CN108659836B - 一种高量子产率氮硫共掺杂荧光碳点及其制备方法和应用 - Google Patents
一种高量子产率氮硫共掺杂荧光碳点及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种高量子产率氮硫共掺杂荧光碳点及其制备方法和应用。采用的技术方案是：将酒石酸和L‑半胱氨酸置于水热反应釜中，在160～210℃温度范围内，加热反应3～8小时，自然冷却至室温后加入超纯水溶解，过滤、离心、透析，冷冻干燥，得到纯化后的荧光碳点粉末。本发明制备的碳点荧光量子产率可达19.1％。本发明制得的氮硫共掺杂荧光碳点可用于指纹检测和Hg2+检测，对指纹显现、提取具有重要意义。此外氮硫共掺杂荧光碳点中的巯基与Hg2+之间具有强烈的亲合作用，使其在环境化学研究中具有重要意义。最后该荧光碳点也可用于印染废水中的亚甲基蓝的降解。
Description
技术领域
本发明涉及碳纳米材料技术领域，具体涉及一种氮和硫共掺杂荧光碳点的制备方法及其应用。
背景技术
碳点(Carbon Dots)作为一种尺寸小于10nm的荧光纳米材料，其表面主要含有-COOH和-OH等官能团，使其具有良好的水溶性和生物相容性，此外它还具有低毒性、光稳定性、抗光漂白性和优良的光致发光性能。在过去的十几年中受到越来越多的科研工作者的关注，将碳点开发并应用于各个领域。比如将碳点作为荧光探针检测金属离子和抗菌药物，或是应用于细胞与活体成像中，或是应用于光催化、光电器件和有机太阳能电池等。虽然关于碳点的制备和相关的应用研究已经有很多，但是依然存在制备过程复杂，荧光量子产率低，发光机理不明确等问题，因此寻找简单，荧光量子产率高的荧光碳点的制备方法非常必要，此外对荧光碳点的应用的不断扩充也是很有必要。
发明内容
本发明的目的在于提供一种制备方法简单，量子产率高，光学性能优异的荧光碳点的制备方法。
为实现本发明的目的，本发明采用的技术方案如下：一种高量子产率氮硫共掺杂荧光碳点，制备方法如下：将酒石酸和L-半胱氨酸置于水热反应釜中，水热反应3～8小时，室温下自然冷却后，加入超纯水溶解，过滤、离心、透析，制得氮硫共掺杂荧光碳点。
优选的，上述的高量子产率氮硫共掺杂荧光碳点，水热反应温度为160℃～210℃。
优选的，上述的高量子产率氮硫共掺杂荧光碳点，按质量比，酒石酸:L-半胱氨酸＝0.3:0.2～0.7。
上述的高量子产率氮硫共掺杂荧光碳点在指纹检测中的应用。方法如下：取淀粉和浓度为100μg/mL的上述的高量子产率氮硫共掺杂荧光碳点的水溶液，混合均匀，加入丙酮，搅拌均匀，超声2h，得到的糊状物在60C°下烘干后，研磨成粉末，将粉末均匀抖落至带有指纹的载体上，用指纹刷顺着指纹纹路刷显，除去多余粉末后，拍摄在365nm紫外灯照射下的指纹图像。
上述的高量子产率氮硫共掺杂荧光碳点在Hg2+检测中的应用。方法如下：于上述的高量子产率氮硫共掺杂荧光碳点的水溶液中加入磷酸盐缓冲溶液，再加入含有Hg2+的溶液，搅拌均匀反应5min后，扫描荧光光谱。
上述的高量子产率氮硫共掺杂荧光碳点在催化降解有机污染物中的应用。方法如下：于含有有机污染物的废水中，加入上述的高量子产率氮硫共掺杂荧光碳点的水溶液，在黑暗环境下搅拌吸附1h，然后加入H2O2，用250W高汞灯下照射100～120min。优选的，所述的有机污染物是亚甲基蓝。
本发明的有益效果是：
1.本发明采用一步高温固相反应法合成荧光碳点，制备方法简单且反应条件温和可控，所
用药品价廉易得，易于实现工业化。
2.本发明制备的荧光碳点可应用于指纹检测、Hg2+检测和降解印染废水中的亚甲基蓝。
3.本发明制备的荧光碳点的荧光量子产率高达19.1％。
4.本发明制备的荧光碳点最大激发波长和最大发射波长分别为360nm和443nm，该荧光
碳点的Stokes位移为83nm，较大的Stokes位移有利于荧光性能的分析与检测。此外该
