CN106927458A - 一种石墨烯与zif‑8复合气凝胶及其制备方法 - Google Patents
一种石墨烯与zif‑8复合气凝胶及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种石墨烯与ZIF‑8复合气凝胶材料及其制备方法，属于功能材料制备技术领域，且该气凝胶具有高的二氧化碳气体吸附性能。所述制备方法包括以氧化石墨烯分散液为原料制得石墨烯水凝胶，和以石墨烯水凝胶为模板原位生长ZIF‑8，得到石墨烯与ZIF‑8复合气凝胶材料。本发明使用水凝胶作为模板既提高了ZIF‑8的负载效率，又简化了制备工艺。该复合气凝胶具有较大的比表面积，对1atm，298K下二氧化碳气体具有良好的吸附性能，有望实现在气体存储领域的应用。
Description
【技术领域】
本发明涉及一种石墨烯与ZIF-8复合气凝胶及其制备方法，尤其是它的CO2吸附性能，属于功能材料制备技术领域。
【背景技术】
氧化石墨烯是石墨通过氧化还原法制备石墨烯的中间产物，它表面具有丰富的含氧基团(碳原子层平面上的羟基和环氧基、层边缘的羰基和羧基)。可以通过一定的方法将二维氧化石墨烯还原组装成为多孔、超轻的三维石墨烯气凝胶。多孔的网络结构赋予石墨烯较大的比表面积和孔隙率，可进一步用于负载各种功能体。金属有机骨架化合物(MOFs)是一种通过金属离子与多官能团有机配体配位而成的多孔晶体材料。它具有较大的孔隙率、比表面积和结构多样性，因此在气体吸附和分离领域得到广泛应用。ZIFs材料是一类具有沸石骨架结构的金属有机骨架材料，与其它类型的MOFs相比，ZIFs材料具有更高的比表面积和孔隙率、较高水热稳定性和耐化学腐蚀性。其中ZIF-8是ZIFs材料中性能稳定且被研究最多的一类物质。ZIF-8具有的微孔尺寸和大于1500m2/g的比表面积，且所含碱性咪唑基团可提供利于某些气体(如二氧化碳)吸附的氮原子。这些性质都使ZIF-8材料在气体储存与分离方面具有潜在的应用价值。
考虑到ZIF-8粉末材料在实际应用中可加工方面存在局限性，因此将其负载于多孔材料中进行应用是一种优选方法。通常石墨烯气凝胶具有三维网络搭建所形成的介孔结构，该介孔结构为二氧化碳气体进入孔材料内部提供通道，而且二氧化碳分子可以与具有微孔结构的ZIF-8中的碱性咪唑基团发生强相互作用。利用石墨烯气凝胶与ZIF-8的协同作用构建的微孔/介孔多级孔结构，使得石墨烯与ZIF-8复合气凝胶材料对二氧化碳气体具有高吸附性能。目前，石墨烯与ZIF-8复合材料的制备主要是通过原位法获得二维复合结构，对于负载ZIF-8的石墨烯三维复合结构却未见报道。
本发明所要解决的技术问题在于突破现有的二维复合结构，以化学还原法获得的石墨烯水凝胶为模板，实现ZIF-8在凝胶体系中的有序成核与生长。并通过常压干燥法，制得具有多层次孔状结构的复合气凝胶材料。本发明所采用的制备方法工艺简单、绿色环保，通过控制还原时间，可以地控制石墨烯表面的氧含量，从而控制石墨烯与ZIF-8复合比例，进而调控二氧化碳的吸附量。该复合气凝胶在二氧化碳吸附和存储，以及超级电容器等领域有着潜在应用价值。
【发明内容】
本发明的目的在于提供一种石墨烯与ZIF-8复合气凝胶。
本发明的目的还在于提供一种石墨烯与ZIF-8复合气凝胶的制备方法。
如前所述，ZIF-8粉末材料在实际应用中可加工方面存在局限性，因此考虑将其负载于多孔材料中进行应用。石墨烯气凝胶具有三维网络搭建所形成的多孔结构，有利于负载ZIF-8材料。由于ZIF-8中的锌离子可以与氧化石墨烯表面的含氧基团发生配位作用，所以ZIF-8可以在氧化石墨烯表面成核并生长。常规石墨烯气凝胶的制备是以水为溶剂，通过冷冻干燥法，制得气凝胶材料。本发明利用ZIF-8成核生长所需的有机溶剂环境，来置换石墨烯凝胶中的水，就可以通过常压干燥法制得相应的石墨烯与ZIF-8复合气凝胶材料。
