CN114989444B - 一种柠檬酸基金属有机框架材料的制备方法及固氮应用 - Google Patents
一种柠檬酸基金属有机框架材料的制备方法及固氮应用 Download PDFInfo
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Abstract
本发明公开了一种柠檬酸基金属有机框架材料的制备方法及固氮应用。本发明方法首先将三水合硝酸铜、六水合硝酸铈和无水柠檬酸加入到去离子水中,搅拌均匀后转移至聚四氟乙烯内衬的反应釜,120~180℃反应36~72小时;反应结束后冷却至常温,静置后用去离子水洗涤多次,真空干燥后制得柠檬酸基金属有机框架CeCu@CA‑X。本发明还提供了用该方法制备的柠檬酸基金属有机框架CeCu@CA‑X在光催化固氮中的应用。本发明制备方法简单,无需添加其他有机溶剂,环境友好,在光催化固氮中具有高效还原氮气的性能。
Description
技术领域
本发明属于半导体材料领域,涉及一种柠檬酸基金属有机框架材料的制备方法及固氮应用。
背景技术
将天然丰富的氮气转化为氨是维持生命的关键过程,也是化学和生物学中的重要挑战。氮是作物发育的三大重要营养素之一,负责光合作用和叶绿素含量的过程。即使氮气占空气的78%,但植物可以立即消耗的氮不是氮气,它以易消化形式的供应是作物健康的必要条件。同时,可再生电力价格的不断下降,氨(NH3)作为替代能源载体,由于其氢容量大(17.6wt%)和高能量密度(4.3kWh h-1)也受到关注。随着对氨的需求不断增长,空气中的氮气作为氮元素较为经济的来源,因此氮气的人工固定转化为有价值的化学品在农业和化学品中具有极其重要的意义。
目前,工业规模较大的NH3生产主要依靠Haber-Bosch工艺在高温高压(400-500℃,100bar)下使用氮气和氢气(H2)作为进料气体,该过程占全球温室气体排放量的近1.0%。在全球能源危机和增长的温室效应的背景下,开发在温和条件下进行的可持续方法正在逐渐成为研究热点,光催化固氮作为一种重要的绿色技术,自开创以来,对它的探索一直蓬勃发展。
金属有机框架(MOFs)具有金属中心和有机配体“1+1>2”的独特优势。因其较大的表面积,有序的多孔结构和可调有机接头或金属簇,在光催化领域引起了广泛的关注,例如光催化还原CO2,光降解有机污染物,光解水等。Jasper Liedtke等人(J.Liedtke etal.ChemBioChem.2021,22:151-155.),用柠檬酸代替固氮酶中的高柠檬酸来探索机理,发现了柠檬酸在其中至关重要的作用。因此以柠檬酸为配体设计MOFs具有很大的潜力。柠檬酸基MOFs在多个领域有所应用,例如,Jing Jiang等人(J.Jiang et al.ACSAppl.Mater.Interfaces.2017,9:7193-7201.),设计了钴-柠檬酸金属有机框架用于电催化全解水。Mostafa Koolivand等人(M.Koolivand et al.Appl.Organomet.Chem.2021,35:e6434.),制备了铜-柠檬酸金属有机框架用于催化Suzuki-Miyaura交叉偶联反应。
发明内容
本发明的一个目的在于提供一种柠檬酸基金属有机框架材料的制备方法。
本发明方法具体如下:
步骤(1)将三水合硝酸铜、六水合硝酸铈和无水柠檬酸加入到去离子水中,搅拌均匀后将溶液转移至聚四氟乙烯内衬的反应釜,120~180℃反应36~72小时;
加入的三水合硝酸铜、六水合硝酸铈和无水柠檬酸的摩尔比为1:2:2~60,每升去离子水中加入0.02~0.04摩尔三水合硝酸铜;
步骤(2)反应结束后冷却至常温,静置12~36小时,将反应产物用去离子水洗涤2~5次,30~60℃真空干燥12~36小时,制得柠檬酸基金属有机框架材料CeCu@CA-X,X为加入的无水柠檬酸与六水合硝酸铈的摩尔比值。
本发明的另一个目的是提供柠檬酸基金属有机框架材料CeCu@CA-X在光催化固氮中的应用。
本发明催化剂的制备是通过水热法制备的,工作表明,CeCu@CA配体的含量对光催化剂的催化性能及其形貌有较大的影响,适当的配体比例下的材料具有较好的结晶度,较高的比表面积以及优异的电子分离效率。
本发明的有益效果包括:
1.本发明在光催化固氮中具有高效还原氮气的性能,最高可达1051.2μg·g-1·h-1。该材料的制备方法简单,无需添加其他有机溶剂,环境友好,有利于实现绿色化学。
2.本发明制备的CeCu@CA材料因柠檬酸加入比例不同呈现出不同的形状,N2吸附-解吸曲线表明材料均为介孔材料,合适的孔径更有利于气体分子的扩散传递和电子-空穴对的分离。
附图说明
图1为CeCu@CA材料扫面电子显微镜图,其中(a)为CeCu@CA-1.5,(b)为CeCu@CA-10,(c)为CeCu@CA-20,(d)为CeCu@CA-30;
图2为CeCu@CA-X系列材料的X射线衍射图;
图3为CeCu@CA-X系列材料的N2吸附-解吸曲线。
具体实施方式
以下结合具体实施例对本发明做进一步的说明,但下述实例绝非对本发明有任何限制。
实施例1.
