiO-66复合材料的制备方法与应用 |
| CN114933709A (zh) * | 2022-05-23 | 2022-08-23 | 江苏理工学院 | 一种高收率UiO-66金属有机框架材料的制备方法及应用 |
-
2022
- 2022-09-06 CN CN202211083987.9A patent/CN115466402A/zh active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3381924A1 (en) * | 2017-03-31 | 2018-10-03 | Toyota Jidosha Kabushiki Kaisha | Metal-organic framework and method of manufacturing the same |
| CN107163258A (zh) * | 2017-05-31 | 2017-09-15 | 同济大学 | 一种乙醇相中金属有机骨架材料UiO‑66的制备方法 |
| CN109400890A (zh) * | 2017-08-18 | 2019-03-01 | 中国石化扬子石油化工有限公司 | 一种多级孔金属有机骨架材料的制备方法 |
| CN108084453A (zh) * | 2018-01-10 | 2018-05-29 | 蚌埠学院 | UiO-66金属有机骨架材料的孔径拓展方法及应用 |
| CN111019152A (zh) * | 2019-12-17 | 2020-04-17 | 浙江大学 | 一种超声辅助合成锆基金属有机骨架材料的方法及其产品 |
| CN113058659A (zh) * | 2021-03-19 | 2021-07-02 | 东南大学 | 一种纳米TiO2/UiO-66复合材料的制备方法与应用 |
| CN114933709A (zh) * | 2022-05-23 | 2022-08-23 | 江苏理工学院 | 一种高收率UiO-66金属有机框架材料的制备方法及应用 |
Non-Patent Citations (2)
| Title |
|---|
| 韩易潼: "锆基金属-有机骨架UiO-66的调控合成研究", 《中国博士学位论文全文数据库 工程科技I辑》, no. 201902, 15 February 2019 (2019-02-15), pages 014 - 56 * |
| 韩易潼: "高稳定性金属有机骨架UiO -66 的合成与应用", 《应用化学》, vol. 33, no. 4, 30 April 2016 (2016-04-30), pages 367 - 378 * |
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