CN118883528B - A three-dimensional TiO2-Ag/AgCl composite material and its preparation method and application - Google Patents
A three-dimensional TiO2-Ag/AgCl composite material and its preparation method and application Download PDFInfo
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- 229910021607 Silver chloride Inorganic materials 0.000 title claims abstract description 86
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 90
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- 238000001514 detection method Methods 0.000 claims abstract description 16
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- C—CHEMISTRY; METALLURGY
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/58—Treatment of other metallic material
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- B82—NANOTECHNOLOGY
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C23C22/83—Chemical after-treatment
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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Abstract
The invention discloses a three-dimensional TiO 2 -Ag/AgCl composite material, a preparation method and application thereof, and belongs to the field of functional materials and Raman spectrum detection, wherein the preparation method comprises the steps of (1) adding titanium isopropoxide into a mixed solution of ethylene glycol, concentrated hydrochloric acid and water, stirring, immersing an Ag foil therein, and carrying out hydrothermal reaction to obtain a substrate; the preparation method comprises the steps of (1) placing a substrate under a xenon lamp light source, controlling the light source current to irradiate the substrate, enabling part of AgCl components in the substrate to generate photo-reduction to generate active simple substance Ag, and (3) placing the substrate subjected to photo-treatment in a protective atmosphere, controlling the heating temperature to be 200-500 ℃ to enable the active simple substance Ag to depend on TiO 2 monomers to carry out thermal migration, so that the three-dimensional TiO 2 -Ag/AgCl composite material is prepared. The composite material has good structural stability, adjustable structure and high and stable SERS activity, and can be used for high-sensitivity detection of water pollutants such as antibiotics.
Description
Technical Field
The invention relates to the technical field of functional materials and Raman spectrum detection, in particular to a three-dimensional TiO 2 -Ag/AgCl composite material, and a preparation method and application thereof.
Background
The detection of trace molecules such as extremely low concentration of carcinogenic mutagens, early disease markers, antibiotics, various pesticide residues, industrial pollutants and the like from a complex system is an important subject in the fields of modern analytical chemistry and biotechnology, and is also one of key technologies for guaranteeing food safety, public health and drug development. The raman spectrum is a fingerprint inelastic scattering spectrum with molecular structure specificity, and is based on surface enhanced raman technology (SERS) developed gradually by the raman spectrum, and the raman spectrum can identify molecules with high sensitivity by utilizing special vibration characteristics of metal nano structures and the like without any external markers, so that the raman spectrum has great potential and value in various fields of material science, biomedicine, environmental monitoring and the like. The SERS technique still faces some challenges (1) uncontrollable heterogeneity of analyte signals and (2) low reproducibility of low concentration analyte signals. In order to solve the problems, researchers obtain a plurality of complex SERS substrates or structures through various assembly technologies, such as substrate structures assembled by primitive units of zero-dimensional nano particles, one-dimensional nano wires, nano rods, two-dimensional nano sheets, nano discs, nano porous structures, multi-stage structures and the like, and the structures all show unique Raman scattering characteristics, but the structures have the advantages of more assembly steps, severe preparation conditions, complex process, higher cost, lower recycling rate and longer practical application.
Development of simple, efficient and stable material preparation, processing and assembly methods is one of the important contents in developing efficient SERS substrates. TiO 2 is a semiconductor material with low price, biological friendliness, simple and convenient processing and high practical value, and the abundant binding sites on the surface provide congenital chemical advantages for material compounding, detection, identification and the like of target molecules, and the relatively wide energy gap structure and adjustability provide convenience for matching the special energy level of the molecules to be detected and meeting related charge transfer resonance. Noble metals (e.g., au, pt, etc.) can induce an electric field in SERS applications due to their characteristic localized surface resonance (LSPR) effect, thereby significantly increasing the detection limit of the molecules to be detected, and are widely used as SERS active components or sites in many SERS substrates. However, in practical applications, stability of the noble metal nano-active unit to temperature, light, acid-base property and air is generally required to be considered, so as to ensure that the whole SERS substrate has continuous detection activity and stability. Therefore, in order to improve the performance of the TiO 2 SERS substrate, besides improving the binding property and electronic interaction of the molecules to be detected of the whole structure of the material, proper metal active ingredients are required to be selected, and various components can be properly coupled with each other through a simple path, so that the structure is stable and adjustable, and the SERS activity of the substrate in indoor light and air environment can be maintained for a long time.
