CN106693935A - 以核‑壳金属有机骨架制备磁性炭材料的方法 - Google Patents
以核‑壳金属有机骨架制备磁性炭材料的方法 Download PDFInfo
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Abstract
一种以核‑壳金属有机骨架材料制备磁性炭材料的方法，将所采用的有机配体与金属盐先后超声溶解于溶剂中，滴加2‑10滴氟硼酸，转移至聚四氟乙烯内衬反应釜中，在烘箱中反应，过滤、干燥得到金属‑有机骨架材料；将合成“壳”材料所需有机配体与金属盐先后超声溶解于溶剂中，滴加2‑10滴氟硼酸，加入为核的金属有机骨架材料，后转移至聚四氟乙烯内衬反应釜中，在烘箱中反应，过滤、干燥得到核‑壳金属有机骨架材料；将上述得到的核‑壳金属有机骨架材料进行高温炭化加热，得到磁性炭材料。该方法制得的炭材料孔道结构规则，孔径分布均匀，具有磁性，在气体吸附储存、工业废物分离等方面具有良好的应用价值，且该方法制备过程简单易行、安全性好。
Description
【技术领域】
本发明涉及一种以核-壳金属有机骨架制备高比表面积磁性炭材料的方法。
【背景技术】
金属-有机骨架材料是由有机配体与金属离子通过自组装形成的拓扑结构，具有结构可设计性和调节性，其中有机配体具有高的含碳量。核-壳金属-有机骨架材料是以某种金属-有机骨架为核，以另一种金属有机骨架为壳组装而成的一种核-壳结构。核-壳结构能结合两种不同材料的优点，可根据实际所需可以设计出相应的核-壳结构。炭材料因为具有较高的比表面积和导电能力，并且化学稳定性、热稳定性高，目前在吸附、分离、电学、超级电容器等领域有极为重要的价值。在炭材料中，磁性炭材料由于具有磁性，使炭材料易于回收循环利用，大幅节省成本。所以通过设计以铁磁性金属为金属中心的核-壳金属有机骨架为前驱体制备多孔炭具有重要的意义。
中国发明专利(ZL201410130580.6)以首先利用水热法制备出具有多孔结构的金属-有机骨架材料Fe-MIL-101或Fe-MIL-100，将其在N2/H2氛围或者真空状态，在温度为500-700℃下锻烧2-8小时，得到磁性多孔碳/氧化铁纳米复合的吸附材料。其具有如下缺点：
1、所制备的磁性炭材料比表面积较小，比表面积在200～450m2/g，限制了它的应用。
2、所选的炭化前驱体只有Fe-MIL-101或Fe-MIL-100，方法使用范围较为狭窄。
3、所制备的磁性材料中金属组分只包含氧化铁，使得该材料难以应用于催化领域。
【发明内容】
本发明所要解决的技术问题在于提供一种以核-壳金属有机骨架材料为前驱体制备高比表面积磁性炭材料的方法，该方法制得的炭材料孔道结构规则，孔径分布均匀，具有磁性，在气体吸附储存、工业废物分离等方面具有良好的应用价值，且该方法制备过程简单易行、安全性好。
本发明是这样实现的：
以核-壳金属有机骨架制备磁性炭材料的方法，包括如下步骤：
步骤1：前驱体核-壳金属有机骨架材料中的“核”材料的合成：
将所采用的有机配体与金属盐先后超声溶解于溶剂中，滴加2-10滴的氟硼酸，搅拌均匀，转移至聚四氟乙烯内衬的反应釜中，在烘箱中反应，过滤、干燥得到金属-有机骨架材料；其中反应温度为80-200℃，金属盐与有机配体的反应比例为0.2-5∶1；
步骤2：前驱体核-壳金属有机骨架材料的合成：
将合成“壳”材料所需的有机配体与金属盐先后超声溶解于溶剂中，滴加2-10滴的氟硼酸，搅拌均匀，加入为核的金属有机骨架材料，后转移至聚四氟乙烯内衬的反应釜中，在烘箱中反应，过滤、干燥得到核-壳金属有机骨架材料；其中反应温度为80-200℃，金属盐与有机配体的反应摩尔比例为0.2-5∶1，金属有机骨架材料与有机配体的投加质量比例为0.01-0.5∶1；
步骤3：高温炭化：
将上述得到的核-壳金属有机骨架材料放在石英舟上，置于管式炉中，在氮气气氛下，进行高温炭化加热，在炭化过程中金属有机骨架材料结构中的铁磁性金属组分被氧化具有磁性的金属氧化物，有机基团被炭化包裹在金属氧化物上，得到磁性金属氧化物与活性炭的复合物，就是磁性炭材料。
进一步地，所述核-壳金属有机骨架中“核”或者“壳”至少有一个具有铁磁性金属组分。
进一步地，所述铁磁性金属组分来源金属盐为铁盐、镍盐、钴盐，其他金属组分来源金属盐为锌盐、钾盐、镁盐、铅盐。
进一步地，所述有机配体指具有配位官能团的配体，为羧酸类配体、含氮配体、含氨基配体或磷酸类配体。
