CN114105103B - Application of composite variable valence metal oxide particles as surface enhanced Raman spectrum substrate - Google Patents
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Abstract
The application discloses a composite variable valence metal oxide particle and a preparation method and application thereof. The composite variable valence metal oxide particles have metal cations with different valence states, wherein the composite variable valence metal oxide particles comprise high valence metal cations and low valence metal cations; the band structure of the material is composed of metal cation orbital energy levels with different valence states, so that the success probability and the number of electron transition can be greatly enhanced, and electrons can be more easily excited out of the material. The composite variable valence metal oxide particles have excellent biocompatibility and surface enhanced Raman spectrum detection sensitivity, can be used as a surface enhanced Raman spectrum substrate, and can be used for effectively detecting low-concentration sample materials.
Description
Technical Field
The application relates to a composite variable valence metal oxide particle and a preparation method and application thereof, belonging to the technical field of material spectra.
Background
With the great progress of the nanometer material science and technology in the material field, various application technologies depending on the nanometer material science are also developed at a high speed. It is well known that the valence, structure, size and morphology of nanomaterials have a significant impact on their own physicochemical properties. Therefore, the synthesis method for preparing the novel nano material with different morphologies so as to improve and enhance the corresponding optical, thermal and electrical properties of the material is always a focus of attention of researchers. In recent years, inorganic nonmetallic nanomaterials have shown great application potential in the optical field, such as the field of Surface Enhanced Raman Spectroscopy (SERS), due to their unique properties.
The metal oxide nanometer material with different valence states and different appearances can be synthesized by different chemical methods and technologies and applied to the SERS field, and the metal oxide material has attracted extensive interest of researchers due to the unique advantages of the metal oxide material in the SERS field, such as good biocompatibility, selective enhancement performance on a detected object, good spectral stability and the like. However, the metal oxide nano material as the SERS substrate has a biggest disadvantage that the generated enhancement factor is weak, which seriously restricts the application and development of the metal oxide material in the SERS field. Thus, a number of strategies have been proposed to increase the enhancement factor of SERS of metal oxide materials. For example, for the crystalline metal oxide material, the enhancement factor of the crystalline metal oxide material is effectively improved by a method of doping a defect state on the surface. In recent years, the weak binding force of the surface of the amorphous metal oxide material to electrons is helpful to improve the photoinduced charge transfer effect of the amorphous semiconductor material and the target detection object by an amorphization method, so that a high enhancement factor is realized. However, at present, no report is available on the utilization of cations with different valence states coexisting in the metal oxide to improve the SERS performance of the metal oxide.
In conclusion, there is an urgent need in the art to develop a method for preparing complex variable valence metal oxide nanoparticles with simple, efficient, safe and feasible preparation process for application in the SERS field.
Disclosure of Invention
According to an aspect of the present application, there is provided a composite variable valence metal oxide particle having excellent biocompatibility and Surface Enhanced Raman Spectroscopy (SERS) detection sensitivity, which can be used as a SERS substrate and can effectively detect a low concentration sample material.
A composite variable valence metal oxide particle having metal cations of different valence states, wherein the metal cations of different valence states include a higher valence state metal cation and a lower valence state metal cation; the energy band structure of the metal ion band is composed of metal cation orbital energy levels with different valence states.
Optionally, the composite variable valence metal oxide particles have multiple absorption/reflection regions in the ultraviolet visible absorption spectrum/diffuse reflection spectrum, and multiple absorption/reflection peaks in the ultraviolet-visible light-near infrared region.
Optionally, the metal element in the metal oxide is selected from any one or a combination of more of Fe element, mn element, ti element, gd element, co element, cu element, ni element, cr element, and Na element.
Optionally, the metal oxide is selected from Fe 3 O 4 、MnO 2 、Mn 2 O 7 、Mn 3 O 4 、TiO 2 、γ-Fe 2 O 3 、Gd 2 O 3 、CoO、CuO、Cu 2 O、Ni 2 O、NiO、CrO 3 、Cr 2 O 3 、NaO 2 And NaO.
Optionally, the morphology of the complex valence variable metal oxide particles is selected from any one of lamellar, tetrahedral, hexahedral, octahedral, dodecahedral, hollow cage, round granular and rod-shaped.
