CN110562957A - 一种高产率和高荧光量子产率绿色荧光碳量子点及其制备方法 - Google Patents
一种高产率和高荧光量子产率绿色荧光碳量子点及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种绿色荧光碳量子点及其制备方法,是以2,7‑二羟基萘为碳源,双氧水为氧化剂,乙二胺为氮掺杂剂,无水乙醇为溶剂,经溶剂热法制备绿色荧光碳量子点。以本发明方法制备的绿色荧光碳量子点兼具高产率和高荧光量子产率,可以作为荧光粉应用于适于室内照明的暖白光LED的制备。
Description
技术领域
本发明属于荧光发光材料技术领域,涉及碳量子点,特别是涉及一种绿色荧光碳量子点,以及该碳量子点的制备方法。本发明制备的绿色荧光碳量子点具有高的产率和高的荧光量子产率,并且可以作为荧光粉应用于暖白光LED。
背景技术
碳量子点作为一种尺寸10nm以下的荧光碳纳米材料,具有好的水溶性、优异的化学惰性、独特的抗光漂白性能、低的毒性以及良好的生物相容性。在这些优异的性能中,由于碳量子点具有一些独特的光学性质(相对长的荧光寿命、好的荧光稳定性)而被广泛应用于白光LED。大量实验结果表明,碳量子点在用于白光LED的荧光粉方面具有巨大的应用潜力。
相关色温是白光LED的基本性能指标之一。目前,在白光LED的应用中所使用的碳量子点大都在紫外灯下发射蓝色荧光,而以蓝光碳量子点作为荧光粉制备的白光LED的相关色温普遍高于6000K,为冷白光,只适用于户外和办公室照明。
长波长碳量子点,例如绿色荧光碳量子点的加入,则可以明显降低白光LED的相关色温,进而可以满足室内照明的需求(相关色温<5000K,属于暖白光),从而拓宽碳量子点在白光LED的应用。
随着白光LED的迅速发展,白光LED对绿色荧光碳量子点的需求量不断增加,要求碳量子点具有高的产率,以适应商业化应用的大规模生产。与此同时,亮度和效率作为白光LED的基本光学性能指标,也要求碳量子点具有高的荧光量子产率。综上所述,探索一种能够合成具有高产率和高荧光量子产率的绿色荧光碳量子点的方法,具有重大的研究意义。
近年来,也有许多工作者在研究绿色荧光碳量子点的合成方法,但是目前绿色荧光碳量子点的荧光量子产率普遍偏低,大都低于50%。例如:Du等(Qin Du, Jingxia Zheng,Junli Wang, Yongzhen Yang, Xuguang Liu. The synthesis of green fluorescentcarbon dots for warm white LEDs [J]. RSC Adv., 2018, 8(35): 19585–19595.)采用焦性没食子酸为碳源,一步溶剂热法获得的绿色荧光碳量子点的荧光量子产率为16.8%。Qu等(Songnan Qu, Xingyuan Liu, Xiaoyang Guo, Minghui Chu, Ligong Zhang, DezhenShen. Amplified spontaneous green emission and lasing emission from carbonnanoparticles [J]. Adv. Funct. Mater., 2014, 24(18): 2689–2695.)采用质量比1∶2的柠檬酸和尿素为原料,乙醇为溶剂,微波法制备的绿色荧光碳量子点的荧光量子产率为36%。Zhang等(Chunfang Zhang, Zhongbo Hu, Li Song, Yanyan Cui, Xiangfeng Liu.Valine-derived carbon dots with colour-tunable fluorescence for the detectionof Hg2+ with high sensitivity and selectivity [J]. New J. Chem., 2015, 39(8):6201–6206.)采用浓磷酸处理L-缬氨酸水溶液在90℃下制备得到绿色荧光碳量子点,荧光量子产率为44.8%。
此外,绿色荧光碳量子点的产率很少被关注,且产率和荧光量子产率普遍偏低。如Cui等(Yanyan Cui, Zhongbo Hu, Chunfang Zhang, Xiangfeng Liu. Simultaneouslyenhancing up-conversion fluorescence and red-shifting down-conversionluminescence of carbon dots by a simple hydrothermal process [J]. J. Mater.Chem. B, 2014, 2(40): 6947–6952.)采用柠檬酸胺为主要原料,通过两步水热法获得的g-CQDs的产率为34%,荧光量子产率为16.5%。
