CN108597911A - 一种具有贯通介孔结构的二维氮掺杂碳材料及其制备方法 - Google Patents
一种具有贯通介孔结构的二维氮掺杂碳材料及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种具有贯通介孔结构的二维氮掺杂碳材料，使用聚苯乙烯‑b‑聚环氧乙烷(PS‑b‑PEO)球形胶束作为孔结构导向剂软模板，采用Co2+‑Ni2+衍生层状双层金属氢氧化物(LDH)纳米片为2D牺牲模板，间苯二胺为碳前驱体。本发明同时提供一种二维氮掺杂碳材料的制备方法，包括以下步骤：LDH自牺牲模板的制备；与BCP、间苯二胺共组装形成六角形纳米片；具有贯通介孔的六角形氮掺杂碳纳米片的制备。本发明直接利用嵌段共聚物(BCP)与LDH的协同共组装，发挥LDH原位自牺牲优势，获得了具有贯通介孔的形状规则的纳米片复合材料。该材料具有良好的氧化还原催化性能和优异的结构稳定性。与现有技术相比本发明兼具成本效益，且合成方法简单，所用材料环境友好。
Description
技术领域
本发明涉及一种应用于催化氧气还原的二维材料，尤其涉及一种双模板法合成具有贯通介孔的氮掺杂碳纳米片的方法。
背景技术
氧还原反应(ORR)是燃料电池的关键一步，但其动力学缓慢从而限制了能量转换效率。常用作ORR的主流催化材料为金属Pt，但由于成本高、资源贮存有限、耐久性差等原因，使其大规模工业化生产受限。因而找到氧还原性能优异又兼具成本效益的替代品，是非常有意义的。经过多年研究发现，杂原子掺杂(如N原子)无金属碳质催化剂可以改善O2的吸附性，从而提高ORR性能；另外，合理设计碳材料的介观结构，对其活性位点进行有效利用，增大可及表面也可提高ORR性能；同时，所采用的高分子材料其低成本这一特点是不容忽视的。
故而有利于活性位点暴露的二维碳材料成为ORR应用强有力的候选者，若同时控制适当的介孔结构，可以促进传质作用，缩短O2分子到活性位点的扩散距离，从而获得更好的氧还原性能。有研究人员将具有介孔性质的导电高分子覆盖在石墨烯两面，形成二维三明治异质结构，有效地减少了石墨烯团聚，提高了电化学性能。例如，冯新亮团队利用PEO-b-PS嵌段聚合物为模板，在石墨烯片两侧原位生成介孔聚吡咯，形成二维三明治异质结构的材料(如图1所示)。该材料具有可调节的孔径(5-20nm)和厚度(35-45nm)，能够应用于超级电容器(Nat.Commun.2015,6,8817)。但该材料所采用的三明治中心层无法进行模板去除，故虽然具有较大的比表面积，但其上介孔为非贯通孔道，大大降低了传质作用，降低了活性物质扩散距离。
目前尚未报道ORR性能优异的以二维无机纳米片为原位牺牲模板的二维氮掺杂碳材料。现有的硬模板制备介孔材料的方法步骤繁琐、模板不易去除，且使用的试剂毒性强、污染性强；且制备的二维介孔复合材料虽具有较大的比表面积，但是贯通介孔很少，氧还原催化活性改善不够。
因此，本领域的技术人员致力于结构优化，开发使用适合的无机纳米片作为原位自牺牲模板的二维氮掺杂材料。
发明内容
有鉴于现有技术的上述缺陷，本发明所要解决的技术问题是：1、提供一种使用适合的无机纳米片作为原位自牺牲模板的二维氮掺杂材料；2、通过结构优化，综合了二维材料活性位点可及性高，以及贯通介孔极大地促进传质作用、缩短O2分子扩散距离的结构优势，使材料获得优异的ORR活性和良好的结构稳定性；3、提供一种二维氮掺杂材料的制备方法，制备方法简单、合成条件温和、使用无毒或低毒试剂、保证化学反应的环境友好性。
为实现上述目的，本发明提供一种具有贯通介孔结构的二维氮掺杂碳材料，使用聚苯乙烯-b-聚环氧乙烷(PS-b-PEO)球形胶束作为孔结构导向剂软模板，采用Co2+-Ni2+衍生层状双层金属氢氧化物(LDH)纳米片为2D牺牲模板，间苯二胺(mPD)为碳前驱体。
本发明同时提供一种应用双模板法合成所述的二维氮掺杂碳材料的制备方法，所述方法包括以下步骤：
步骤1、层状双层金属氢氧化物(LDH)自牺牲模板的制备；
