CN118090661A - Trace detection method of rare earth ions, terahertz metamaterial chemical sensor and application thereof - Google Patents
Trace detection method of rare earth ions, terahertz metamaterial chemical sensor and application thereof Download PDFInfo
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- 229910052706 scandium Inorganic materials 0.000 description 1
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- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3581—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation
- G01N21/3586—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation by Terahertz time domain spectroscopy [THz-TDS]
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
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- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention provides a trace detection method of rare earth ions, a terahertz metamaterial chemical sensor and application thereof; based on the existing rare earth ion detection technology, the problems of long time consumption, expensive instrument, complex sample treatment and the like exist; according to the invention, the terahertz metamaterial is combined with the rare earth ion imprinting nanomaterial, the rare earth ion imprinting nanospheres are used for capturing specific rare earth ions, and the terahertz signals of the rare earth ions are amplified through BIC resonance, so that noise interference can be inhibited, the trace detection of the rare earth ions with the nanomole level and above is realized, and the selectivity and sensitivity of the rare earth ion terahertz detection are obviously improved. Based on the method, the research and development of the quasi-BIC metamaterial array structure attached with the rare earth ion imprinting nano material are realized, trace detection of rare earth ions can be realized by applying the quasi-BIC metamaterial array structure to various terahertz detection systems, and the method has a good application prospect.
Description
Technical Field
The invention relates to the technical field of trace detection of rare earth ions, in particular to a trace detection method of rare earth ions with high sensitivity and accurate detection, a terahertz metamaterial chemical sensor and application thereof.
Background
Rare earth elements refer to 15 elements (lanthanoids) of atomic numbers from 57 (La) to 71 (Lu) in the third subgroup of the periodic table of elements, and scandium (Sc) and yttrium (Y) which are similar in their electronic structure and chemical properties. Rare earth elements have characteristics such as large atomic magnetic moment and strong spin-orbit coupling due to their unique 4f electron structure, and are the subject of extensive attention and exploration in the scientific and industrial fields at present. With the massive development of rare earth resources, rare earth elements inevitably enter the ecological environment through various approaches. The rare earth concentration in biological samples (such as animals and plants) is generally in the ppm-ppb (1×10 -6–1×10-9) level; the rare earth concentration in environmental samples (e.g., atmosphere, water, soil, etc.) is on the order of ppm-ppt (1X 10 -6–1×10-12). The difficulty of rare earth detection is that the chemical properties are similar, so that the qualitative identification is difficult; and, as various disciplines develop, the lower limit of detection of rare earth impurities is required to be lower and lower, so that the accuracy and sensitivity of rare earth detection become critical.
The existing common rare earth ion detection methods mainly comprise an atomic absorption spectrometry, an inductively coupled plasma mass spectrometry and a neutron activation analysis. The atomic absorption spectrometry is to irradiate an atomic vapor layer of a sample solution, which is atomized and atomized, with characteristic radiation emitted by the same kind of atoms, measure the transmitted light intensity or absorbance of the characteristic radiation, calculate the content of a measured element in the sample according to the relation of absorbance to concentration, and has the advantages of simple operation and quick analysis, but is easy to be interfered during the analysis of the mixture and is not suitable for the detection of mixed rare earth ions. The inductively coupled plasma mass spectrometry is to take an inductively coupled plasma source as a high-temperature ion source to dissociate and atomize a sample, and to scan ions with specific element mass numbers by a mass spectrometer so as to determine the rare earth ion type and content, and has the advantages of high sensitivity and simultaneous detection of multiple elements, but the instrument has high price, and complex and time-consuming sample pretreatment and enrichment process. The neutron activation analysis method utilizes neutrons to bombard isotopes of rare earth elements in a sample to carry out nuclear reaction, and carries out qualitative and quantitative analysis of the rare earth elements through transient gamma generated by measurement, so that the method has the advantages of high sensitivity and high accuracy, but the detection accuracy is easily interfered by uranium elements, and the sample preparation process is tedious and time-consuming. In summary, the existing rare earth ion detection technology has the problems of long time consumption, expensive instrument, complex sample processing and the like, so that a quick, efficient and accurate technology is necessary to be explored for detecting rare earth ions.
