CN103436255A - Preparation method of lanthanide ion loaded metal-organic framework material capable of realizing lighting adjustability and sensing property - Google Patents

Preparation method of lanthanide ion loaded metal-organic framework material capable of realizing lighting adjustability and sensing property Download PDF

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CN103436255A
CN103436255A CN2013104223678A CN201310422367A CN103436255A CN 103436255 A CN103436255 A CN 103436255A CN 2013104223678 A CN2013104223678 A CN 2013104223678A CN 201310422367 A CN201310422367 A CN 201310422367A CN 103436255 A CN103436255 A CN 103436255A
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title complex
lanthanide
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adjustability
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罗峰
罗明标
许文苑
刘淑娟
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East China Institute of Technology
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Abstract

The invention discloses a preparation method of a lanthanide ion loaded metal-organic framework material capable of realizing lighting adjustability and sensing property. The preparation method comprises the following steps: with Zn(NO3)2.6H2O, (NH4)6Mo7O24.4H2O and pyromellitic dianhydride as raw materials, complexing all the raw materials to obtain a complex; soaking the complex into an EuCl3 or Tb(ClO4)3 solution to respectively obtain a lanthanide doped complex; and soaking the doped complex into an MClx solution to respectively obtain complexes M-Eu@[NH4]2[ZnL].6H2O and M-Tb@[NH4]2[ZnL].6H2O. According to the invention, a novel lanthanide MOFs molecule with lighting adjustability and sensing property can be obtained through simple soaking; and the lanthanide doping operation is convenient, stable, efficient, strong in repeatability and favorable in control effect on the lighting adjustability and sensing property of MOFs.