本发明通过下述实验方案实现的，具体是：以氧化石墨烯为原料，通过化学还原制备石墨烯水凝胶，以该水凝胶为三维模板，通过锌盐与2-甲基咪唑反应，在三维石墨烯表面均匀形成ZIF-8，通过常压干燥最终制得石墨烯与ZIF-8复合气凝胶，该方法操作方便，实验简单易行。
1.一种石墨烯与ZIF-8复合气凝胶，其特征在于：该复合气凝胶的重量百分比组分为石墨烯占15％～30％，ZIF-8占70％～85％；该复合气凝胶的密度为11.0mg/cm3～23.1mg/cm3；该复合气凝胶具有多级孔状结构，其中大孔径尺寸分布范围为500μm～50μm，介孔径分布范围为7nm～3nm，微孔径分布范围为小于1.2nm；在298K，1atm条件下，该气凝胶对CO2的吸附量为0.80mmol/g～0.99mmol/g；
2.制备所述石墨烯与ZIF-8复合气凝胶的制备方法，其特征在于该方法包括以下步骤：
(1)石墨烯水凝胶的制备：将氧化石墨烯分散液进行化学还原制得石墨烯水凝胶；还原剂为水合肼、抗坏血酸和碘化氢中的一种或几种，还原温度为90℃～95℃，还原时间为20min～40min，氧化石墨烯与还原剂的质量比为1:2～1:1；
(2)石墨烯与ZIF-8复合气凝胶的制备：将步骤(1)所得石墨烯水凝胶浸入甲醇或异丙醇中进行溶剂置换，再将其多次交替浸入到无机锌盐的有机溶液和2-甲基咪唑的有机溶液中，经浸泡洗涤干燥，最终得到具有不同组分比例的石墨烯与ZIF-8复合气凝胶材料；
置换溶剂与石墨烯水凝胶的体积比为3:1～4:1，置换时间为6h～12h；
步骤(2)中无机锌盐溶液和2-甲基咪唑溶液浓度分别为5mmol/L～10mmol/L和40mmol/L～80mmol/L，无机锌盐溶液和2-甲基咪唑溶液体积比为1:1，反应温度为25℃～40℃，反应时间为2h～4h。
3.进一步，步骤(2)中的无机锌盐为硝酸锌或氯化锌。
4.进一步，步骤(2)中的有机溶液中有机溶剂为甲醇或异丙醇。
5.进一步，步骤(2)中浸泡时间为30min～60min。
6.进一步，步骤(2)中干燥的温度为40～60℃，干燥时间为12h～24h。
本发明由于采取上述技术方案，具有以下优点：
(1)本发明选用石墨烯水凝胶作为模板，ZIF-8能够均匀负载于石墨烯气凝胶内外表面。
(2)本发明采用有机溶剂置换法，实现了常压干燥法制备石墨烯与ZIF-8复合气凝胶。
(3)本发明所制备的石墨烯与ZIF-8复合气凝胶具有微孔、介孔和大孔的多层次孔状结构。
(4)本发明所制备的石墨烯与ZIF-8复合气凝胶具有轻质特性，ZIF-8的负载重量百分比为70％-85％，气凝胶密度范围在11.0mg/cm3到23.1mg/cm3。
(5)本发明所制备的石墨烯与ZIF-8复合气凝胶具有很好的二氧化碳吸附性能，高于同等条件下纯石墨烯气凝胶或纯ZIF-8晶体的二氧化碳吸附量。
(6)通过选择复合次数，来控制ZIF-8的负载量。ZIF-8的负载量越高，其CO2的吸附性能越好。
【附图说明】
图1是本发明实施例1所得的石墨烯与ZIF-8复合气凝胶断面的扫描电镜图；
图2a是本发明实施例1所得的石墨烯与ZIF-8复合气凝胶表面的扫描电镜图；
图2b是对比例1所制备的气凝胶表面的扫描电镜图；
图3是本发明实施例1所得的石墨烯与ZIF-8复合气凝胶的孔径分布曲线。
图4是本发明实施例1所得的石墨烯与ZIF-8复合气凝胶与对比例1纯石墨烯基气凝胶、纯ZIF-8样品在298K，1atm下CO2吸附量曲线。
【具体实施方式】
下面结合实施例对本发明进一步描述，但不因此将本发明限制在所述的实例范围之中。
实施例1.
