CN114605990B - 一种高单色性的近红外荧光碳点及其合成方法和应用 - Google Patents
一种高单色性的近红外荧光碳点及其合成方法和应用 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 48
- 238000001308 synthesis method Methods 0.000 title claims abstract description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001447 alkali salts Chemical class 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000012445 acidic reagent Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 20
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004220 aggregation Methods 0.000 claims description 4
- 230000002776 aggregation Effects 0.000 claims description 4
- 238000012984 biological imaging Methods 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 3
- 239000000447 pesticide residue Substances 0.000 claims description 3
- 239000000523 sample Substances 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000012769 display material Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 claims 1
- 229940124597 therapeutic agent Drugs 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 2
- UZCGKGPEKUCDTF-UHFFFAOYSA-N fluazinam Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=C(Cl)C([N+]([O-])=O)=C1NC1=NC=C(C(F)(F)F)C=C1Cl UZCGKGPEKUCDTF-UHFFFAOYSA-N 0.000 description 13
- 239000005780 Fluazinam Substances 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
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- 238000002360 preparation method Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
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- 238000001514 detection method Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
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- GJUABKCEXOMRPQ-UHFFFAOYSA-N 1-[(2,5-dimethoxyphenyl)diazenyl]naphthalen-2-ol Chemical compound COC1=CC=C(OC)C(N=NC=2C3=CC=CC=C3C=CC=2O)=C1 GJUABKCEXOMRPQ-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- 235000010149 Brassica rapa subsp chinensis Nutrition 0.000 description 1
- 235000000536 Brassica rapa subsp pekinensis Nutrition 0.000 description 1
