CN103602333B - 荧光碳点材料的制备及作为氧还原催化剂的应用 - Google Patents

荧光碳点材料的制备及作为氧还原催化剂的应用 Download PDF

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CN103602333B
CN103602333B CN201310580889.0A CN201310580889A CN103602333B CN 103602333 B CN103602333 B CN 103602333B CN 201310580889 A CN201310580889 A CN 201310580889A CN 103602333 B CN103602333 B CN 103602333B
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CN103602333A (zh
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王荣方
马妍姣
王辉
冯汉青
季山
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Northwest Normal University
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Abstract

本发明提供了一种荧光碳点材料的制备，属于复合材料技术领域。本发明荧光碳点材料的制备，是将水溶性蛋白质溶于的超纯水后，加入硝酸铁，混合均匀后加入无水乙醇，在120～200℃水热反应10～20h，得到荧光碳点溶液；再向荧光碳点溶液中加入碳粉，氮气保护下，于600～1000℃下碳化反应2～6h，即得。本发明制备的荧光碳点材料具有传统荧光碳点优异的荧光特性。以该荧光碳点材料制备的燃料电池阴极电极表现出良好的氧还原性能，将其应用到燃料电池电催化领域，实现了荧光碳点的双功能化。

Description

荧光碳点材料的制备及作为氧还原催化剂的应用
技术领域
本发明属于复合材料技术领域，涉及一种荧光碳点材料的制备方法；本发明还涉及该荧光碳点材料作为氧还原反应催化剂在燃料电池中的应用。 
背景技术
作为碳纳米家族中的一个新成员，荧光碳点具有激发波长和发射波长可调谐、荧光稳定耐光漂白且无光闪烁现象等优异的荧光性能，从而引起了科研工作者的极大兴趣。然而，荧光碳点的应用还基本限制在生物标记和生物成像领域。因此探索荧光碳点新的应用领域是一项重要的挑战。
燃料电池作为一种环境友好的能源利用技术，可以直接将化学能转换为电能，一直以来受到人们的广泛关注。研究发现，高含氮量碳材料在碱性环境下对氧化剂具有很好的氧还原催化活性，可以代替传统的价格高昂的铂钌等贵金属催化剂材料。因此，研究开发高含氮量碳的非贵金属材料作为氧还原催化剂是实现燃料电池工业化的必然途径。 
发明内容
本发明的目的是提供一种荧光碳点材料的制备方法。
本发明的另一目的是提供上述荧光碳点材料作为氧还原催化剂在燃料电池中的应用。
本发明荧光碳点材料的制备方法，是将水溶性蛋白质溶于的超纯水后，加入硝酸铁，混合均匀后加入无水乙醇，在120 ～200℃下水热反应10～20h，得到荧光碳点溶液；再向荧光碳点溶液中加入碳粉，氮气保护下，于600～1000℃碳化反应2～6 h，得到荧光碳点修饰的碳材料。
所述水溶性蛋白质与硝酸铁的质量比为5:1～10:1。
所述无水乙醇与超纯水的体积比为1:1～3:1。
所述XC-72碳粉与水溶性蛋白质的质量比为1:1～1:5。
下面对本发明制备的荧光碳点材料进行物理表征和性能测试。
1、紫外光谱分析
图1为荧光碳点溶液的紫外可见吸收光谱图。从图1可以看出，在280nm左右出现了明显的碳点特征吸收峰，具有传统荧光碳点优异的荧光特性。 
2、荧光测试分析
图2为本发明荧光碳点溶液在不同激发下的荧光发射光谱图，图3为归一化的发射光谱图。图2、3显示，荧光碳点溶液的荧光发射峰随着激发波长的增加，最大发射峰的荧光强度下降，峰位置出现红移的趋势，碳点最大发射峰位置红移现象的原因可能是由于碳点表面发射位点的不同或者缺陷造成的。