Disclosure of Invention
The invention aims to provide a method and a sensor which have the capability of selectively capturing specific rare earth ions and amplify terahertz signals of the rare earth ions through quasi-BIC resonance so as to remarkably improve the selectivity and sensitivity of terahertz detection of the rare earth ions and realize trace detection of the rare earth ions.
In order to achieve the aim, the invention provides a trace detection method of rare earth ions, which captures specific rare earth ions through rare earth ion imprinted nanospheres, amplifies terahertz signals of the rare earth ions through BIC resonance and realizes trace detection of the rare earth ions at a nanomole level or above.
The invention also provides a terahertz metamaterial chemical sensor, which comprises a quasi-BIC metamaterial unit array structure and rare earth ion imprinting nano materials, wherein the rare earth ion imprinting nano materials are uniformly distributed on the surface of the quasi-BIC metamaterial unit array structure; the quasi-BIC metamaterial has a high Q value terahertz enhancement function, the magnetic rare earth ion imprinting nanospheres provide rare earth ion selective recognition sites, and the magnetic rare earth ion imprinting nanospheres and the rare earth ion selective recognition sites are combined to form the high-sensitivity and high-selectivity terahertz metamaterial chemical sensor.
Further, the quasi-BIC metamaterial unit array structure is formed by aligning and arranging a plurality of same quasi-BIC metamaterial units in the transverse direction and the longitudinal direction;
The quasi-BIC metamaterial unit comprises a dielectric substrate and a resonator unit attached to the surface of the dielectric substrate; the resonator unit is a double-opening resonator, and can induce a quasi-BIC resonance peak with an ultrahigh Q value;
Further, the shape of the double-opening resonator can be a double-opening resonator with various shapes, including a circular ring shape, a triangular ring shape and a square ring shape;
the relative widths of the two openings of the same double-opening resonator are variable; the shape of the opening is variable, including circular, triangular and rectangular; the open position is movable on the cantilever of the dual-open resonator. By introducing asymmetric disturbance to induce quasi-BIC, the quasi-BIC resonance peak with high Q value can be realized in the frequency domain, and the peak position is consistent with the peak position of the target rare earth ion.
Further, the dielectric substrate is prepared from a material with good terahertz wave band permeability and comprises monocrystalline silicon, quartz or polyethylene;
The double-opening resonator is prepared by adopting a mixed material, and comprises a metal material, a dielectric material and a tunable material; the metal material comprises one or more of gold, silver, copper and aluminum; the dielectric material is a material with good photoelectric response and comprises silicon; the tunable material comprises one or more of graphene, vanadium dioxide and indium antimonide;
The Y-direction material and the X-direction material of the dual-split resonator may be different.
Further, the rare earth ion imprinting nanomaterial comprises magnetic nanospheres and rare earth ion imprinting polymers; the rare earth ion imprinted polymer is attached to the surface of the magnetic nanospheres in a deposition or coating mode; the rare earth ion imprinting nano material is uniformly adsorbed on the surface of the quasi-BIC metamaterial unit array structure through the magnetic nanospheres. When a sample solution containing rare earth ions is dripped on the surface of a terahertz metamaterial chemical sensor, the rare earth ion imprinting nano material selectively adsorbs specific rare earth ions through functional groups and imprinting cavities.
Further, the rare earth ion imprinted polymer comprises a base polymer, an imprinted cavity and a functional group which can be subjected to complexation with rare earth ions;
the base polymer adopts a material which has high reaction efficiency and mild and controllable reaction conditions and is stably combined with the magnetic nanospheres, and comprises polyacrylic acid, polyethylene glycol or polyethyleneimine;
the imprinting cavity is provided with a specific three-dimensional space matched with the size of the rare earth ions to be detected, so that the rare earth ions are selectively adsorbed;
the functional group interacts with rare earth ions to be detected, and realizes selective adsorption of the rare earth ions together with the imprinting cavity.
Furthermore, by adjusting the size and the volume of the material and the imprinting cavity of the magnetic nanospheres and the types of the functional monomers, the high-selectivity identification of different rare earth ions is realized;
by adjusting the structural parameters and materials of the double-split resonator, terahertz resonance with high Q value is realized.
