CN110876960A - 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0.9~1.1:1,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。
2.根据权利要求1所述的制备方法,其特征在于,步骤1中,所述的反应时间为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,所述的硝酸银的浓度为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,所述的反应时间为2小时。
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