Optionally, the composite valence metal oxide particles are mixed crystalline materials.
Optionally, the composite variable valence metal oxide particles are amorphous materials.
Optionally, the composite valence-variable metal oxide particles are crystalline materials.
Optionally, the composite variable valence metal oxide particles have a particle size distribution between 0.1nm and 1000nm.
Optionally, the upper limit of the particle size of the composite structure semiconductor particles is selected from 1.7, 2.2, 4.6, 6.5, 20, 50, 100, 500, 1000nm.
Optionally, the lower limit of the particle size of the composite structure semiconductor particles is selected from 1.7, 2.2, 4.6, 6.5, 20, 50, 100, 500, 1000nm.
According to another aspect of the present application, there is provided a method of producing composite variable valence metal oxide particles as described in any one of the above, the method comprising the steps of: carrying out reduction reaction on a solution I containing metal salt and a reducing agent to obtain the composite valence-variable metal oxide particles;
the metal salt is a combination at least comprising a metal salt I and a metal salt II containing metal cations with different valence states;
the metal elements in the metal salt I and the metal salt II are the same.
Optionally, the metal element in the metal salt is selected from any one or more of Fe element, mn element, ti element, gd element, co element, cu element, ni element, cr element, and Na element.
Optionally, the solvent of solution I is selected from water and/or an acid.
Optionally, the metal salt is FeCl 3 And FeCl 2 Combinations of (a) and (b).
Optionally, feCl in the solution I 3 The concentration of (A) is 0.01-10M, and the FeCl is 2 The concentration of (B) is 0.01-10M.
Optionally, feCl in the solution I 3 The upper concentration limit of (b) is selected from 0.032, 0.05, 0.1, 2, 5, 10M.
Optionally, feCl in the solution I 3 The lower limit of the concentration of (b) is selected from 0.01, 0.02 and 0.032M.
Optionally, feCl in the solution I 2 The upper concentration limit of (b) is selected from 0.016, 0.032, 0.05, 0.1, 2, 5 and 10M.
Optionally, feCl in the solution I 2 The upper concentration limit of (3) is selected from 0.01 and 0.016M. Alternatively, the conditions of the reduction reactionComprises the following steps: at N 2 Under the protection of (3), the pH value is 9-11, the reaction temperature is 0-200 ℃, and the reaction time is 40-180 min.
Optionally, the pH is 9 to 10.
Optionally, the pH is 10 to 11.
Optionally, the reaction temperature is 0 to 200 ℃.
Alternatively, the upper reaction temperature limit is selected from 20, 40, 60, 80, 100, 120, 150, 200 ℃.
Alternatively, the lower limit of the reaction temperature is selected from 0, 20, 40, 60, 80, 100, 120, 150 ℃.
Optionally, the upper limit of the reaction time is selected from 60min, 120min, 180min.
Optionally, the lower limit of the reaction time is selected from 40min, 60min, 120min.
Optionally, the reducing agent is selected from any one or more of ammonia water, stannous chloride, oxalic acid, potassium borohydride and sodium borohydride.
Optionally, the concentration of the reducing agent in the solution I is 15-30%.
Optionally, the concentration of the reducing agent in the solution I is 20 to 30%.
Optionally, the concentration of the reducing agent in the solution I is 20 to 28%.
Optionally, the concentration of the reducing agent in the solution I is 24-28%.
According to another aspect of the present application, there is provided a use of the composite variant valence metal oxide particle according to any one of the above items or the composite variant metal oxide particle prepared by the preparation method according to any one of the above items as a substrate for surface enhanced raman spectroscopy.
Optionally, in the application, the raman molecule is selected from at least one of crystal violet, rhodamine, methylene blue and alizarin red.
According to another aspect of the present application, there is provided a surface-enhanced raman spectroscopy substrate comprising any one or more of the composite variant valence metal oxide particles of any one of the above or prepared according to the preparation method of any one of the above.
According to another aspect of the present application, there is provided a use of the surface-enhanced raman spectroscopy substrate as described in any one of the above in molecular detection and/or biological detection, wherein the excitation light used in the laser raman spectroscopy has a wavelength of 266 to 1064nm.