(1)石墨烯水凝胶的制备。以325目鳞片石墨为原料，通过Hummer法制备氧化石墨烯，得到4mg/mL的氧化石墨烯水溶液。取3mL氧化石墨烯水溶液加入到平底试管中，加入12mg抗坏血酸搅拌均匀后，置于95℃反应20min形成1.7cm3石墨烯水凝胶。
(2)将上述1.7cm3石墨烯水凝胶浸入到6mL甲醇中6h进行溶剂置换。然后将凝胶充分浸入到5mL，10mmol/L的六水合硝酸锌的40℃甲醇中，2h后将凝胶取出。再浸入到5mL，80mmol/L的2-甲基咪唑的40℃甲醇中，将反应体系静置2h。将凝胶用硝酸锌和2-甲基咪唑的40℃甲醇溶液交替浸泡8次后，放到甲醇中浸泡1h，以除去未反应的物质。最后将凝胶取出，放在40℃烘箱干燥12h，即制得石墨烯与ZIF-8复合气凝胶。该气凝胶的密度为23.1mg/cm3，ZIF-8重量百分比为84％。
图1是本发明实施例1中石墨烯与ZIF-8复合气凝胶的截面形貌图。
图2是本发明实施例1和对比例2中石墨烯与ZIF-8复合气凝胶的表面形貌图。
图3是本发明实施例1中石墨烯与ZIF-8复合气凝胶的孔径分布曲线。
图4是本发明实施例1中石墨烯与ZIF-8复合气凝胶、对比例1中纯石墨烯基气凝胶、以及纯ZIF-8样品在298K，1atm下CO2吸附量曲线。
实施例2
(1)石墨烯水凝胶的制备。以325目鳞片石墨为原料，通过Hummer法制备氧化石墨烯，得到4mg/mL的氧化石墨烯水溶液。取3mL氧化石墨烯水溶液加入到平底试管中，加入12mg抗坏血酸搅拌均匀后，置于90℃反应40min形成1.7cm3石墨烯水凝胶。
(2)将上述1.7cm3石墨烯水凝胶浸入到6mL甲醇中6h进行溶剂置换。然后将凝胶充分浸入到5mL，10mmol/L的六水合硝酸锌的40℃甲醇中，2h后将凝胶取出。再浸入到5mL，80mmol/L的2-甲基咪唑的40℃甲醇中，将反应体系静置2h。将凝胶用硝酸锌和2-甲基咪唑的40℃甲醇溶液交替浸泡8次后，放到甲醇中浸泡1h，以除去未反应的物质。最后将凝胶取出，放在40℃烘箱干燥12h，即制得石墨烯与ZIF-8复合气凝胶。其密度见表1。
表1.石墨烯与ZIF-8复合气凝胶的密度
表2.石墨烯与ZIF-8复合气凝胶在298K，1atm下CO2的吸附量
实施例3
(1)石墨烯水凝胶的制备。以325目鳞片石墨为原料，通过Hummer法制备氧化石墨烯，得到4mg/mL的氧化石墨烯水溶液。取1.5mL氧化石墨烯水溶液加入到平底试管中，加入12mg抗坏血酸搅拌均匀后，置于95℃反应20min形成0.8cm3石墨烯水凝胶。
(2)将上述0.8cm3石墨烯水凝胶浸入到2.4mL甲醇中6h进行溶剂置换。然后将凝胶充分浸入到5mL，5mmol/L的六水合硝酸锌的40℃甲醇中，2h后将凝胶取出。再浸入到5mL，40mmol/L的2-甲基咪唑的40℃甲醇中，将反应体系静置2h。将凝胶用硝酸锌和2-甲基咪唑的40℃甲醇溶液交替浸泡8次后，放到甲醇中浸泡1h，以除去未反应的物质。最后将凝胶取出，放在40℃烘箱干燥12h，即制得石墨烯与ZIF-8复合气凝胶。其密度见表1。