The invention discloses a flexible and recyclable SERS substrate with the publication number of CN105372223A and a preparation method thereof, wherein a thin Ti sheet is used as a Ti source, a TiO 2 nanobelt array with Ti as a substrate is prepared by a hydrothermal synthesis method, a SERS substrate material with the publication number of CN113670893A is prepared by a continuous ion deposition method, the Chinese patent publication number of CN113670893A discloses a surface-enhanced Raman scattering substrate, a preparation method and application thereof, the method firstly utilizes the hydrothermal method to put titanium foil into a reaction kettle filled with a mixed solution of NaOH and urea for reaction, tiO 2 nanocone arrays with different morphologies are prepared by controlling the content of urea, and the TiO 2 nanocone arrays are subjected to Ag plating treatment by a magnetron sputtering method to obtain the Ag/TiO 2 substrate. The Ag/TiO 2 substrate can be used for detecting SARS-CoV-2S1 protein. However, the magnetron sputtering technology has high cost, complex equipment and possibly adverse phenomena such as gas discharge and the like to influence the deposition quality.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the three-dimensional TiO 2 -Ag/AgCl composite material and the preparation method thereof, which have the advantages of good structural stability, adjustable structure, simple and efficient preparation method, mild condition, high and stable SERS activity and can be used for high-sensitivity detection of water pollutants such as antibiotics.
The technical scheme adopted is as follows:
a preparation method of a three-dimensional TiO 2 -Ag/AgCl composite material comprises the following steps:
(1) Adding titanium isopropoxide into a mixed solution of ethylene glycol, concentrated hydrochloric acid and water, stirring, immersing the cleaned and dried Ag foil therein, and reacting for 1.5-7.5 hours in a heating environment of 80-150 ℃ to prepare a base material Ag-based TiO 2 -AgCl;
(2) Placing a base material Ag-based TiO 2 -AgCl under a xenon lamp light source, controlling a light source current to irradiate the base material, and enabling part of AgCl components in the base material to generate photo-reduction to generate active simple substance Ag;
(3) And placing the substrate subjected to the light treatment in a protective atmosphere, and controlling the heating temperature to be 200-500 ℃ to enable the active simple substance Ag to be subjected to thermal migration by depending on the TiO 2 monomer, so as to prepare the three-dimensional TiO 2 -Ag/AgCl composite material.
According to the preparation method, an Ag foil is used as a base material, a proper amount of concentrated hydrochloric acid is introduced, meanwhile, the chlorination rate of the surface of the Ag foil and the hydrolysis rate of titanium isopropoxide are controlled, so that in-situ deposition of a TiO 2 nano structure unit and in-situ evolution of AgCl crystals on the surface of the Ag foil are coordinated, a disordered TiO 2 nano needle-shaped lawn is finally planted on the Ag base, the evolution spreading rate of the AgCl crystal layer is relatively fast, when a TiO 2 nano structure monomer is deposited on the surface of the Ag foil, the rapid spreading AgCl crystal layer is extruded by soil, finally, the TiO 2 monomer is firmly planted on slits of the AgCl crystal layer, a layer of TiO 2 nano needle-shaped lawn structure is successfully assembled on the Ag base, the AgCl crystal layer is sensitive to light, a plurality of active Ag (0) can be generated on the surface of the Ag by illumination, and the active Ag (0) can migrate depending on a nearby compatible TiO 2 crystal face under heating conditions, so that the crystallinity of the TiO 2 nano structure can be regulated and controlled, and the distribution of TiO 2 nano unit (Ag 0) can be controlled to obtain the three-dimensional composite TiO 24/nano-TiO 2.