The invention also provides application of the terahertz metamaterial chemical sensor, and trace detection of rare earth ions is realized after the terahertz metamaterial chemical sensor is applied to a detection system;
The detection system comprises a terahertz emission module, a terahertz metamaterial chemical sensor and a terahertz detection module, wherein the terahertz emission module, the terahertz metamaterial chemical sensor and the terahertz detection module are sequentially arranged on the same optical axis, and the data processing and display module are used for carrying rare earth ion samples; the terahertz emission module spectrum range and the terahertz detection module spectrum range comprise and are larger than the working frequency range of the terahertz metamaterial chemical sensor.
Further, the detection steps of the detection system are as follows:
S1: taking a clean and complete terahertz metamaterial chemical sensor, and measuring and recording the quasi-BIC resonant frequency of the terahertz metamaterial chemical sensor;
S2: dropping a rare earth ion sample to be detected on the surface of a terahertz metamaterial chemical sensor, then washing the sample by deionized water to remove other interferents in the sample, and removing free water molecules in the sample by vacuum drying;
s3: fixing a terahertz metamaterial chemical sensor with rare earth ions loaded on the surface on a sample rack according to the polarization direction requirement, measuring the absorption spectrum of the terahertz metamaterial chemical sensor by using a terahertz detection module, and recording the absorption spectrum by using a data processing and display module; when terahertz waves sequentially pass through the magnetic imprinting nano material and the terahertz metamaterial adsorbed with specific rare earth ions, the dielectric constant of the sensor surface can change, and the sensor surface shows the frequency shift and amplitude change of a quasi-BIC resonance peak.
S4: and S3, repeatedly performing the operation step, reading a terahertz resonance peak with rare earth ion information, recording the frequency shift quantity and amplitude change of the resonance peak, analyzing the rare earth ion type and content through the frequency shift and the amplitude change, and calculating the concentration of the rare earth ions in the sample.
Compared with the prior art, the invention has the advantages that:
The invention aims at the rare earth ion trace detection to construct the terahertz metamaterial chemical sensor, and combines the quasi-BIC terahertz metamaterial and the rare earth ion imprinting nano material. The rare earth ion imprinting nano material can selectively adsorb target rare earth ions from a sample to be detected. Under the radiation of terahertz waves, the quasi-BIC terahertz metamaterial can realize a quasi-BIC resonance peak with an ultra-high Q value, and meanwhile, the resonance frequency of the quasi-BIC resonance peak is matched with the terahertz characteristic absorption frequency of the target rare earth ions, so that resonance between the quasi-BIC terahertz metamaterial and the quasi-BIC resonance peak is enhanced. Under the comprehensive action, the detection precision and the identification capability of the terahertz metamaterial chemical sensor on rare earth ions are greatly improved, and the problem that trace ion detection is difficult at present is effectively solved;
2. the metamaterial structure provided by the invention has the characteristics of simplicity, easiness in use, reusability and suitability for various terahertz detection systems, is simple and convenient to operate, has processing precision of only microns, is mature in production process and low in cost, can realize large-scale production, and has good commercial application potential.
Drawings
FIG. 1 is a schematic diagram of a quasi-BIC metamaterial unit structure in the present invention;
FIG. 2 is a schematic diagram of rare earth ion imprinted nanomaterial in the invention;
FIG. 3 is a schematic diagram of rare earth ion imprinted polymer structure in the invention;
FIG. 4 is a schematic structural diagram of a terahertz metamaterial chemical sensor in the invention;
FIG. 5 is a schematic diagram of a detection flow of the terahertz metamaterial chemical sensor in the invention;
FIG. 6 is a quasi-BIC resonance peak of a terahertz metamaterial chemical sensor designed for praseodymium ions, showing terahertz characteristic absorption peaks of praseodymium oxide in the invention;
FIG. 7 shows the detection results of the terahertz metamaterial chemical sensor for praseodymium ions and other interferents.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be further described below.
The existing rare earth ion detection technology based on the background technology has the problems of long time consumption, expensive instrument, complex sample treatment and the like; the application combines the terahertz metamaterial and the rare earth ion imprinting nanomaterial to realize high-sensitivity and high-precision detection of rare earth ions.
