CN110876960B - 0d/2d导电金属化合物/石墨烯复合功能材料的制备方法 - Google Patents
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Abstract
本发明公开了一种0D/2D导电金属化合物/石墨烯复合功能材料的制备方法。所述方法将硝酸银溶于水中，先加入1‑甲基‑2吡咯烷酮，搅拌混合均匀后加入石墨烯水凝胶，静置反应得到石墨烯水凝胶/银复合材料，然后将石墨烯水凝胶/银复合材料加入到饱和的7，7，8，8‑四氰基对苯二醌二甲烷的乙腈溶液中，静置反应即得0D/2D导电金属化合物/石墨烯复合功能材料。本发明制得的0D/2D导电金属化合物/石墨烯复合功能材料具有良好的电化学氧还原性能，适用于能源、催化等领域。
Description
技术领域
本发明涉及一种0D/2D导电金属化合物/石墨烯复合功能材料的制备方法，属于复合催化材料技术领域。
背景技术
低维纳米材料因其小尺寸效应、表面与界面效应、量子尺寸效应等重要特性而具有广泛的应用前景。零维材料由于表面原子占了显著比例，其表面态密度将大大增加，在一些催化反应中具有更丰富的活性位点；同时，对于这样小尺寸的颗粒，由于维度的降低各种量子效应(量子是寸效应、量子局限效应、量子隧道效应、量子干涉效应等)十分显著。但0D材料其表面能较大，容易团聚形成块体材料而失活。
导电金属化合物(Ag-TCNQ)可以在多种条件下合成，例如自发电解技术、化学气相沉积、光结晶法、液相化学转换等。这些方法合成的导电金属化合物的微观形貌一般为二维的纳米线，并且因为材料独特的光学和电子性质，使其在存储设备和光学激光盘制造方面有很大的应用前景。
二维纳米材料由于其维度的降低有很多特殊的性能。尤其以石墨烯为例，其十分良好的强度、柔韧、导电、导热、光学特性，在物理学、材料学、电子信息、计算机、航空航天等领域都得到了长足的发展，是目前发现的最薄、强度最大、导电导热性能最强的一种新型纳米材料。通过对0D/2D材料的设计及结合，可以结合两者的优势，得到具有高活性和稳定性的材料。目前已经有一些基于石墨烯的0D/2D材料，例如：石墨烯负载氧化锌量子点，石墨烯负载铜等金属纳米粒子，石墨烯负载钴纳米粒子等等，并在光学、电容器等领域展现了非常诱人的应用前景。然而，基于石墨烯和金属有机化合物的 0D/2D的复合材料至今还未有报道。
发明内容
本发明的目的在于提供一种导电性良好、制备方法简单且具有优异电催化性能的0D/2D导电金属化合物/石墨烯复合功能材料的制备方法。
实现本发明目的的技术解决方案为：
0D/2D导电金属化合物/石墨烯复合功能材料的制备方法，以硝酸银、对苯二醌二甲烷、氧化石墨等为前驱体通过简单的化学过程合成复合功能材料，具体包括以下步骤：
步骤1，将硝酸银溶于水中，按硝酸银的质量与1-甲基-2吡咯烷酮的体积比为0.9～1.1：1，先加入1-甲基-2吡咯烷酮，搅拌混合均匀后加入石墨烯水凝胶，静置反应 3～5h，反应结束后，乙腈洗涤，得到石墨烯水凝胶/银复合材料；
步骤2，将石墨烯水凝胶/银复合材料加入到饱和的7，7，8，8-四氰基对苯二醌二甲烷的乙腈溶液中，静置反应，反应结束后用乙醇和水充分洗涤，得到0D/2D导电金属化合物/石墨烯复合功能材料(Ag-TCNQ/石墨烯复合材料)。
优选地，步骤1中，所述的反应时间为4h。
优选地，步骤1中，所述的硝酸银的浓度为1mg/ml。
优选地，步骤2中，所述的反应时间为2小时。
与现有技术相比，本发明具有以下优点：
(1)金属有机化合物采用Ag与7，7，8，8-四氰基对苯二醌二甲烷进行配位化合反应，其中有机物配体7，7，8，8-对苯二醌二甲烷(TCNQ)是一种电子受体分子，可以与金属Ag进行配位化合反应，形成的Ag-TCNQ，具有较好的导电性；
(2)制备方法简单，反应条件温和，在室温下静置，通过溶液的扩散和溶质的结晶逐步析出就能生成目标产物，并且这一过程缓慢温和进行，使其产物也能较为均一和稳定；
(3)本发明制得的0D/2D导电金属化合物/石墨烯复合功能材料具有优异的氧还原性能，对材料进行氧还原(ORR)测试，表现出较为优异的氧还原生成双氧水的性能，反应起始电位为0.82V vs.RHE，双氧水产率为0.35mg/h，在电催化领域存在潜在的应用价值。