- 241000499436 Brassica rapa subsp. pekinensis Species 0.000 description 1
- 241000026010 Dendrobium candidum Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 244000299452 Gouania lupuloides Species 0.000 description 1
- 235000000292 Gouania lupuloides Nutrition 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- 241000488583 Panonychus ulmi Species 0.000 description 1
- 244000025272 Persea americana Species 0.000 description 1
- 235000008673 Persea americana Nutrition 0.000 description 1
- 241000233622 Phytophthora infestans Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
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- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 238000007146 photocatalysis Methods 0.000 description 1
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
本发明属于荧光碳点的技术领域,具体涉及一种高单色性的近红外荧光碳点及其合成方法和应用。其合成方法如下:1)将邻苯二胺、氧化剂和强酸强碱盐溶于去离子水中,搅拌均匀之后加入酸性试剂,于120~260℃下反应1~36小时;2)步骤1)的反应物冷却至室温,将反应液和沉淀物分离,将沉淀物用去离子水、正丁醇洗涤、烘干,即得到碳点粉末,所制得的近红外荧光碳点的荧光单色性好,具有双发性质,碳点的纯化通过过滤与洗涤即可得到,纯化方式简单,耗时短,表明通过本发明的合成方法得到的近红外荧光碳点性能较为优异,具高单色性以及高产率。
Description
技术领域
本发明属于荧光碳点的技术领域,具体涉及一种高单色性的近红外荧光碳点及其合成方法和应用。
背景技术
碳量子点是一种碳基零维材料,由于其具有生物相容性好、细胞低毒性、制备成本低、光致发光以及发射波长可调控等优势,在光催化、发光设备、生物成像、光电转换、分析检测等多领域应用广泛。例如具高荧光量子产率的碳点可以作为制备LED的材料,具有超窄发射的碳点可以作为激光材料,具有深红色或者近红外发射的碳点用于生物成像,利用碳点的光电性质作为制备太阳能电池材料,利用其催化性能作为电催化材料和光催化材料,利用其荧光可被淬灭或增强性质作为光学传感探针用于分析检测。
现有技术所制备的碳量子点主要存在如下问题,1)碳点的荧光单色性差,荧光单色性在荧光光谱中用发射峰半高峰宽(FWHM)表示,荧光单色性高对改善具有最小背景噪声的成像对比度,增加显示器高色纯度,甚至可作为激光发射材料等要重要意义;2)碳点的分离纯化以及高产率制备有困难,现阶段碳点的分离纯化主要是透析和色谱柱,这两种方法繁琐耗时,无法扩大规模,而高产率生产是广泛应用的基础;3)荧光调节有困难,难以达到要求,使得荧光调节的方法方便对于拓展荧光碳点的应用尤为关键。
氟啶胺作农作物的光谱抑菌剂,氟啶胺对鳄梨白根腐病、大白菜根肿病、马铃薯晚疫病、铁皮石斛灰霉病、柑橘红蜘蛛等均具有良好的防治效果。农药残留联合专家会议(JMPR)在2018年的报告中指出将植物源中氟啶胺残留定义为氟啶胺,而建立快速灵敏检测氟啶胺的方法非常重要。
发明内容
针对上述问题,本发明的目的在于提供一种高单色性的近红外荧光碳点及其合成方法和应用,通过本发明的合成方法得到的近红外荧光碳点性能较为优异,具高单色性以及高产率。
本发明的技术内容如下:
本发明的一种高单色性的近红外荧光碳点的合成方法,包括如下步骤:
1)将邻苯二胺、氧化剂和强酸强碱盐溶于去离子水中,搅拌均匀之后加入酸性试剂,于120~260℃下反应1~36小时;
2)步骤1)的反应物冷却至室温,将反应液和沉淀物分离,将沉淀物用去离子水、正丁醇洗涤、烘干,即得到碳点粉末;
步骤1)所述邻苯二胺的使用浓度为1 mol/L;
所述氧化剂的使用浓度为0.1~3 mol/L;
所述强酸强碱盐的使用浓度为0~3 mol/L;