Terahertz waves are electromagnetic waves with frequencies in the range of 0.1-10 THz, are positioned between microwaves and infrared rays, and are highly sensitive to low-frequency fingerprint information such as lattice vibration, intermolecular interaction and the like. This makes terahertz spectroscopy a unique advantage in terms of material characterization and component analysis. The combination of the terahertz wave and the metamaterial fully utilizes the characteristics of rich fingerprint information, coherent physical parameters and the like of the terahertz wave, and has the advantages of rich electromagnetic modes, flexible functional design and the like of the metamaterial device, and is widely applied to the fields of environmental monitoring, biomedicine, wireless communication and the like. But lack of selective recognition mechanism is currently the main bottleneck restricting the practical application of terahertz chemical sensors.
The ion blotting material is an "artificial antibody" constructed to mimic the antibody-antigen effect. Compared with the natural antibody, the rare earth ion imprinting nano material has a binding site acting with a target ion and a three-dimensional cavity matched with the target ion, so that the unique advantage of ion selective recognition is given. The material has the characteristics of simple and convenient preparation process, stable chemical property, low cost and easy storage, and is of remarkable attention in the field of optical sensing detection. However, rare earth ion imprinting materials have the problem of insufficient mechanical properties, which limits the application field.
Therefore, the invention provides the following technical scheme:
FIG. 1 is a schematic diagram of a quasi-BIC metamaterial unit structure. The metamaterial structure unit comprises a dielectric substrate 1-1 and interconnected resonator units attached to the surface of the dielectric substrate; the resonator unit comprises two double-split resonators 1-2 made of mixed materials, the relative widths of the two openings 1-3 on the same double-split resonator 1-2 are variable, and the positions of the openings 1-3 can be moved on the cantilever of the double-split resonator. The double-split resonator unit can induce a quasi-BIC resonance peak with a high Q value; and a plurality of the same quasi-BIC metamaterial units are aligned and arranged longitudinally and transversely, and finally a complete quasi-BIC metamaterial unit array structure is formed.
In the present embodiment, the double-opening resonator 1-2 may be set in various configurations including a doughnut shape, a triangular doughnut shape, a square doughnut shape, and the like. Wherein the openings 1-3 can be set to different shapes, widths and positions. The shape includes various openable shapes such as a circle, a triangle, a rectangle, and the like, the relative width of two openings on the same double-opening resonator 1-2 is variable, and the position of the opening 1-3 can move on the cantilever of the double-opening resonator 1-2. The dual-opening resonator 1-2 adopts mixed materials including but not limited to materials in Y direction, materials in X direction and the like, metal materials including gold, silver, copper, aluminum and the like, dielectric materials including materials with good photoelectric response such as silicon and the like, and tunable materials including materials with tunable photoelectric properties such as graphene, vanadium dioxide, indium antimonide and the like.
In the present embodiment, the material used for the dielectric substrate 1-1 in the metamaterial unit includes materials having good permeability in the terahertz band such as single crystal silicon, quartz, polyethylene, and the like.
Fig. 2 is a schematic diagram of rare earth ion imprinted nanomaterial. The rare earth ion imprinting nano material comprises a magnetic nano sphere 2-1 and a rare earth ion imprinting polymer 2-2 attached to the surface of the magnetic nano sphere; attachment means include, but are not limited to, deposition, coating, and the like.
FIG. 3 is a schematic diagram showing the structure of a rare earth ion imprinted polymer 2-2 attached to the surface of a magnetic nanosphere 2-1. The rare earth ion imprinted polymer 2-2 comprises a base polymer 3-1, an imprinted cavity 3-2 and a functional group 3-3 which can be subjected to complexation with rare earth ions.
In this embodiment, the magnetic nanospheres 2-1 include, but are not limited to, nanomaterials composed of magnetic elements (e.g., iron, nickel, cobalt, chromium, manganese, gadolinium, etc.) and compounds thereof.
In the embodiment, the base polymer 3-1 adopts materials with high reaction efficiency, mild and controllable reaction conditions and stable combination with the magnetic nanospheres, including but not limited to polyacrylic acid, polyethylene glycol, polyethyleneimine and the like; the imprinting cavity 3-2 is provided with a specific three-dimensional space matched with the size of the rare earth ions to be detected, and can realize selective adsorption of the rare earth ions.
