CN110540836A - 一种石墨相氮化碳基绿光材料的制备方法 - Google Patents
一种石墨相氮化碳基绿光材料的制备方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- SDQJTWBNWQABLE-UHFFFAOYSA-N 1h-quinazoline-2,4-dione Chemical compound C1=CC=C2C(=O)NC(=O)NC2=C1 SDQJTWBNWQABLE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012071 phase Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
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- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000009102 absorption Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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Abstract
一种绿光材料的制备方法,将三聚氰胺和2,4‑喹唑啉二酮按一定质量比混合均匀在惰性气体保护下,高温聚合得到发射明亮绿光的石墨相氮化碳基绿光材料。本发明制备的绿光材料的发射波段在440~580 nm,最大发射波长在500 nm左右,且与没有掺杂2,4‑喹唑啉二酮的石墨相氮化碳相比,其荧光强度有明显的提高以及波长红移了约45 nm。由于本发明石墨相氮化碳基绿光材料是利用高温固相反应法制备的,具有工艺流程短、使用设备少、成本低、材料本身耐高温等优点,在荧光粉、化学传感、生物成像等方面具有潜在的应用价值。
Description
技术领域
本发明属于材料制备领域,具体涉及一种石墨相氮化碳基绿光材料的制备方法。
背景技术
近年来,石墨相氮化碳可作为一种优秀的二维叠加材料。在环境催化、能源催化、生物成像、电池、荧光材料、指纹识别等方面具有良好的应用价值。石墨相氮化碳的合成简易且成本低,直接用尿素、三聚氰胺、氰氨等聚合而得,上述优点表明可对其进行批量生产。
石墨相氮化碳作为一种发光材料,具有耐高温、原料成本低廉、荧光强度高、良好的生物相容性等优点,在荧光材料、生物成像、可视化荧光传感器的构建、防伪墨水等上均得到了较好的应用。其光致发光光谱位于蓝光区,通常为400~580 nm,最大发射波长为455nm。但是,将石墨相氮化碳改性后用作绿色、红色的荧光材料的研究和应用较少,因此可改进的空间还很大。目前可以调控石墨相氮化碳的发射波长的方法主要有以下两种:第一,将苯环等芳香环引入氮化碳的共轭结构,会引起氮化碳的π离域共轭体系和能带发生变化,从而导致氮化碳的荧光光谱发生红移[Cui Q , Xu J , Wang X , et al. Phenyl-ModifiedCarbon Nitride Quantum Dots with Distinct Photoluminescence Behavior[J].Angewandte Chemie, 2016, 128(11):3736-3740;CN 106833609A]。第二,以掺杂的方式将P等其他元素的原子掺入氮化碳中,石墨相氮化碳的最大发射峰会发生改变。[Jiang W,Yang S, Li J, et al. Electron Injection of Phosphorus Doped g‐C3N4 QuantumDots: Controllable Photoluminescence Emission Wavelength in the Whole VisibleLight Range with High Quantum Yield[J]. Advanced Optical Materials, 2016, 4]。但上述文献中所提到的合成石墨相氮化碳的方法均需要先进行预处理,再经过高温煅烧或者要在反应釜中进行才能获得产物,过程及反应条件较为苛刻。因此,研发一种合成工艺简易、成本低、可发射绿光的氮化碳具有重要的研究意义。
发明内容
本发明的目的在于提供一种石墨相氮化碳基绿光材料的简易制备方法。
为实现上述目的,本发明采用的制备方法是高温固相反应法。其具体步骤如下:将三聚氰胺和2,4-喹唑啉二酮按一定质量比混合放在研钵中研磨约30分钟,然后将研磨均匀的混合物置于500℃且有氩气保护的环境下高温聚合反应2~3小时。反应结束后,冷却至室温,最后得到黄色粉末,产率为58%~70%。
附图说明
图1为掺杂不同量2,4-喹唑啉二酮的氮化碳基绿光材料与未掺杂2,4-喹唑啉二酮的氮化碳粉末的荧光发射光谱对比图。
图2为实例1的绿光材料与未掺杂的氮化碳粉末的红外吸收光谱对比图。
图3为实例1所得的绿光材料与未掺杂的氮化碳粉末固体核磁碳谱对比图。
具体实施方式
实施例1
将三聚氰胺和2,4-喹唑啉二酮按质量比为18:1,分别称取1.89 g三聚氰胺和0.13 g2,4-喹唑啉二酮置于玛瑙研钵中研磨30分钟,然后放入刚玉坩埚中,于500 ℃在氩气保护下反应2小时。最后所得到黄色粉末为石墨相氮化碳基绿光材料。
实施例2
将三聚氰胺和2,4-喹唑啉二酮按质量比为20:1,分别称取1.89 g三聚氰胺和0.12 g2,4-喹唑啉二酮置于玛瑙研钵中研磨30分钟,然后放入刚玉坩埚中,于500 ℃在氩气保护下反应2小时。最后所得到黄色粉末为石墨相氮化碳基绿光材料。
实施例3
将三聚氰胺和2,4-喹唑啉二酮按质量比为22:1,分别称取1.89 g三聚氰胺和0.11 g2,4-喹唑啉二酮置于玛瑙研钵中研磨30分钟,然后放入刚玉坩埚中,于500 ℃在氩气保护下反应2小时。最后所得到黄色粉末为石墨相氮化碳基绿光材料。
对比实例
称取5 g三聚氰胺研磨后移入刚玉坩埚,于600 ℃下反应2小时,最后得到淡黄色的粉末为未掺杂的石墨相氮化碳荧光粉。
图1为2,4-喹唑啉二酮不同量掺杂的氮化碳粉末与对比实例未掺杂的氮化碳粉末的荧光发射光谱对比图。从图1可知,相较于发射蓝光的未掺杂的氮化碳粉末,本发明制备的绿光材料的最强发射峰红移了45 nm。
图2为实例1所得的绿光材料与对比实例所得未掺杂的氮化碳粉末的红外吸收光谱图对比图。从图2可知,在3426 cm-1、3485 cm-1处有双峰,但对比实例的谱图并未观察到明显的振动峰,表明−NH2、>NH数量增多了,源于2,4-喹唑啉二酮掺杂对原来较为完美的石墨相氮化碳结构有较大的破坏作用,处于边际的−NH2、>NH数量在增多。在3100~3000 cm-1处有两个小肩峰,此处是芳环(C−H)的伸缩振动产生的吸收峰。而实例1的氮化碳粉末1650~1450 cm-1处有吸收,表明结构中具有苯环。此外,实例1和未掺杂的氮化碳粉末在800 cm-1处均有吸收,说明2,4-喹唑啉二酮掺杂的氮化碳仍然保留了其七嗪环的结构。
图3为实例1所得的绿光材料与对比实例所得未掺杂的氮化碳粉末固体核磁碳谱对比图。图3中矩形范围内(128ppm~117ppm)的峰属于苯环上碳的核磁共振所得到的峰。
Claims (3)
1.利用高温固相反应法制备合成一种石墨相氮化碳基绿光材料,所需的原料为三聚氰胺和2,4-喹唑啉二酮按质量比18:1~22:1混合。
2.如权利要求1所述的绿光材料,其特征在于掺杂原料为2,4-喹唑啉二酮。
3.如权利要求1所述的绿光材料,其特征在于制备方法为高温固相反应法。包括如下步骤:将三聚氰胺和2,4-喹唑啉二酮按一定质量比混合,在研钵中研磨均匀,然后将研磨后的混合物置于500℃在氩气保护的下反应2~3小时。反应结束后,冷却至室温,得到的黄色粉末为最终产物。
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