CN112390959A - 含席夫碱配体的金属有机骨架材料、催化剂及制备与应用 - Google Patents
含席夫碱配体的金属有机骨架材料、催化剂及制备与应用 Download PDFInfo
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Abstract
本发明涉及基于溶剂热法制备一种具有高比表面积的含席夫碱配体的金属有机骨架材料及其负载金纳米粒子在催化方面的应用。具体制备过程是首先采用N,N’‑(4‑羧基苯亚甲基)‑肼(N,N'‑bis(4‑carboxybenzylidene)‑hydrazine,CBH)和四氯化锆(ZrCl4)通过溶剂热法制备含席夫碱配体的金属有机骨架材料(UiO‑66‑CBH),然后与HAuCl4水溶液反应,在金属有机骨架材料UiO‑66‑CBH上成功固载金纳米粒子,得到Au@UiO‑66‑CBH材料。本发明所述的UiO‑66‑CBH材料比表面积大,负载金纳米粒子后可以有效催化还原对硝基苯酚为对氨基苯酚,且有很好的重复使用性。
Description
技术领域
本发明涉及一种含席夫碱配体的金属有机骨架材料及其负载金纳米粒子在催化还原对硝基苯酚中的应用。具体制备过程是首先采用水合肼和对甲酰基苯甲酸通过醛胺缩合反应制备席夫碱配体CBH,然后CBH和四氯化锆通过溶剂热法制备金属有机骨架材料UiO-66-CBH。采用双溶剂法负载金纳米粒子得到 Au@UiO-66-CBH,并应用于将对硝基苯酚的催化还原为对氨基苯酚。
背景技术
金属有机骨架材料由于其结构规律性和合成可调性,成功地使用了晶体工程和/或网状化学策略,因此受到学术界和工业界的高度关注。尽管近年来MOFs 材料的数量呈爆炸性增长,但在目标性应用方面设计新的多孔结构和功能框架方面仍做出了巨大努力。根据已建立的金属—有机配位化学的原理和技术诀窍,结合增强周期网络的拓扑结构(“网状化学”),给出了MOFs合成指南和可能的结构库(O'Keeffe,M.,M.A.Peskov,S.J.Ramsdenand O.M.Yaghi(2008)."The Reticular Chemistry Structure Resource(RCSR)Databaseof,and Symbols for, Crystal Nets."Accounts of Chemical Research 41(12):1782-1789;Deng,H.X.,C.J. Doonan,H.Furukawa,R.B.Ferreira,J.Towne,C.B.Knobler,B.Wangand O.M. Yaghi(2010)."Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks."Science 327(5967):846-850;Eddaoudi,M.,J.Kim,N.Rosi,D.Vodak, J.Wachter,M.O'Keeffe and O.M.Yaghi(2002)."Systematic design of poresize and functionality in isoreticular MOFs and their application in methanestorage."Science 295(5554):469-472.)。除了有机化学为设计桥接分子提供了大量的机会外,网状化学的概念也是这种材料最吸引人的特征之一。其思想是,通过改变连接体的长度或功能,但保持初始的拓扑结构,可以系统地调控MOFs材料的孔尺寸和性质。 Lin等人设计了一系列具有相同结构但不同尺寸通道的手性MOFs作为不对称催化的可调平台(Ma,L.,J.M.Falkowski,C.Abney and W.Lin(2010)."A series of isoreticular chiral metal-organic frameworks as a tunable platform for asymmetric catalysis."Nat Chem 2(10):838-846.)。