In this embodiment, the functional group 3-3 capable of complexing with rare earth ions interacts with the rare earth ions to be detected, and selectively adsorbs the rare earth ions together with the imprinting cavity 3-2.
Fig. 4 is a schematic structural diagram of the terahertz metamaterial chemical sensor. The same quasi-BIC metamaterial unit structures are aligned and arranged longitudinally and transversely to form a complete quasi-BIC metamaterial unit array structure 4-1, meanwhile, the magnetic rare earth ion imprinting nanospheres 4-2 are uniformly distributed on the surface of the quasi-BIC metamaterial unit array structure 4-1, and a plurality of rare earth ion imprinting vacancies 4-3 are formed on the surface of the magnetic rare earth ion imprinting nanospheres.
The detection flow diagram of the terahertz metamaterial chemical sensor for detecting rare earth ions shown in fig. 5 comprises a terahertz emission module 5-1, a terahertz chemical sensor 5-2 loaded with rare earth ion samples, a terahertz detection module 5-3 and a data processing and display module 5-4, which are sequentially arranged on the same optical axis. The terahertz emission module spectrum range and the terahertz detection module spectrum range should contain and be larger than the working frequency range of the metamaterial chemical sensor.
First, the metamaterial is fixed on a sample holder according to the polarization direction of the metamaterial, and terahertz waves are aligned. The terahertz wave is generated by the terahertz transmitting module 5-1, is vertically incident and penetrates through the terahertz chemical sensor 5-2 loaded to be sequentially vertically incident and penetrates through the rare earth ion imprinting nano material and the quasi-BIC metamaterial, is finally detected by the terahertz detecting module 5-3, and generates an obvious terahertz resonance peak reference signal through the data processing and displaying module 5-4. Then, the rare earth ion sample is dripped on the surface of the terahertz chemical sensor 5-2, target rare earth ions are captured by rare earth ion imprinting nano materials, and other interferents are removed by washing with deionized water, and are dried and then to be measured. And then, fixing the metamaterial chip with the rare earth ions to be detected on the sample frame again according to the polarization direction requirement. The terahertz wave is generated by a terahertz transmitting module 5-1, sequentially passes through a rare earth ion imprinting nano material and a terahertz metamaterial which adsorb rare earth ions, and finally the change of the dielectric constant of the sensor surface is detected by a terahertz detecting module 5-3, so that a terahertz resonance peak sample signal with rare earth information to be detected is obtained. The rare earth ion imprinting nano material has selective recognition to specific rare earth ions, and a structural unit array formed by double-opening resonators in the metamaterial only absorbs terahertz waves with specific frequency to form a high-Q-value quasi-BIC resonance peak. When rare earth ion samples are dripped on the surface of the designed terahertz metamaterial chemical sensor, the selective absorption characteristics of the metamaterial on terahertz waves change, the terahertz resonance peak position deviation and the amplitude change are shown, and the changes directly reflect the differences of the types and the concentrations of the samples. And comparing the reference signal with the sample signal, reading the terahertz resonance peak frequency shift and the amplitude variation obtained by two times of acquisition in a data processing and display module 5-4, and obtaining the concentration of the rare earth ions to be detected through mathematical treatment.
In the following, the technical effects of the present invention will be further discussed by specific detection of praseodymium ions as an example.
The present invention will be described in detail by taking praseodymium ions as an example. Fig. 6 is a quasi-BIC resonance peak of a terahertz metamaterial chemical sensor designed for praseodymium ions, and the terahertz characteristic absorption peak of praseodymium oxide. Fig. 7 shows the detection result of the terahertz metamaterial chemical sensor on praseodymium ions and other interferents. In the embodiment, the metamaterial dielectric substrate 1-1 is made of quartz, and the thickness is 500 mu m; the resonance unit is a rectangle with the side length of 80 multiplied by 50 mu m and comprises two double-opening resonators 1-2; the material of the double-opening resonator is a combination of gold and a dielectric material, and the thickness is 100 nm; the width of the double openings is 2 mu m and 3 mu m respectively, and the two openings are rectangular. The surface geometry is prepared by a photolithographic process and an etching process. And preparing the rare earth ion imprinting nanospheres by adopting a surface imprinting technology. And uniformly attaching the rare earth ion imprinting nanospheres on the surface of the quasi-BIC metamaterial by spraying. The side length of the obtained terahertz metamaterial chemical sensor is 10 mm. The dielectric substrate may be replaced with other materials having good transmission in the terahertz band, and the material of the dual-port resonator may be replaced with a combination of other metallic materials, dielectric materials, and tunable materials. All the parameters are designed and processed according to the terahertz absorption spectrum characteristics of the target rare earth ions. In the embodiment, the resonance frequency band of the terahertz metamaterial chemical sensor is designed aiming at the absorption peak of praseodymium ions at the position of 5.73 THz, and the implementation method for enhancing the characteristic peak absorption of the terahertz wave band of other rare earth ions is consistent with the implementation method.