Optionally, in the application, the upper limit of the wavelength of the excitation light used in the laser raman spectrum is selected from 325, 488, 514, 532, 633, 647, 785 and 1064nm.
Optionally, in the application, the lower limit of the wavelength of the excitation light used in the laser raman spectrum is selected from 266, 325, 488, 514, 532, 633, 647, 785nm.
Optionally, in the application, the excitation light wavelength used in the laser raman spectrum is any one selected from 266nm, 325nm, 488nm, 514nm, 532nm, 633nm, 647nm, 785nm and 1064nm.
According to another aspect of the present application, there is provided a device article comprising composite variable valence metal oxide particles according to any one of the above or prepared according to the preparation method of any one of the above.
Optionally, the device article is selected from any one of a sensor, a detector, a spectral responder.
According to another aspect of the present application there is provided the use of a device article as defined in any one of the preceding claims in material science detection, trace molecule detection, molecular detection, food detection, bioanalytical detection, biosensing, cellular imaging.
The beneficial effect that this application can produce includes:
1) The composite valence-variable metal oxide particles have metal cations with different valence states, and the energy band structure of the composite valence-variable metal oxide particles is formed by metal cation track energy levels with different valence states, so that the success probability and the number of electronic transition can be greatly enhanced, electrons can be more easily excited from materials, and the composite valence-variable metal oxide particles are favorable for detecting molecular tracks to targets under the action of excitation wavelengths with different energiesThe electronic transition of energy level has SERS detection sensitivity and excellent biocompatibility, and the SERS detection sensitivity can reach 10 -9 M, as shown in figure 4, has good application prospect as a surface enhanced Raman spectrum substrate.
2) The composite variable valence metal oxide particles provided by the application have a plurality of reflection regions in an ultraviolet visible diffuse reflection spectrum, and a plurality of absorption peaks/reflection peaks in an ultraviolet-visible light-near infrared region, so that the electron transfer and transition efficiency can be improved under the action of different excitation wavelengths, and the photon absorption/reflection of the variable valence metal oxide under different optical wave bands can be promoted.
3) The preparation method of the composite variable valence metal oxide particles has the advantages of being simple in process, simple in equipment, low in cost, safe and feasible, controllable preparation of the particle size of the composite particles can be achieved by adjusting reaction temperature and reaction time, and meanwhile, the prepared composite variable valence metal oxide particles have better SERS detection sensitivity and excellent biocompatibility by selecting appropriate reaction raw materials, reducing agents and reaction conditions.
Drawings
FIG. 1 shows a composite valence-variable metal oxide Fe obtained in example 4 of this application 3 O 4 Particles and crystals of Fe 2 O 3 Transmission Electron Microscopy (TEM) images of the particles. Wherein FIG. 1a is Fe 3 O 4 Particles with a particle size of 5-10 nm, wherein FIG. 1b is Fe 2 O 3 Particles with a particle size of 5-10 nm.
FIG. 2 composite valence-variable metal oxide Fe obtained in example 4 of the present application 3 O 4 Particles and crystals of Fe 2 O 3 The particles are used as a SERS substrate under the action of 532nm excitation wavelength, wherein a graph 2a shows the enhancement result of a surface enhanced Raman spectrum corresponding to Crystal Violet (CV) and a graph 2b shows mercaptobenzoic acid (4 MBA).
FIG. 3 shows a composite valence-variable metal oxide Fe obtained in example 4 of this application 3 O 4 The ultraviolet-visible diffuse reflectance spectrum corresponding to the particles.
FIG. 4 shows a composite valence-variable metal oxide Fe obtained in example 4 of this application 3 O 4 The particles adsorbed the SERS detection limit of crystal violet molecules (CV) (fig. 4 a), mercaptobenzoic acid molecules (4 MBA) (fig. 4 b).
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
TEM analysis was performed using a transmission electron microscope (TF 20).
Raman spectroscopy was performed using a raman spectrometer (renishawinvivia refiex).
UV diffuse reflectance spectroscopy was performed using a UV spectrometer (Perkin-Elmer Lambda 950).
