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CN-121974959-A - Fluorescent temperature sensing material based on 3d/4f complex and preparation method and application thereof

CN121974959ACN 121974959 ACN121974959 ACN 121974959ACN-121974959-A

Abstract

The invention belongs to the technical field of luminescent functional materials and temperature sensing, and particularly relates to a fluorescent temperature sensing material based on a 3d/4f complex, and a preparation method and application thereof. The fluorescent temperature sensing material based on the 3d/4f complex is prepared from Schiff base ligand H 2 L, samarium nitrate hexahydrate and anhydrous zinc acetate serving as reaction raw materials by an evaporation crystallization method, wherein the structural formula of the Schiff base ligand H 2 L is as follows The fluorescent temperature sensing material based on the 3d/4f complex provided by the invention has the molecular structural formula of [ ZnLSm (CH 3 OH)(NO 3 ) 2 ]. The fluorescent temperature sensing material based on the 3d/4f complex can be kept stable in a wide temperature range and has a linear fluorescence intensity ratio, can realize quantitative detection or visual detection of temperature, has high detection sensitivity, can provide a technical foundation and development direction for development of the temperature sensing material, and has excellent application value and prospect.

Inventors

  • GAO SONG
  • XIA YE

Assignees

  • 华南理工大学

Dates

Publication Date
20260505
Application Date
20260129

Claims (10)

  1. 1. The fluorescent temperature sensing material based on the 3d/4f complex is characterized in that the fluorescent temperature sensing material based on the 3d/4f complex is prepared by taking Schiff base ligand H 2 L, samarium nitrate hexahydrate and anhydrous zinc acetate as reaction raw materials through an evaporation crystallization method, wherein the structural formula of the Schiff base ligand H 2 L is as follows The molecular structural formula of the fluorescent temperature sensing material based on the 3d/4f complex is [ ZnLSm (CH 3 OH)(NO 3 ) 2 ].
  2. 2. A method for preparing a 3d/4f complex-based fluorescent temperature sensing material according to claim 1, comprising the steps of: Mixing Schiff base ligand H 2 L, samarium nitrate hexahydrate and anhydrous zinc acetate in a solvent, then heating, stirring and reacting, and filtering after the reaction to obtain crystals, namely the fluorescent temperature sensing material based on the 3d/4f complex.
  3. 3. The preparation method of the fluorescent temperature sensing material based on the 3d/4f complex according to claim 2, wherein the molar ratio of the Schiff base ligand H 2 L, the samarium nitrate hexahydrate and the anhydrous zinc acetate is 1:0.8-1.2:0.8-1.2.
  4. 4. The method for preparing a fluorescent temperature sensing material based on a 3d/4f complex according to claim 2, wherein the solvent is one or two of methanol and acetonitrile.
  5. 5. The method for preparing a fluorescent temperature sensing material based on a 3d/4f complex according to claim 2, wherein the corresponding solvent dosage is 4-6 mL per 0.1mmol of Schiff base ligand H 2 L.
  6. 6. The method for preparing a fluorescent temperature sensing material based on a 3d/4f complex according to any one of claims 2 to 5, wherein the temperature of the heating and stirring reaction is 60 to 80 ℃, the stirring speed is 600 to 1000r/min, and the time is 10 to 20 hours.
  7. 7. Use of a 3d/4f complex-based fluorescent temperature sensing material according to claim 1 for quantitative or visual detection of temperature.
  8. 8. The application of the 3d/4f complex-based fluorescent temperature sensing material in quantitative detection or visual detection of temperature, according to claim 7, wherein the detection temperature range of the 3d/4f complex-based fluorescent temperature sensing material is 233-333K.
  9. 9. The use of a 3d/4f complex-based fluorescent temperature sensing material for quantitative or visual detection of temperature according to claim 7, wherein the quantitative detection of temperature using a 3d/4f complex-based fluorescent temperature sensing material comprises the following detection steps: (1) Preparing a fluorescent temperature sensing material based on a 3d/4f complex into a solution form to obtain a fluorescent temperature sensing solution; (2) Contacting a sample to be detected by adopting a fluorescent temperature sensing solution to realize temperature detection; (3) And (3) measuring the fluorescence intensity of the fluorescence temperature sensing solution at 644nm and 470nm after contacting the sample to be measured, and substituting the ratio of the fluorescence intensity at 644nm and 470nm into a pre-established standard curve to obtain the temperature of the sample to be measured.
  10. 10. The use of a 3d/4f complex-based fluorescent temperature sensing material in quantitative or visual detection of temperature according to claim 7, wherein the visual detection of temperature using a 3d/4f complex-based fluorescent temperature sensing material comprises the following detection steps: (a) Preparing a fluorescent temperature sensing material based on a 3d/4f complex into a solution form to obtain a fluorescent temperature sensing solution; (b) Contacting a sample to be detected by adopting a fluorescent temperature sensing solution to realize temperature detection; (c) And observing the color of the fluorescent temperature sensing solution after contacting the sample to be detected by naked eyes, and judging the temperature range of the sample to be detected according to the color.