Optionally, the thickness of the Ag foil is 0.005-2.0 mm, the purity is 99.00% -99.998%, the area size is 0.5 cm multiplied by 1.0 cm-4.0 cm multiplied by 8.0 cm, the Ag foil is sequentially immersed into HNO 3 solution, isopropanol, acetone, ethanol and deionized water with the mol/L of 0.01-0.5 to ultrasonically wash more than 30 min, and the Ag foil is taken out and dried by high-purity nitrogen to obtain the clean and dried Ag foil for standby.
Preferably, in the mixed solution in the step (1), the volume ratio of the ethylene glycol to the concentrated hydrochloric acid to the water is 0.2-1:0.2-1:1, and the adding amount of the titanium isopropoxide is 1-5 v/v% based on the volume of the water in the mixed solution.
Optionally, the base material Ag-based TiO 2 -AgCl is respectively cleaned with isopropanol, acetone, ethanol and deionized water for multiple times for later use.
Specifically, in the step (2), the wavelength of the xenon lamp light source is 300 nm- λ -1100 nm, the distance between the exit window of the xenon lamp light source and the substrate is 5.0-50 cm, the light source current is controlled to enable the irradiation intensity received by the substrate to be 10.0-200 mW/cm 2, and the irradiation time is controlled to be 2.0-30 min. AgCl has photosensitive property, and the surface of AgCl component in the substrate can be subjected to photo-reduction to generate active Ag (0) by controlling the irradiation of light source current.
Optionally, in the step (3), the protective atmosphere is a nitrogen atmosphere or a nitrogen-hydrogen mixed atmosphere, and the heating time is 30-120 min. The three-dimensional structure of the base material Ag-based TiO 2 -AgCl is free from structural damage in a protective atmosphere at the temperature of 500 ℃, and Ag (0) nano particles are thermally migrated from a substrate along the TiO 2 nano needle, so that the three-dimensional TiO 2 -Ag/AgCl composite material with adjustable structure and performance is prepared.
The invention also provides the three-dimensional TiO 2 -Ag/AgCl composite material prepared by the preparation method of the three-dimensional TiO 2 -Ag/AgCl composite material.
In the three-dimensional TiO 2 -Ag/AgCl composite material, tiO 2 nanoneedles are assembled in situ on an Ag foil substrate based on the inlaying effect of AgCl, the TiO 2 nanoneedles form a lawn-shaped three-dimensional structure, ag nanoparticles are randomly distributed on the TiO 2 nanoneedles, the length of the TiO 2 nanoneedles is 0.1-1 mu m, the diameter of the TiO 2 nanoneedles is 10-60 nm, the particle size of the Ag nanoparticles is 5-40 nm, and the Ag nanoparticles are highly dispersed and not agglomerated.
The invention also provides application of the three-dimensional TiO 2 -Ag/AgCl composite material in surface enhanced Raman scattering detection.
The invention also provides a detection method of antibiotics in the aqueous phase solution, and the three-dimensional TiO 2 -Ag/AgCl composite material is used. Specifically, the three-dimensional TiO 2 -Ag/AgCl composite material is contacted with an aqueous phase solution to be tested, and is dried and then subjected to Raman spectrum test.
Optionally, the antibiotic is quinolone antibiotics such as norfloxacin, ofloxacin, ciprofloxacin, fleroxacin and the like.
Experiments prove that the norfloxacin solution with the concentration lower than 10 - 6 mol/L can be stably detected by using the three-dimensional TiO 2 -Ag/AgCl composite material, the detection limit can reach 10 -10 mol/L, and the three-dimensional TiO 2 -Ag/AgCl composite material has long-acting SERS activity.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides an in-situ preparation method of a three-dimensional TiO 2 -Ag/AgCl composite material, which is characterized in that an Ag foil is selected as a source material of a base material, tiO 2 nano-structure units are synchronously assembled on the surface of the Ag foil by virtue of an in-situ hydrothermal reaction of the Ag foil, the chlorination process of the surface of the Ag foil, an AgCl component in the composite structure is used as a photosensitizer, an active Ag (0) migration source is provided for the composite structure by photo-reduction, and then the active Ag (0) migration source is subjected to heat treatment in inert gas or 5% reducing atmosphere, so that the three-dimensional TiO 2 -Ag/AgCl composite material is finally obtained.
