CN107175107A - 蛋黄蛋壳结构空心球复合材料的制备方法 - Google Patents
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Abstract
蛋黄蛋壳结构空心球复合材料的制备方法，涉及纳米催化剂生产技术领域。将CTAB的水溶液、HAuCl4和硼氢化钠混合反应，得AuNRs纳米粒子溶液，再与表面活性剂F127、邻甲氧基苯胺、过硫酸铵混合后静置，得AuNRs/POMA复合材料；超声条件下，再将AuNRs/POMA复合材料的水溶液和HCl、高锰酸钾水溶液依次混合搅拌反应，经烘干煅烧，得复合材料AuNRs@C/Mn3O4。结果表明该复合材料在碱性电解质中表现出良好的析氧电催化性能。
Description
技术领域
本发明涉及纳米催化剂生产技术领域。
背景技术
电解水制氢气和氧气被认为是储存可再生资源（如风能，太阳能等）的可行方法，将风能、太阳能通过电能转化为能量较高的化学燃料。
电解水装置能广泛应用面临的一大难题是制备价格低廉高效的电催化剂。贵金属和贵重金属氧化物，包括Au、Ru、PtO2、RuO2具有较好的电催化活性，且锰氧化合物作为电催化剂已被广泛报道。最近研究发现，过渡金属氧化物（如MnOx、CoO、NiO）与贵金属（Pt、Au、Pd）具复合有较好的电催化活性。而导电聚合物的加入，能增强复合材料的导电性，常见的导电聚合物有聚苯胺（PANI）及苯胺衍生物、聚吡咯（Pyy）等。
发明内容
本发明的目的在于提供一种活性位点利用率高的蛋黄蛋壳结构空心球的制备方法。
本发明包括以下步骤：
1）将CTAB的水溶液、HAuCl4和硼氢化钠混合反应，得AuNRs纳米粒子溶液。
2）超声条件下，将表面活性剂F127溶于水中，加入所述金纳米粒子溶液，常温搅拌1 h后加入邻甲氧基苯胺，搅拌1h后加入引发剂过硫酸铵，常温搅拌2 h后静置4 h，得AuNRs/POMA复合材料；
先常温搅拌1 h，在1h内表面活性剂F127能够完全地分散在金纳米棒溶液中，并且均匀地包围在金纳米棒表面，起到修饰金纳米棒表面的作用。若时间过短，F127不能完全修饰金纳米棒表面；若时间过长，则影响复合效率。然后再加入邻甲氧基苯胺搅拌1h，在该时间内邻甲氧基苯胺能够完全的均匀缓慢地包裹在金纳米棒表面。若时间过短，邻甲氧基苯胺不能完全包覆上去；因为单体在1h内已经能够完全包覆上去，若时间过长，则影响复合效率。
加入引发剂过硫酸铵，常温搅拌2 h后静置4 h，在搅拌的两小时过程中，引发剂过硫酸铵均匀分散在溶液中，使邻甲氧基苯胺单体发生聚合。静置4h中，聚合物能够稳定地包裹在金纳米棒表面，使得后期不会因为剧烈搅拌或者高速离心而从金纳米棒表面脱离。
3）超声条件下，将AuNRs/POMA复合材料的水溶液和HCl混合搅拌，再加入高锰酸钾水溶液搅拌反应，得AuNRs/POMA/MnO2复合材料；
先加入HCl，经混合搅拌后再加入高锰酸钾水溶液的机理：利用聚邻甲氧基苯胺的还原性，在酸性条件下，将KMnO4还原生成MnO2，先加入HCl，使得体系达到一定的酸度，为后续的氧化还原反应做准备。
4）取AuNRs/POMA/MnO2烘干后于N2保护下煅烧，得复合材料AuNRs@C/Mn3O4。
本发明中导电聚合物选用的是苯胺衍生物邻甲氧基苯胺，贵金属纳米粒子Au以AuNRs形貌呈现，与导电聚合物、锰氧化合物，利用材料间的协同效应来提高复合材料的电催化性能。其中过硫酸铵为引发剂。
以AuNRs为核，表面活性剂F127辅助合成形貌较好的AuNRs/POMA核/壳结构复合材料。在酸性条件下，利用POMA的还原性，将KMnO4还原生成MnO2，包覆在核/壳结构复合材料的最外层，在氮气保护下对AuNRs/POMA/MnO2进行煅烧，得到一种粒径可控且具有高比表面，良好的催化活性和稳定性的具有蛋黄蛋壳结构空心球结构的复合材AuNRs@C/Mn3O4。