进一步地，所述溶剂为N,N-二甲基甲酰胺、水、甲醇、乙醇。
进一步地，所述步骤3中的高温炭化是以1～10℃/min的升温速度从室温加热到450～1000℃，并在450～1000℃保持10-600min小时，之后自然冷却到室温。
本发明的优点在于：
1、提高所制备的磁性多孔炭的比表面积及孔容得到高性能的磁性炭材料。
2、开发炭化前驱体的种类，增加制备磁性炭的材料多样性；以及可根据需求，采用合适的金属盐和配体构建核-壳金属有机骨架。
3、制备方法简单快捷，有益于工业化生产。
以下实施案例和附图仅为详细说明本发明的示例，并不用来限制本发明的范围。
【附图说明】
图1是实施例1中的Fe-MOF和Fe-Zn核-壳MOF的粉末X-射线衍射图。
图2是实施例2中的Co-MOF和Co-Zn核-壳MOF的粉末X-射线衍射图。
图3是实施例3中的Ni-MOF和Ni-Zn核-壳MOF的粉末X-射线衍射图。
图4是实施例1、2、3中核-壳MOF的热重曲线图。
图5是实施例1、2、3中磁性炭材料的N2吸附/脱附曲线图。
【具体实施方式】
实施例1：
以Fe-MOF为核，MOF-5(Zn)为壳制备Fe-Zn核-壳MOF，以Fe-Zn核-壳MOF为前驱体，通过高温炭化制备高比表面积的磁性炭材料。
Fe-MOF中金属元素是铁(Fe)，配位的有机化合物是对苯二甲酸，此物质的制备方法为称取1.6230g六水合氯化铁和0.8405g均苯三甲酸溶解于40mL蒸馏水中，滴加4滴的氟硼酸，搅拌均匀转入带四氟乙烯内衬的高压反应釜中，在150℃下反应24小时，得到产品，在150℃下真空干燥12小时后得到Fe-MOF。
Fe-Zn核-壳MOF的制备首先配制MOF-5(Zn)的反应液，将2.9749g六水合硝酸锌和0.8310g对苯二甲酸溶解于80mL N,N-二甲基甲酰胺溶液中，滴加4滴的氟硼酸，搅拌均匀，后按Fe-MOF与对苯二甲酸质量比为0.05:1的比例添加Fe-MOF，转入带四氟乙烯内衬的高压反应釜中，在100℃下反应48小时，得到产品，在100℃下真空干燥4小时后得到Fe-Zn核-壳MOF。经粉末X-射线衍射分析(见图1)，发现有明显的衍射峰，说明Fe-Zn核-壳MOF结晶性较好。通过热失重分析(见图4)，得到Fe-Zn核-壳MOF的分解温度约为400℃。
将所得Fe-Zn核-壳MOF放在石英舟上，置于高温管式炉中，以5℃/min的升温速度从室温加热到950℃，并在950℃保持3小时，之后自然冷却到室温，得到磁性炭材料Fe-Zn-MOF-C。其BET比表面积经低温氮气吸附/脱附等温线测得为783.56m2/g(见图5)，孔容为0.80cm3/g，平均孔径为5.40nm，室温条件下的饱和磁化强度为8.32emu/g。
实施例2：
主要方法同实施例1，不同之处在于，本实施例以另一种金属有机骨架材料Co-MOF为核，以MOF-5(Zn)为壳制备Co-Zn核-壳MOF，以Co-Zn核-壳MOF为前驱体，通过高温炭化制备高比表面积的磁性炭材料。
Co-MOF中金属元素是钴(Co)，配位的有机化合物是对苯二甲酸，此物质的制备方法为将2.9103g六水合硝酸钴和0.8310g对苯二甲酸溶解于80mL N,N-二甲基甲酰胺溶液中，搅拌均匀转入带四氟乙烯内衬的高压反应釜中，在100℃下反应24小时，得到产品，在100℃下真空干燥4小时后得到Co-MOF。
Co-Zn核-壳MOF的制备首先配制MOF-5(Zn)的反应液，将2.9749g六水合硝酸锌和0.8310g对苯二甲酸溶解于80mL N,N-二甲基甲酰胺溶液中，滴加4滴的氟硼酸，搅拌均匀，后按Co-MOF与对苯二甲酸质量比为0.05:1的比例添加Co-MOF，转入带四氟乙烯内衬的高压反应釜中，在100℃下反应48小时，得到产品，在100℃下真空干燥4小时后得到Co-Zn核-壳MOF。经粉末X-射线衍射分析(见图2)，发现有明显的衍射峰，说明Co-Zn核-壳MOF结晶性较好。通过热失重分析(见图4)，得到Co-Zn核-壳MOF的分解温度约为400℃。
将所得Co-Zn核-壳MOF放在石英舟上，置于高温管式炉中，以2.5℃/min的升温速度从室温加热到750℃，并在750℃保持1小时，之后自然冷却到室温，得到磁性炭材料Co-Zn-MOF-C。其BET比表面积经低温氮气吸附/脱附等温线测得为974.11m2/g(见图5)，孔容为0.87cm3/g，平均孔径为3.71nm，室温条件下的饱和磁化强度为10.5emu/g。