(2) The method expands the composite form among materials with unmatched lattices by continuous in-situ assembly and processing, expands the application range of the materials, ensures that functional material components of the structure are distributed more randomly and uniformly, is beneficial to the increase of specific surface area, ensures that TiO 2 nanoneedle units are extruded by AgCl crystal layers on the surfaces of substrates, ensures that each TiO 2 nanoneedle lawn structure can be firmly planted on an Ag substrate and has structural stability, and ensures that the heterogeneous interface and SERS performance of the three-dimensional TiO 2 -Ag/AgCl composite material structure have high stability and can maintain the SERS activity in indoor light, temperature and air environment for a long time.
Drawings
FIG. 1 is an SEM image of a three-dimensional TiO 2 -Ag/AgCl composite prepared in example 1, scale 40 μm.
FIG. 2 is an SEM image of a three-dimensional TiO 2 -Ag/AgCl composite prepared in example 1, scale 100 nm.
FIG. 3 is a process XRD pattern for the three-dimensional TiO 2 -Ag/AgCl composite prepared in example 1.
FIG. 4 is an SEM image of a three-dimensional TiO 2 -Ag/AgCl composite prepared in example 2, scale 100 μm.
FIG. 5 is an SEM image of a three-dimensional TiO 2 -Ag/AgCl composite prepared in example 2, scale 200 nm.
FIG. 6 is a process XRD pattern for the three-dimensional TiO 2 -Ag/AgCl composite prepared in example 2.
FIG. 7 is an SEM image of a three-dimensional TiO 2 -Ag/AgCl composite prepared in example 3, scale 15 μm.
FIG. 8 is an SEM image of a three-dimensional TiO 2 -Ag/AgCl composite prepared in example 3, scale 2 μm.
FIG. 9 is a process XRD pattern for the three-dimensional TiO 2 -Ag/AgCl composite prepared in example 3.
FIG. 10 is a SERS detection spectrum of the three-dimensional TiO 2 -Ag/AgCl composite prepared in example 1 for a10 -4～10-10 mol/L norfloxacin solution.
FIG. 11 is a comparative chart of the SERS assay stability of the three-dimensional TiO 2 -Ag/AgCl composite prepared in example 1 for 10 days for a10 -6 mol/L norfloxacin solution.
Detailed Description
The invention is further elucidated below in connection with the examples and the accompanying drawing. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer. What is not described in detail in this specification is prior art known to those skilled in the art.
In the embodiment, the thickness of the used flat Ag foil is 0.005-2.0 mm, the purity is 99.00% -99.998%, the flat Ag foil is cut into a foil with the area size of 0.5cm multiplied by 1.0 cm-4.0 cm multiplied by 8.0cm, the foil is immersed in HNO 3 solution, isopropanol, acetone, ethanol and deionized water with the mol/L of 0.1-1 in sequence, ultrasonic washing is carried out for more than 30 min, and the foil is taken out and dried by high-purity nitrogen for standby.
Example 1
Firstly, in-situ assembling a base material Ag-based TiO 2 -AgCl;
Adding 2 ml concentrated hydrochloric acid into 10 ml deionized water, fully stirring, adding 4 ml glycol, fully mixing to obtain a mixed solution, dropwise and slowly dropwise adding titanium isopropoxide, adding 0.2 ml of volume, fully stirring, fully mixing, immersing a washed and dried Ag foil sequentially subjected to ultrasonic washing in dilute nitric acid, isopropanol, acetone, ethanol and deionized water in the solution, sealing, carrying out hydrothermal reaction at 120 ℃, controlling the reaction time to be 2.5 h, preparing a base material Ag-based TiO 2 -AgCl, and sequentially washing the base material with isopropanol, acetone, ethanol and deionized water for multiple times for later use.