实验结果表明该复合材料在碱性电解质中表现出良好的析氧电催化性能。
进一步地，所述步骤2）中邻甲氧基苯胺与过硫酸铵的投料摩尔比为1∶1，使用该比例，过硫酸铵能够使邻甲氧基苯胺发生完全聚合，既达到了实验要求，也不会浪费化学药品。
所述步骤4）中煅烧温度为300℃。当煅烧温度为300℃时得到的复合材料AuNRs@C/Mn3O4结构氧析出空心球催化剂交换电流密度最大。说明该复合材料AuNRs@C/Mn3O4结构氧析出空心球催化剂不仅具有独特的形貌结构，同时具有良好的氧析出电催化性能。
附图说明
图1是制备得到的AuNRs@C/Mn3O4蛋黄@蛋壳结构空心球催化剂TEM照片。
图2是AuNRs@C/Mn3O4复合材料及其它不同材料的线性扫描伏安曲线图。
具体实施方式
一、制备工艺：
1、制备AuNRs纳米粒子溶液：
称取0.3645 g的十六烷基三甲基溴化铵（CTAB）溶于5 mL水中，然后加入浓度为0.5mmol/L的HAuCl4水溶液5 mL，加硼氢化钠0.6 mL，1200 rpm搅拌2 min后静置，得金纳米种子。以上反应都是在水浴恒温30℃中进行的。
称取3.5 g的CTAB和0.617 g的油酸钠溶于50 ℃的去离子水中，然后将温度降到30 ℃加入浓度为4 mmol/L的AgNO3水溶液9 mL，静置15 min，然后再加入浓度为1 mmol/L的HAuCl4水溶液125 mL，在700 rpm条件下搅拌90 min，调整溶液的pH至1，然后再加入浓盐酸0.75 mL，于400 rpm条件下搅拌15 min，再加入浓度为64 mmol/L的抗坏血酸水溶液0.625 mL，搅拌30 s后，加入制备好的金纳米种子0.2 mL，30 ℃恒温12 h，得AuNRs纳米粒子溶液。
2、制备AuNRs/POMA复合材料：
取0.0185 g过硫酸铵（APS）溶解在1 g水中，得过硫酸铵水溶液，待用。
从上述AuNRs纳米粒子溶液中取40mL离心去水后加2mL去离子水，形成AuNRs纳米粒子水溶液，待用。
称取0.02 g表面活性剂F127溶于8 mL水中，超声分散，加入从上述AuNRs纳米粒子水溶液，常温搅拌1 h后加入10 μL邻甲氧基苯胺，搅拌1h后加入以上全量过硫酸铵水溶液（此处邻甲氧基苯胺与过硫酸铵的摩尔比为1:1），常温搅拌2 h后再静置4 h左右，离心洗涤，将得到的复合材料离心去上层液后溶于2 mL去离子水中，得AuNRs/POMA复合材料。
3、制备AuNRs/POMA/MnO2复合材料：
将AuNRs/POMA复合材料分散在8 mL去离子水中，超声10 min左右使其分散均匀，冰浴下加入100 μL、浓度为 0.1 M的HCl水溶液，搅拌2 min后加入浓度为0.01 M的KMnO4溶液8mL，冰浴搅拌3 h，离心洗涤，得AuNRs/POMA/MnO2复合材料。
4、制备AuNRs@C/Mn3O4复合材料：
取AuNRs/POMA/MnO2烘干后，在N2保护下，于300℃高温条件下煅烧2h，得AuNRs@C/Mn3O4复合材料。
二、AuNRs@C/Mn3O4复合材料形貌特征：
如图2的TEM形貌特征图可见：制备的AuNRs@C/Mn3O4复合材料具有蛋黄蛋壳结构的形貌特征。
三、应用及效果验证：
1、将以上AuNRs@C/Mn3O4复合材料5 mg置于一个研钵中，再加入5 mg 炭黑，研磨混合后倒入5 mL烧杯中，再加950 μL 溶剂（由水和异丙醇以等体积比混合组成）和50 μL 、浓度为0.5 wt%的 Nafion混合液，经超声分散，形成电极溶液。
再用移液枪准确量取7 μL电极溶液滴加到玻碳电极表面，自然晾干，即得工作电极。
将以上AuNRs@C/Mn3O4复合材料分别以AuNRs/POMA复合材料、POMA/MnO2复合材料、AuNRs/POMA/MnO2复合材料替换，以相似的方法分别制得各相应的工作电极。
