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

doi:10.15541/jim20190642

Abstract

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

CLC Number:

TQ174

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.

Figures/Tables 9

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

Fig. 1 XRD patterns of MOF and composite materials

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

Fig. 3 Excitation spectrum and fluorescence emission spectrum (a), and optical photo of MOF (b)

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)

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)

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)

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)

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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