CN112221540B - Pd2+负载的金属有机框架复合催化剂及制备方法与应用 - Google Patents

Pd2+负载的金属有机框架复合催化剂及制备方法与应用 Download PDF

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CN112221540B
CN112221540B CN202010904586.XA CN202010904586A CN112221540B CN 112221540 B CN112221540 B CN 112221540B CN 202010904586 A CN202010904586 A CN 202010904586A CN 112221540 B CN112221540 B CN 112221540B
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孙亚光
由立新
赵柏蓓
姚善欣
王淑菊
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Shenyang University of Chemical Technology
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Abstract

Pd2+负载金属有机框架复合催化剂及制备方法与应用,涉及一种化工功能材料技术领域,本发明为一种Pd2+负载的金属有机框架复合催化剂Pd@ZIF‑92,包括以下制备步骤:(本发明以氨基乙醇修饰ZIF‑90,形成N,O双配位点获得ZIF‑92;进一步通过配位作用与Pd2+络合,得到具有高活性Pd催化位点,用于催化水相中Suzuki偶联反应,并且可通过离心进行分离的多相催化剂。该制备方法简单、产率高,催化剂在空气和水中稳定,能高效、多相催化Suzuki偶联反应。催化剂可以通过离心进行分离,循环利用。

Description

Pd2+负载的金属有机框架复合催化剂及制备方法与应用
技术领域
本发明涉及一种化工功能材料技术领域,特别是涉及一种Pd2+负载金属有机框架复合催化剂及制备方法与应用。
背景技术
有机化合物的基本骨架是由碳-碳键或者碳-氮键相互连接构成的,特别是含有碳-碳键的联芳基类化合物,所以,碳-碳偶联反应是有机化学反应中重要反应之一。钯催化的Suzuki-Miyaura偶联反应,具有良好的官能团耐受性、有机硼的低毒性、反应条件温和、商业可用性等特点,在构建联苯及其衍生物中扮演着重要的角色,广泛应用于精细化学品和高度复杂药物的工业合成。相对于均相钯催化剂而言,非均相钯催化剂催化的Suzuki-Miyaura偶联反应在产物分离、催化剂循环利用等方面有着其独特的优势-----保持与均相催化剂相媲美的催化性能的同时,非均相催化剂可以进行数次甚至数十次的循环利用,回收,很大程度上降低了催化成本和改善对环境的污染。
金属有机框架(MOFs)因具有高的物理、化学稳定性,大的比表面积,以及可修饰等特点,近年来被广泛用于非均相催化中。2013年,Kleist等通过MIL-53(Al)-AMMal中的有机配体侧链固定Pd2+离子,以催化Heck型C-C偶联反应;Stanley采用后合成金属化方法,将MOF浸入Pd(OAc)2的丙酮溶液中,构建bpy-UiO-67-Pd(OAc)2和MOF-235-Pd(OAc)2,合成的两种配合物在催化水溶液中芳基硼酸共轭加成为二取代的烯酮表现出良好的催化性能;2016年,Sun等报道了通过后合成修饰方法合成了两种含Pd的非均相催化剂UiO-66-Mix-PI-Pd和UiO-67-Mix-PI-Pd,这两种催化剂基于锆的UiO-66-Mix和UiO-67-Mix为模板经后合成修饰合成的多孔的含钯催化剂,其对Suzuki-Miyaura和Heck偶联反应都有很好的催化性能;在2018年,sun等报道了一种磁性纳米粒子负载与PSM相结合而制备的非均相催化剂Fe3O4@La-MOF-Schiff base-Pd,在Suzuki-Miyaura偶联反应中表现出优异的催化性能;Pascanu等制备了Pd@MIL-101-NH2,即将钯负载在经氨基修饰的MIL-101上,用于催化碘代、溴代芳烃与硼酸的Suzuki-Miyaura偶联反应。可见开发一种高效、易分离、可 循环利用的基于金属有机框架(MOFs)后修饰的新型异相催化剂已经成为突破方向。
2008年加州大学洛杉矶分校的Omar M. Yaghi等在JACS上公开发表2-醛基咪唑(H-ICA)与Zn2+构筑的金属有机框架ZIF-90(Zn(C4H3N2O)2),其具有制备方法简单(见说明书附图1)、产率高(>61.5%)、结构稳定且具有高孔隙度等优点,是本申请Pd2+负载的金属有机框架复合催化剂开发的基础。
发明内容
本发明的目的在于提供一种Pd2+负载金属有机框架复合催化剂及制备方法与应用,本发明选择 ZIF-90为框架,以氨基乙醇进行修饰,形成N,O双配位点;最后通过配位作用与Pd2+络合,得到具有高活性Pd催化位点,用于催化水相中Suzuki偶联反应。
本发明是通过以下技术方案实现的:
Pd2+负载金属有机框架复合催化剂,所述催化剂以高孔隙度 ZIF-90为框架,以氨基乙醇修饰,形成含有N,O双配位点ZIF-92,最后与Pd2+配位,得到具有高活性Pd催化位点,并于水相中催化Suzuki偶联反应,其分子式为: Pd@ZIF-90,其结构式为:
Pd2+负载金属有机框架复合催化剂制备方法,包括以下过程:
(1)ZIF-90的制备
取0.13 g (0.50 mmol) Zn(NO3)2•6H2O和0.07 g (0.75 mmol) 的2-醛基咪唑溶于10 mL DMF中,将溶液放置在装有5 mL三乙胺和200 mL正己烷的混合溶剂的干燥器内,放置24 h,然后将白色沉淀抽滤并用甲醇洗涤三次,用甲醇溶液浸泡3天,以对其活化,最后对其抽滤并常温下真空干燥24 h即得到ZIF-90;其分子式为:Zn(C4H3N2O)2,其结构式为:
(2)ZIF-92的制备
取0.15 g (0.59 mmol) 的ZIF-90分散在10 mL无水甲醇中,向其中加入0.11 mL(1.76 mmol) 氨基乙醇,60℃下回流24 h,待反应液冷却后将其抽滤并用甲醇洗涤3次,然后将抽滤得到的固体浸泡在甲醇溶液中3 h,再将其抽滤并在常温下真空干燥24 h即得到ZIF-92。其分子式为:Zn(C6H8N3O)2,其结构式为:
(3)Pd@ZIF-92的合成
取3 g ( 88 mmol)的ZIF-92, 0.887 g (5 mmol)的PdCl2,150 mL的无水甲醇于单口烧瓶中;机械搅拌48 h,得到的混合物抽滤并用无水甲醇洗涤、烘干即得到Pd@ZIF-92;其分子式为:Pd@ZIF-92,其结构式为:
(4)Pd2+负载金属有机框架复合催化剂应用,即 Pd@ZIF-92的催化应用
Pd2+负载的金属有机框架复合催化剂Pd@ZIF-92在Suzuki偶联反应具有催化活性,其芳基卤化物1 mmol 、溴苯或碘苯、1.2 mmol苯硼酸、2mmol碳酸钾和作为催化剂的 8mg的Pd@ZIF-92加入到25 mL的史兰克反应管中,6mL去离子水作反应溶剂,在温度 80 ℃下磁力搅拌 6 h,将反应后的溶液用乙酸乙酯萃取,并用无水硫酸钠干燥,再将有机溶剂去除得到最终产物,产率用气相色谱中的内标法测得,产率99%,证明化合物 Pd@ZIF-92对Suzuki C-C 偶联反应具有高的催化活性。
(5)Pd2+负载的金属有机框架复合催化剂 Pd@ZIF-92循环利用
所述Pd2+负载的金属有机框架复合催化剂 Pd@ZIF-92,有效催化 Suzuki偶联反应后,通过离心分离,循环利用催化 Suzuki偶联反应5次。
本发明的优点与效果是:
1.本发明与通常的多相催化剂相比,本催化剂Pd@ZIF-92具有制备工艺简单、成本低、产率高、结构稳定且容易回收再利用等优点。
2.高效、多相催化碳-碳偶联反应,催化活性高,催化剂易于分离、循环利用多次催化产率没有明显降低。具备潜在的工业生产应用价值。
附图说明
图1金属有机框架ZIF-90的3D结构图和拓扑图;
图2本发明实现技术方案的结构式;
图3 Pd2+负载的金属有机框架复合催化剂元素分析能谱(EDS)图;
图4 Pd@ZIF-92催化碳-碳偶联反应方程式。
具体实施方式
以下通过实例对本发明做进一步阐述,本发明涉及Pd2+负载的金属有机框架复合催化剂Pd@ZIF-92的制备方法及其在Suzuki偶联反应的催化作用。该制备方法的操作步骤为:以高孔隙度的Zn-MOF 即ZIF-90为框架,以氨基乙醇修饰,形成含有N,O的双配位点,最后与Pd2+配位,得到具有高活性Pd2+催化位点,用于多相催化Suzuki偶联反应,并可以通过离心分离循环利用。
实施例1:Pd@ZIF-92的制备
(1)取(0.13 g, 0.50 mmol) 的Zn(NO3)2•6H2O和(0.07 g, 0.75 mmol) 的2-醛基咪唑溶于10 mL DMF中,将溶液放置在装有5 mL三乙胺和200 mL正己烷的混合溶剂的干燥器内,放置24 h,将白色沉淀抽滤并用甲醇洗涤三次,并在甲醇溶液中浸泡3天,以对其活化,抽滤并常温下真空干燥24 h即得到ZIF-90。(参考2008年加州大学洛杉矶分校的OmarM. Yaghi等在JACS上公开发表2-醛基咪唑(H-ICA)与Zn2+构筑的金属有机框架ZIF-90(Zn(C4H3N2O)2) )
(2)取(0.15 g, 0.59 mmol) 的ZIF-90分散在10 mL无水甲醇中,向其中加入(0.11 mL, 1.76 mmol) 氨基乙醇,60℃下回流24 h,待反应液冷却后将其抽滤并用甲醇洗涤3次,然后将抽滤得到的固体浸泡在甲醇溶液中3 h,再将其抽滤并在常温下真空干燥24h即得到ZIF-92。
(3)取 (3 g, 88 mmol)的ZIF-92,(0.887 g,5 mmol)的PdCl2,150 mL的无水甲醇于单口烧瓶中;在机械搅拌下搅拌48 h,得到的混合物用抽滤并用无水甲醇洗涤并烘干即得到Pd@ZIF-92。
所述的Pd2+负载的金属有机框架复合催化剂Pd@ZIF-92及其制备方法,步骤(2)、(3)所述的溶剂包括无水乙醇、甲醇中的一种或几种混合物。
实施例2:Pd@ZIF-92对Suzuki C-C 偶联反应的催化活性
(1)将得到的Pd@ZIF-92用于芳基卤化物和苯硼酸的 Suzuki C-C 偶联反应中验证其催化活性。具体操作方法是将1 mmol芳基卤化物(溴苯或碘苯)、1.2 mmol 苯硼酸、2mmol碳酸钾和作为催化剂的8mg的Pd@ZIF-92加入到25 mL的史兰克反应管中,6mL去离子水作反应溶剂,在温度 80 ℃下磁力搅拌 6 h,将反应后的溶液用乙酸乙酯萃取,并用无水硫酸钠干燥,再将有机溶剂去除得到最终产物,产率用气相色谱中的内标法测得,产率99%,证明化合物 Pd@ZIF-92对Suzuki C-C 偶联反应具有高的催化活性。
实施例3:Pd@ZIF-92在Suzuki C-C 偶联反应中循环利用的催化活性
在实施例1的Suzuki C-C 偶联反应结束后,将上述反应中的催化剂Pd@ZIF-92离心分离,再次投入到芳基卤化物和苯硼酸的 Suzuki C-C 偶联反应中验证其循环催化活性。具体操作方法是将1 mmol芳基卤化物(氯苯、溴苯或碘苯)、1.2 mmol 苯硼酸、2mmol碳酸钾,以及分离出来的Pd@ZIF-92加入25 mL的史兰克反应管中,6mL去离子水反应溶剂,在温度 80 ℃下磁力搅拌 6 h,将反应后的溶液用乙酸乙酯萃取,并用无水硫酸钠干燥,再将有机溶剂去除得到最终产物,产率用气相色谱中的内标法测得,产率大于90%。重复上述循环实验5次,产率均大于80%,证明化合物 Pd@ZIF-92在Suzuki C-C 偶联反应中可以循环利用,并且仍然具有高的催化活性。

