CN108579815B - 一种双金属有机框架结构催化剂及其制备方法和应用 - Google Patents
一种双金属有机框架结构催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种双金属有机框架结构催化剂及其制备方法和应用。该催化剂由镍、铜两种金属离子作为金属节点,和对苯二甲酸有机配体结合起来,在高温反应釜中一步反应而成。这种催化剂有铜和镍两个催化活性位点,是一种协同催化剂。在对硝基苯酚向对氨基苯酚还原反应中,该催化剂快速、高效且能重复使用。
Description
技术领域
本发明属于催化剂领域,具体涉及了一种对硝基苯酚催化加氢生成对氨基苯酚用双金属有机框架结构催化剂的制备方法和应用。
背景技术
对氨基苯酚,结构式中含有两个官能团,因此既属于芳胺类又属于酚类,是一种很重要的化工原料。在化工、医药、燃料、橡胶及油品添加剂等工业领域都有着很广泛 的应用,作为一种很重要的精细化工和医药中间体,可以用来合成扑热息痛、安妥明、 维生素B1等药物及复合剂烟酰胺、6-羟基喹啉等化工产品。其中,由对氨基苯酚衍生 合成的解热镇痛药早在40年代英国就开始推广使用。并且,在同类药物中,对氨基苯 酚合成的扑热息痛既避免了阿司匹林对肠胃的刺激,又不像安乃近对身体有变态行为, 广受大众欢迎。近年来,扑热息痛的使用量大幅增加,使得对氨基苯酚的需求量迅猛增 长。根据这一趋势,近几年我们对于对氨基苯酚的生产能力也开始迅速扩张。到2008 年仅国内的对氨基苯酚产量就已达到12万吨以上,占世界近一半的生产能力。因此, 对氨基苯酚是一种拥有巨大发展前景的物质,对其合成工艺的研究一直没有停止过,到 目前为止,制备对氨基苯酚的主要方法有两种,分别是硝基苯法与对硝基苯酚法。硝基 苯催化加氢法是一种相对较好的化学工艺,但反应条件为强酸介质,反应过程非常复杂, 并且容易产生大量的苯胺等其他杂质,对产品的生产效率和质量影响很大。对硝基苯酚 法是以对硝基苯酚为原料,在催化剂的作用下加氢还原得到对氨基苯酚,工艺流程简单, 产品质量高,污染小,发展前景广阔。
国内外研究者开发了系列对硝基苯酚加氢催化剂,包括Ni催化剂、Au催化剂和 Pd催化剂。大量研究表明,微量的ⅤA族(N、P、As、Sb)和ⅥA族(O、S、Se、Te)非金属元素的存在都可以引起Ni催化剂中毒而失活。除常规镍催化剂外,贵金属 Au催化剂占有重要位置。此类催化剂具有催化活性高、反应条件温和等优点,但是贵 金属价格昂贵,且重复使用性不好,使得对氨基苯酚的合成成本大大增加。金属有机框 架结构是由金属节点和有机配体结合而成,具有比表面积大,孔洞尺寸可调谐,结构多 样性等特点,使其在催化领域的优势非常明显。尤其金属有机框架结构中金属节点不局 限于单一的金属,可以是双金属,这种结构使其成为最具有前景的协同催化剂。协同催 化剂能有效降低反应能量壁垒,进一步提高催化反应的效率。
发明内容
为了替代贵金属材料,并提高合成对氨基苯酚的效率,本发明使用水热法制备了一种双金属有机框架结构材料。该结构由Cu、Ni两种金属节点和对苯二甲酸这种有机 配体组成。形貌类似花型,尺寸达到微米尺度,由多个很薄的片层结构组成,在片边缘 位置尤其薄,片与片之间的间隔较大,并且这种材料具有丁达尔效应。这种金属有机框 架结构是一个一步反应合成的整体,相较于几个纳米的贵金属催化剂,更容易收集;对 比于贵金属沉积或者掺杂在基底上的结构,制备方法更为简单,且用于催化的金属位点 分散均匀,也不像沉积的结构易于脱落。