步骤(1)将1mmol的三水合硝酸铜、2mmol的六水合硝酸铈和2mmol的无水柠檬酸加入到25ml的去离子水中,搅拌均匀后将溶液转移至聚四氟乙烯内衬的反应釜,120℃反应72小时;
步骤(2)反应结束后冷却至常温,静置12小时,将反应产物用去离子水洗涤2次,30℃真空干燥36小时,制备得到目标产品。
实施例2.
步骤(1)将1mmol的三水合硝酸铜、2mmol的六水合硝酸铈和15mmol的无水柠檬酸加入到30ml的去离子水中,搅拌均匀后将溶液转移至聚四氟乙烯内衬的反应釜,150℃反应60小时;
步骤(2)反应结束后冷却至常温,静置18小时,将反应产物用去离子水洗涤3次,40℃真空干燥24小时,制备得到目标产品。
实施例3.
步骤(1)将1mmol的三水合硝酸铜、2mmol的六水合硝酸铈和35mmol的无水柠檬酸加入到40ml的去离子水中,搅拌均匀后将溶液转移至聚四氟乙烯内衬的反应釜,160℃反应48小时;
步骤(2)反应结束后冷却至常温,静置24小时,将反应产物用去离子水洗涤4次,50℃真空干燥18小时,制备得到目标产品。
实施例4.
步骤(1)将1mmol的三水合硝酸铜、2mmol的六水合硝酸铈和60mmol的无水柠檬酸加入到50ml的去离子水中,搅拌均匀后将溶液转移至聚四氟乙烯内衬的反应釜,180℃反应36小时;
步骤(2)反应结束后冷却至常温,静置36小时,将反应产物用去离子水洗涤5次,60℃真空干燥12小时,制备得到目标产品。
实施例5.
步骤(1)将0.5mmol的三水合硝酸铜、1mmol的六水合硝酸铈和1.5mmol的无水柠檬酸加入到16ml的去离子水中,搅拌均匀后将溶液转移至聚四氟乙烯内衬的反应釜,150℃反应48小时;
步骤(2)反应结束后冷却至常温,静置24小时,将反应产物用去离子水洗涤3次,50℃真空干燥24小时,制得柠檬酸基金属有机框架CeCu@CA-1.5。
实施例6.
其它同实施例5,加入的无水柠檬酸为10mmol,制得柠檬酸基金属有机框架CeCu@CA-10。
实施例7.
其它同实施例5,加入的无水柠檬酸为20mmol,制得柠檬酸基金属有机框架CeCu@CA-20。
实施例8.
其它同实施例5,加入的无水柠檬酸为30mmol,制得柠檬酸基金属有机框架CeCu@CA-30。
实施例9.
将实施例1-8任一方法制备的柠檬酸基金属有机框架材料CeCu@CA-X应用在光催化固氮中。
为了观察本材料的形貌特点,本发明利用扫描电子显微镜对CeCu@CA进行表征。如图1所示,随着柠檬酸量的增加,样品的形貌逐渐发生了显著的变化。CeCu@CA-1.5为多孔微米球,CeCu@CA-10逐渐变为具有片层结构的球形聚集状,具有较大的比表面积。与前两者相比,CeCu@CA-20和CeCu@CA-30的结构为棒状,还存在一定的片层堆积。比表面积的增大,更有助于提高材料的光催化活性。
为了考察材料的晶体结构,本发明利用X射线衍射技术对样品进行表征。如图2所示,随着柠檬酸量的增加,衍射峰强度逐渐变强,结晶度逐渐增强,其特征衍射峰的位置与参考文献(S.F.Weng et al.Journal of Solid State Chemistry.2012,188:77-83.)基本一致,表明CeCu@CA的成功制备。
如图3所示,为了观察材料的多孔性质,样品的N2吸附-脱附等温线显示在P/P0接近1时有显著的毛细管冷凝步骤和H1类滞后回线,显示出IV型曲线,表明它们的介孔结构。合适的孔径更有利于气体分子的扩散传递和电子-空穴对的分离。
Claims (2)
1.一种柠檬酸基金属有机框架材料的制备方法,其特征在于,具体是:
步骤(1)将三水合硝酸铜、六水合硝酸铈和无水柠檬酸加入到去离子水中,搅拌均匀后将溶液转移至聚四氟乙烯内衬的反应釜,120~180℃反应36~72小时;
加入的三水合硝酸铜、六水合硝酸铈和无水柠檬酸的摩尔比为1:2:2~60,每升去离子水中加入0.02~0.04摩尔三水合硝酸铜;
步骤(2)反应结束后冷却至常温,静置12~36小时,将反应产物用去离子水洗涤2~5次,30~60℃真空干燥12~36小时,制得柠檬酸基金属有机框架材料CeCu@CA-X,X为加入的无水柠檬酸与六水合硝酸铈的摩尔比值。
2.如权利要求1所述方法制备的柠檬酸基金属有机框架材料CeCu@CA-X在光催化固氮中的应用。
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