Example 1 composite variable valence Metal oxide Fe 3 O 4 Preparation of particles
FeCl is added 3 .6H 2 O (0.1459g, 0.54mM) and FeCl 2 .4H 2 O (0.0554g, 0.279mM) was dissolved in dilute hydrochloric acid solution (2ml, 1M), followed by introduction of N 2 And stirring vigorously; simultaneously injecting a concentrated ammonia water (15 ml, 28%) solution to obtain a solution I, wherein FeCl is contained in the solution I 3 Has a concentration of 0.032M 2 The concentration of (2) is 0.016M, the concentration of ammonia is 24.7%, the pH value is adjusted to 10, the solution is heated to 80 ℃, the solution is continuously kept at 80 ℃ for reaction for 40min, and the composite valence-variable metal oxide Fe with the average grain diameter of 1.7nm is obtained 3 O 4 Particles. The reaction solution was then concentrated to 10ml by suspension and dialyzed for 72h using a 5000d dialysis bag. Finally, magnetic separation is used to obtain the composite valence-variable metal oxide Fe 3 O 4 And (3) particles.
Example 2 composite variable valence Metal oxide Fe 3 O 4 Preparation of particles
FeCl is added 3 .6H 2 0 (0.1459g, 0.54mM) and FeCl 2 .4H 2 0 (0.0554g, 0.279mM) was dissolved in dilute hydrochloric acid solution (2ml, 1M), followed by introduction of N 2 And stirring vigorously; simultaneously injecting strong ammonia water (15 ml, 28)%) solution to obtain a solution I in which FeCl is present 3 Has a concentration of 0.032M 2 The concentration of (3) is 0.016M, the concentration of ammonia is 24.7%, the pH value is adjusted to 10, the solution is heated to 80 ℃, the solution is continuously kept at 80 ℃ for reaction for 60min, and Fe with the average grain diameter of 2.2nm is obtained 3 O 4 Particles. The reaction solution was then concentrated to 10ml by suspension and dialyzed for 72h using a 5000d dialysis bag. Finally, centrifugal separation is used to obtain the composite valence-variable metal oxide Fe 3 O 4 Particles.
Example 3 composite variable valence Metal oxide Fe 3 O 4 Preparation of particles
FeCl is added 3 .6H 2 O (0.1459g, 0.54mM) and FeCl 2 .4H 2 O (0.0554g, 0.279mM) was dissolved in dilute hydrochloric acid solution (2ml, 1M), followed by introduction of N 2 And stirring vigorously; simultaneously injecting a concentrated ammonia water (15 ml, 28%) solution to obtain a solution I, wherein FeCl is contained in the solution I 3 Has a concentration of 0.032M 2 The concentration of (2) is 0.016M, the concentration of ammonia is 24.7%, the pH value is adjusted to 10, the solution is heated to 80 ℃, the solution is continuously kept at 80 ℃ for reaction for 120min, and the composite valence-variable metal oxide Fe with the average grain diameter of 4.6nm is obtained 3 O 4 Particles. The reaction solution was then concentrated to 10ml by suspension and dialyzed for 72h using a 5000d dialysis bag. Finally, magnetic separation is used to obtain the composite valence-variable metal oxide Fe 3 O 4 Particles.
Example 4 composite variable valence Metal oxide Fe 3 O 4 Preparation of particles
FeCl 3 .6H 2 O (0.1459g, 0.54mM) and FeCl 2 .4H 2 O (0.0554g, 0.279mM) was dissolved in dilute hydrochloric acid solution (2ml, 1M), followed by introduction of N 2 And stirring vigorously; simultaneously injecting a concentrated ammonia water (15 ml, 28%) solution to obtain a solution I, wherein FeCl is contained in the solution I 3 Has a concentration of 0.032M 2 The concentration of (2) is 0.016M, the concentration of ammonia is 24.7%, the pH value is adjusted to 10, the solution is heated to 80 ℃, the solution is continuously kept at 80 ℃ for reaction for 180min, and the composite valence-variable metal oxide Fe with the average grain diameter of 6.5nm is obtained 3 O 4 Particles. The reaction solution was then concentrated to 10ml by suspension and dialyzed for 72h using a 5000d dialysis bag. Finally, magnetic separation or centrifugation is used to obtain the composite valence-variable metal oxide Fe 3 O 4 As shown in FIG. 1a, the particles have a particle size of 5 to 10nm, and the particle size distribution is uniform and mainly concentrated in the 6.5nm region. For commercial Fe 2 O 3 The particle size of the particles was measured and was between 5 and 10nm as shown in FIG. 1 b.