一种双金属有机框架结构催化剂的制备方法,该催化剂由镍、铜两种金属离子作为金属节点,和对苯二甲酸有机配体结合起来,在高温反应釜中一步反应而成,具体方 法为:称取氯化镍、醋酸铜和对苯二甲酸溶解在二甲基甲酰胺和乙醇的混合溶液中,并 大力搅拌至绿色澄清溶液;之后把这一溶液倒入高压釜,并在高温反应釜中加热;反应 完成后,室温下用N,N-二甲基甲酰胺和乙醇分别清洗反应完成获得的固体,并干燥获得 最后的产物;氯化镍、醋酸铜、对苯二甲酸摩尔比例为0.031/1/5-1/1/5。
所述的双金属有机框架结构催化剂的制备方法,氯化镍、醋酸铜、对苯二甲酸摩尔比例为0.25/1/5、0.125/1/5、0.062/1/5、0.031/1/5。
所述的双金属有机框架结构催化剂的制备方法,在高温反应釜中150℃加热6小时。
任一所述的制备方法制备的双金属有机框架结构催化剂。
所述的双金属有机框架结构催化剂的应用,应用于对硝基苯酚催化加氢生成对氨基苯酚。
这种双金属结构可以看作协同催化剂,相比于单一的催化剂,反应速度更快。且这种催化剂的结构方便反应物对硝基苯酚的进入,并随之在其表面还原生成对氨基苯酚离开。这种双金属有机框架催化剂是使用镍离子和铜离子作为金属节点,邻苯二甲酸作 为有机配体在水热环境下合成的。
本发明的优点是:1.制备的双金属有机框架结构是一种非贵金属催化剂,采用的镍和铜金属价格只有金的二千分之一不到(以上期所交易价格为证,2018年2月:沪金 略高于270元/g,沪铜略高于0.05元/g,沪镍在0.1元/g左右浮动),可以极大程度上降 低合成对氨基苯酚的催化剂成本;2.这种催化剂快速(30s),高效(近100%),且 能重复利用(至少5次),既能有效避免其他杂质的掺入,又能实现快速反复的催化过 程。
附图说明
图1是本发明的双金属有机框架结构材料的XRD图;
图2是本发明的双金属有机框架结构材料的SEM和TEM图;
图3是本发明的双金属有机框架结构材料的XPS图;
图4是本发明的双金属有机框架结构材料用作催化剂合成对氨基苯酚的图;
图5是本发明的双金属有机框架结构材料用作催化剂合成对氨基苯酚的重复利用的图;
图6是本发明实施例4双金属有机框架结构材料在电子显微镜下的形貌图;
具体实施方式
以下结合具体实施例,对本发明进行详细说明。
实施例1:
单金属有机框架结构材料制备方法:称取1*10-4moL氯化镍,和5*10-4moL对苯 二甲酸溶解在8ml二甲基甲酰胺和5ml乙醇的混合溶液中,并大力搅拌至绿色澄清溶 液。之后把这一溶液倒入高压釜,并在150℃下加热6小时。反应完成后,室温下用二 甲基甲酰胺和乙醇分别清洗反应完成获得的固体,并干燥获得最后的产物。
产物结构可通过扫描电子显微镜分析确定。通过观察电子显微镜形貌像图2(a-b)看出:产物的尺寸达到数微米;结构似花型,由许多超薄的片层组成;边缘的地方尤其 薄。
实施例2:
双金属有机框架结构材料制备方法:称取1*10-4moL氯化镍,1*10-4moL醋酸铜, 和5*10-4moL对苯二甲酸溶解在8ml二甲基甲酰胺和5ml乙醇的混合溶液中,并大力 搅拌至绿色澄清溶液。之后把这一溶液倒入高压釜,并在150℃下加热6小时。反应完 成后,室温下用N,N-二甲基甲酰胺和乙醇分别清洗反应完成获得的固体,并干燥获得最 后的产物。
产物结构可通过扫描电子显微镜及透射电子显微镜分析确定。通过观察电子显微镜 形貌像图2(c-f)看出:产物的尺寸达到数微米;结构似花型,由许多超薄的片层组成;边缘的地方尤其薄;并且有明显的丁达尔现象。
产物中金属的价态可通过X射线光电子谱得到,X射线光电子谱数据如图3所示:在i中,855.0和873.1eV分别属于Ni 2p3/2和2p1/2,代表Ni(II)。在ii中,933.5和954.4 eV分别属于Cu 2p3/2和2p1/2,代表Cu(II)。产物成分、结构及价态分析很好的展示了 CuNi-BDC的形成。
