CN111668498B - 多枝晶Au@GQDs@PtPb核壳结构纳米复合材料的制备及应用 - Google Patents
多枝晶Au@GQDs@PtPb核壳结构纳米复合材料的制备及应用 Download PDFInfo
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Abstract
本发明公开了一种表面多枝晶Au@GQDs@PtPb核壳结构复合材料，以Au纳米颗粒为核，GQDs为夹层，PtPb合金作为壳层，三者结合形成了多枝晶的核壳结构。本发明采用Au@GQDs@Pt核壳纳米枝晶作为基底，通过抗坏血酸还原前驱体Pb(NO3)2反应获得Au@GQDs@PtPb核壳结构纳米复合材料。由于PtPb的电子效应和Au‑Pt金属的协同效应，GQDs的分散性以及特殊的核壳结构，大大地提高了对甲醇的电催化活性（其催化性能是商业Pt/C的30‑40倍）和对CO中毒的耐受性和稳定性，在DMFCs中具有潜在的应用前景。
Description
技术领域
本发明属于化学领域，具体涉及一种用AA作为绿色还原剂，GQDs为分散剂，多枝晶Au@GQDs@PtPb纳米催化剂的制备及对碱性甲醇催化氧化性能的研究。
背景技术
近年来，直接甲醇燃料电池（DMFCs）因其燃料来源广泛，存储运输安全方便，工作温度低，能量转换效率高，绿色友好且电池结构简单，装配灵活而引起了广泛的关注。贵金属催化剂（主要是铂）由于其有效的催化活性具有进一步改进的显著潜力，被广泛用作甲醇氧化反应（MOR）的阳极催化剂。但是，其差的抗CO中毒性，低的Pt利用率和较高的成本，严重阻碍了DMFC的商业化进程。因此，在电催化领域中，很多研究都围绕着Pt催化剂的更高效利用。而Pt基多金属核-壳催化剂由于比纯Pt催化剂具有更高的催化活性和较低的Pt消耗而备受瞩目。
Pt和Pb的协同作用提高MOR催化性能的报道很少，因此Pb的引入很受关注。首先，Pb在碱性环境中可以提供一些含氧物种，加速中间产物的氧化，这有利于提高催化剂的抗中毒性。其次，由于Pt和Pb之间的电子效应，通常可以在与Pb合金化后提高Pt基催化剂的催化性能。将Au掺入Pt基催化剂中亦带来许多好处。一方面，Au具有良好的导电性，是用于构造功能化层的出色基材，还可以有效去除氧化中间体并提高催化剂的耐久性。另一方面，Au可以改变Pt的电子结构，从而提高Pt基催化剂的催化活性。石墨烯量子点由于其良好的化学稳定性、高的电导率和大的比表面积，无论是作为催化剂载体还是分散剂都备受欢迎。核壳结构因其具有特殊的电子结构和表面性质，使其在催化、储能等领域的研究前景和价值远远高于单金属和传统双金属。本发明采用绿色简便的方法合成了一种多枝晶的Au@GQDs@PtPb核壳结构纳米复合材料并应用于碱性甲醇的催化氧化研究。
发明内容
本发明的目的是提供一种多枝晶Au@GQDs@PtPb核壳结构纳米复合材料的制备方法；
本发明的另一目的是提供上述多枝晶Au@GQDs@PtPb核壳结构纳米复合材料对于催化氧化甲醇的性能进行研究，以期用于甲醇燃料电池的阳极催化剂。
一、多枝晶Au@GQDs@PtPb核壳结构纳米复合材料的制备
（1）Au@GQDs纳米颗粒的制备：将石墨烯量子点(GQDs)、氯金酸加入水中搅拌混合均匀后加热到80℃~100℃；再加入柠檬酸钠，反应20~40min；冷却至室温，离心，得到Au@GQDs纳米颗粒。其中，氯金酸与石墨烯量子点(GQDs)的质量比为0.5:1~0.7:1；氯金酸与柠檬酸钠的质量比为0.2:1~0.6:1。
（2）Au@GQDs@Pt核壳纳米球的制备：在Au@GQDs溶液中加入氯铂酸溶液，搅拌并培养3~8min，再加入还原剂抗坏血酸（AA），室温反应0.5~2h；反应产物离心分离后用乙醇和水连续冲洗去除残余物，得到Au@GQDs@Pt核壳纳米球。其中，氯铂酸的浓度为0.01~0.1M；氯铂酸与氯金酸的质量比为0.5:1~2:1；氯铂酸与还原剂抗坏血酸的质量比为0.05:1~0.50:1；离心分离是以10000~14000转/分的速度离心10~30分钟。