The terahertz transmitting module 5-1 outputs a signal with the frequency of 0-7 THz, and the terahertz detecting module 5-3 detects a signal with the frequency of 0-7 THz.
Firstly, a clean and complete terahertz metamaterial chemical sensor is taken and fixed on a sample frame according to the polarization direction requirement as shown in fig. 4, the absorption spectrum of the terahertz metamaterial chemical sensor is measured by a terahertz detection module 5-3, and the terahertz metamaterial chemical sensor is recorded by a data processing and display module 5-4; at this time, the quasi-BIC resonance frequency of the terahertz metamaterial chemical sensor is at 5.73 THz, as shown by b in fig. 6.
Secondly, taking a 10 mu L praseodymium ion sample to be measured, dripping the sample on the surface of a clean and complete terahertz metamaterial chemical sensor, then flushing the sample by deionized water to remove other interferents in the sample, and removing free water molecules in the sample by vacuum drying;
Thirdly, fixing the terahertz metamaterial chemical sensor with praseodymium ions loaded on the surface on a sample rack according to the polarization direction requirement, measuring the absorption spectrum of the terahertz metamaterial chemical sensor by using a terahertz detection module 5-3, and recording the absorption spectrum by a data processing and display module 5-4;
fourthly, performing the third step for a plurality of times, reading a terahertz resonance peak with praseodymium ion information, recording the frequency shift quantity and amplitude change of the resonance peak, and calculating the concentration of praseodymium ions in the sample;
fifthly, replacing praseodymium ions with other interference ions, and repeating the above operation;
Sixth, the terahertz resonance peak frequency shift response curves caused by praseodymium ions with different concentrations and interfering ions are compared, as shown in fig. 7. In the praseodymium ion solution test, the resonance peak of the terahertz metamaterial chemical sensor is obviously enhanced at a position of 5.73 THz, and the frequency shift quantity is obvious for the change of the praseodymium ion concentration. In contrast, the same operation was performed with the interfering ionic solution, and the resonant peak frequency of the sensor was substantially unchanged. The detection result verifies the selective identification and high-sensitivity detection capability of the terahertz metamaterial chemical sensor designed for praseodymium ions.
By adjusting the size and the material of the magnetic nanospheres, the volume of the imprinting cavity and the types of the functional monomers, the sensor can realize high-selectivity identification of different types of rare earth ions. By adjusting the structural parameters and materials of the resonance unit, the sensor can realize terahertz resonance with high Q value. The combination of the two can accurately detect rare earth ion samples with the level as low as nanomole.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any person skilled in the art will make any equivalent substitution or modification to the technical solution and technical content disclosed in the invention without departing from the scope of the technical solution of the invention, and the technical solution of the invention is not departing from the scope of the invention.
Claims (10)
1. A trace detection method of rare earth ions is characterized in that specific rare earth ions are captured by rare earth ion imprinting nanospheres, terahertz signals of the rare earth ions are amplified by BIC resonance, and trace detection of the rare earth ions with nanomolar level and above is realized.
2. A terahertz metamaterial chemical sensor for trace detection of rare earth ions as set forth in claim 1, comprising a quasi-BIC metamaterial unit array structure and rare earth ion imprinting nanomaterials, wherein the rare earth ion imprinting nanomaterials are uniformly distributed on the surface of the quasi-BIC metamaterial unit array structure.
3. The terahertz metamaterial chemical sensor according to claim 2, wherein the quasi-BIC metamaterial unit array structure is formed by aligning and arranging a plurality of identical quasi-BIC metamaterial units in the transverse direction and the longitudinal direction;
the quasi-BIC metamaterial unit comprises a dielectric substrate and a resonator unit attached to the surface of the dielectric substrate; the resonator unit is a double-split resonator.
