基于镉的MOF/染料复合材料的制备及荧光性能研究
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Preparation and Luminescence Properties of Cd-based MOF/Dye Composites
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通讯作者: 邢彦军, 教授. E-mail:yjxing@mail.dhu.edu.cn.
收稿日期: 2019-12-18 修回日期: 2020-02-2 网络出版日期: 2020-10-20
基金资助: |
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Corresponding authors: XING Yanjun, professor. E-mail:yjxing@mail.dhu.edu.cn
Received: 2019-12-18 Revised: 2020-02-2 Online: 2020-10-20
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作者简介 About authors
刘明珠(1993-),女,硕士研究生.E-mail:mingzhu@163.com.
LIUMingzhu(1993-),female,Mastercandidate.E-mail:mingzhu@163.com
采用常温原位一步法, 以Cd为金属离子, 间苯二甲酸和苯并咪唑为配体制备Cd基发光金属有机骨架(MOF)材料, 然后分别与钙黄绿素(CA)、罗丹明B(RhB)、结晶紫(CV)组装得到一系列荧光可调的MOF/CA、MOF/CA+RhB、MOF/CA+CV和MOF/CA+RhB+CV四种复合材料。探讨了染料初始添加量、比例对MOF/染料复合材料荧光性能的影响。结果表明, 随CA添加量的增加, 四种复合材料中CA特征荧光强度先增后减, 且呈现红移。添加量不变的RhB或CV荧光峰位置虽保持不变, 但荧光强度随CA量的增加而增强, 表明MOF和染料间存在能量转移。以Cd-MOF为平台, 通过调控三种染料摩尔配比制备得到具有白荧光的MOF/CA3+RhB+CV复合材料, 其色度坐标为(0.335, 0.321), 与理论白光坐标(0.333, 0.333)接近。
关键词:
A series of tunable-luminescence MOF/CA, MOF/CA+RhB, MOF/CA+CV and MOF/CA+RhB+CV composite light-emitting materials were prepared by combining calcein (CA), rhodamine B (RhB), crystal violet (CV) with MOF using Cd as metal ion, isophthalic acid and benzimidazole as ligand by the one-step method at room temperature. The influence of the initial addition amount and ratio of dyes on the fluorescence properties of MOF/Dye composites was discussed. With the increase of CA amount, the characteristic fluorescence emission intensity of CA increased firstly and then decreased accompanied with red-shift. Although the position of the characteristic fluorescence emission wavelength of RhB or CV remained unchanged due to the unchanged addition amount, the characteristic fluorescence emission intensity of CA changed like CA. MOF/CA3+RhB+CV composite with white light emission was further prepared by adjusting the molar ratio of dyes using MOF as a platform. Its chromaticity coordinate (0.335, 0.321) was close to the ideal white light coordinate (0.333, 0.333).
Keywords:
本文引用格式
刘明珠, 牛传文, 张欢欢, 邢彦军.
LIU Mingzhu, NIU Chuanwen, ZHANG Huanhuan, XING Yanjun.
目前已经报道的基于MOF的白光发光材料, 通常掺杂稀土元素(RE)实现白光发射[7,8]。但近来因稀土材料的高成本[9]、稀土离子类型的限制, 越来越多的研究者将有机荧光染料封装在MOF孔内[10,11], 制备具有丰富发光特性的MOF/Dye复合材料[12]。同时, 虽然有机染料的热稳定性较低, 但当染料被MOF包覆后热分解温度比纯染料高, 表明MOF包覆在一定程度上减少了染料的热分解损失[13]。由于MOF孔洞的可装载性、有机荧光染料种类的多样性, 以及MOF通道对染料分子的隔离可有效防止因聚集引起的猝灭(ACQ)[14,15]等特点, 使白光发射MOF/Dye复合材料的制备具有更多的选择性。同时, 有机荧光染料分子较高的量子产率、简单的化学调谐能力和快速的辐射发射率也极大地推动了MOF/Dye复合材料的发展。