Yaghi小组则将大量不同的功能基团嵌入桥接分子,与金属反应后形成的MOFs材料结构与大量相同长度的桥接分子跟金属反应后形成的材料结构相同,但有机功能基差异很大(Deng,H.X.,C.J.Doonan, H.Furukawa,R.B.Ferreira,J.Towne,C.B.Knobler,B.Wang and O.M.Yaghi (2010)."Multiple Functional Groups of Varying Ratios inMetal-Organic Frameworks."Science 327(5967):846-850.)。简而言之,网状化学是制备新的 MOFs材料富有成效的新概念。因此,可结合有机化学和网状化学的概念设计新的有机配体,再与金属中心反应制备新的MOFs。
近年来,通过在MOFs材料的骨架中包埋具有活性的物质可进一步扩大材料的应用范围。MOFs可作为一种不溶性的载体,可使负载的客体分子易于恢复,并在反应条件下为客体分子提供稳定性。在众多客体分子中金属纳米颗粒尤其是金纳米颗粒是最广泛的研究的对象。开发这种复合材料来激发增强材料的性能是当前的研究热点。众所周知,只有当金纳米颗粒的粒径小于10nm时,才能观察到金的催化活性。这种金属的催化活性与平均粒径有着明显的关系,这意味着金纳米颗粒的催化性能会受到粒度的影响(Corma,A.andH.Garcia(2008). "Supported gold nanoparticles as catalysts for organicreactions."Chemical Society Reviews 37(9):2096-2126.)。在多孔MOFs材料中嵌入金纳米颗粒,通过金属与载体材料的相互作用和几何限制来稳定金纳米颗粒,从而避免其生长和聚集。 Jiang等人以ZIF-8为载体,采用简单的固体研磨法制备金纳米颗粒催化剂,应用于一氧化碳催化氧化反应,具有相当大的催化活性(Jiang,H.L.,B.Liu,T.Akita,M.Haruta,H.Sakurai and Q.Xu(2009)."Au@ZIF-8:CO Oxidation over GoldNanoparticles Deposited to Metal-Organic Framework."Journal of the AmericanChemical Society 131(32):11302-11309.)。王等人合成了一种具有双功能催化行为的Au@Cu(II)-MOF催化剂,该催化剂能够逐步促进选择性苯甲醇氧化 -Knoevenagel缩合反应(Wang,J.S.,F.Z.Jin,H.C.Ma,X.B.Li,M.Y.Liu,J.L. Kan,G.J.Chen and Y.B.Dong(2016)."Au@Cu(II)-MOF:Highly Efficient Bifunctional Heterogeneous Catalystfor Successive Oxidation-Condensation Reactions."Inorganic Chemistry 55(13):6685-6691.)。
发明内容
本发明的目的在于提供一种含席夫碱配体的金属有机骨架材料的制备及其负载金纳米粒子的应用,可有效催化还原对硝基苯酚为对氨基苯酚。
UiO-66-CBH在水、醇类、丙酮、N,N’-二甲基甲酰胺等溶剂中非常稳定;具有较高的结晶度和规整有序的晶体结构;材料粒径为3-8μm,比表面积为500-700 m2/g,孔尺寸主要分布在0.5-1.5nm;由于合成该MOFs材料的有机配体中含有席夫碱官能团,可以有效地与金属形成配位键;另外,有机配体的链长比合成 UiO-66材料的对苯二甲酸更长,形成的UiO-66-CBH具有较大的孔径,固载金纳米颗粒后用作催化还原时的较大的孔更利于传质,金纳米颗粒的固载量为59-295mg/g。
首先采用水合肼和对甲酰基苯甲酸通过醛胺缩合反应制备席夫碱配体CBH,然后CBH和四氯化锆通过溶剂热法制备金属有机骨架材料UiO-66-CBH。采用双溶剂法负载金纳米粒子得到Au@UiO-66-CBH,并应用于对硝基苯酚的催化还原。
具体包括如下步骤:
