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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