实施例4
(1)石墨烯水凝胶的制备。以325目鳞片石墨为原料，通过Hummer法制备氧化石墨烯，得到4mg/mL的氧化石墨烯水溶液。取3mL氧化石墨烯水溶液加入到平底试管中，加入12mg抗坏血酸搅拌均匀后，置于95℃反应20min形成1.7cm3石墨烯水凝胶。
(2)将上述1.7cm3石墨烯水凝胶浸入到6.8mL异丙醇中12h进行溶剂置换。然后将凝胶充分浸入到5mL，40mmol/L的六水合硝酸锌的25℃异丙醇中，2h后将凝胶取出。再浸入到5mL，80mmol/L的2-甲基咪唑的25℃异丙醇中，将反应体系静置4h。将凝胶用硝酸锌和2-甲基咪唑的25℃异丙醇溶液交替浸泡8次后，放到异丙醇中浸泡30min，以除去未反应的物质。最后将凝胶取出，放在60℃烘箱干燥24h，即制得石墨烯与ZIF-8复合气凝胶。其密度见表1。
实施例5
工艺流程同实施例1，不同的是分别用硝酸锌和2-甲基咪唑的甲醇溶液循环浸泡2次。制得气凝胶的密度为11.0mg/cm3，ZIF-8重量百分比为70％。CO2吸附性能见表2。
实施例6
工艺流程同实施例1，不同的是分别用硝酸锌和2-甲基咪唑的甲醇溶液循环浸泡4次。制得气凝胶的密度为11.7mg/cm3，ZIF-8重量百分比为73％。CO2吸附性能见表2。
实施例7
工艺流程同实施例1，不同的是分别用硝酸锌和2-甲基咪唑的甲醇溶液循环浸泡6次。制得气凝胶的密度为20.5mg/cm3，ZIF-8重量百分比为83％。CO2吸附性能见表2。
对比例1
石墨烯气凝胶的制备。以325目鳞片石墨为原料，通过Hummer法制备氧化石墨烯，得到4mg/mL的氧化石墨烯水溶液。取3mL氧化石墨烯水溶液加入到平底试管中，加入12mg抗坏血酸搅拌均匀后，置于95℃反应25min形成石墨烯水凝胶。将该水凝胶进行冷冻干燥制得1.4cm3石墨烯气凝胶。该气凝胶的密度为5.0mg/cm3，CO2吸附性能见表2。
对比例2
(1)石墨烯气凝胶的制备。以325目鳞片石墨为原料，通过Hummer法制备氧化石墨烯，得到4mg/mL的氧化石墨烯水溶液。取3mL氧化石墨烯水溶液加入到平底试管中，加入12mg抗坏血酸搅拌均匀后，置于95℃反应25min形成石墨烯水凝胶。将该水凝胶进行冷冻干燥制得1.4cm3石墨烯气凝胶。
(2)将上述墨烯气凝胶充分浸入到5mL，10mmol/L的六水合硝酸锌的40℃甲醇中，2h后将凝胶取出。再浸入到5mL，80mmol/L的2-甲基咪唑的40℃甲醇中，将反应体系静置2h。将凝胶用硝酸锌和2-甲基咪唑的40℃甲醇溶液交替浸泡4次后，放到甲醇中浸泡1h，以除去未反应的物质。最后将凝胶取出，放在40℃烘箱干燥12h，即制得石墨烯与ZIF-8复合气凝胶。该气凝胶的密度为10.8mg/cm3，ZIF-8重量百分比为69％。CO2吸附性能见表2。