(1)席夫碱有机配体的制备:取0.3-3.0g 4-甲酰基苯甲酸溶于15-80mL乙醇中;0.04-0.4g水合肼溶于10-50mL乙醇后滴加至容器中;在70-80℃油浴锅中搅拌反应4-6h,然后过滤产物并用50-70℃的热乙醇洗涤3-5次;在60-80℃下真空干燥后得到黄色固体粉末CBH;
(2)金属有机骨架材料UiO-66-CBH的制备:在密封瓶中加入0.1-0.7g四氯化锆、0.2-0.8g CBH和1.8-9.0g苯甲酸,再加入20-100mL DMF,溶解后置于烘箱中,在80-130℃下反应24-48h;待产物冷却至室温,离心后收集沉淀;得到的固体浸泡在10-30mL DMF中2-6h,离心去除上清液;再将固体浸泡在10-30 mL乙醇中2-6h,离心去除上清液,在100-120℃下真空干燥后得到黄色固体粉末UiO-66-CBH。
(3)在有机骨架材料中负载金纳米粒子:取0.1-0.5g UiO-66-CBH于烧瓶内,加入20-100mL正己烷,超声10-30min,使材料均匀混合;搅拌下滴加0.15-0.75 mL HAuCl4水溶液(0.1-0.3mol/L),10-30min内滴加完成;继续搅拌3-10h,反应停止后固体产物沉淀至瓶底;去除反应液,待固体干燥;加入5-15mL 0.4-0.6 mol/L NaBH4水溶液至圆底烧瓶,搅拌使Au3+还原,最后将得到的产物用水洗涤 3-5次,在100-120℃下真空干燥12-24h,得到Au@UiO-66-CBH。
所述Au@UiO-66-CBH可用于室温下催化还原对硝基苯酚为对氨基苯酚。
本发明具有如下优点:
1.该合成路线步骤较少,操作过程简单,反应条件温和;
2.含席夫碱配体的金属有机骨架材料UiO-66-CBH由于配体的链长比对苯二甲酸更长使得孔尺寸较最常见的UiO-66的更大,该孔结构可容更多的反应物,有利于后续的催化传质。
3.材料中的C=N官能团提供活性位点,可以有效负载金纳米粒子。
附图说明
图1为含席夫碱配体的金属有机骨架材料的制备示意图。
图2为含席夫碱配体的金属有机骨架材料的N2吸附/脱附曲线和孔径分布图。UiO-66-CBH的比表面积为596m2/g,表明其固有的多孔特性。孔的平均尺寸为 0.9nm,在P/P0=0.99时计算得到材料的总孔隙体积为0.73m3/g。UiO-66-CBB 的比表面积为507m2/g,表明其固有的多孔特性。孔的平均尺寸为0.78nm,在 P/P0=0.99时计算得到材料的总孔隙体积为0.45m3/g。
图3为含席夫碱配体的金属有机骨架材料的光学图片和扫描电镜图片。图3A、B分别为含席夫碱配体的金属有机骨架材料为光学图片和扫描电镜图片。 UiO-66-CBH主要为3-8μm微米尺寸的晶体材料。在扫描电镜下,这些微米级的晶体呈现八面体形态和规则的表面。而UiO-66-CBB由于结晶度较差,没有形成高规整度的晶体,见图3C。
图4为含席夫碱配体的金属有机骨架材料及负载金纳米粒子的粉末X射线衍射图。UiO-66-CBH具有较高的结晶度和规整有序的结构,从图4B可以看出,负载金纳米颗粒后,Au@UiO-66-CBH的粉末X射线衍射图在2θ<30°时没有变化,表明UiO-66-CBH的特征峰都在,并没有明显的结晶度损失,说明 UiO-66-CBH的晶体结构基本保持不变。此外,在2θ=38.2°处观察到一个很强的衍射峰,这是Au(1,1,1)平面的布拉格反射,证明Au@UiO-66-CBH中金纳米颗粒的存在。每次催化还原4-硝基苯酚后,用水充分洗涤Au@UiO-66-CBH后继续下一次的催化。使用一次后测试Au@UiO-66-CBH的X射线粉末衍射图,可以看到UiO-66-CBH的特征衍射峰消失,表明材料失去了结晶度从有序结构变为无序结构;但重复使用5次后属于的金纳米颗粒的衍射峰仍在,由此可推测金纳米颗粒依然负载在变为无定形态的UiO-66-CBH材料中。
图5为金属有机骨架材料负载金纳米粒子的电镜图及金纳米粒子的尺寸分布。从图5A可以观察到金纳米颗粒均匀分散在UiO-66-CBH材料中。金纳米颗粒的具体尺寸分布如图5B所示,平均粒径为3.7nm,粒径范围为1.5-6nm。该金纳米颗粒尺寸具有很强的催化性,有利于后续应用于催化还原对硝基苯酚。