Example 5 composite variable valence Metal oxide Fe 3 O 4 Particle SERS performance vs. non-valence metal oxide Fe 2 O 3 The particles are obviously lifted
The composite valence-variable metal oxide Fe prepared in example 4 3 O 4 Particles and non-valence metal oxides Fe 2 O 3 The particles are used as the SERS substrate to carry out SERS spectrum detection on crystal violet molecules with the same concentration as shown in figure 2a under the action of 532nm excitation wavelength, and the valence-variable metal oxide Fe is compounded under the action of 532nm excitation wavelength 3 O 4 The intensity of SERS signal of the particle is higher, the SERS spectrum detection of mercaptobenzoic acid with the same concentration shown in figure 2b is carried out, and the valence-variable metal oxide Fe is compounded under the obvious action of 532nm excitation wavelength 3 O 4 The intensity of the SERS signal of the particle is higher, and as a result, as shown in FIG. 2, it can be seen that the intensity is higher than that of Fe 2 O 3 Metal oxide particles, composite valence-variable metal oxide Fe 3 O 4 The surface enhanced Raman effect of the particles is obviously enhanced.
Example 6 composite variable valence Metal oxide Fe 3 O 4 Ultraviolet-visible diffuse reflectance testing of particles
The composite valence-variable metal oxide Fe prepared in example 4 3 O 4 The particles are subjected to ultraviolet visible diffuse reflection spectrum test, and have a plurality of absorption regions and a plurality of absorption peaks, which are beneficial to the light absorption of the material under different wavebands, as shown in figure 3, the composite valence-variable metal oxide Fe can be seen 3 O 4 The different valence states of the particles have different electron orbital overlaps, the electronic transitions that can be generated are also different, the probability of the electronic transition can be greatly increased, and thusSo as to reflect different incident light energy, and is favorable for improving the photoinduced charge transfer between the light energy and the electron orbit of the target molecule to be detected, thereby enhancing the composite valence-variable metal oxide Fe 3 O 4 The surface enhanced raman spectroscopy effect of the particles.
Example 7 composite variable valence Metal oxide Fe 3 O 4 SERS Effect of particles
The composite valence-variable metal oxide Fe prepared in example 4 3 O 4 The particles and crystal violet molecules with different concentrations are mixed and adsorbed for 4 hours; then, raman spectrogram detection is carried out, the excitation wavelength is 532nm, the SERS signal of the crystal violet molecule is obviously enhanced, and the optimal detection sensitivity is 10 -9 M, mixing and adsorbing with mercaptobenzoic acid molecules with different concentrations for 6 hours; then, raman spectrogram detection is carried out, the excitation wavelength is 532nm, the mercaptobenzoic acid molecule SERS signal is obviously enhanced, and the optimal detection sensitivity is 10 -7 M, as shown in FIG. 4.