3、催化氧还原性能分析
图4为本发明荧光碳点材料与商业XC-72碳粉及商业Pt/C的催化氧还原反应的极化曲线图。从图4可以直观看出，本发明制备的荧光碳点修饰的碳材料电极上，氧还原反应的起始电位和半波电位分别比商业XC-72碳粉正移129 mV和107 mV，并且该催化剂材料的稳态扩散电流比商业Pt/C大了0.08 mA，表明本发明制备的荧光碳点材料具有较好的氧还原催化性能。
综上所述，本发明制备的荧光碳点材料具有传统荧光碳点优异的荧光特性。以该荧光碳点材料制备的燃料电池阴极电极表现出良好的氧还原性能，将其应用到燃料电池电催化领域，实现了荧光碳点的双功能化。
附图说明
图1为本发明制备的荧光碳点水溶液的紫外可见吸收光谱图；
图2为本发明制备的荧光碳点水溶液在不同激发发射下的荧光光谱图；
图3为本发明制备的荧光碳点水溶液的归一化发射光谱图；
图4为本发明的荧光碳点修饰的碳材料与商业XC-72碳粉及商业Pt/C的催化氧还原反应的极化曲线图。
具体实施方式
下面通过具体实施例对本发明的荧光碳点修饰的碳材料的制备及作为催化剂在催化氧还原反应中的应用作进一步说明。
实施例1
将1 g水溶性蛋白质溶于20 mL的超纯水中，加入100 mg 硝酸铁，混合均匀后加入20 mL的无水乙醇，在180℃下水热反应10 h，得到荧光碳点溶液；再向荧光碳点溶液中加入1 g XC-72碳粉，氮气保护，600℃下反应2h，得到荧光碳点材料。
氧还原测试结果：利用上述制备的荧光碳点修饰的碳材料作为氧还原催化剂进行反应，氧还原反应的起始电位和半波电位比商业XC-72碳粉正移110 mV和89 mV；并且该催化剂的稳态扩散电流比商业Pt/C大了0.07 mA。
实施例2
将1 g水溶性蛋白质溶于20 mL的超纯水中，加入120 mg 硝酸铁，混合均匀后加入20 mL的无水乙醇，在180℃水热反应12 h，得到荧光碳点溶液；再向荧光碳点溶液中加入0.8g XC-72碳粉，氮气保护，700℃下反应2h，制得荧光碳点材料。
氧还原测试结果：利用上述制备的荧光碳点修饰的碳材料作为氧还原催化剂进行反应，氧还原反应的起始电位和半波电位比商业XC-72碳粉正移117 mV和102 mV，并且该催化剂的稳态扩散电流比商业Pt/C大了0.09 mA。
实施例3
将1 g水溶性蛋白质溶于20 mL的超纯水中，加入140 mg 硝酸铁，混合均匀后加入20 mL的无水乙醇，在180℃水热反应14 h，得到荧光碳点溶液；向该溶液中加入0.6g XC-72碳粉，氮气保护，700℃下反应2h，制得荧光碳点材料。
氧还原测试结果，利用上述制备的荧光碳点修饰的碳材料作为氧还原催化剂进行反应，氧还原反应的起始电位和半波电位比商业XC-72碳粉正移123 mV和110 mV。并且该催化剂的稳态扩散电流比商业Pt/C大了0.05 mA。
实施例4
将1 g水溶性蛋白质溶于20 mL的超纯水中，加入160 mg 硝酸铁，混合均匀后加入20 mL的无水乙醇，在180℃下水热反应16 h，得到荧光碳点溶液；向该溶液中加入0.4g XC-72碳粉，氮气保护，800℃下反应2h，制得荧光碳点材料。
氧还原测试发现，在利用上述制备的复合碳材料为?电极进行氧还原反应，氧还原反应的起始电位和半波电位比商业XC-72碳粉正移131 mV和116 mV；并且该催化剂的稳态扩散电流比商业Pt/C大了0.08 mA。 

Claims (2)

1.荧光碳点材料的制备方法，是将水溶性蛋白质溶于超纯水后，加入硝酸铁，混合均匀后加入无水乙醇，在120 ～200℃下水热反应10～20h，得到荧光碳点溶液；再向荧光碳点溶液中加入碳粉，氮气保护，于600～1000℃下碳化反应2～6 h，得到荧光碳点修饰的碳材料；
所述水溶性蛋白质与硝酸铁的质量比为5:1～10:1；
所述无水乙醇与超纯水的体积比为1:1～3:1；
所述碳粉为XC-72碳粉，XC-72碳粉与水溶性蛋白质的质量比为1:1～1:5。
2.如权利要求1所述方法制备的荧光碳点材料作为氧还原反应催化剂的应用。 
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