（3）多枝晶Au@GQDs@PtPb核壳结构纳米复合材料的制备：在Au@GQDs@Pt溶液中加入硝酸铅，再加入还原剂抗坏血酸（AA），40℃~60℃下反应1~3h；反应产物用乙醇和水离心洗涤去除残留物，得到目标产物Au@GQDs@PtPb核壳结构纳米复合材料。其中，硝酸铅的浓度为2~20mM；硝酸铅与氯铂酸质量比为0.05:1~0.2:1；硝酸铅与还原剂抗坏血酸的质量比为0.01:1~0.05:1。
二、多枝晶Au@GQDs@PtPb核壳结构纳米复合材料的结构
以实施例制备的Au@GQDs@Pt3.5Pb（Pt与Pb的摩尔比为3.5:1）核壳结构纳米复合材料为例说明多枝晶的Au@GQDs@PtPb核壳结构纳米复合材料的结构。
为考察催化剂核壳结构的合成，通过TEM、HRTEM、XPS等一系列手段进行物理表征，各表征均表明Au@GQDs@Pt3.5Pb核壳纳米复合材料成功合成。
1、TEM分析
图1为Au@GQDs、Au@GQDs@Pt、Au@GQDs@Pt3.5Pb的HRTEM、TEM图。图1（a）为Au@GQDs的TEM图，如图所示，Au@GQDs纳米颗粒分散的非常均匀，未看见有团聚颗粒存在，这些纳米颗粒的平均尺寸约为17.0nm。图1（b）为Au@GQDs@Pt的TEM图。从图可以清楚地观察到较深的核和较浅的壳区域，证实了Au@GQDs@Pt核-壳结构的存在。在核-壳Au@GQDs@Pt纳米颗粒的边缘区域观察到间距为0.225 nm的晶格条纹，这与Pt的（111）（0.225nm）衍射平面是一致的。图1（c）、（d）为Au@GQDs@Pt3.5Pb的TEM图和HRTEM图，从图中可以看出所制备的Au@GQDs@Pt3.5Pb纳米绒球分布的比较均匀，分散性好，而且可以看到在合成Au@GQDs@Pt3.5Pb纳米复合物中，每个颗粒外都拥有丰富的枝晶。显然，在合成的Au@GQDs@Pt3.5Pb中未发现其它独立的Pt或Pb纳米颗粒，几乎没有发现其它副产物。
2、XPS分析
为了进一步检查Au@GQDs@Pt3.5Pb催化剂的电子结构和化学价态，我们使用XPS测试了样品。图2 (a)为Au@GQDs@Pt3.5Pb的XPS 总谱图；(b) (c) (d)分别为Au，Pt，Pb的4f分峰谱图。在对Au@GQDs@Pt3.5Pb样品的XPS调查中(图2（a）)，确认了Pt、Pb、Au、C、O的存在，Pt、Pb、Au、C、O元素的质量百分比分别为：16.62%、5.82%、7.45%、52.26%、17.85%，说明成功制备了Au@GQDs@Pt3.5Pb纳米催化剂。图2（b-d），可见Au和Pt原子大部分处于零价态，Pb原子主要处于二价态。Au@GQDs@Pt3.5Pb与Au@GQDs@Pt的标准值相比，Pt 4f的峰位置有所降低，这表明铂和铅之间发生了强电子耦合，Pt与Pb形成了合金，这主要归因于Pb比Pt的电负性低。较低的d带能通常与较弱的吸附剂和金属结合有关，这会提高催化性能。
三、多枝晶Au@GQDs@PtPb核壳结构纳米复合材料的催化性能
以实施例制备的Au@GQDs@Pt3.5Pb（Pt与Pb的摩尔比为3.5:1）核壳结构纳米复合材料为例说明多枝晶的Au@GQDs@PtPb核壳结构纳米复合材料的催化性能。
取Au@GQDs@Pt3.5Pb 5~10μL，滴到已经打磨好的电极上，自然晾干，然后利用三电极系统进行电催化及稳定性测试。
采用循环伏安法（Cyclic Voltammetry，CV），在1M NaOH包含0.5M CH3OH的混合溶液中进行CV测试的电势范围为-0.8~0.4V，在0.5M H2SO4中CV测试的电位范围为-0.20~1.0V，电势扫描速率为50mV/s。