Example 8 composite variable valence Metal oxide Fe 3 O 4 SERS Effect of particles
The composite valence-variable metal oxide Fe prepared in example 4 3 O 4 Mixing the particles with rhodamine molecules with different concentrations, and adsorbing for 4 hours; then carrying out Raman spectrogram detection, wherein the excitation wavelength is 532nm, the SERS signal of the crystal violet molecule is obviously enhanced, and the optimal detection sensitivity is 10 -8 M。
Example 9 composite variable valence Metal oxide Fe 3 O 4 SERS Effect of particles
The composite valence-variable metal oxide Fe prepared in example 4 3 O 4 Mixing the particles with methylene blue molecules with different concentrations for adsorption for 4 hours; then, raman spectrogram detection is carried out, the excitation wavelength is 532nm, the SERS signal of the crystal violet molecule is obviously enhanced, and the optimal detection sensitivity is 10 -9 M。
Example 10 composite variable valence Metal oxide Fe 3 O 4 SERS Effect of particles
The composite valence-variable metal oxide Fe prepared in example 4 3 O 4 Particles and/orMixing alizarin red molecules with the same concentration, and adsorbing for 4 hours; then, raman spectrogram detection is carried out, the excitation wavelength is 532nm, the SERS signal of the crystal violet molecule is obviously enhanced, and the optimal detection sensitivity is 10 -8 M。
Example 11 composite valence-changing Metal oxide CuO @ Cu 2 The SERS performance of the O particles is obviously improved relative to the non-valence-variable metal oxide particles
The prepared composite valence-variable metal oxide CuO @ Cu 2 O particles, cuO metal oxide particles, cu 2 Relative to CuO and Cu, the O metal oxide particles can be seen under the action of 532nm excitation wavelength when being used as the SERS substrate 2 O metal oxide particles, composite valence-variable metal oxide CuO @ Cu 2 The surface enhanced Raman effect of the O particles is obviously enhanced.
Example 12 composite variable valence Metal oxide MnO 2 @Mn 2 O 7 The SERS performance of the particles is obviously improved relative to that of non-valence-variable metal oxide particles
MnO is added to the prepared composite valence-variable metal oxide 2 @Mn 2 O 7 Particles, mnO 2 Metal oxide particles, mn 2 O 7 Under the action of 532nm excitation wavelength, the metal oxide particles serving as the SERS substrate can be seen relative to MnO 2 And Mn 2 O 7 Metal oxide particle, composite valence-variable metal oxide MnO 2 @Mn 2 O 7 The surface enhanced Raman effect of the particles is obviously enhanced.
Example 13 composite variable valence Metal oxide NaO 2 The SERS performance of the @ NaO particle is obviously improved relative to that of the non-valence-variable metal oxide particle
The prepared composite variable valence metal oxide NaO 2 Particles of @ NaO, naO 2 The metal oxide particles and NaO metal oxide particles are used as SERS substrates, and relative to NaO can be seen under the action of 532nm excitation wavelength 2 And NaO metal oxide particles, composite valence-variable metal oxide NaO 2 The surface enhanced Raman effect of the @ NaO particle is obviously enhanced.
Example 14 composite variable valence Metal oxide Cr 2 O 3 @CrO 3 The SERS performance of the particles is obviously improved relative to that of non-valence-variable metal oxide particles
The prepared composite variable valence metal oxide Cr 2 O 3 @CrO 3 Particles of Cr 2 O 3 Metal oxide particles, crO 3 Under the action of 532nm excitation wavelength, the metal oxide particles serving as the SERS substrate are observed to be relative to Cr 2 O 3 And CrO 3 Metal oxide particles, composite valence-variable metal oxide Cr 2 O 3 @CrO 3 The surface enhanced Raman effect of the particle is obviously enhanced.
Example 15 composite valence-changing Metal oxide CuO @ Cu 2 Uv-vis diffuse reflectance test of O particles
The prepared composite valence-variable metal oxide CuO @ Cu 2 The O particles are subjected to ultraviolet visible diffuse reflection spectrum test, and the composite valence-variable metal oxide CuO @ Cu can be seen 2 Different valence states of the O particles have different electron orbitals for overlapping, and the generated electron transitions are different, so that different incident light energy can be reflected, and photoinduced charge transfer between the O particles and the electron orbitals of the target molecule to be detected is facilitated, and the composite valence-variable metal oxide CuO @ Cu is enhanced 2 Surface enhanced raman spectroscopy effect of O particles.
Example 16 composite variable valence Metal oxide MnO 2 @Mn 2 O 7 Ultraviolet-visible diffuse reflectance testing of particles
MnO is added to the prepared composite valence-variable metal oxide 2 @Mn 2 O 7 The particles are subjected to ultraviolet visible diffuse reflection spectrum test, and MnO of the composite valence-variable metal oxide can be seen 2 @Mn 2 O 7 The different valence states of the particles have different electron orbital overlaps, and the generated electron transitions are different, so that different incident light energy can be reflected, and photoinduced charge transfer with the electron orbits of the target molecules to be detected is facilitated, and the composite valence-variable metal oxide MnO is enhanced 2 @Mn 2 O 7 The surface enhanced raman spectroscopy effect of the particles.