因此,目前迫切需要探索一种可以合成具有高产率和高荧光量子产率的绿色荧光碳量子点的方法。
发明内容
本发明的目的是提供一种绿色荧光碳量子点及其制备方法,以本发明方法制备的绿色荧光碳量子点兼具高产率和高荧光量子产率,可以作为荧光粉应用于暖白光LED。
本发明所述的绿色荧光碳量子点是以2,7-二羟基萘为碳源,双氧水为氧化剂,乙二胺为氮掺杂剂,无水乙醇为溶剂,经溶剂热法合成得到的绿色荧光碳量子点。
进而,本发明提供了一种所述绿色荧光碳量子点的制备方法,是将双氧水、乙二胺与2,7-二羟基萘混合反应后,以无水乙醇溶解,于密闭反应釜中加热进行溶剂热反应,制备得到绿色荧光碳量子点固体粉末。
其中,本发明所述制备方法中,所述原料乙二胺与2,7-二羟基萘的摩尔用量比为12~48∶1。
进一步地,本发明所述溶剂热反应优选在180~200℃的反应温度下进行。
更进一步地,本发明所述溶剂热反应的反应时间优选为11~13h。
更具体地,本发明需要对上述溶剂热反应得到的产物进行进一步的提纯,具体是除去溶剂热反应产物中的溶剂后,以乙酸乙酯洗涤不少于1次,离心除去乙酸乙酯后干燥得到绿色荧光碳量子点固体粉末。
本发明制备的绿色荧光碳量子点粒径分布1.5~5.0nm,在紫外灯照射下能发出明亮的绿色荧光。其激发波长460nm,发射峰位位于513nm处,且具有激发波长依赖性,随着激发波长增加,其最强发射峰的峰位发生红移。
本发明制备的绿色荧光碳量子点具有较高的荧光量子产率,可以达到40%以上,以其作为荧光粉,可以解决LED器件的发光亮度和效率问题。
同时,采用本发明方法制备绿色荧光碳量子点,其产率能够达到50%以上,适合于规模化大批量生产,解决了碳量子点的商业化应用问题。
以本发明制备的长波长绿色荧光碳量子点作为荧光粉制备白光LED,可以降低白光LED的色温,其色坐标(0.45,0.37),相关色温2520K,属于暖白光,适用于室内照明。
附图说明
图1是绿色荧光碳量子点的形貌图和粒径尺寸分布图。
图2是绿色荧光碳量子点的XRD图。
图3是绿色荧光碳量子点的红外光谱图。
图4是绿色荧光碳量子点的紫外-可见吸收光谱图。
图5是绿色荧光碳量子点的激发光谱。
图6是绿色荧光碳量子点在不同激发波长下的荧光光谱图。
图7是绿色荧光碳量子点的红绿蓝光谱组成。
图8是绿色荧光碳量子点制备的白光LED的照片及其性能指标图。
具体实施方式
下述实施例仅为本发明的优选技术方案,并不用于对本发明进行任何限制。对于本领域技术人员而言,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
实施例1。
在0.4g 2,7-二羟基萘中加入4mL乙二胺,再加入2mL 30wt%双氧水,此时发生剧烈反应,在冒出气泡的同时放出大量热量。反应后再加入40mL无水乙醇,搅拌得到均匀的深酒红色溶液。
将溶液转移到100mL聚四氟乙烯不锈钢高压反应釜中,加热到180℃进行溶剂热反应12h。反应结束后自然冷却至室温,得到绿色荧光碳量子点反应液。
将上述绿色荧光碳量子点反应液转移到旋瓶中,置于旋蒸仪上,旋蒸浓缩至少量液体残留,加入少量乙酸乙酯,8000rpm转速下离心5min,重复3次后,于烘箱中干燥,得到纯化的绿色荧光碳量子点粉末。
在透射电子显微镜下观察所述绿色荧光碳量子点粉末的形貌。从图1a的形貌图可以看出,绿色荧光碳量子点呈类球形,分散均匀,粒径大小在1.5~5.0nm,没有发生明显的团聚现象。尺寸分布图(图1b)表明,绿色荧光碳量子点的平均尺寸为3.31nm,从HRTEM图像(图1a左上角小图)可以看到绿色荧光碳量子点具有明显的晶格条纹,晶格间距为0.22nm,接近于石墨的(100)晶面,表明绿色荧光碳量子点具有一定的结晶度。
进而,从图2的XRD图可以看出,绿色荧光碳量子点在2θ=25.15°处具有一个窄的衍射峰,这也进一步说明了绿色荧光碳量子点的结晶性结构。
采用FTIR光谱对绿色荧光碳量子点的结构进行表征,图3表明在3370cm-1处的吸收峰归因于O-H和N-H的伸缩振动,证明了绿色荧光碳量子点具有氮掺杂,促进了荧光量子产率的提高。3082cm-1处的吸收峰归因于O-H的伸缩振动,2888cm-1处的吸收峰归因于C-H和O-H振动。1562cm-1处的吸收峰归因于C=N和C=C振动。1481cm-1处的吸收峰归因于C=N、C=C和C-OH振动。1329cm-1处的吸收峰归因于C-N振动,1219cm-1处的吸收峰归因于C-O-C、=C-H和C-OH振动。上述结果证实,绿色荧光碳量子点表面含有丰富的官能团。