图3为Au@GQDs@Pt3.5Pb、Au@Pt、Au@Pt3.5Pb、Pt/C催化剂修饰电极在0.5M H2SO4溶液中的CV曲线（扫描电位从-0.4~1.2V，扫速为50mVs-1）。由图3可见，Au@GQDs@Pt3.5Pb催化剂在0.5M H2SO4中测试的CV曲线，-0.3和0.1V之间的电流峰值归因于氢吸附和解吸，并且它是获得催化剂的电化学活性表面积（ECSA）的可用参数。ECSA可以通过以下公式计算：
在该式中，“QH”表示氢吸附的库仑电荷；0.21mC-2表示Pt的清洁表面上的单层氢吸附电荷。“MPt”是Pt在电极上的负载量，其值通过ICP测量。计算结果表明，Au@GQDs@Pt3.5Pb具有大的电化学活性表面积。说明GQDs作为分散剂增大了PtPb合金的附着位点。
图4为Au@GQDs@Pt3.5Pb、Au@Pt、Au@Pt3.5Pb、Pt/C催化剂修饰电极在含0.5M甲醇1.0M NaOH溶液中的CV曲线（电势范围为-0.8~0.4V，电势扫描速率为50mV/s。）。图4的测试结果表明，Au@GQDs@Pt3.5Pb表面上的甲醇氧化比其他催化剂表面上的甲醇氧化更容易且更快。此外，Au@GQDs@Pt3.5Pb的峰值电流密度（98.86mA cm-2）比Au@Pt（20.00mA cm-2）、Au@Pt3.5Pb（39.14mA cm-2）和Pt/ C（2.61mA cm-2）大得多，进一步证明Au@GQDs@Pt3.5Pb催化剂对甲醇氧化有更高的电催化活性。
图5为Au@GQDs@Pt3.5Pb 、Au@Pt、Au@Pt3.5Pb、Pt/C催化剂修饰电极在含0.5M甲醇的1.0M NaOH溶液中的CA曲线：电压为0.268V，扫描速率为50mV/s，测试3000s。图5显示，经过3000s，Au@GQDs@Pt3.5Pb纳米催化剂电极的电流密度速率比Au@Pt、Au@Pt3.5Pb和商业Pt/C电极降的慢，表明其优异的催化稳定性。
综上所述，本发明采用Au@GQDs@Pt核壳纳米枝晶作为基底，通过抗坏血酸还原前驱体Pb(NO3)2反应获得Au@GQDs@PtPb核壳结构纳米复合材料。本发明制备的多枝晶Au@GQDs@Pt3.5Pb电极与Au@Pt、Au@Pt3.5Pb和商业Pt/C电极相比，由于PtPb的电子效应和Au-Pt金属的协同效应，GQDs的分散性以及特殊的核壳结构，大大地提高了对甲醇的电催化活性（其催化活性约为商业Pt/C的30-40倍）和对CO中毒的耐受性和稳定性，在DMFCs中具有潜在的应用前景。
附图说明
图1为Au@GQDs@Pt、多枝晶Au@GQDs@Pt3.5Pb核壳纳米材料的TEM，HRTEM图。
图2为Au@GQDs@Pt3.5Pb的XPS图。
图3为Au@GQDs@Pt3.5Pb 、Au@Pt、Au@Pt3.5Pb、Pt/C催化剂修饰电极在0.5M H2SO4溶液中的CV曲线。
图4为Au@GQDs@Pt3.5Pb、Au@Pt、Au@Pt3.5Pb、Pt/C催化剂修饰电极在含0.5M甲醇的1.0M NaOH溶液中的CV曲线。
图5为Au@GQDs@Pt3.5Pb、Au@Pt、Au@Pt3.5Pb、Pt/C催化剂修饰电极在含0.5M甲醇的1.0M NaOH溶液中的i-t曲线。
具体实施方式
下面通过具体实施例对本发明的多枝晶Au@GQDs@PtPb核壳纳米复合催化剂的制备及性能做进一步说明。
实施例1.一种多枝晶Au@GQDs@Pt3.5Pb核壳纳米催化剂的制备
（1）GQDs的制备：称取300mg的石墨粉，超声混合在20mL硝酸和60mL硫酸的混合酸中，然后在120℃的油浴锅中连续搅拌回流12h，待反应终止后自然降至室温，将溶液稀释到300mL的去离子水中，并用碳酸钠中和，接着用240nm滤膜在-4℃冰水浴中去除溶液中的硫酸钠和硝酸钠盐。最后，将制备的溶液在透析袋（保留分子量3500da）中用去离子水透析2天，得到石墨烯量子点（GQDs）。
（2）Au@GQDs纳米颗粒的制备：取步骤（1）制备的GQDs35mg，加入35mL的水搅拌5min，逐滴加入25.4mM 200μL氯金酸（HAuCl4），然后搅拌加热到100℃后加入0.1M 200μL柠檬酸钠回流反应30min，冷却至室温后离心得到Au@GQDs纳米颗粒。