实施例3:
双金属框架结构催化剂其催化合成对氨基苯胺的技术方案如下:0.1mL对硝基苯酚水溶液(10-3mmoL/mL)、0.4ml硼氢化钠水溶液(0.1mmoL/mL)、2.4ml蒸馏水, 搅拌混合均匀后,加入0.1ml实施例2制备的催化剂(100mg/mL)。作为对照,我们也 做了单金属框架结构催化剂的催化效果实验。技术方案为:其他的反应物不变,加入0.1 ml实施例1制备的催化剂(100mg/mL)。使用紫外-可见分光光度计实时检测反应进行 情况,并记录下来。
催化反应进行的情况如图4(a)和4(b)所示。首先,随着反应时间的延长,400 nm处的吸收峰减弱直至消失,代表原料对硝基苯酚已经被完全还原。同时,295nm处 的吸收峰开始出现,代表对氨基苯酚的生成。此外,从图4(a)和4(b)的对比中可 知,双金属框架结构催化剂的催化效果要明显优于单金属框架结构催化剂。从图4(a) 的催化产率看,产物的生成率达到近100%,双金属框架结构催化剂的表观速率常数达 到4.74min-1,远超过一些贵金属催化剂的催化速率(0.3min-1for Au@Ag/ZIF-8,0.33 min-1for Au/MIL-100(Fe),和0.632min-1for Pd NPs/CNT-220)。并在进一步的催化剂循 环使用实验中(图5),展示出了较好的循环使用能力(不少于5次)。
实施例4:
实施案例2中制备的双金属框架结构的Cu/Ni比例是1/1,除此其他的双金属比例(Cu/Ni:0.25/1、0.125/1、0.062/1、0.031/1)的有机框架结构材料制备方法:分别称取 1*10-4moL氯化镍,(0.25*10-4moL、0.1250.25*10-4moL、0.062*10-4moL、0.031*10-4moL) 醋酸铜,和5*10-4moL对苯二甲酸溶解在8ml二甲基甲酰胺和5ml乙醇的混合溶液中, 并大力搅拌至绿色澄清溶液。之后把这一溶液倒入高压釜,并在150℃下加热6小时。 反应完成后,室温下用N,N-二甲基甲酰胺和乙醇分别清洗反应完成获得的固体,并干燥 获得最后不同Cu/Ni比例的产物。
产物结构可通过扫描电子显微镜分析确定。通过观察电子显微镜形貌,从图6(a-d) 看出:不同比例的Cu/Ni产物其结构都类似花型,是由许多超薄的片层组成;边缘的地方特别薄。
应当理解的是,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,而所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (3)
1.一种双金属有机框架结构催化剂的的应用,应用于对硝基苯酚催化加氢生成对氨基苯酚,所述双金属有机框架结构催化剂的制备方法为:该催化剂由镍、铜两种金属离子作为金属节点,和对苯二甲酸有机配体结合起来,在高温反应釜中一步反应而成,具体方法为:称取氯化镍、醋酸铜和对苯二甲酸溶解在二甲基甲酰胺和乙醇的混合溶液中,并大力搅拌至绿色澄清溶液;之后把这一溶液倒入高压釜,并在高温反应釜中加热;反应完成后,室温下用N,N-二甲基甲酰胺和乙醇分别清洗反应完成获得的固体,并干燥获得最后的产物;氯化镍、醋酸铜、对苯二甲酸摩尔比例为0.031/1/5-1/1/5。
2.根据权利要求1所述的应用,其特征在于,氯化镍、醋酸铜、对苯二甲酸摩尔比例为0.25/1/5、0.125/1/5、0.062/1/5、0.031/1/5。
3.根据权利要求1所述的应用,其特征在于,在高温反应釜中150℃加热6小时。
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