Description

The preparation method of the existing luminous metal-organic framework materials that is in harmonious proportion sensing of load group of the lanthanides ion core
Technical field
The invention belongs to domain of inorganic chemistry, particularly the preparation method of the existing luminous metal-organic framework materials that is in harmonious proportion sensing of a kind of load group of the lanthanides ion core.
Background technology
Due to luminescent metal-organic framework materials (MOFs) have large specific surface area, aperture large and be evenly distributed, synthetic simple, the advantage such as structure can be predicted, be doomed that it has potential using value at aspects such as biomedicine, environment, molecule sensing, luminescent devices.The MOFs material has organic ligand and two kinds of compositions of inorganic metal ion, and its structural performance, than luminous organic material and phosphor, more complicated.Therefore MOFs material luminescence phenomenon can have multiple origin, as: luminous based on organic ligand, luminous based on lanthanide ion, luminous based on guest molecule, based on charge transfer, cause luminous.
Based on the luminous of lanthanide ion, it is one of modal luminous form of MOFs material.The transition of electron of lanthanide ion is protected because it is subject to the 5d shell, seldom is subject to the impact of chemical environment around it, thereby the light high color purity that sends of the MOFs material formed, and is the narrow characteristic emission peak of lanthanide ion substantially.Eu particularly 3+and Tb 3+
Utilizing emitted light there is long, the advantage such as intensity is strong, light is linear of life-span, and be subject to broad research.But, because 4f track transition in lanthanide ion is impossible occur, thus to the specific absorption of light a little less than, produce inefficient electron excitation, the light intensity sent very a little less than.Therefore it is unpractical using separately lanthanide ion luminous.In the MOFs material, the existence due to the coordination of organic ligand and lanthanide ion, solved this difficult problem just.Its luminescence mechanism can be explained by antenna effect, roughly can be divided into three steps: organic ligand absorbs energy; Energy is transferred to lanthanide ion from part; Lanthanide ion produces light.The sensitizing effect of organic ligand directly has influence on the quality of luminescent material, therefore when preparing lanthanide luminous MOFs, must carefully select suitable organic ligand.When considering suitable organic ligand, mandatory condition is: the lowest triplet state energy level of organic ligand higher than or equal the resonance energy of lanthanide ion, so just can make the charge transfer of organic ligand go to lanthanide ion, formation lanthanide luminous MOFs.
Although the luminous mechanism of lanthanide ion (coordination between metal-ligand or supramolecule orientation property) provides thinking for designing and preparing lanthanide luminous MOFs, yet the research situation according to current crystal engineering, reasonable design and prepare lanthanide luminous MOFs and still fail well to realize, the luminous sensing Study of An of relevant group of the lanthanides MOFs also is in the immature stage both at home and abroad.At present, a maximum difficult problem is exactly to explore the luminous sensing that is in harmonious proportion that a kind of efficient, repeated strong preparation method realizes MOFs.
Summary of the invention
Purpose of the present invention just is to provide the preparation method of the existing luminous metal-organic framework materials that is in harmonious proportion sensing of a kind of easy to operate, stable, efficient, strong load group of the lanthanides ion core of repeatability.
The preparation method of the existing luminous metal-organic framework materials that is in harmonious proportion sensing of load group of the lanthanides ion core of the present invention is with Zn (NO 3) 26H 2o, (NH 4) 6mo 7o 244H 2o and pyromellitic acid anhydride are raw material, a title complex [NH who obtains through coordination 4] 2[ZnL] 6H 2o, wherein L is Pyromellitic Acid, the rhombus duct of its one dimension is by counter ion NH 4 +occupied, this title complex is immersed in to EuCl 3or Tb (ClO 4) 3solution in, can obtain respectively the lanthanide ion doped complexes eu@[NH 4] 2[ZnL] 6H 2o and tb@[NH 4] 2[ZnL] 6H 2o.Then will eu@[NH 4] 2[ZnL] 6H 2o, tb@[NH 4] 2[ZnL] 6H 2o is immersed in MCl xin solution, (M=Na +or K +or Zn 2+or Ni 2+or Mn 2+or Co 2+or Cu 2+, when M is Na +or K +the time, X is 1; When M is Zn 2+or Ni 2+or Mn 2+or Co 2+or Cu 2+the time, X is 2), obtain respectively title complex m – Eu@[NH 4] 2[ZnL] 6H 2o and m – Tb@[NH 4] 2[ZnL] 6H 2o, its concrete preparation method is:
(1) get 1mmol Zn (NO 3) 26H 2o, 1mmol (NH 4) 6mo 7o 244H 2o and 0.5mmol pyromellitic acid anhydride are put into the tetrafluoroethylene reactor, add the 10ml water as solvent, are placed in retort furnace, be heated to 200 ℃, constant temperature 144 hours, then with per hour 3 degrees centigrade drop to room temperature or natural air drying, obtain colourless bulk crystals title complex [NH 4] 2[ZnL] 6H 2o, the L=Pyromellitic Acid.
(2) by title complex [NH 4] 2[ZnL] 6H 2o is immersed in 10 -3– 10 -6mol/L EuCl 3or 10 -3– 10 -7mol/L Tb (ClO 4) 3solution in, obtain respectively the lanthanide ion doped complexes eu@[NH 4] 2[ZnL] 6H 2o and tb@[NH 4] 2[ZnL] 6H 2o.