实施例3：
主要方法同实施例1，不同之处在于，本实施例以另一种金属有机骨架材料Ni-MOF为核，以MOF-5(Zn)为壳制备Ni-Zn核-壳MOF，以Ni-Zn核-壳MOF为前驱体，通过高温炭化制备高比表面积的磁性炭材料。
Ni-MOF中金属元素是镍(Ni)，配位的有机化合物是均苯三甲酸，此物质的制备方法为将1.4560g硝酸镍和0.8306g均苯三甲酸溶解于80mL N,N-二甲基甲酰胺溶液中，搅拌均匀转入带四氟乙烯内衬的高压反应釜中，在100℃下反应48小时，得到产品，在100℃下真空干燥4小时后得到Ni-MOF。经粉末X-射线衍射分析(见图3)，发现有明显的衍射峰，说明Co-Zn核-壳MOF结晶性较好。通过热失重分析(见图4)，得到Co-Zn核-壳MOF的分解温度约为400℃。
Ni-Zn核-壳MOF的制备首先配制MOF-5(Zn)的反应液，将2.9749g六水合硝酸锌和0.8310g对苯二甲酸溶解于80mL N,N-二甲基甲酰胺溶液中，滴加4滴的氟硼酸，搅拌均匀，后按Ni-MOF与对苯二甲酸质量比为0.1:1的比例添加Ni-MOF，转入带四氟乙烯内衬的高压反应釜中，在100℃下反应48小时，得到产品，在100℃下真空干燥4小时后得到Ni-Zn核-壳MOF。将所得Ni-Zn核-壳MOF放在石英舟上，置于高温管式炉中，以10℃/min的升温速度从室温加热到950℃，并在950℃保持5小时，之后自然冷却到室温，得到磁性炭材料Ni-Zn-MOF-C。其BET比表面积经低温氮气吸附/脱附等温线测得为961.05m2/g(见图5)，孔容为1.06cm3/g，平均孔径为1.36nm，室温条件下的饱和磁化强度为13.74emu/g。
以上所述仅为本发明的较佳实施用例而已，并非用于限定本发明的保护范围。凡在本发明的精神和原则之内，所作的任何修改、等同替换以及改进等，均应包含在本发明的保护范围之内。
Claims (6)
1.以核-壳金属有机骨架制备磁性炭材料的方法，其特征在于：包括如下步骤：
步骤1：前驱体核-壳金属有机骨架材料中的“核”材料的合成：
将所采用的有机配体与金属盐先后超声溶解于溶剂中，滴加2-10滴的氟硼酸，搅拌均匀，转移至聚四氟乙烯内衬的反应釜中，在烘箱中反应，过滤、干燥得到金属-有机骨架材料；其中反应温度为80-200℃，金属盐与有机配体的反应比例为0.2-5∶1；
步骤2：前驱体核-壳金属有机骨架材料的合成：
将合成“壳”材料所需的有机配体与金属盐先后超声溶解于溶剂中，滴加2-10滴的氟硼酸，搅拌均匀，加入为核的金属有机骨架材料，后转移至聚四氟乙烯内衬的反应釜中，在烘箱中反应，过滤、干燥得到核-壳金属有机骨架材料；其中反应温度为80-200℃，金属盐与有机配体的反应摩尔比例为0.2-5∶1，金属有机骨架材料与有机配体的投加质量比例为0.01-0.5∶1；
步骤3：高温炭化：
将上述得到的核-壳金属有机骨架材料放在石英舟上，置于管式炉中，在氮气气氛下，进行高温炭化加热，在炭化过程中金属有机骨架材料结构中的铁磁性金属组分被氧化具有磁性的金属氧化物，有机基团被炭化包裹在金属氧化物上，得到磁性金属氧化物与活性炭的复合物，就是磁性炭材料。
2.如权利要求1所述的以核壳金属有机骨架制备磁性炭材料的方法，其特征在于：
所述核-壳金属有机骨架中“核”或者“壳”至少有一个具有铁磁性金属组分。
3.如权利要求2所述的以核壳金属有机骨架制备磁性炭材料的方法，其特征在于：所述铁磁性金属组分来源金属盐为铁盐、镍盐、钴盐，其他金属组分来源金属盐为锌盐、钾盐、镁盐、铅盐。
4.如权利要求1所述的以核壳金属有机骨架制备磁性炭材料的方法，其特征在于：所述有机配体指具有配位官能团的配体，为羧酸类配体、含氮配体、含氨基配体或磷酸类配体。
5.如权利要求1所述的以核-壳金属有机骨架制备磁性炭材料的方法，其特征在于：所述溶剂为N,N-二甲基甲酰胺、水、甲醇、乙醇。
6.如权利要求1所述的以核-壳金属有机骨架制备磁性炭材料的方法，其特征在于：所述步骤3中的高温炭化是以1～10℃/min的升温速度从室温加热到450～1000℃，并在450～1000℃保持10-600min，之后自然冷却到室温。
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Application publication date: 20170524 |