本研究采用常温原位一步合成法, 以Cd为金属离子, 间苯二甲酸和苯并咪唑为配体, 将其与多组分荧光染料进行组装。通过调控三种染料的摩尔比, 制备具有白光发射的MOF/CA+RhB+CV复合材料。研究结果将为组装白光发射材料提供参考。
1 实验方法
1.1 材料
硝酸镉(Cd(NO3)2 4H2O)、间苯二甲酸、苯并咪唑和钙黄绿素(简称CA)均购于国药集团化学试剂有限公司; 醋酸钠购于上海凌风化学试剂有限公司; 罗丹明B(RhB)和结晶紫(CV)购于Adamas。实验用水均为蒸馏水。
1.2 Cd基双配体MOF的合成
在参照文献[16]的基础上, 以水作为溶剂, 在常温常压下合成Cd基双配体MOF材料: 将四水硝酸镉水溶液(0.32 gCd(NO3)2×4H2O, 10 mLH2O)加入到间苯二甲酸、苯并咪唑、醋酸钠的水溶液中 (0.16 g m-BDC、0.06 g BIM、0.574 g CH3COONa、10 mLH2O), 在常温条件下搅拌反应30 min后, 静置1 h, 然后离心, 用乙醇、蒸馏水依次清洗, 最后冷冻干燥, 得到白色固体粉末。
1.3 MOF/Dye复合材料的合成
将硝酸镉和染料混合水溶液, 加入到含有间苯二甲酸及苯并咪唑配体的水溶液中, 搅拌反应30 min, 室温静置1 h, 离心, 蒸馏水洗涤, 冷冻干燥得到粉末。
各样品编号及染料用量见表1, 其中, CA添加量以CA与制备MOF时Cd2+添加量的摩尔比表示。载有染料的MOF样品为染料CA时, 表示为MOF/CA; 多组分染料, 如CA+RhB, 表示为MOF/CA+RhB。次
级编号中, 数字下标表示染料的添加摩尔比, 如MOF/CA5+RhB+CV表示制备过程中, CA、RhB和CV的添加摩尔比为5 : 1 : 1。MOF/CA-3中CA的添加量与MOF/CA10+RhB、MOF/CA10+CV或MOF/ CA10+RhB+CV中CA的添加量相同。
表1 样品编号及染料添加量
Table 1
Sample | CA addition (mol/1×10-3mol Cd2+) | Addition ratio | ||
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CA/RhB | CA/CV | |||
MOF/CA | MOF/CA-1 | 1.25×10-7 | - | - |
MOF/CA-2 | 2.50×10-7 | - | - | |
MOF/CA-3(MOF/CA10) | 5.00×10-7 | - | - | |
MOF/CA-4 | 1.00×10-6 | - | - | |
MOF/CA-5 | 2.00×10-6 | - | - | |
MOF/CA+RhB | MOF/CA5+RhB | 2.5×10-7 | 5 : 1 | - |
MOF/CA10+RhB | 5.0×10-7 | 10 : 1 | - | |
MOF/CA20+RhB | 1.0×10-6 | 20 : 1 | - | |
MOF/CA+CV | MOF/CA5+CV | 2.5×10-7 | - | 5 : 1 |
MOF/CA10+CV | 5.0×10-7 | - | 10 : 1 | |
MOF/CA20+CV | 1.0×10-6 | - | 20 : 1 | |
MOF/CA+RhB+CV | MOF/CA1+RhB+CV | 5.0×10-8 | 1 : 1 | 1 : 1 |
MOF/CA3+RhB+CV | 1.5×10-7 | 3 : 1 | 3 : 1 | |
MOF/CA5+RhB+CV | 1.5×10-7 | 5 : 1 | 5 : 1 | |
MOF/CA10+RhB+CV | 5.0×10-7 | 10 : 1 | 10 : 1 | |
MOF/CA20+RhB+CV | 1.0×10-6 | 20 : 1 | 20 : 1 |
1.4 表征
使用D/MAX-2500VB+/PC型X射线衍射仪(Rigaku, 日本)对粉末的晶体结构进行测定, 测试条件为Cu靶、40 kV和200 mA, 扫描速度为20 (°)/min, 波长为0.15406 nm。使用TM-1000型扫描电子显微镜(HITACHI, 日本)对粉末表面形态进行表征。使用FS-5型荧光光谱仪(英国)测试样品的荧光激发和发射光谱。在WFH-204B型手持紫外灯照射(365 nm)下, 使用A7m3型索尼相机拍摄粉末光学照片。由荧光发射光谱, 在CIE1931标准色度系统中依据公式$X=\int_{380}^{780}{\bar{x}(\lambda )S(\lambda )\text{d}\lambda }$、$Y=\int_{380}^{780}{\bar{y}(\lambda )S(\lambda )\text{d}\lambda }$、$Z=\int_{380}^{780}{\bar{z}(\lambda )}S(\lambda )\text{d}\lambda $和$x=\frac{X}{X+Y+Z}$$、$$y=\frac{Y}{X+Y+Z}$$计算样品的CIE色度坐标。
2 结果与讨论
2.1 MOF和MOF/Dye的结构及形貌分析
图1
图2
图2
MOF及MOF/Dye的SEM照片
Fig. 2
SEM images of MOF and MOF/Dye
(a) MOF; (b) MOF/CA-3;(c) MOF/CA10+RhB; (d) MOF/CA10+CV; (e) MOF/CA10+RhB+CV
2.2 MOF/CA复合材料的荧光发光特性分析
图3
图3
MOF的激发光谱和荧光发射光谱(a)以及光学照片(b)
Fig. 3
Excitation spectrum and fluorescence emission spectrum (a), and optical photo of MOF (b)
图4
图4
MOF和MOF/CA的荧光发射图谱(a); CIE色度图(b), 日光和紫外光下光学照片(c)
Fig. 4