Description

Fluorescent temperature sensing material based on 3d/4f complex and preparation method and application thereof Technical Field The invention belongs to the technical field of luminescent functional materials and temperature sensing, and particularly relates to a fluorescent temperature sensing material based on a 3d/4f complex, and a preparation method and application thereof. Background In recent years, the market size and market prospect of global temperature sensors have been expanding. The traditional thermocouple, thermistor and infrared temperature measuring material expose three short plates with unknown contact interference and emissivity and invalid electromagnetic shielding in the scenes of lithium batteries, high-power chips, aeroengines and the like. Meanwhile, the 5G base station, the solid-state battery and the silicon carbide electric drive system require the temperature sensor to realize sub-millisecond response in the interval of-40 ℃ to 1000 ℃, the accuracy of +/-0.1 ℃ and micron-sized spatial resolution, and can stably work for a long time under high voltage, strong radiation and severe vibration, which provides unprecedented challenges for temperature sensing materials and packaging technology. The fluorescence temperature sensing utilizes the internal law that the energy level of the luminescence center is changed along with the temperature, the non-contact, electromagnetic interference resistance, micron space resolution and millisecond response can be realized without electric connection, and the self-calibration Fluorescence Intensity Ratio (FIR) mode can offset the fluctuation of a light source and the concentration difference of a probe, and the long-term drift is less than 0.5%. At present, the fluorescent temperature sensing technology is used for early warning of thermal runaway in a lithium battery, junction temperature mapping of a high-power LED, surface temperature monitoring of an aviation turbine blade, real-time temperature control of tumor photothermal therapy and three-dimensional heat management of an integrated circuit, and provides an irreplaceable means for safety evaluation and failure analysis of extreme working conditions. The existing fluorescent temperature sensing materials can be divided into four types of rare earth doped inorganic solid solutions (YAG: tm, naYF 4: yb/Er), transition metal doped semiconductors (ZnO: mn, tiO 2: cr), organic/coordination polymers (MOF, B≡N tetra-coordinated boron) and carbon dots/quantum dots. The quantum dot, the carbon dot and the organic dye have the advantages of visible region emission and solution processing, but the signal drift is more than 5% due to surface oxidation and fluorescence bleaching at high temperature, the long-term working at the temperature of more than 150 ℃ is difficult, the d-d transition of a transition metal single doping system is easily influenced by lattice distortion and valence state fluctuation, the sensitivity changes +/-20% along with the partial pressure of environmental oxygen, the rare earth oxide block material has good thermal stability, but the bottlenecks of low phonon energy, narrow excitation band, high-power ultraviolet light source and the like exist, and the energy level cleavage is easily caused by the thermal expansion of the lattice, so that the calibration curve is irreversibly deviated. Therefore, how to develop a novel fluorescent temperature sensing material which can keep stable in a wide temperature range and realize accurate and sensitive detection of temperature has important application value. Disclosure of Invention Aiming at the problems, the invention aims to provide a fluorescent temperature sensing material based on a 3d/4f complex, and a preparation method and application thereof. The fluorescent temperature sensing material provided by the invention can keep stable in a wide temperature range and has linear fluorescent intensity ratio through the coordination of ligand field regulation and energy transmission, can realize quantitative detection or visual detection of temperature, and has high detection sensitivity. In order to achieve the above object, according to a first aspect of the present invention, a technical scheme is as follows: A fluorescent temperature sensing material based on a 3d/4f complex is prepared from Schiff base ligand H 2 L, samarium nitrate hexahydrate and anhydrous zinc acetate serving as reaction raw materials by an evaporation crystallization method, wherein the structural formula of the Schiff base ligand H 2 L is as follows The molecular structural formula of the fluorescent temperature sensing material based on the 3d/4f complex is [ ZnLSm (CH 3OH)(NO3)2 ]. In a second aspect of the present invention, the following technical solutions are adopted: the preparation method of the fluorescent temperature sensing material based on the 3d/4f complex comprises the following steps: Mixing Schiff base ligand H 2 L, samarium nitrate hexahydr