以柠檬酸、尿素和丙烯酰胺为前驱体,制备了具有高稳定性的氮掺杂荧光碳点油墨应用于防伪包装。首先以柠檬酸、尿素为前驱体,采用水热法在180℃条件下反应6h,制备氮掺杂碳点(记作NCDs-1);然后以柠檬酸、尿素和丙烯酰胺为前驱体制备氮掺杂碳点(记作NCDs-2);将NCDs-1、NCDs-2分散在水中制备了氮掺杂荧光碳点油墨。通过透射电子显微镜、扫描电子显微镜、X射线衍射仪、傅里叶变换红外光谱仪、X射线光电子能谱仪、荧光光谱仪等对样品的形貌、结构和表面元素组成、荧光性能进行了表征并考察了不同环境下油墨的稳定性。结果表明:NCDs-2粒径分布在2～9nm之间,在水中分散均匀;氮掺杂碳点的最佳激发波长为370nm,最佳发射峰位置在450nm;在无荧光背景的纤维素纸基上油墨表现出良好的稳定性,且在紫外光照射下发出明亮的蓝色荧光;以柠檬酸、尿素、丙烯酰胺为前驱体制备的氮掺杂荧光碳点油墨稳定性良好,可用于香烟盒的防伪包装。
A highly stable nitrogen-doped carbon dots (NCDs) fluorescent ink for anti-counterfeiting packaging was prepared using citric acid,urea and acrylamide as precursors.Firstly,nitrogen-doped carbon dots (NCDs-1) were prepared by hydrothermal method at 180℃ for 6h with citric acid and urea as precursors.Subsequently,nitrogen-doped carbon dots (NCDs-2) were prepared with citric acid,urea and acrylamide as precursors.Finally,nitrogen-doped carbon dots fluorescent ink was prepared by dispersing NCDs-1 and NCDs-2 in water.The morphology,structure,surface element composition and fluorescence properties of the samples were characterized by transmission electron microscope,scanning electron microscope,X-ray diffractometer,Fourier transform infrared spectrometer,X-ray photoelectron spectrometer and fluorescence spectrometer,and the stability of the ink under different environments was investigated.The results showed that the particle size of NCDs-2 was between 2～9nm,and these particles were dispersed evenly in water.In addition,the best excitation wavelength of NCDs was 370nm,and the best emission peak was 450nm.The inks exhibited good stability on cellulose paper base without fluorescent background,and emitted bright blue fluorescence under UV light.The NCDs fluorescent ink prepared with citric acid,urea and acrylamide as precursors had good stability and could be used for anti-counterfeiting packaging on cigarette boxes.
[1] 胡维友.包装印刷防伪技术探究[J].广东印刷,2022(3):36-38.
[2] 周子钰.新防伪技术在包装印刷中的应用[J].丝网印刷,2022(12):34-37.
[3] 王晓磊.烟包印刷防伪技术应用浅析[J].印刷杂志,2022(5):52-55.
[4] 蒋斌,刘斌,唐博.防伪印刷技术的发展与应用[J].造纸装备及材料,2020,49(6):103-105.
[5] 刘丽,杨文杰,汪雅婷,等.信息技术在印刷包装防伪上的应用研究进展[J].包装工程,2019,40(9):216-223.
[6] 邢颖,王瑛,王永华,等.防伪功能用光致变色染料的研究进展[J].染料与染色,2017,54(2):16-18;31.
[7] Kanika P,Singh S,Gupta B K.A novel approach to synthesise a dual-mode luminescent composite pigment for uncloneable high-security codes to combat counterfeiting[J].Chem Eur J,2017,23(67):17144-17151.
[8] Hoekstra D C,Nickmans K,Lub J,et al.Air-curable,high-re-solution patternable oxetane-based liquid crystalline photonic films via flexographic printing[J].ACS Appl Mater Interfaces,2019,11(7):7423-7430.
[9] Xu X,Ray R,Gu Y,et al.Electrophoretic analysis and purification of fluorescent single-walled carbon nanotube fragments[J].J Am Chem Soc,2004,126(40):12736-12737.
[10] Huo F,Karmaker P G,Liu Y,et al.Preparation and biomedical applications of multicolor carbon dots:recent advances and future challenges[J].Particle & Particle Systems Characte-rization,2020,37(4):1900489.
[11] Li P,Sun L,Xue S,et al.Recent advances of carbon dots as new antimicrobial agents[J].Smart Mat,2022,3(2):226-248.
[12] Li W,Liu Y,Wang B,et al.Kilogram-scale synthesis of carbon quantum dots for hydrogen evolution,sensing and bioimaging[J].Chinese Chem Lett,2019,30(12):2323-2327.
[13] Muthamma K,Sunil D,Shetty P.Carbon dots as emerging luminophores in security inks for anti-counterfeit applications—An up-to-date review[J].Appl Mater Today,2021,23:101050.
[14] Zhang Y,He J.Facile synthesis of S,N co-doped carbon dots and investigation of their photoluminescence properties[J].Phys Chem Chem Phys,2015,17(31):20154-20159.
[15] Long P,Feng Y,Cao C,et al.Self-protective room-temperature phosphorescence of fluorine and nitrogen codoped carbon dots[J].Adv Funct Mater,2018,28(37):1800791.
[16] Gao Y,Han H,Lu W,et al.Matrix-free and highly efficient room-temperature phosphorescence of nitrogen-doped carbon dots[J].Langmuir,2018,34(43):12845-12852.
[17] Pang Y,Zhao R,Lu Y,et al.Facile preparation of N-doped graphene quantum dots as quick-dry fluorescent ink for anti-counterfeiting[J].New J Chem,2018,42(20):17091-17095.
[18] 唐志姣,李攻科,胡玉玲.氮掺杂碳点的制备及在定量分析中的应用[J].化学进展,2016,28(10):1455-1461.
[19] Berdimurodov E,Verma D K,Kholikov A,et al.The recent development of carbon dots as powerful green corrosion inhi-bitors:a prospective review[J].J Mol Liq,2022,349:118124.
[20] Li H,Ye S,Guo J,et al.The design of room-temperature-phosphorescent carbon dots and their application as a security ink[J].J Mater Chem C,2019,7(34):10605-10612.
[21] Cao L,Zan M,Chen F,et al.Formation mechanism of carbon dots:from chemical structures to fluorescent behaviors[J].Carbon,2022,194:42-51.
[22] Xu A,Wang G,Li Y,et al.Carbon-based quantum dots with solid-state photoluminescent:mechanism,implementation,and application[J].Small,2020,16(48):2004621.
[23] Kwon W,Do S,Kim J H,et al.Control of photoluminescence of carbon nanodots via surface functionalization using para-substituted anilines[J].Sci Rep,2015,5(1):1-10.
[24] Shi B,Su Y,Zhang L,et al.Nitrogen and phosphorus co-doped carbon nanodots as a novel fluorescent probe for highly sensitive detection of Fe3+ in human serum and living cells[J].ACS Appl Mater Interfaces,2016,8(17):10717-10725.
[25] 岑丝丝,刘丽,陈彤,等.柠檬酸碳点荧光油墨的制备及其荧光性能[J].包装工程,2021,42(21):98-104.
[26] 王子儒,张光华,郭明媛.N掺杂碳量子点光稳定剂的制备及光学性能[J].发光学报,2016,37(6):655-661.
基金资助
安徽省自然科学基金(2008085ME138)
PDF