图6为金属有机骨架材料负载金纳米粒子的X射线光电子能谱图。从图6A可以观察到元素C、N、O、Zr和Au的结合能峰,表明除了氢元素外,表明 Au@UiO-66-CBH主要由这几种元素组成。图6B为Au4f的高分辨XPS谱图和对应的分峰拟合曲线。结合能83.1eV和86.6eV处的峰为自旋轨道耦合双峰源于金属态的Au0,分别对应于Au 4f7/2和Au4f5/2。这证明吸附在UiO-66-CBH上的Au3+经过还原后已经形成了金纳米颗粒。
图7为负载金纳米粒子的有机骨架材料催化还原对硝基苯酚的紫外-可见吸收光谱图及对硝基苯酚转化率随时间的变化。室温下,在石英反应池中加入对硝基苯酚水溶液,然后加入NaBH4和Au@UiO-66-CBH(或Au@UiO-66-CBB)进行测试。图7A为反应过程中测定的紫外-可见吸收光谱图,扫描波长范围是 200~500nm,分别在反应进行0、5、10、15、25、40、60min时进行测量。从图中可以明显看到400nm处的吸收峰,为反应物对硝基苯酚。反应开始阶段400 nm处存在强烈的吸收,随着反应时间增加,峰强度降低,待反应进行到60min 左右时,400nm处的吸收峰强度基本不再变化,从图7B可以看到此时对硝基苯酚的转化率达47%,表明反应物对硝基苯酚部分转化为对氨基苯酚。图7C为反应过程中测定的紫外-可见吸收光谱图,扫描波长范围是200~500nm,分别在反应进行0、1、3、5、10、15、20、30、40min时进行测量。从图中可以明显看到400nm处的吸收峰,为反应物4-硝基苯酚。反应开始阶段400nm处存在强烈的吸收,待反应进行到30min左右时,400nm处的吸收峰几乎完全消失,从图7D可以看到此时对硝基苯酚的转化率达96%,表明反应物对硝基苯酚基本完全转化为对氨基苯酚。反应液的颜色也从最初的亮黄色变为无色。同时我们做了空白对照组,在不加Au@UiO-66-CBH时,反应40min后溶液仍为亮黄色,需要放置一天后颜色才渐渐变浅,但也没有到无色,说明不加催化剂的情况下反应一天的时间也没有完全转化。
图8为Au@UiO-66-CBH使用5次后的透射电镜图,(B)Au@UiO-66-CBH 重复使用情况。从图8A观察到没有发生金纳米颗粒团聚的情况,这可能是由于还原反应体系中的强碱环境所致。有趣的是,如此连续催化还原5个循环后,从图8B可以看到Au@UiO-66-CBH催化还原4-硝基苯酚的催化活性没有明显的损失。因此,当Au@UiO-66-CBH作为催化剂时,虽然载体材料会“降解”,但仍具有良好的可重复利用性。
具体实施方式
实施例1
在100mL圆底烧瓶内加入0.5g 4-甲酰基苯甲酸和20mL乙醇,超声溶解; 0.5g 4-氨基苯甲酸溶于15mL乙醇后缓慢滴加至烧瓶中。在80℃油浴锅中搅拌反应4h,然后过滤产物并用热的乙醇洗涤3次。在60℃下真空干燥后得到0.70 g浅黄色固体粉末,即含席夫碱配体CBB。
在密封玻璃小瓶中加入0.18g四氯化锆、0.14g CBB和1.8g苯甲酸,再加入20mLDMF,超声溶解后置于烘箱中,在120℃下反应24h。待产物冷却至室温,离心后收集沉淀。得到的固体浸泡在20mL DMF中4h,离心去除上清液;再将固体浸泡在20mL乙醇中4h,离心去除上清液,在120℃下真空干燥后得到浅黄色固体粉末,即UiO-66-CBB。
取100mg UiO-66-CBB于圆底烧瓶内,加入20mL正己烷,超声约20min,使材料均匀混合。磁力搅拌下滴加0.15mL HAuCl4水溶液(0.2mol/L),10min 内滴加完成。继续搅拌3h,反应停止后固体产物沉淀至瓶底。去除反应液,待固体干燥。加入5mL 0.6mol/L NaBH4水溶液至圆底烧瓶,剧烈搅拌使Au3+还原,最后将得到的产物用水洗涤5次,在100℃下真空干燥12h,得到 Au@UiO-66-CBB。
实施例2
在100mL圆底烧瓶内加入0.3g 4-甲酰基苯甲酸和15mL乙醇,超声溶解; 0.06g水合肼溶于10mL乙醇后缓慢滴加至烧瓶中。在80℃油浴锅中搅拌反应 4h,然后过滤产物并用热的乙醇洗涤3次。在60℃下真空干燥后得到0.25g 黄色固体粉末。