所述酸性试剂(H+浓度)的使用浓度为0.1~3 mol/L;
所述氧化剂包括双氧水、高氯酸、硝酸、高氯酸钠、硝酸银、氯化铁、硝酸铁、硫酸铁中的一种或以上的组合;
所述强酸强碱盐包括氯化钠、硫酸钠、硝酸钠、硝酸钾、氯化钾、硫酸钾、硝酸钙、硝酸钡、氯化钡、氯化钙的一种;
所述酸性试剂包括98.0%硫酸、36.0%盐酸、85%磷酸、65.0%硝酸、70.0%高氯酸、40.0%硒酸、48.0%氢溴酸、55.0%氢碘酸的一种;
所述用于碳点的分散剂包括但不限于乙醇、N,N-二甲基甲酰胺、二甲基亚砜的一种,在溶液中测得碳点的紫外-可见吸收光谱、激发光谱和发射光谱。
本发明还提供了一种上述制备方法得到的近红外荧光碳点,其在600 nm的发射峰半高峰宽达到20 nm,近红外区发射的发射半高峰宽达到30 nm;
所述近红外区的发射波长为658-683 nm;
所述近红外光区的发射类型为聚集诱导发射。
本发明还提供了一种上述制备方法得到的近红外荧光碳点应用于制备LED的材料、激光材料和显示器材料以及用于生物成像、光热治疗试剂,用于制备光电转换材料、电催化材料、光催化材料,用于制备作为光学探针检测金属离子、阴离子、疾病标志物、环境污染物、物及杂质和农作物农药残留药等(如氟啶胺)。
本发明的有益效果如下:
本发明的近红外荧光碳点具有如下优点:1)荧光单色性好,荧光光谱中半高峰宽(FWHM)越窄、其荧光单色性越高,本发明的近红外荧光碳点在600 nm处发射的半高峰宽能达到20 nm,近红外区的发射半高峰宽能达到30 nm,具备超窄发射的特点; 2)具有双发性质,分别为600 nm处发射和聚集诱导发射,其中聚集诱导发射随着碳点浓度升高,其发射能达近红外区;3)通过控制氧化剂剂量使得碳点产率高于80%,高效合成碳点能够降低合成成本;4)碳点的纯化通过过滤与洗涤即可得到,纯化方式简单,耗时短,表明通过本发明的合成方法得到的近红外荧光碳点性能较为优异,具高单色性以及高产率。
本发明的近红外荧光碳点的合成方法中,采用邻苯二胺、氧化剂以及酸作为反应原料,其中,氧化剂的用量与碳点产量具有线性关系;碳点发射峰展宽与脱水碳化程度相关,酸能够使得脱水碳化更为剧烈。强酸强碱盐的作用是改变离子强度和疏水作用,最终导致碳点自组装形成类硝酸石墨结构。
附图说明
图1为本发明的近红外荧光碳点的XRD图;
图2为本发明的近红外荧光碳点的SEM图;
图3为本发明的近红外荧光碳点的傅里叶转换红外光谱图;
图4为本发明的近红外荧光碳点的XPS图谱;
图5为本发明的近红外荧光碳点的TEM和HRTEM图;
图6为本发明的近红外荧光碳点的紫外—可见吸收光谱;
图7为本发明的近红外荧光碳点的近红外发射的光谱图;
图8为本发明的近红外荧光碳点的粒径分布图;
图9为本发明的近红外荧光碳点的氧化剂用量与碳点产量的线性关系图;
图10为随着氟啶胺浓度增加碳点荧光光谱的变化;
图11为碳点600 nm处荧光强度与氟啶胺浓度的曲线关系。
具体实施方式
以下通过具体的实施案例以及附图说明对本发明作进一步详细的描述,应理解这些实施例仅用于说明本发明而不用于限制本发明的保护范围,在阅读了本发明之后,本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定。
若无特殊说明,本发明的所有原料和试剂均为常规市场的原料、试剂。
实施例1
一种高单色性的近红外荧光碳点的合成方法
1)将10 mmol 邻苯二胺、10 mmol NaClO4和1 mmol NaCl溶于19 mL去离子水中,搅拌均匀之后加入10 mmol HCl,于200℃下反应10小时;
2)步骤1)的反应物冷却至室温,将反应液和沉淀物分离,将沉淀物用去离子水、正丁醇洗涤、烘干,即得到近红外荧光碳点粉末,其产率为83.3%;
如图1所示,为近红外荧光碳点的XRD图,表明碳点粉末中含有高度有序的晶体结构,这种晶体结构为类硝酸石墨结构;
如图2所示,为近红外荧光碳点的SEM图,表明碳点粉末为层状结构的块状晶体结构,这种块状晶体结构为类硝酸石墨结构;
如图3所示,为近红外荧光碳点的傅里叶转换红外光谱图,表明近红外荧光碳点在500~3500 cm-1波数下的管光吸收;
如图4所示,为近红外荧光碳点的XPS图谱,其中,图a显示了碳点含有的元素,图b显示了碳原子种类,图c显示了氮原子种类,图d显示了氧原子种类;表明近红外荧光碳点主要由碳、氮和氧组成;
如图5所示,为近红外荧光碳点的TEM和HRTEM图,表明近红外荧光碳点分散性好,而且碳核形成了石墨烯结构;
如图6所示,为近红外荧光碳点溶液的紫外-可见吸收光谱图,表明近红外光碳点在250-660 nm内有吸收;