步骤2、应用双模板法组装六角形纳米片；
步骤3、具有贯通介孔的六角形氮掺杂碳纳米片(NMHCSs)的制备。
进一步地，所述步骤1采用以六亚甲基四胺(HMT)作为水解剂的共沉淀法制备Co2+-Ni2+衍生的六角形LDH纳米片，具体包括以下步骤：
步骤1.1、将氯化钴、氯化镍、聚乙烯吡咯烷酮(PVP)和六亚甲基四胺(HMT)于去离子水中溶解完全；
步骤1.2、在磁力搅拌和氮气保护下回流5小时；
步骤1.3、经过滤纯化步骤、再室温风干收集得到产物层状双层金属氢氧化物(LDH)自牺牲模板。
更进一步地，所述步骤1.1中的聚乙烯吡咯烷酮的分子量为15000；所述步骤1.3的提取纯化步骤为过滤后取沉淀物，用去离子水和无水乙醇洗涤三次以上。
进一步地，所述步骤2具体包括以下步骤：
步骤2.1、将PS-b-PEO嵌段共聚物于THF、乙醇和H2O的混合溶液中组装为球形胶束溶液；
步骤2.2、将LDH纳米片和间苯二胺(mPD)加入到所述球形胶束溶液中以进行协同共组装为三明治结构；
步骤2.3、滴加过硫酸铵水溶液引发mPD聚合，在聚合过程过中H+释放，满足LDH溶解的条件而伴随发生无机纳米片的原位自牺牲，从而获得二维PS-b-PEO/PmPD纳米片；
步骤2.4、清洗所述二维PS-b-PEO/PmPD纳米片即可得具有贯通介孔的六角形二维纳米片复合材料。
更进一步地，所述步骤2.1中THF、乙醇、H2O的相对体积比为1：1：2；所述步骤2.2中LDH纳米片和间苯二胺的相对重量比为3:2。
进一步地，所述步骤3具体为：将所述纳米片复合材料于惰性气氛保护下进行热解，获得氮掺杂的具有贯通介孔孔道的六方碳纳米片。
更进一步地，所述步骤3的热解温度为800℃。
本发明直接利用嵌段共聚物(BCP)与层状双层金属氢氧化物(LDH)的协同共组装，发挥LDH原位自牺牲优势，获得了具有贯通介孔的形状规则的纳米片复合材料。得到的新颖形貌为2-5μm六角形LDH纳米片，介孔孔径16±1nm，纳米片厚度约为20nm，材料比表面积为256m2g-1。
本发明综合了二维纳米片大比表面积与贯通介孔对于电化学性能的贡献，ORR测试得其半波电位(E1/2)和极限电流密度(JL)分别为0.77V和5.0mA cm-2，优于许多报道的具有更高表面积(>400m2g-1)但缺乏贯通介孔的二维碳基材料，且具有优异的结构稳定性。与现有技术相比本发明兼具成本效益，且合成方法简单，所用材料环境友好。
以下将结合附图对本发明的构思、具体结构及产生的技术效果作进一步说明，以充分地了解本发明的目的、特征和效果。
附图说明
图1是现有技术2D介孔聚吡咯纳米片合成路线示意图；
图2是本发明的一个较佳实施例的双模板法合成具有贯通介孔的氮掺杂碳材料路线示意图；
图3是本发明的一个较佳实施例的LDH扫描电子显微图；
图4是本发明的一个较佳实施例的六角形纳米片煅烧前透射电子显微图；
图5是本发明的一个较佳实施例的六角形纳米片煅烧后扫描电子显微图；
图6是本发明的一个较佳实施例的LDH纳米片原子力显微图。
具体实施方式
以下参考说明书附图介绍本发明的多个优选实施例，使其技术内容更加清楚和便于理解。本发明可以通过许多不同形式的实施例来得以体现，本发明的保护范围并非仅限于文中提到的实施例。
实施例1PS-b-PEO二嵌段共聚物(BCP)的制备
采用原子转移自由基聚合(ATRP)方法合成多分散性指数(PDI)为1.05的二嵌段共聚物PS113-b-PEO114作为孔结构导向剂软模板。
实施例2具有贯通介孔结构的二维氮掺杂碳材料的制备
合成示意图如图2所示，包括以下三个步骤：
步骤1、制备层状双层金属氢氧化物(LDH)。
步骤1.1、将3.5mmol氯化钴、1.75mmol氯化镍、0.35mmol聚乙烯吡咯烷酮(PVP，Mw＝15000)和31.5mmol六亚甲基四胺(HMT)于700ml去离子水中溶解完全。
步骤1.2、在连续磁力搅拌和氮气保护下将溶液回流5小时后。
步骤1.3、过滤取沉淀物，并用去离子水和无水乙醇洗涤三次以上，最后在室温下风干后收集得到LDH，如图3所示，LDH为六角形二维纳米结构。