Example 17Valence of the valence metal oxide NaO 2 Testing of ultraviolet-visible diffuse reflectance of @ NaO particles
The prepared composite variable valence metal oxide NaO 2 Testing ultraviolet visible diffuse reflection spectrum of @ NaO particles can show that the composite variable valence metal oxide NaO 2 The different valence states of the @ NaO particle have different electron orbits for overlapping, and the generated electron transitions are different, so that different incident light energy can be reflected, and photoinduced charge transfer with the electron orbit of the target molecule to be detected is facilitated, thereby enhancing the composite valence-variable metal oxide NaO 2 The surface enhanced Raman spectroscopy effect of @ NaO particles.
Example 18 composite variable valence Metal oxide Cr 2 O 3 @CrO 3 Ultraviolet-visible diffuse reflectance testing of particles
The prepared composite variable valence metal oxide Cr 2 O 3 @CrO 3 The particles are subjected to ultraviolet visible diffuse reflection spectrum test, and the variable composite valence metal oxide Cr can be seen 2 O 3 @CrO 3 Different valence states of the particles have different electron orbital overlaps, and the generated electron transitions are different, so that different incident light energy can be reflected, photoinduced charge transfer between the particles and the electron orbitals of the target molecules to be detected is facilitated, and the composite valence-variable metal oxide Cr is enhanced 2 O 3 @CrO 3 The surface enhanced raman spectroscopy effect of the particles.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (5)
1. The application of composite variable valence metal oxide particles as a surface-enhanced Raman spectrum substrate is characterized in that the composite variable valence metal oxide particles have metal cations with different valence states, wherein the metal cations with different valence states comprise a high valence metal cation and a low valence metal cation; the energy band structure of the metal ion band consists of metal cation orbital energy levels with different valence states; the composite valence-change metal oxide utilizes different electron orbitals to overlap to generate different electron transitions, and the electron transition probability is improved; under the action of exciting light, different scattered light energy is emitted, photoinduced charge transfer between the scattered light energy and an electron orbit of a target molecule to be detected is improved, and the scattered light energy is used for enhancing the surface enhanced Raman spectroscopy effect of the composite valence-variable metal oxide;
the composite valence-variable metal oxide particles are selected from CuO @ Cu 2 O、MnO 2 @Mn 2 O 7 、NaO 2 @NaO、Cr 2 O 3 @CrO 3 Any one of (a);
the morphology of the composite variable valence metal oxide particles is selected from any one of lamellar, tetrahedral, hexahedral, octahedral, dodecahedral, hollow cage, round granular and rod-shaped;
the particle size distribution of the composite variable valence metal oxide particles is between 0.1nm and 1000nm.
2. The use of the composite variable valence metal oxide particles of claim 1 as a substrate for surface enhanced raman spectroscopy, wherein the composite variable valence metal oxide particles have multiple absorption/reflection regions in the uv-vis absorption spectrum/diffuse reflection spectrum and multiple absorption/reflection peaks in the uv-vis-nir region.
3. The use of the composite variable valence metal oxide particles as a surface-enhanced Raman spectrum substrate according to any one of claims 1 to 2, wherein the preparation method of the composite variable valence metal oxide particles comprises the following steps: carrying out reduction reaction on a solution I containing metal salt and a reducing agent to obtain the composite valence-variable metal oxide particles;
the metal salt is a combination at least comprising a metal salt I and a metal salt II containing metal cations with different valence states;
the metal elements in the metal salt I and the metal salt II are the same.
4. A surface-enhanced Raman spectroscopy substrate, characterized in that the substrate comprises the complex variable valence metal oxide particles as defined in any one of claims 1 to 3 in the application of the substrate as a surface-enhanced Raman spectroscopy substrate.
5. The use of the surface-enhanced Raman spectroscopy substrate according to claim 4 in molecular detection and/or biological detection, wherein the wavelength of excitation light used in laser Raman spectroscopy is 266 to 1064nm.
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