Fluorescence emission spectra of MOF and MOF/CA (a); CIE chromaticity diagram (b)( where 1: MOF/CA-1; 2: MOF/CA-2; 3: MOF/CA-3; 4: MOF/CA-4; 5: MOF/CA-5) and optical photos under daylight and UV light at 365 nm (c)
2.3 MOF/CA+RhB的荧光发光特性分析
保持RhB量不变, 改变CA的添加量, 制备MOF/CA+RhB(表1), 测定荧光发射光谱。从图5(a)可以看出: 在330 nm激发下, 三种MOF/CA+RhB均明显呈现MOF、CA、RhB的特征荧光发射。随CA添加量的增加, 荧光强度逐渐增强, 但不呈线性增强。当CA添加量由5 : 1增至10 : 1时, 荧光强度增强明显, 当CA添加量增至20 : 1时, 荧光强度增强不明显。同时, CA荧光峰从525 nm红移到535 nm。与CA荧光增强不同, 由于能量转移所致[18], MOF在364 nm处的荧光强度随CA添加量增加逐渐减弱。三种样品中RhB添加量不变, RhB荧光峰(588 nm)位置保持不变; 在CA添加量为5 : 1和10 : 1时, RhB荧光强度不变, 增至20 : 1时, 强度减弱。
图5
图5
MOF/CA+RhB的荧光发射光谱(a), CIE色度图(b), 日光和365 nm紫外光下的光学照片(c)
Fig. 5
Fluorescence emission spectra of MOF/CA+RhB (a), CIE chromaticity diagram (b) (where 1: MOF/CA5+RhB; 2: MOF/CA10+RhB; 3: MOF/CA20+RhB) and optical photos under sunlight and UV light at 365 nm (c)
2.4 MOF/CA+CV的荧光发光特性分析
图6
图6
MOF/CA+CV的荧光发射光谱(a), CIE色度图(b), 日光和365 nm紫外光下光学照片(c)
Fig. 6
Fluorescence emission spectra of MOF/CA+CV (a), CIE chromaticity diagram (b)(where 4: MOF/CA5+CV; 5: MOF/CA10+CV; 6: MOF/CA20+CV)and optical photos under sunlight and UV light at 365 nm (c)
2.5 MOF/CA+RhB+CV的荧光发光特性分析
图7
图7
MOF/CA+RhB+CV的荧光发射光谱(a), CIE色度图(b), 日光和365 nm紫外光下光学照片(c)
Fig. 7
Fluorescence emission spectra of MOF/CA+RhB+CV
(a), CIE chromaticity diagram (b), where 7: MOF/CA20+RhB+CV; 8: MOF/CA10+RhB+CV; 9: MOF/CA5+RhB+CV; 10: MOF/CA3+RhB+CV; 11: MOF/CA1+RhB+CV; 1, 2, 3 are CIE chromaticity coordinates of MOF/CV+RhB in
对MOF/CA+RhB+CV中特征荧光峰强度变化进行了计算, 见表2。特征荧光峰强度变化R计算方式, 以RMOF为例: $${{R}_{\text{MOF}}}=\frac{{{I}_{\text{MOF in MOF/C}{{\text{A}}_{x}}\text{+}}}_{\text{RhB+CV}}}{{{I}_{\text{MOF in MOF/C}{{\text{A}}_{\text{1}}}\text{+}}}_{\text{RhB+CV}}}$$从表2中可知, 随CA添加量增加, 特征荧光峰强度变化RMOF逐渐降低, RCA、RRhB和RCV呈现先增后减的趋势。由于RhB或CV的添加量不变, RhB或CV的荧光强度变化与CA的添加量密切相关。
表2 MOF/CA+RhB+CV中特征荧光峰强度的变化(R)
Table 2
Sample | Changes of intensity of characteristic fluorescence peak R | |||
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RMOF | RCA | RRhB | RCV | |
MOF/CA1+RhB+CV | 1.00 | 1.00 | 1.00 | 1.00 |
MOF/CA3+RhB+CV | 0.71 | 1.79 | 0.92 | 0.95 |
MOF/CA5+RhB+CV | 0.70 | 2.70 | 1.28 | 1.17 |
MOF/CA10+RhB+CV | 0.52 | 4.31 | 1.69 | 1.38 |
MOF/CA20+RhB+CV | 0.28 | 3.15 | 1.30 | 1.12 |
3 结论
通过调控染料的初始添加量及摩尔比, 本研究采用常温原位一步法制备了一系列荧光可调的四种复合材料MOF/CA、MOF/CA+RhB、MOF/CA+CV和MOF/CA+RhB+CV。研究结果表明, 染料聚集诱导荧光减弱或猝灭, MOF与染料间存在能量转移。随CA添加量的增加, 四种复合材料中MOF的特征荧光强度逐渐减弱, CA特征荧光强度先增后减, 且荧光发射波长呈现单一红移。RhB或CV添加量不变, 虽然RhB或CV的荧光发射峰位置保持不变, 但它们的荧光强度随CA添加量的增加而增强。以MOF为平台, 利用染料间、MOF与染料间的能量转移和色光三原色的发光原理制备得到MOF/CA+RhB+ CV。其中, MOF/CA3+RhB+CV的色度坐标为(0.335, 0.321), 与理论白光坐标接近。
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