4. The terahertz metamaterial chemical sensor according to claim 3, wherein the shape of the double-opening resonator can be a double-opening resonator of various shapes, including a circular ring shape, a triangular ring shape and a square ring shape;
The relative widths of the two openings of the same double-opening resonator are variable; the shape of the opening is variable, including circular, triangular and rectangular; the open position is movable on the cantilever of the dual-open resonator.
5. The terahertz metamaterial chemical sensor according to claim 3, wherein the dielectric substrate is made of a material with good terahertz wave band permeability, and comprises monocrystalline silicon, quartz or polyethylene;
The double-opening resonator is prepared from a mixed material, and comprises a metal material, a dielectric material and a tunable material; the metal material comprises one or more of gold, silver, copper and aluminum; the dielectric material is a material with good photoelectric response and comprises silicon; the tunable material comprises one or more of graphene, vanadium dioxide and indium antimonide;
The Y-direction material and the X-direction material of the dual-split resonator may be different.
6. The terahertz metamaterial chemical sensor according to claim 2, wherein the rare earth ion imprinted nanomaterial comprises magnetic nanospheres and rare earth ion imprinted polymers; the rare earth ion imprinted polymer is attached to the surface of the magnetic nanospheres in a deposition or coating mode; the rare earth ion imprinting nano material is uniformly adsorbed on the surface of the quasi BIC metamaterial unit array structure through the magnetic nanospheres.
7. The terahertz metamaterial chemical sensor according to claim 6, wherein the rare earth ion imprinted polymer comprises a base polymer, imprinted cavities, and functional groups that can complex with rare earth ions;
The base polymer is made of a material which has high reaction efficiency and mild and controllable reaction conditions and is stably combined with the magnetic nanospheres, and comprises polyacrylic acid, polyethylene glycol or polyethyleneimine;
the imprinting cavity is provided with a specific three-dimensional space matched with the size of the rare earth ions to be detected, so that the rare earth ions are selectively adsorbed;
The functional group interacts with rare earth ions to be detected, and selectively adsorbs the rare earth ions together with the imprinting cavity.
8. The terahertz metamaterial chemical sensor according to claim 7, wherein high-selectivity identification of different types of rare earth ions is achieved by adjusting the size and material of the magnetic nanospheres, the volume of the imprinting cavity and the type of the functional monomer;
By adjusting the structural parameters and materials of the double-opening resonator, terahertz resonance with a high Q value is realized.
9. The application of the terahertz metamaterial chemical sensor is characterized in that trace detection of rare earth ions is realized after the terahertz metamaterial chemical sensor is applied to a detection system;
the detection system comprises a terahertz emission module, a terahertz metamaterial chemical sensor and a terahertz detection module, wherein the terahertz emission module, the terahertz metamaterial chemical sensor and the terahertz detection module are sequentially arranged on the same optical axis, and the terahertz detection module, the data processing and display module are used for carrying rare earth ion samples; the terahertz transmitting module spectrum range and the terahertz detecting module spectrum range comprise and are larger than the working frequency range of the terahertz metamaterial chemical sensor.
10. The use of a terahertz metamaterial chemical sensor according to claim 9, wherein the detection steps of the detection system are as follows:
S1: taking a clean and complete terahertz metamaterial chemical sensor, and measuring and recording the quasi-BIC resonant frequency of the terahertz metamaterial chemical sensor;
S2: dropping a rare earth ion sample to be detected on the surface of the terahertz metamaterial chemical sensor, then washing the sample by deionized water to remove other interferents in the sample, and drying the sample in vacuum to remove free water molecules contained in the sample;
s3: fixing a terahertz metamaterial chemical sensor with rare earth ions loaded on the surface on a sample rack according to the polarization direction requirement, measuring the absorption spectrum of the terahertz metamaterial chemical sensor by using a terahertz detection module, and recording the absorption spectrum by using a data processing and display module;
S4: and S3, repeatedly performing the operation step, reading a terahertz resonance peak with rare earth ion information, recording the frequency shift quantity and amplitude change of the resonance peak, and calculating the concentration of the rare earth ions in the sample.
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