在密封玻璃小瓶中加入0.18g四氯化锆、0.15g CBH和1.8g苯甲酸,再加入20mLDMF,超声溶解后置于烘箱中,在120℃下反应24h。待产物冷却至室温,离心后收集沉淀。得到的固体浸泡在20mL DMF中4h,离心去除上清液;再将固体浸泡在20mL乙醇中4h,离心去除上清液,在120℃下真空干燥后得到黄色固体粉末。
取100mg UiO-66-CBH于圆底烧瓶内,加入20mL正己烷,超声约20min,使材料均匀混合。磁力搅拌下滴加0.15mL HAuCl4水溶液(0.2mol/L),10min 内滴加完成。继续搅拌3h,反应停止后固体产物沉淀至瓶底。去除反应液,待固体干燥。加入5mL 0.6mol/L NaBH4水溶液至圆底烧瓶,剧烈搅拌使Au3+还原,最后将得到的产物用水洗涤5次,在100℃下真空干燥12h,得到 Au@UiO-66-CBH。
催化性能测试:以NaBH4还原对硝基苯酚为对氨基苯酚的反应为模型,考察催化剂的催化性能。室温环境下,催化还原反应在可透光的石英反应池中进行。首先,加入3mL0.01mmol/L的对硝基苯酚水溶液于反应池中,再依次加入0.3 mg Au@UiO-66-CBH作催化剂、1.13mg NaBH4作还原剂。用紫外分光光度计测量前,于振荡器上轻轻震荡反应液,以一定的时间间隔记录反应液的紫外-可见吸收光谱,以此监测催化还原反应的进展。记录波长范围在200~500nm范围内的光谱图,通过测量波长λ=400nm处的吸光度值随时间的变化情况,以确定催化还原过程的速率常数。为了研究催化剂的可回收性,将反应后的 Au@UiO-66-CBH用水洗涤3次,继续再次催化还原对硝基苯酚。
注:Au@UiO-66-CBB也用于催化还原对硝基苯酚,但由于本身结晶度不够高,使得催化还原时材料易降解,其效果远不如Au@UiO-66-CBH。
结论
采用水合肼和对甲酰基苯甲酸通过醛胺缩合反应制备席夫碱配体CBH,然后CBH和四氯化锆通过溶剂热法制备金属有机骨架材料UiO-66-CBH。含席夫碱配体的金属有机骨架材料UiO-66-CBH提供了更长的有机链长和更大的孔径,且比表面较大,该孔结构可容更多的反应物,有利于后续的催化应用。材料中的 C=N官能团提供活性位点,可以有效负载金纳米粒子。UiO-66-CBH负载金纳米颗粒,能够有效控制金纳米颗粒的尺寸并避免了金纳米颗粒的团聚。 Au@UiO-66-CBH在还原对硝基苯酚时具有很高的催化性能及良好的可重复使用性,说明其具有一定的催化潜力。
Claims (7)
2.根据权利要求1所述的金属有机骨架材料,其特征在于:材料粒径为3-8μm,比表面积为500-700m2/g,孔尺寸主要分布在0.5-1.5nm。
4.根据权利要求3所述的制备方法,其特征在于:可按如下步骤操作,
(1)席夫碱有机配体的制备:取0.3-3.0g4-甲酰基苯甲酸溶于15-80mL乙醇中;0.04-0.4g水合肼溶于10-50mL乙醇后滴加至容器中;在70-80℃油浴锅中搅拌反应4-6h,然后过滤产物并用50-70℃的热乙醇洗涤3-5次;在60-80℃下真空干燥后得到黄色固体粉末CBH;
(2)金属有机骨架材料UiO-66-CBH的制备:在密封瓶中加入0.1-0.7g四氯化锆、0.2-0.8g CBH和1.8-9.0g苯甲酸,再加入20-100mL DMF,溶解后置于烘箱中,在80-130℃下反应24-48h;待产物冷却至室温,离心后收集沉淀;得到的固体浸泡在10-30mL DMF中2-6h,离心去除上清液;再将固体浸泡在10-30mL乙醇中2-6h,离心去除上清液,在100-120℃下真空干燥后得到黄色固体粉末UiO-66-CBH。
5.一种权利要求1或2所述的含席夫碱配体的金属有机骨架材料负载金纳米粒子的催化剂,其特征在于:催化剂中活性组份金的质量负载量为59-295mg/g,金纳米粒子的粒径范围1.5-6nm。
6.一种权利要求5所述的催化剂的制备方法,其特征在于:
采用双溶剂法并通过硼氢化钠还原使UiO-66-CBH负载金纳米粒子;
在有机骨架材料中负载金纳米粒子:取0.1-0.5g UiO-66-CBH于烧瓶内,加入20-100mL正己烷,超声10-30min,使材料均匀混合;搅拌下滴加0.15-0.75mL HAuCl4水溶液(0.1-0.3mol/L),10-30min内滴加完成;继续搅拌3-10h,反应停止后固体产物沉淀至瓶底;去除反应液,待固体干燥;加入5-15mL 0.4-0.6mol/L NaBH4水溶液至圆底烧瓶,搅拌使Au3+还原,最后将得到的产物用水洗涤3-5次,在100-120℃下真空干燥12-24h,得到Au@UiO-66-CBH。