图4给出了绿色荧光碳量子点乙醇溶液的紫外-可见吸收光谱图。图中所示,该绿色荧光碳量子点在488nm处具有明显的吸收峰,这归因于C=O键的n-π*跃迁。进而,绿色荧光碳量子点乙醇溶液的激发光谱(图5)也在493nm处具有明显的吸收峰。
图6是绿色荧光碳量子点乙醇溶液在不同激发波长下的荧光光谱图。随着激发波长从360nm增加到500nm,绿色荧光碳量子点的发射峰值发生了明显的移动,说明绿色荧光碳量子点具有激发波长依赖的性质,这可能和绿色荧光碳量子点不均匀的表面态有关。在激发波长为460nm时,绿色荧光碳量子点的发射峰位为513nm。
在以罗丹明B水溶液为标准溶液的条件下,计算出上述绿色荧光碳量子点的相对荧光量子产率为62.98%。
此外,通过相对法计算出绿色荧光碳量子点的产率为70.9%。这表明该绿色荧光碳量子点同时具有高荧光量子产率和高产率,适合碳量子点的大批量制备。
根据图7给出的绿色荧光碳量子点的红绿蓝光谱组成可以看出,绿色荧光碳量子点的红绿蓝光谱组成为93.86%。高的红绿蓝光谱组成表明了绿色荧光碳量子点将蓝光转换成白光的能力较高。
图8是以绿色荧光碳量子点作为荧光粉制备的白光LED的照片及其性能指标图。所制备的绿色荧光碳量子点基白光LED的色坐标为(0.45,0.37),相关色温为2520K,属于暖白光,适用于室内照明。
实施例2。
在0.4g 2,7-二羟基萘中加入2mL乙二胺,再加入2mL 30wt%双氧水,此时发生剧烈反应,在冒出气泡的同时放出大量热量。反应后再加入40mL无水乙醇,搅拌得到均匀的深酒红色溶液。
将溶液转移到100mL聚四氟乙烯不锈钢高压反应釜中,加热到180℃进行溶剂热反应12h。反应结束后自然冷却至室温,得到绿色荧光碳量子点反应液。
将上述绿色荧光碳量子点反应液转移到旋瓶中,置于旋蒸仪上,旋蒸浓缩至少量液体残留,加入少量乙酸乙酯,8000rpm转速下离心5min,重复3次后,于烘箱中干燥,得到纯化的绿色荧光碳量子点粉末。
经检测,本实施例制备绿色荧光碳量子点的荧光量子产率为41.07%,产率88.58%。
实施例3。
在0.4g 2,7-二羟基萘中加入4mL乙二胺,再加入2mL 30wt%双氧水,此时发生剧烈反应,在冒出气泡的同时放出大量热量。反应后再加入40mL无水乙醇,搅拌得到均匀的深酒红色溶液。
将溶液转移到100mL聚四氟乙烯不锈钢高压反应釜中,加热到200℃进行溶剂热反应12h。反应结束后自然冷却至室温,得到绿色荧光碳量子点反应液。
将上述绿色荧光碳量子点反应液转移到旋瓶中,置于旋蒸仪上,旋蒸浓缩至少量液体残留,加入少量乙酸乙酯,8000rpm转速下离心5min,重复3次后,于烘箱中干燥,得到纯化的绿色荧光碳量子点粉末。
经检测,本实施例制备绿色荧光碳量子点的荧光量子产率为43.05%,产率50.50%。
比较例。
向0.4g 2,7-二羟基萘中加入2mL 30wt%双氧水,待溶液无明显反应后,再加入40mL无水乙醇,搅拌得到均匀的透明溶液。
将溶液转移到100mL聚四氟乙烯不锈钢高压反应釜中,加热到180℃进行溶剂热反应12h。反应结束后自然冷却至室温,得到绿色荧光碳量子点反应液。
将上述绿色荧光碳量子点反应液转移到旋瓶中,置于旋蒸仪上,旋蒸浓缩至少量液体残留,加入少量乙酸乙酯,8000rpm转速下离心5min,重复3次后,于烘箱中干燥,得到纯化的绿色荧光碳量子点粉末。
经检测,本比较例制备绿色荧光碳量子点的荧光量子产率为5.29%,产率0.60%。
Claims (8)
1.一种绿色荧光碳量子点,是以2,7-二羟基萘为碳源,双氧水为氧化剂,乙二胺为氮掺杂剂,无水乙醇为溶剂,经溶剂热法制备得到。
2.权利要求1所述绿色荧光碳量子点的制备方法,是将双氧水、乙二胺与2,7-二羟基萘混合反应后,以无水乙醇溶解,于密闭反应釜中加热进行溶剂热反应,制备得到绿色荧光碳量子点固体粉末。
3.根据权利要求2所述的制备方法,其特征是所述乙二胺与2,7-二羟基萘的摩尔用量比为12~48∶1。
4.根据权利要求2所述的制备方法,其特征是所述溶剂热反应温度为180~200℃。
5.根据权利要求2所述的制备方法,其特征是所述溶剂热反应时间为11~13h。
6.根据权利要求2所述的制备方法,其特征是除去溶剂热反应产物中的溶剂后,以乙酸乙酯洗涤不少于1次,离心除去乙酸乙酯后干燥得到绿色荧光碳量子点固体粉末。
7.权利要求1所述绿色荧光碳量子点作为荧光粉的应用。
8.权利要求1所述绿色荧光碳量子点作为荧光粉制备暖白光LED的应用。
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