附图说明
图1是本发明的0D/2D导电金属化合物/石墨烯复合功能材料的制备流程示意图。
图2(a)为实施例1制备的0D/2D导电金属化合物/石墨烯复合功能材料的TEM 图，2(b)为实施例1制备出的材料的STEM图。
图3(a)为实施例2制备的0D/2D导电金属化合物/石墨烯复合功能材料的XRD图，图3(b)为实施例2制备的0D/2D导电金属化合物/石墨烯复合功能材料的Raman图。
图4(a)为实施例4制备的0D/2D导电金属化合物/石墨烯复合功能材料的ORR LSV曲线，图4(b)为实施例5制备的复合材料不同电位下双氧水产率图，图4(c)为对比例2步骤二中材料在硝酸银溶液中的不同的反应时间所得的LSV曲线。
具体实施方式
下面结合附图和具体实施方式对本发明作进一步详细说明。
下述实施例中采用的石墨烯水凝胶的制备参考文献[Three-Dimensional N-Doped Graphene Hydrogel/NiCo Double Hydroxide Electrocatalysts for HighlyEfficient Oxygen Evolution]。
实施例1
步骤一，取2ml质量浓度为2mg/ml的氧化石墨放入容器，150℃下在密闭反应釜中反应6小时，待其自然冷却后取出产物，制备得到石墨烯水凝胶；
步骤二，将20mg硝酸银固体溶解于1ml去离子水中，再加入19ml甲基吡咯烷酮，混合均匀得到硝酸银溶液。将步骤一得到的石墨烯水凝胶静置在硝酸银溶液中反应4小时，然后用乙腈溶剂充分洗涤；
步骤三：将7，7，8,8-四氰基对苯二醌二甲烷加入10ml乙腈中，充分混合，再将步骤二得到的材料放入7，7，8，8-四氰基对苯二醌二甲烷溶液，中静置反应2小时，然后用水充分清洗；
步骤四：将第三步得到的产物放在1ml水中，超声30min，用去离子水进行离心洗涤并分离产物，然后低温干燥即得到Ag-TCNQ/石墨烯复合材料。
图2中的TEM测试及STEM测试可以看出0D的颗粒的大小为5nm左右。
实施例2
步骤一，取2ml质量浓度为2mg/ml的氧化石墨放入容器，150℃下在密闭反应釜中反应6小时，待其自然冷却后取出产物，制备得到石墨烯水凝胶；
步骤二：将200mg硝酸银固体溶解于1ml去离子水中，再加入19ml甲基吡咯烷酮，混合均匀得到硝酸银溶液。将步骤一得到的石墨烯水凝胶静置在硝酸银溶液中反应 4小时，然后用乙腈溶剂充分清洗；
步骤三：将100mg 7，7，8，8-四氰基对苯二醌二甲烷加入10ml乙腈中，充分混合，再将步骤二得到的材料放入7，7，8，8-四氰基对苯二醌二甲烷溶液中，静置反应 2小时，然后用水充分清洗；
步骤四：将第三步得到的产物放在1ml水中，超声30min，用去离子水进行离心洗涤并分离产物，然后低温干燥即得到Ag-TCNQ/石墨烯复合材料。
由于硝酸银溶液的浓度变大，图3(b)拉曼谱图中图中Ag/石墨烯中Ag金属的峰更尖锐明显，说明在此过程中确实有Ag粒子形成并生长在还原氧化石墨烯的表面。
实施例3
步骤一，取2ml质量浓度为2mg/ml的氧化石墨放入容器，150℃下在密闭反应釜中反6小时，待其自然冷却后取出产物，制备得到石墨烯水凝胶；
步骤二：将20mg硝酸银固体溶解于1ml去离子水中，再加入19ml甲基吡咯烷酮，混合均匀得到硝酸银溶液。将步骤一得到的石墨烯水凝胶静置在硝酸银溶液中反应4小时，然后用乙腈溶剂充分洗涤；
步骤三：将100mg 7，7，8，8-四氰基对苯二醌二甲烷加入10ml乙腈中，充分混合，再将步骤二得到的材料放入7，7，8，8-四氰基对苯二醌二甲烷溶液中，静置反应 10小时，然后用水充分清洗；
步骤四：将第三步得到的产物放在1ml水中，超声30min，用去离子水进行离心洗涤并分离产物，然后低温干燥即得到Ag-TCNQ/石墨烯复合材料。
实施例4
步骤一，取2ml质量浓度为2mg/ml的氧化石墨放入容器，150℃下在密闭反应釜中反应6小时，制备得到石墨烯水凝胶；
步骤二：将20mg硝酸银固体溶解于1ml去离子水中，再加入19ml甲基吡咯烷酮，混合均匀得到硝酸银溶液。将步骤一得到的石墨烯水凝胶静置在硝酸银溶液中反应4小时，然后用乙腈溶剂充分洗涤；
步骤三：将100mg 7，7，8，8-四氰基对苯二醌二甲烷加入10ml乙腈中，充分混合，再将步骤二得到的材料放入7，7，8，8-四氰基对苯二醌二甲烷溶液中，静置反应 2小时，然后用乙醇和水充分清洗；