图1展示了实施例1复合气凝胶的内部结构状态，石墨烯气凝胶的三维蜂窝状结构在50-500μm之间，属于大孔。图2展示了实施例1所得的石墨烯与ZIF-8复合气凝胶的表面形态，ZIF-8均匀地分布于石墨烯气凝胶表面。而对比例2所得的石墨烯与ZIF-8复合气凝胶中，在石墨烯片层表面ZIF-8分布稀疏，且ZIF-8的复合量小于实施例1。图3展示了石墨烯与ZIF-8复合气凝胶的孔径分布曲线，可以看出，孔径大小主要为0.9～1.2nm的微孔、3～7nm的介孔，结合扫描电镜看到的石墨烯气凝胶的三维蜂窝状结构，可以得出石墨烯与ZIF-8复合气凝胶的多孔级结构。图4为本发明实施例1所得的石墨烯与ZIF-8复合气凝胶、对比例1所得纯石墨烯基气凝胶和纯ZIF-8样品在298K，1atm下CO2吸附量曲线。可以看出本发明所制备的石墨烯与ZIF-8复合气凝胶具有很好的二氧化碳吸附性能，高于同等条件下纯石墨烯气凝胶或纯ZIF-8晶体的二氧化碳吸附量。
Claims (6)
1.一种石墨烯与ZIF-8复合气凝胶，其特征在于：该复合气凝胶的重量百分比组分为石墨烯占15％～30％，ZIF-8占70％～85％；该复合气凝胶的密度为11.0mg/cm3～23.1mg/cm3；该复合气凝胶具有多级孔状结构，其中大孔径尺寸分布范围为500μm～50μm，介孔径分布范围为7nm～3nm，微孔径分布范围为小于1.2nm；在298K，1atm条件下，该气凝胶对CO2的吸附量为0.80mmol/g～0.99mmol/g。
2.制备如权利要求1所述石墨烯与ZIF-8复合气凝胶的制备方法，其特征在于该方法包括以下步骤：
(1)石墨烯水凝胶的制备：将氧化石墨烯分散液进行化学还原制得石墨烯水凝胶；还原剂为水合肼、抗坏血酸和碘化氢中的一种或几种，还原温度为90℃～95℃，还原时间为20min～40min，氧化石墨烯与还原剂的质量比为1:2～1:1；
(2)石墨烯与ZIF-8复合气凝胶的制备：将步骤(1)所得石墨烯水凝胶浸入甲醇或异丙醇中进行溶剂置换，再将其多次交替浸入到无机锌盐的有机溶液和2-甲基咪唑的有机溶液中，经浸泡洗涤干燥，最终得到具有不同组分比例的石墨烯与ZIF-8复合气凝胶材料；
置换溶剂与石墨烯水凝胶的体积比为3:1～4:1，置换时间为6h～12h；
步骤(2)中无机锌盐溶液和2-甲基咪唑溶液浓度分别为5mmol/L～10mmol/L和40mmol/L～80mmol/L，无机锌盐溶液和2-甲基咪唑溶液体积比为1:1，反应温度为25℃～40℃，反应时间为2h～4h。
3.如权利要求2所述的方法，其特征在于，步骤(2)中的无机锌盐为硝酸锌或氯化锌。
4.如权利要求2所述的方法，其特征在于，步骤(2)中的有机溶液中有机溶剂为甲醇或异丙醇。
5.如权利要求2所述的方法，其特征在于，步骤(2)中浸泡时间为30min～60min。
6.如权利要求2所述的方法，其特征在于，步骤(2)中干燥的温度为40～60℃，干燥时间为12h～24h。
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