(3) get above-mentioned title complex eu@[NH 4] 2[ZnL] 6H 2o or tb@[NH 4] 2[ZnL] 6H 2o is immersed in 10 -2mol/L MCl xin solution, obtain respectively the lanthanide doped title complex that metal ion immerses m – Eu@[NH 4] 2[ZnL] 6H 2o or m – Tb@[NH 4] 2[ZnL] 6H 2o, M=Na +or K +or Zn 2+or Ni 2+or Mn 2+or Co 2+or Cu 2+.
The preparation method of the existing luminous metal-organic framework materials that is in harmonious proportion sensing of load group of the lanthanides ion core of the present invention, be that logical structure is crossed simple immersion and obtained a kind of novel luminous group of the lanthanides MOFs molecule that is in harmonious proportion sensing that has, this lanthanide ion doping is easy to operate, stable, efficient, repeated by force, the luminous sensing capabilities that is in harmonious proportion of MOFs is had to good regulating and controlling effect.
The accompanying drawing explanation
Fig. 1 is title complex [NH of the present invention 4] 2[ZnL] 6H 2o is along the rhombus duct of tomograph and the one dimension thereof of c-axis direction;
Fig. 2 is title complex [NH of the present invention 4] 2[ZnL] 6H 2o is immersed in different concns EuCl 3fluorescence spectrum figure in the aqueous solution;
Fig. 3 is title complex [NH of the present invention 4] 2[ZnL] 6H 2o is immersed in different concns Tb (ClO 4) 3fluorescence spectrum figure in the aqueous solution;
Fig. 4 is title complex of the present invention eu@[NH 4] 2[ZnL] 6H 2o is immersed in 10 -2mol/L MCl x(M=Na +, K +, Zn 2+, Ni 2+, Mn 2+, Co 2+, Cu 2+) exist respectively in the aqueous solution 5d 0- 7f 2or 5d 4- 7f 5transition intensity figure;
Fig. 5 is title complex of the present invention tb@[NH 4] 2[ZnL] 6H 2o is immersed in 10 -2mol/L MCl x(M=Na +, K +, Zn 2+, Ni 2+, Mn 2+, Co 2+, Cu 2+) exist respectively in the aqueous solution 5d 0- 7f 2or 5d 4- 7f 5transition intensity figure;
Fig. 6 is title complex of the present invention eu@[NH 4] 2[ZnL] 6H 2o is immersed in different concns CuCl 2or CoCl 2fluorescence spectrum figure in the aqueous solution;
Fig. 7 is title complex of the present invention tb@[NH 4] 2[ZnL] 6H 2o is immersed in different concns CuCl 2or CoCl 2fluorescence spectrum figure in the aqueous solution.
Embodiment
Embodiment 1:
Get 1mmolZn (NO 3) 26H 2o, 1mmol (NH 4) 6mo 7o 244H 2o and 0.5mmol pyromellitic acid anhydride are put into the tetrafluoroethylene reactor, add the 10mL water as solvent, are placed in retort furnace, are heated to 200 ℃, constant temperature 144 hours, and natural air drying can obtain colourless bulk crystals title complex [NH 4] 2[ZnL] 6H 2o, wherein L is Pyromellitic Acid; By title complex [NH 4] 2[ZnL] 6H 2o is immersed in 10 -3– 10 -6mol/L EuCl 3or 10 -3– 10 -7mol/L Tb (ClO 4) 3solution in, can obtain respectively lanthanide doped title complex eu@[NH 4] 2[ZnL] 6H 2o, tb@[NH 4] 2[ZnL] 6H 2o; By title complex eu@[NH 4] 2[ZnL] 6H 2o, tb@[NH 4] 2[ZnL] 6H 2o is immersed in 10 -2mol/L MCl x((M=Na +, K +, Zn 2+, Ni 2+, Mn 2+, Co 2+, Cu 2+) in solution, can obtain respectively again the lanthanide doped title complex that metal ion immerses m – Eu@[NH 4] 2[ZnL] 6H 2o, m – Tb@[NH 4] 2[ZnL] 6H 2o.
Respectively these several title complexs are carried out to EA, ICP, PXRD analysis, by PXRD, analyze and can find eu@[NH 4] 2[ZnL] 6H 2o, tb@[NH 4] 2[ZnL] 6H 2o and [NH 4] 2[ZnL] 6H 2the lattice difference of O, and m – Eu@[NH 4] 2[ZnL] 6H 2o, m – Tb@[NH 4] 2[ZnL] 6H 2o (M=Co 2+, Cu 2+) lattice also respectively with eu@[NH 4] 2[ZnL] 6H 2o, tb@[NH 4] 2[ZnL] 6H 2o is not identical; Known by icp analysis, by title complex [NH 4] 2[ZnL] 6H 2o arrives eu@[NH 4] 2[ZnL] 6H 2o, tb@[NH 4] 2[ZnL] 6H 2eu (III) or Tb (III) and (NH, occurred in O 4) +cationic exchange, and eu@[NH 4] 2[ZnL] 6H 2o, tb@[NH 4] 2[ZnL] 6H 2o arrives m – Eu@[NH 4] 2[ZnL] 6H 2o, m – Tb@[NH 4] 2[ZnL] 6H 2o, Co 2+or Cu 2+replaced Eu (III)/Tb (III) and (NH 4) +.Luminous, sensing capabilities research show: (1) title complex is at [NH 4] 2[ZnL] 6H 2o is that the 437nm place has hyperfluorescenceZeng Yongminggaoyingguang at wavelength, is blue emission, and this may be part to due to the charge transfer of metal.(2) title complex [NH 4] 2[ZnL] 6H 2o is immersed in 10 -3mol/L EuCl 3gained eu@[NH 4] 2[ZnL] 6H 2o is luminous is red emission; Work as EuCl 3strength of solution 10 -6when mol/L is following, the title complex of lanthanide ion doping is very little to luminous adjustable effect.(3) title complex [NH 4] 2[ZnL] 6H 2o is immersed in 10 -3mol/L Tb (ClO 4) 3gained tb@[NH 4] 2[ZnL] 6H 2o is green emission; As Tb (ClO 4) 3strength of solution 10 -7when mol/L is following, the title complex of lanthanide ion doping is insignificant to luminous adjustable effect.The emmission spectrum of the title complex of these two kinds of lanthanide ion doping presents the characteristic emission spectrum of Eu (III) or Tb (III) ion.(4) the lanthanide doped title complex that metal ion immerses m – Eu@[NH 4] 2[ZnL] 6H 2o, m – Tb@[NH 4] 2[ZnL] 6H 2the luminous of O depends primarily on metal ion characteristic: Na +, K +, Zn 2+on the not impact of luminous intensity of title complex, other several metal ion species have quenching effect to the luminous intensity of title complex.Particularly, exist m – Eu@[NH 4] 2[ZnL] 6H 2in O, Cu 2+there is the most significantly impact, and m – Tb@[NH 4] 2[ZnL] 6H 2in O, Co 2+there is impact the most significantly.The title complex of lanthanide ion doping eu@[NH 4] 2[ZnL] 6H 2o or tb@[NH 4] 2[ZnL] 6H 2the luminescence sensor that O can be used as highly selective, highly sensitive, low detectability detects the Cu in the aqueous solution 2+or Co 2+.