7.一种权利要求5所述催化剂的应用,其特征在于:室温下催化还原对硝基苯酚为对氨基苯酚。
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Cited By (4)
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CN114534791A (zh) * | 2022-03-24 | 2022-05-27 | 东南大学 | 一种多功能非均相催化剂及其制备方法和应用 |
CN114632551A (zh) * | 2022-02-22 | 2022-06-17 | 东南大学 | 一种双功能手性催化剂及其制备方法和应用 |
CN114669328A (zh) * | 2021-03-31 | 2022-06-28 | 北京理工大学 | 一种氮还原用复合材料光催化剂、其制备及应用 |
CN116571268A (zh) * | 2023-07-13 | 2023-08-11 | 山东久元新材料有限公司 | 一种高强度石化催化剂载体及其制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100226991A1 (en) * | 2007-10-01 | 2010-09-09 | Centre National De La Recherche Scientifique - Cnrs- | Solid inorganic/organic hybrid with modified surface |
WO2015183090A1 (en) * | 2014-05-28 | 2015-12-03 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | A fiber bragg grating optical sensor having a nanoporous coating |
CN105622490A (zh) * | 2016-02-03 | 2016-06-01 | 齐齐哈尔大学 | 一种非对称氮氧配体及Ti、Zr、Hf配合物制备方法和应用 |
CN106861627A (zh) * | 2017-01-20 | 2017-06-20 | 四川大学 | 一种去除废水中钴离子的金属有机骨架材料及其制备方法 |
CN108285465A (zh) * | 2017-01-09 | 2018-07-17 | 南开大学 | 金属有机框架材料、其制备方法、修饰的金属有机框架材料及其制备方法 |
CN109562363A (zh) * | 2016-06-13 | 2019-04-02 | 巴斯夫公司 | 催化剂复合材料及其在选择性催化还原NOx中的应用 |
-
2019
- 2019-08-15 CN CN201910753773.XA patent/CN112390959B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100226991A1 (en) * | 2007-10-01 | 2010-09-09 | Centre National De La Recherche Scientifique - Cnrs- | Solid inorganic/organic hybrid with modified surface |
WO2015183090A1 (en) * | 2014-05-28 | 2015-12-03 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | A fiber bragg grating optical sensor having a nanoporous coating |
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