步骤四：将第三步得到的产物放在1ml水中，超声30min，用去离子水进行离心洗涤并分离产物，然后低温干燥即得到Ag-TCNQ/石墨烯复合材料。
步骤五：称取5mg步骤四的产物，与10μL 5wt％Nafion溶液、75mL异丙醇、 25mL去离子水混合均匀形成悬浮液。
步骤六：用移液器取10μL滴在玻碳电极上，室温下静置干燥后进行ORR制备双氧水的电化学性能测试。
图4(a)中为在不同转速下旋转圆盘圆环电极的电化学测试，测试显示反应的起始电位为0.82V vs.RHE。
实施例5
步骤一，取2ml质量浓度为2mg/ml的氧化石墨放入容器，在其中再放入一片面积为1cm*1cm大小的碳布，150℃下在密闭反应釜中反应6小时，待其自然冷却后取出产物，轻轻刮去多余的水凝胶制备得到石墨烯水凝胶/碳布；
步骤二：将20mg硝酸银固体溶解于1ml去离子水中，再加入19ml甲基吡咯烷酮，混合均匀得到硝酸银溶液。将步骤一得到的石墨烯水凝胶静置在硝酸银溶液中反应4小时，然后用乙腈溶剂充分洗涤；
步骤三：将100mg 7，7，8，8-四氰基对苯二醌二甲烷加入10ml乙腈中，充分混合，再将步骤二得到的材料放入7，7，8，8-四氰基对苯二醌二甲烷溶液，中静置反应 2小时，然后用水充分清洗；
步骤四：产物在电解池中进行ORR产双氧水的产率的测试。
图4(b)中为ORR产双氧水产率的测试，实验测得双氧水产率为0.35mg/h。
对比例1
步骤一，取2ml质量浓度为2mg/ml的氧化石墨放入容器，150℃下在密闭反应釜中反应6小时，待其自然冷却后取出产物，制备得到石墨烯水凝胶；
步骤二：将20mg硝酸银固体溶解于1ml去离子水中，再加入19ml甲基吡咯烷酮，混合均匀得到硝酸银溶液。将步骤一得到的石墨烯水凝胶静置在硝酸银溶液中反应2小时，然后用乙腈溶剂充分洗涤；
步骤三：将7，7，8,8-四氰基对苯二醌二甲烷加入10ml乙腈中，充分混合，再将步骤二得到的材料放入7，7，8，8-四氰基对苯二醌二甲烷溶液中，静置反应2小时，然后用水充分清洗；
步骤四：将第三步得到的产物放在1ml水中，超声30min，用去离子水进行离心洗涤并分离产物，然后低温干燥即得到Ag-TCNQ/石墨烯复合材料。
对比例2
步骤一，取2ml质量浓度为2mg/ml的氧化石墨放入容器，150℃下在密闭反应釜中反应6小时，待其自然冷却后取出产物，制备得到石墨烯水凝胶；
步骤二：将20mg硝酸银固体溶解于1ml去离子水中，再加入19ml甲基吡咯烷酮，混合均匀得到硝酸银溶液。将步骤一得到的石墨烯水凝胶静置在硝酸银溶液中反应12 小时，然后用乙腈溶剂充分洗涤；
步骤三：将7，7，8,8-四氰基对苯二醌二甲烷加入10ml乙腈中，充分混合，再将步骤二得到的材料放入7，7，8，8-四氰基对苯二醌二甲烷溶液中中静置反应2小时，然后用水充分清洗；
步骤四：将第三步得到的产物放在1ml水中，超声30min，用去离子水进行离心洗涤并分离产物，然后低温干燥即得到Ag-TCNQ/石墨烯复合材料。
如图4(c)所示为步骤二中材料在硝酸银溶液中的不同的反应时间所得的LSV曲线，分析可得当反应时间为4小时为最佳反应时间。
Claims (4)
1.0D/2D导电金属化合物/石墨烯复合功能材料的制备方法，其特征在于，具体包括以下步骤：
步骤1，将硝酸银溶于水中，按硝酸银的质量与1-甲基-2吡咯烷酮的体积比为0.9~1.1mg：1mL，先加入1-甲基-2吡咯烷酮，搅拌混合均匀后加入石墨烯水凝胶，静置反应3~5h，反应结束后，乙腈洗涤，得到石墨烯水凝胶/银复合材料；
步骤2，将石墨烯水凝胶/银复合材料加入到饱和的7，7，8，8-四氰基对苯二醌二甲烷的乙腈溶液中，静置反应，反应结束后用乙醇和水充分洗涤，得到0D/2D导电金属化合物/石墨烯复合功能材料。
2.根据权利要求1所述的制备方法，其特征在于，步骤1中，反应时间为4h。
3.根据权利要求1所述的制备方法，其特征在于，步骤1中，硝酸银的浓度为 1mg/mL 。
4.根据权利要求1所述的制备方法，其特征在于，步骤2中，反应时间为 2小时。
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