（3）Au@GQDs@Pt核壳纳米枝晶的制备：取步骤（2）制备的Au@GQDs定容至10ml，磁力搅拌5min后加入19.3mM 120μL的氯铂酸，搅拌并培养5min，然后在25℃下加入0.1M 500μL抗坏血酸（AA），反应1h；然后以10000转/分的速度离心20分钟，最后用乙醇和水连续冲洗三次去除残余物，得到黑色的Au@GQDs@Pt核壳纳米球。
（4）Au@GQDs@Pt3.5Pb核壳结构纳米催化剂的制备：取步骤（3）中制备的Au@GQDs@Pt，加入5mL的水，加入8.39mM 80μL硝酸铅，43℃下加入0.1M 500μL抗坏血酸（AA），搅拌反应1h，最终用乙醇和水离心四次去除残留物得到复合Au@GQDs@Pt3.5Pb核壳纳米催化剂。
（5）Au@GQDs@Pt3.5Pb核壳结构纳米催化剂的的活性：Au@GQDs@Pt3.5Pb用作碱性甲醇氧化反应（MOR）的阳极催化剂，其催化活性约为商业Pt/C的37倍，且表现出很大的电催化性能和耐毒性，在DMFCs中具有潜在的应用前景。
Claims (9)
1.一种多枝晶Au@GQDs@PtPb核壳结构纳米复合材料，其特征在于：以Au纳米颗粒为核，GQDs为夹层，PtPb合金作为壳层，三者结合形成了多枝晶的核壳结构；
所述多枝晶Au@GQDs@PtPb核壳结构纳米复合材料的制备方法，包括以下步骤：
（1）Au@GQDs纳米颗粒的制备：将石墨烯量子点(GQDs)、氯金酸加入水中搅拌混合均匀后加热到80℃~100℃；再加入柠檬酸钠，反应20~40min；冷却至室温，离心，得到Au@GQDs纳米颗粒；
（2）Au@GQDs@Pt核壳纳米球的制备：在Au@GQDs溶液中加入氯铂酸溶液，搅拌并培养3~8min，再加入还原剂抗坏血酸，室温反应0.5~2h；反应产物离心分离后用乙醇和水连续冲洗去除残余物，得到Au@GQDs@Pt核壳纳米球；
（3）多枝晶Au@GQDs@PtPb核壳结构纳米复合材料的制备：在Au@GQDs@Pt溶液中加入硝酸铅，再加入还原剂抗坏血酸，40℃~60℃下反应1~3h；反应产物用乙醇和水离心洗涤去除残留物，得到目标产物Au@GQDs@PtPb核壳结构纳米复合材料。
2.如权利要求1所述一种多枝晶Au@GQDs@PtPb核壳结构纳米复合材料，其特征在于：步骤（1）中，氯金酸与石墨烯量子点(GQDs)的质量比为0.5:1~0.7:1。
3.如权利要求1所述一种多枝晶Au@GQDs@PtPb核壳结构纳米复合材料，其特征在于：步骤（1）中，氯金酸与柠檬酸钠的质量比为0.2:1~0.6:1。
4.如权利要求1所述一种多枝晶Au@GQDs@PtPb核壳结构纳米复合材料，其特征在于：步骤（2）中，氯铂酸的浓度为0.01~0.1M；氯铂酸与氯金酸的质量比为0.5:1~2:1。
5.如权利要求1所述一种多枝晶Au@GQDs@PtPb核壳结构纳米复合材料，其特征在于：步骤（2）中，氯铂酸与还原剂抗坏血酸的质量比为0.05:1~0.50:1。
6.如权利要求1所述一种多枝晶Au@GQDs@PtPb核壳结构纳米复合材料，其特征在于：步骤（2）中，离心分离是以10000~14000转/分的速度离心10~30分钟。
7.如权利要求1所述一种多枝晶Au@GQDs@PtPb核壳结构纳米复合材料，其特征在于：步骤（3）中，硝酸铅的浓度为2~20mM；硝酸铅与氯铂酸质量比为0.05:1~0.2:1。
8.如权利要求1所述一种多枝晶Au@GQDs@PtPb核壳结构纳米复合材料，其特征在于：步骤（3）中，硝酸铅与还原剂抗坏血酸的质量比为0.01:1~0.05:1。
9.如权利要求1所述多枝晶Au@GQDs@PtPb核壳结构纳米复合材料作为催化剂用于甲醇氧化反应（MOR）中。
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