Claims (1)

1. the preparation method of the existing luminous metal-organic framework materials that is in harmonious proportion sensing of a load group of the lanthanides ion core, it is characterized in that: concrete steps are to get 1mmolZn (NO 3) 26H 2o, 1mmol (NH 4) 6mo 7o 244H 2o and 0.5mmol pyromellitic acid anhydride are put into the tetrafluoroethylene reactor, add the 10mL water as solvent, be placed in retort furnace, be heated to 200 ℃, constant temperature 144 hours, then with per hour 3 degrees centigrade drop to room temperature or natural air drying can obtain colourless bulk crystals title complex [NH 4] 2[ZnL] 6H 2o, wherein L is Pyromellitic Acid; By title complex [NH 4] 2[ZnL] 6H 2o is immersed in 10 -3– 10 -6mol/L EuCl 3or 10 -3– 10 -7mol/L Tb (ClO 4) 3solution in, obtain respectively the title complex of lanthanide ion doping eu@[NH 4] 2[ZnL] 6H 2o, tb@[NH 4] 2[ZnL] 6H 2o; By title complex eu@[NH 4] 2[ZnL] 6H 2o, tb@[NH 4] 2[ZnL] 6H 2o is immersed in 10 -2mol/L MCl xin solution, obtain respectively the lanthanide doped title complex that metal ion immerses m – Eu@[NH 4] 2[ZnL] 6H 2o, m – Tb@[NH 4] 2[ZnL] 6H 2o, M=Na +or K +or Zn 2+or Ni 2+or Mn 2+or Co 2+or Cu 2+.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109663575A (en) * 2019-01-22 2019-04-23 内蒙古农业大学 A kind of adsorbable rare earth special metal La-MOFs adsorbent material of australene targeting intelligence and preparation method thereof
CN109810256A (en) * 2019-01-30 2019-05-28 江苏理工学院 A kind of ternary heteronuclear metal organic framework luminescent material and its preparation method and application
CN110498930A (en) * 2019-09-17 2019-11-26 江西省吉安市水文局(江西省吉安市水资源监测中心) A kind of preparation method and applications of Lanthanide Coordination Polymers nano material
CN112816414A (en) * 2021-01-07 2021-05-18 武汉大学 Alkaline phosphatase detection kit based on dual-emission lanthanide MOF and detection method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011081779A2 (en) * 2009-12-15 2011-07-07 Uop Llc Metal organic framework polymer mixed matrix membranes
WO2011133999A1 (en) * 2010-04-30 2011-11-03 Commonwealth Scientific And Industrial Research Organisation Crystallisation facilitators for the synthesis of metal organic frameworks
CN102584865A (en) * 2012-01-30 2012-07-18 东华理工大学 Preparation method of zinc complex with light emitting adjustability and white light emitting property

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011081779A2 (en) * 2009-12-15 2011-07-07 Uop Llc Metal organic framework polymer mixed matrix membranes
WO2011133999A1 (en) * 2010-04-30 2011-11-03 Commonwealth Scientific And Industrial Research Organisation Crystallisation facilitators for the synthesis of metal organic frameworks
CN102584865A (en) * 2012-01-30 2012-07-18 东华理工大学 Preparation method of zinc complex with light emitting adjustability and white light emitting property

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FENG LUO等: "Metal–organic framework (MOF): lanthanide(III)-doped approach for luminescence modulation and luminescent sensing", 《DALTON TRANSACTIONS》 *
SHUJUAN LIU等: "The first transition-metal metal–organic framework showing cation exchange for highly selectively sensing of aqueous Cu(II) ions", 《INORGANIC CHEMISTRY COMMUNICATIONS》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109663575A (en) * 2019-01-22 2019-04-23 内蒙古农业大学 A kind of adsorbable rare earth special metal La-MOFs adsorbent material of australene targeting intelligence and preparation method thereof
CN109663575B (en) * 2019-01-22 2021-10-26 内蒙古农业大学 Special rare earth metal La-MOFs adsorption material for alpha-pinene targeted intelligent adsorption and preparation method thereof
CN109810256A (en) * 2019-01-30 2019-05-28 江苏理工学院 A kind of ternary heteronuclear metal organic framework luminescent material and its preparation method and application
CN109810256B (en) * 2019-01-30 2021-08-24 江苏理工学院 Ternary heteronuclear metal organic framework luminescent material and preparation method and application thereof
CN110498930A (en) * 2019-09-17 2019-11-26 江西省吉安市水文局(江西省吉安市水资源监测中心) A kind of preparation method and applications of Lanthanide Coordination Polymers nano material
CN112816414A (en) * 2021-01-07 2021-05-18 武汉大学 Alkaline phosphatase detection kit based on dual-emission lanthanide MOF and detection method

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Application publication date: 20131211