荧光碳点表现出优异的发光性能，在365nm的紫外灯照射下发出明亮的蓝色荧光。最
后本发明所制备的荧光碳点水溶性好、稳定性好，常温放置在暗处一年不会变质。
附图说明
图1a是荧光碳点的透射电镜图。
图1b是荧光碳点的粒径分布图。
图2是荧光碳点的X射线衍射图。
图3是荧光碳点的红外光谱。
图4是荧光碳点溶液的zeta电位。
图5a是荧光碳点的X射线光电子能谱图。
图5b是荧光碳点的C1s的X射线光电子能谱图。
图5c是荧光碳点的N1s的X射线光电子能谱图。
图5d是荧光碳点的O1s的X射线光电子能谱图。
图5e是荧光碳点的S2p的X射线光电子能谱图。
图6是荧光碳点溶液的紫外-可见吸收光谱。
图7是荧光碳点溶液荧光激发和发射光谱。
图8是不同波长光激发下荧光碳点溶液的荧光发射光谱。
图9是pH值对碳点溶液荧光的影响(λex＝360nm)。
图10是NaCl浓度对荧光碳点溶液荧光的影响(λex＝360nm)。
图11是光照对荧光碳点溶液荧光的影响(λex＝360nm)。
图12是荧光碳点在365nm紫外灯下的指纹检测图。
图13是在荧光碳点溶液中加入一系列浓度Hg2+后的荧光光谱，内嵌图是ΔF和Hg2+浓度的线性关系曲线。
图14随光照时间的不同亚甲基蓝的降解情况。
具体实施方式
实施例1
(一)高量子产率氮硫共掺杂荧光碳点的制备方法
将0.30g的酒石酸和0.50g的L-半胱氨酸置于聚四氟乙烯的反应釜中，在210℃水热反应5小时后，自然冷却至室温，加入20mL超纯水溶解，之后用滤纸过滤，离心机离心(10000rpm，10min)，再用0.22μm的滤头过滤，最后进行透析，即可得到棕色的氮硫共掺杂荧光碳点溶液。将此碳点溶液置于365nm紫外灯照射下，可观察到该碳点溶液发射出明亮的蓝色荧光。将该碳点溶液冷冻干燥，可得到荧光碳点固体粉末。
本实施例制备的碳点溶液以硫酸奎宁为标准物，可测得该碳点的荧光量子产率为19.1％。
(二)结果
图1a和图1b为氮硫共掺杂荧光碳点的透射电镜图和粒径分布图，由图可知，所制备的碳点为球形且粒径大小均匀，未出现团聚现象，其粒径在2-3nm。
图2是氮硫共掺杂荧光碳点的X射线衍射图。由图可知，在2θ＝25°处出现一个较宽的衍射峰，对应于碳(002)晶面，表明所制备的碳点是以无定型碳和石墨碳的复合体形式存在的。
图3是氮硫共掺杂荧光碳点的红外光谱图，3404cm-1吸收峰为N-H的伸缩振动峰，3245cm-1吸收峰为O-H的伸缩振动峰，2980cm-1吸收峰为C-H的伸缩振动峰，2365cm-1吸收峰为S-H的伸缩振动峰，1707cm-1吸收峰为C＝O伸缩振动峰，1595cm-1吸收峰为N-H的弯曲振动峰，1402cm-1吸收峰为C-N伸缩振动峰，1205cm-1吸收峰为C-S的伸缩振动峰。说明合成的荧光碳点带有-NH2、-OH、-COOH和-SH等官能团。
图4是氮硫共掺杂荧光碳点溶液的zeta电位图，在pH为6.0时的溶液中，碳点的zeta电位值为-5.24，这表明碳点表面带负电荷。
图5a-图5e是氮硫共掺杂荧光碳点的X射线光电子能谱图，由图5a可知，该荧光碳点含有以下几种元素C、N、O和S，说明N元素和S元素被成功掺杂到荧光碳点上。由图5b可知，该荧光碳点有五种不同的碳元素，281.5eV、282.1eV、282.6eV、283.4eV、285.3eV分别对应于C-N、C-H、C-O、C-C和C＝O基团。由图5c可知，该荧光碳点有两种不同的氮元素，396.5eV、397.4eV分别对应于C-N和N-H基团。由图5d可知，该荧光碳点有三种不同的氧元素，528.7eV、528.9eV、529.2eV分别对应于C＝O、C-O和O-H基团。由图5e可知，该荧光碳点有两种不同的硫元素，161.3eV、161.7eV分别对应于C-S和S-H基团。荧光碳点的XPS图再一次证明了合成的碳点带有-NH2、-OH、-COOH和-SH等官能团。