如图7所示,为近红外荧光碳点溶液在不同光波长下的荧光强度,图a显示在468nm的激发光下,在640-750 nm内有发射,表明在高浓度下发射可以达近红外区;图b显示碳点在458-503 nm的激发光下,在550-750 nm内有发射,表明600 nm处发射峰的FWHM为20nm,近红外发射峰的FWHM为30 nm;
实施例2
一种高单色性的近红外荧光碳点的合成方法
1)将10 mmol邻苯二胺、8 mmol氧化剂(H2O2、HClO4以摩尔数比为1:1组合)和1mmol NaSO4溶于19 mL去离子水中,搅拌均匀之后加入18 mmol H2SO4,于260℃下反应1小时;
2)步骤1)的反应物冷却至室温,将反应液和沉淀物分离,将沉淀物用去离子水、正丁醇洗涤、烘干,即得到碳点粉末。
实施例3
一种高单色性的近红外荧光碳点的合成方法
1)将10 mmol邻苯二胺、5 mmol氧化剂(HNO3、Fe(NO3)3以摩尔数比为1:1组合)和4mmol强酸强碱盐(NaNO3、KNO3以摩尔数比为1:1组合)溶于19 mL去离子水中,搅拌均匀之后加入5 mmol HClO4,于120℃下反应36小时;
2)步骤1)的反应物冷却至室温,将反应液和沉淀物分离,将沉淀物用去离子水、正丁醇洗涤、烘干,即得到碳点粉末。
实施例4
一种高单色性的近红外荧光碳点的合成方法
1)将10 mmol邻苯二胺、4 mmol氧化剂(HClO4、NaClO4以摩尔数比为1:1组合)和3mmol强酸强碱盐(NaCl、CaCl2以质量比为1:1组合)溶于19 mL去离子水中,搅拌均匀之后加入4 mmol酸性试剂(HBr、HI以摩尔数比为1:1组合),于150℃下反应15小时;
2)步骤1)的反应物冷却至室温,将反应液和沉淀物分离,将沉淀物用去离子水、正丁醇洗涤、烘干,即得到碳点粉末。
将以上所制备的碳点粉末分散于二甲基亚砜溶液中,并在其溶液中测得碳点的紫外-可见吸收光谱、激发光谱和发射光谱。
溶液传感法检测步骤如下:
1)将碳点分散在DMSO中,配置成为0.02 mg/mL的碳点溶液;
2) 将氟啶胺溶于DMF中,分别配置成为108 μmol/L、130 μmol/L、150 μmol/L、172μmol/L、194 μmol/L、218 μmol/L和258 μmol/L溶液;
3)取1.5 ml 步骤1)中的碳点溶液分别加入到1.5 mL步骤2)配置的氟啶胺溶液,测定碳点溶液的荧光变化。
如图8所示,为本发明的近红外荧光碳点的粒径分布图,表明所制备的碳点粒径较小且分布均匀。
如图9所示,图a为本发明的近红外荧光碳点的氧化剂(高氯酸)用量和碳点产量的线性关系图;图b为本发明的近红外荧光碳点的氧化剂(双氧水)用量和碳点产量的线性关系图。表明能通过氧化剂用量调节碳点产量,且得到的碳点纯度、产量高。
图10为随着氟啶胺浓度增加碳点荧光光谱的变化,表明氟啶胺能淬灭碳点荧光。
图11为碳点600 nm处荧光强度与氟啶胺浓度的曲线关系,表明碳点作为荧光传感器检测氟啶胺。
Claims (6)
1.一种高单色性的近红外荧光碳点的合成方法,其特征在于,包括如下步骤:
1)将邻苯二胺、氧化剂和强酸强碱盐溶于去离子水中,搅拌均匀之后加入酸性试剂,于120~260℃下反应1~36小时;
所述氧化剂包括双氧水、高氯酸、硝酸、高氯酸钠、硝酸银、氯化铁、硝酸铁、硫酸铁中的一种或以上的组合;
所述强酸强碱盐包括氯化钠、硫酸钠、硝酸钠、硝酸钾、氯化钾、硫酸钾、硝酸钙、硝酸钡、氯化钡、氯化钙的一种;
所述酸性试剂包括硫酸、盐酸、磷酸、硝酸、高氯酸、硒酸、氢溴酸、氢碘酸中的一种;
2)步骤1)的反应物冷却至室温,将反应液和沉淀物分离,将沉淀物用去离子水、正丁醇洗涤、烘干,即得到碳点粉末。
2.根据权利要求1所述的近红外荧光碳点的合成方法,其特征在于,步骤1)所述邻苯二胺的使用浓度为1 mol/L;
所述氧化剂的使用浓度为0.1~3 mol/L;
所述强酸强碱盐的使用浓度为0~3 mol/L;
所述酸性试剂的使用浓度为0.1~3 mol/L。
3.一种权利要求1或2所述合成方法得到的近红外荧光碳点,其特征在于,所述近红外荧光碳点在600 nm处的发射峰半高峰宽达到20 nm,近红外区的发射半高峰宽达到30 nm。
4.根据权利要求3所述的近红外荧光碳点,其特征在于,所述近红外区荧光的波长为658-683 nm。
5.根据权利要求3所述的近红外荧光碳点,其特征在于,所述近红外区发射为聚集诱导发射。
6.一种权利要求3~5任一项所述的近红外荧光碳点的应用,其特征在于,所述近红外碳点用于制备LED的材料、激光材料和显示器材料以及用于生物成像、光热治疗试剂,用于制备光电转换材料、电催化材料和光催化材料,用于制备光学传感探针检测农作物农药残留药氟啶胺。
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