步骤2、制备介孔六角形碳纳米片。
步骤2.1、将0.06g PS133-b-PEO114共聚物溶解于12mLTHF、12mL乙醇和24mL H2O的混合溶液中以自组装为球形胶束聚集体。
步骤2.2、将120mg LDH纳米片和80mg间苯二胺(mPD)加入到溶液中，温和搅拌混合溶液1小时以进行充分吸附。
步骤2.3、将20mL过硫酸铵(APS)水溶液(浓度：20mg/mL)缓慢滴加至上述混合溶液中以引发mPD的聚合，聚合反应持续24小时，离心收集产物。
步骤2.4、用乙醇和水洗涤至少3个循环，产物于40℃下空气干燥12小时，得到如图4所示的PS-b-PEO/PmPD纳米复合材料。
步骤3、六角形介孔纳米片的碳化：将收集得到的纳米片复合材料在氮气气氛下、以2℃/min的加热速率升温至在800℃后，保温2小时进行碳化，得到如图5和图6所示六角形氮掺杂贯通介孔纳米片(NMHCSs)，图6清晰的显示了六角形二维纳米的结构。所得六角形氮掺杂贯通介孔纳米片可作为氧还原反应的良催化剂应用。
以上详细描述了本发明的较佳具体实施例。应当理解，本领域的普通技术无需创造性劳动就可以根据本发明的构思作出诸多修改和变化。因此，凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。
Claims (10)
1.一种具有贯通介孔结构的二维氮掺杂碳材料，其特征在于，使用聚苯乙烯-b-聚环氧乙烷(PS-b-PEO)球形胶束作为孔结构导向剂软模板，采用Co2+-Ni2+衍生层状双层金属氢氧化物(LDH)纳米片为2D牺牲模板，间苯二胺(mPD)为碳前驱体。
2.一种应用双模板法合成权利要求1所述的二维氮掺杂碳材料的制备方法，其特征在于，所述方法包括以下步骤：
步骤1、层状双层金属氢氧化物(LDH)自牺牲模板的制备；
步骤2、应用双模板法组装六角形纳米片；
步骤3、具有贯通介孔的六角形氮掺杂碳纳米片(NMHCSs)的制备。
3.如权利要求2所述的二维氮掺杂碳材料的制备方法，其特征在于，所述步骤1具体包括以下步骤：
步骤1.1、将氯化钴、氯化镍、聚乙烯吡咯烷酮(PVP)和六亚甲基四胺(HMT)于去离子水中溶解完全；
步骤1.2、在磁力搅拌和氮气保护下回流5小时；
步骤1.3、经过滤纯化步骤、再室温风干收集得到产物层状双层金属氢氧化物(LDH)自牺牲模板。
4.如权利要求2所述的二维氮掺杂碳材料的制备方法，其特征在于，所述步骤2具体包括以下步骤：
步骤2.1、将PS-b-PEO嵌段共聚物于THF、乙醇和H2O的混合溶液中组装为球形胶束溶液；
步骤2.2、将LDH纳米片和间苯二胺(mPD)加入到所述球形胶束溶液中以进行协同共组装为三明治结构；
步骤2.3、滴加过硫酸铵水溶液引发mPD聚合，获得二维PS-b-PEO/PmPD纳米片；
步骤2.4、清洗所述二维PS-b-PEO/PmPD纳米片即可得具有贯通介孔的六角形二维纳米片复合材料。
5.如权利要求2所述的二维氮掺杂碳材料的制备方法，其特征在于，所述步骤3具体为：将所述纳米片复合材料于惰性气氛保护下进行热解，获得氮掺杂的具有贯通介孔孔道的六方碳纳米片。
6.如权利要求3所述的二维氮掺杂碳材料的制备方法，其特征在于，所述步骤1.3的提取纯化步骤为过滤后取沉淀物，用去离子水和无水乙醇洗涤三次以上。
7.如权利要求3所述的二维氮掺杂碳材料的制备方法，其特征在于，所述步骤1.1中的聚乙烯吡咯烷酮的分子量为15000。
8.如权利要求4所述的二维氮掺杂碳材料的制备方法，其特征在于，所述步骤2.1中THF、乙醇、H2O的相对体积比为1：1：2。
9.如权利要求4所述的二维氮掺杂碳材料的制备方法，其特征在于，所述步骤2.2中LDH纳米片和间苯二胺的相对重量比为3:2。
10.如权利要求5所述的二维氮掺杂碳材料的制备方法，其特征在于，所述步骤3中的热解温度为800℃。
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