图6是氮硫共掺杂荧光碳点溶液的紫外-可见吸收光谱图。由图可知，碳点溶液在a(307nm)处有明显的特征吸收峰。
如图7为氮硫共掺杂荧光碳点溶液的荧光激发和发射光谱。由图可见，本实验所制备的荧光碳点的最大激发波长和最大发射波长分别为360nm和443nm。
在不同波长光激发下荧光碳点溶液的荧光发射光谱如图8所示。随着激发波长的不断增加(从310nm增加到400nm)，可以观察到荧光碳点的发射峰逐渐红移，这说明所制备的碳点对激发波长具有一定的依赖性。
pH值的影响如图9所示。当pH值从3到11变化时，荧光碳点的强度先升高后降低，当pH为7时荧光最强，说明溶液的酸碱度对碳点的发光有一定的影响。
图10为NaCl浓度对荧光碳点的影响。如图所示，在0～2.0mol/L范围内，碳点溶液的荧光强度并未发生明显变化。说明所制备的荧光碳点有良好的抗盐能力。
图11是光照对碳点溶液荧光的影响。将荧光碳点溶液用250W高汞灯连续照射0.5、1、2、3、4、5h，之后分别测其荧光强度。由图11可以看出，碳点的荧光强度并未随着光照时间发生明显的变化，说明制备的荧光碳点具有良好的稳定性和抗光漂白性。
实施例2氮硫共掺杂荧光碳点在指纹检测中的应用
取0.5g淀粉和1mL浓度为100μg/mL的实施例1制备的荧光碳点水溶液，混合后，加入5mL丙酮，搅拌均匀，之后超声2h，得到糊状物，在60C°下烘干，用玛瑙研钵研磨成粉末，待用。之后用刑侦专用指纹刷，将上述粉末均匀抖落至带有指纹的玻璃片上，然后顺着指纹纹路刷显，除去多余粉末后，拍摄在365nm紫外灯照射下的指纹图像。如图12所示，该荧光碳点在365nm紫外光照射下显示出清晰的指纹图像。
实施例3氮硫共掺杂荧光碳点在Hg2+检测中的应用
在2mL浓度为150μg/mL的实施例1制备的荧光碳点水溶液中，加入1mL(pH5.91)磷酸盐缓冲溶液，之后再加入梯度体积的Hg2+溶液，搅拌均匀反应5min后，扫描荧光光谱得到图13。由图13可知，随着Hg2+的不断加入，碳点的荧光强度逐渐降低，在50～125μg/mL范围内有良好的线性关系，线性方程为F＝0.396[Hg2+]+147.5，相关系数R2＝0.996，检出限为5.69μg/mL。该检测方法操作方便，灵敏度高，是一种优秀的Hg2+荧光探针。
实施例4氮硫共掺杂荧光碳点在降解亚甲基蓝中的应用
方法：将50mL(10mg/L)的亚甲基蓝溶液置于烧杯中，之后加入2mL(150μg/mL)的实施例1制备的荧光碳点水溶液，在黑暗环境下搅拌吸附1h，然后加入0.1mL(30％)的H2O2，用250W高汞灯照射，每隔20min取一次样，最后测定亚甲基蓝溶液在波长664nm处的吸光度，亚甲基蓝脱色率的计算公式为：
脱色率＝(A0–At)/A0×100％
其中：A0为亚甲基蓝降解前的吸光度，At为降解不同t时刻亚甲基蓝的吸光度。
如图14所示，氮硫共掺杂荧光碳点具有一定的光催化性能，可用于印染废水中亚甲基蓝的降解。
Claims (2)
1.高量子产率氮硫共掺杂荧光碳点在Hg2+检测中的应用，其特征在于，所述高量子产率氮硫共掺杂荧光碳点的制备方法如下：将0.30 g的酒石酸和0.50 g的L-半胱氨酸置于聚四氟乙烯的反应釜中，在210 ℃反应5小时后，自然冷却至室温，加入20 mL超纯水溶解，之后用滤纸过滤，离心机10000 rpm ，离心10 min，再用0.22 μm的滤头过滤，最后进行透析，得棕色的氮硫共掺杂荧光碳点溶液。
2.根据权利要求1所述的应用，其特征在于，检测方法如下：于高量子产率氮硫共掺杂荧光碳点的水溶液中加入磷酸盐缓冲溶液，再加入含有Hg2+的溶液，搅拌均匀反应5 min后，扫描荧光光谱。
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