2、测定各工作电极氧析出电催化性能：
LSV测试，即稳态极化曲线测定，电解质浓度0.1 M KOH，电极活化后，调节旋转圆盘电极转速为1600 rpm，扫描速率为10 mV/s，由低电势向进行扫描即正向扫描。
比较同一电压下的不同材料的交换电流密度，这是衡量催化剂电催化活性的一个重要标准，在同一电位下交换电流密度越大，材料的析氧电催化性能越好。通常取1.85 V电位下催化剂对应的交换电流密度做对比。
图2中反映了分别以导电炭黑（Vc-72）、AuNRs/POMA复合材料（AuNRs/POMA）、POMA/MnO2复合材料（POMA/MnO2）、AuNRs/POMA/MnO2复合材料（AuNRs/POMA/MnO2）、AuNRs@C/Mn3O4复合材料（AuNRs@C/Mn3O4）为材料制得的相应工作电极在同一电压下的交换电流密度。
从图2可以得出，在电位为1.85 V(RHE)时，本发明方法制备的AuNRs@C/Mn3O4的交换电流密度最大，说明该复合材料具有良好的氧析出电催化性能。
Claims (4)
1.蛋黄蛋壳结构空心球复合材料的制备方法，其特征在于包括以下步骤：
1）将CTAB的水溶液、HAuCl4和硼氢化钠混合反应，得AuNRs纳米粒子溶液；
2）超声条件下，将表面活性剂F127溶于水中，加入所述金纳米粒子溶液，常温搅拌1 h后加入邻甲氧基苯胺，搅拌1h后加入引发剂过硫酸铵，常温搅拌2 h后静置4 h，得AuNRs/POMA复合材料；
3）超声条件下，将AuNRs/POMA复合材料的水溶液和HCl混合搅拌后，再加入高锰酸钾水溶液搅拌反应，得AuNRs/POMA/MnO2复合材料；
4）取AuNRs/POMA/MnO2烘干后于N2保护下煅烧，得复合材料AuNRs@C/Mn3O4。
2.根据权利要求1所述的制备方法，所述步骤2）中邻甲氧基苯胺与过硫酸铵的投料摩尔比为1∶1。
3.根据权利要求1或2所述的制备方法，其特征在于：所述步骤3）中反应在冰浴条件下进行。
4.根据权利要求1或2所述的制备方法，其特征在于：所述步骤4）中煅烧温度为300℃。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102408712A (zh) * | 2011-09-22 | 2012-04-11 | 扬州大学 | 聚苯胺纳米纤维/二氧化锰纳米棒复合材料及其制备方法 |
| CN103936987A (zh) * | 2014-05-08 | 2014-07-23 | 扬州大学 | 一种碳纳米管复合材料及其制备方法 |
| CN105771934A (zh) * | 2016-05-06 | 2016-07-20 | 扬州大学 | 一种核壳结构的纳米磁性吸附剂的制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408712A (zh) * | 2011-09-22 | 2012-04-11 | 扬州大学 | 聚苯胺纳米纤维/二氧化锰纳米棒复合材料及其制备方法 |
| CN103936987A (zh) * | 2014-05-08 | 2014-07-23 | 扬州大学 | 一种碳纳米管复合材料及其制备方法 |
| CN105771934A (zh) * | 2016-05-06 | 2016-07-20 | 扬州大学 | 一种核壳结构的纳米磁性吸附剂的制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| 韩娜: "金/金属氧化物复合材料的制备及其氧析出电催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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