Claims (4)

1.一种Pd2+负载金属有机框架复合催化剂Pd@ZIF-92在Suzuki偶联反应中的应用,其特征在于,所述复合催化剂以高孔隙度ZIF-90为框架,以氨基乙醇修饰,形成含有N,O的双配位点的ZIF-92,最后与Pd2+配位,得到具有高活性Pd催化位点,并于水相中催化Suzuki偶联反应的复合催化剂;
所述Pd@ZIF-92的结构式为:
2.根据权利要求1所述的应用,所述的Pd@ZIF-92的制备方法包括如下步骤:
(1)取0.50 mmol的 Zn(NO3)2•6H2O和0.75 mmol的2-醛基咪唑溶于10 mL DMF中,将溶液放置在装有5 mL三乙胺和200 mL正己烷的混合溶剂的干燥器内,放置24 h,然后将白色沉淀抽滤并用甲醇洗涤三次,用甲醇溶液浸泡3天,以对其活化,最后对其抽滤并常温下真空干燥24 h即得到ZIF-90;
(2)取0.59 mmol 的ZIF-90分散在10 mL无水甲醇中,向其中加入1.76 mmol的氨基乙醇,60℃下回流24 h,待反应液冷却后将其抽滤并用甲醇洗涤3次,然后将抽滤得到的固体浸泡在甲醇溶液中3 h,再将其抽滤并在常温下真空干燥24 h即得到ZIF-92;
(3)取 88 mmol的ZIF-92,5 mmol的PdCl2,150 mL的无水甲醇于单口烧瓶中;机械搅拌48 h,得到的混合物抽滤并用无水甲醇洗涤、烘干即得到Pd@ZIF-92。
3.根据权利要求1所述的应用,其特征在于,将芳基卤化物1 mmol、1.2 mmol 苯硼酸、2mmol碳酸钾和作为催化剂的 8mg的Pd@ZIF-92加入到25mL的史兰克反应管中,6mL去离子水作反应溶剂,在温度 80 ℃下磁力搅拌 6 h,将反应后的溶液用乙酸乙酯萃取,并用无水硫酸钠干燥,再将有机溶剂去除得到最终产物;产率用气相色谱中的内标法测得,产率为99%;
所述的芳基卤化物为溴苯或碘苯。
4.根据权利要求3所述的应用,所述Pd@ZIF-92在有效催化Suzuki偶联反应后,通过离心进行分离,循环利用催化 Suzuki偶联反应5次。
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