基于镉的MOF/染料复合材料的制备及荧光性能研究

doi:10.15541/jim20190642

无机材料学报 ›› 2020, Vol. 35 ›› Issue (10): 1123-1129.DOI: 10.15541/jim20190642

所属专题：功能材料论文精选(二)：发光材料(2020)

基于镉的MOF/染料复合材料的制备及荧光性能研究

刘明珠^1,²(),牛传文^1,²,张欢欢³,邢彦军^1,²()

^1. 东华大学生态纺织教育部重点实验室, 上海201620
^2. 东华大学化学化工与生物工程学院, 上海 201620
^3. 上海市质量监督检验技术研究院, 上海 200030

收稿日期:2019-12-18 修回日期:2020-02-02 出版日期:2020-10-20 网络出版日期:2020-03-06
作者简介:刘明珠(1993-), 女, 硕士研究生. E-mail: mingzhu@163.com.
基金资助:
国家科技支撑计划项目(ID2012BAK30B03);中央高校基本科研业务费专项资金(2232013A3-05)

Preparation and Luminescence Properties of Cd-based MOF/Dye Composites

LIU Mingzhu^1,²(),NIU Chuanwen^1,²,ZHANG Huanhuan³,XING Yanjun^1,²()

^1. Key Laboratory of Science and Technology of Eco-Textiles, Ministry of Education, Donghua University, Shanghai 201620, China
^2. College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620, China
^3. Shanghai Institute of Quality Inspection and Technical Research, Shanghai 200030,China

Received:2019-12-18 Revised:2020-02-02 Published:2020-10-20 Online:2020-03-06
About author:LIU Mingzhu (1993-), female, Master candidate. E-mail: mingzhu@163.com
Supported by:
National Science and Technology Ministry(ID2012BAK30B03);Fundamental Research Funds for the Central Universities(2232013A3-05)

摘要/Abstract

摘要：

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: MOF, 染料, 复合材料, 荧光, 白光

Abstract:

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).

Key words: MOF, dye, composite, fluorescence, white light

中图分类号:

TQ174

刘明珠, 牛传文, 张欢欢, 邢彦军. 基于镉的MOF/染料复合材料的制备及荧光性能研究[J]. 无机材料学报, 2020, 35(10): 1123-1129.

LIU Mingzhu, NIU Chuanwen, ZHANG Huanhuan, XING Yanjun. Preparation and Luminescence Properties of Cd-based MOF/Dye Composites[J]. Journal of Inorganic Materials, 2020, 35(10): 1123-1129.

图/表 9

表1 样品编号及染料添加量

Table 1 Sample abbreviation and dye addition amount

Sample		CA addition (mol/1×10^-3mol Cd²⁺)	Addition ratio
Sample		CA addition (mol/1×10^-3mol Cd²⁺)	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

图1 MOF及复合材料的XRD图谱

Fig. 1 XRD patterns of MOF and composite materials

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

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 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)

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)

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)

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 Fig. 5(b); 4, 5 and 6 are CIE chromaticity coordinates of MOF/CA+CV in Fig. 6(b), and optical photos under sunlight and UV light at 365 nm (c)

表2 MOF/CA+RhB+CV中特征荧光峰强度的变化(R)

Table 2 Changes of intensity of characteristic fluorescence peaks(R)in MOF/CA+RhB+CV

Sample	Changes of intensity of characteristic fluorescence peak R
Sample	R_MOF	R_CA	R_RhB	R_CV
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

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基于镉的MOF/染料复合材料的制备及荧光性能研究

Preparation and Luminescence Properties of Cd-based MOF/Dye Composites

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