Step two, photo-inducing the surface of AgCl to generate active simple substance Ag;
The prepared base material Ag-based TiO 2 -AgCl is horizontally placed under a xenon lamp light source (lambda is more than or equal to 300nm and less than or equal to 1100 nm), the light source emergent window is distant from the base material sample 30 cm, the light source current is controlled by utilizing the light control mode of the light source, the irradiation intensity received by the base material sample is 100 mW/cm 2, the irradiation time is 5 min, the photosensitive characteristic of AgCl is utilized, the surface of an AgCl component in the composite structure is subjected to photo-reduction to generate active simple substance Ag, and the obtained sample is stored at room temperature in a drying manner for standby.
Thirdly, active simple substance Ag is subjected to thermal migration to form Ag particles which are distributed on the TiO 2 structural monomer;
Placing the Ag-based TiO 2 -AgCl composite structure subjected to light treatment in a tube furnace in nitrogen atmosphere, controlling the heating temperature to be 300 ℃, heating to be 60 min, enabling active Ag on the AgCl surface to depend on TiO 2 nanometer monomers to carry out thermal migration, and randomly distributing stable Ag nanometer particles on the TiO 2 monomers in batches to finally prepare the three-dimensional TiO 2 -Ag/AgCl composite material, wherein an SEM (scanning electron microscope) chart of the three-dimensional TiO 2 -Ag/AgCl composite material is shown in fig. 1 and 2, the length of a TiO 2 nanometer needle is about 200-300 nm, the diameter is 20-50 nm, the particle size of the Ag nanometer particles is about 5-20 nm, XRD characterization of the three-dimensional TiO 2 -Ag/AgCl composite material is shown in fig. 3, typical diffraction peaks of rutile phase TiO 2, cubic AgCl and Ag crystals appear in a diffraction pattern, and other heterogeneous signals are avoided.
Example 2
The difference between this example and example 1 is that in the first step, 10ml deionized water is added and 7 ml deionized water is added, ethylene glycol added with 4ml can be changed and 7 ml ethylene glycol is added, other parameters and processes are the same as those of example 1, and a three-dimensional TiO 2 -Ag/AgCl composite material is prepared, wherein the aspect ratio of the TiO 2 monomer structure is different from that of example 1, the SEM diagram of the three-dimensional TiO 2 -Ag/AgCl composite material is shown in fig. 4 and 5, the length of a TiO 2 nanoneedle is about 0.8-1 μm, the diameter is about 50-60 nm, the particle size of Ag nanoparticles is about 10-30 nm, the process XRD characterization is shown in fig. 6, the diffraction pattern shows typical diffraction peaks of rutile phase TiO 2, cubic AgCl and Ag crystals, and no other heterogeneous signals.
Example 3
The embodiment is different from the embodiment 1 only in that in the first step, 2ml concentrated hydrochloric acid is added to 7 ml concentrated hydrochloric acid, 10ml deionized water is added to 7 ml deionized water, other parameters and processes are the same as those of the embodiment 1, and the three-dimensional TiO 2 -Ag/AgCl composite material is prepared, wherein a micro-sphere composed of TiO 2 nano needles is filled in an AgCl block gap, the SEM images of the three-dimensional TiO 2 -Ag/AgCl composite material are shown in fig. 7 and 8, the length of the TiO 2 nano needles is about 0.4-0.8 mu m, the diameter is about 5-20 nm, the particle size of Ag nano particles is about 5-40 nm, the process XRD image is shown in fig. 9, and typical diffraction peaks of rutile phase TiO 2, cubic AgCl and Ag crystals are shown in the diffraction pattern, and other miscellaneous phase signals are not shown.
Sample analysis
Testing SERS activity and stability of the three-dimensional TiO 2 -Ag/AgCl composite material prepared in the example 1 in indoor light, temperature and air environments;
Cutting the three-dimensional TiO 2 -Ag/AgCl composite material prepared in the same batch into 4 pieces, randomly numbering 1-4 pieces, sequentially dripping 10 -4 mol/L、10-6 mol/L、10-8 mol/L、10-10 mol/L norfloxacin solution into 1-4 pieces of samples, naturally drying under the same condition, carrying out Raman spectrum test, wherein the wavelength of laser used for test is 633 nm, the integration times are 3, each sample randomly detects 20 points for 20 times, and the surface enhancement spectrum obtained after averaging is shown in figure 10. As can be seen from FIG. 10, when the three-dimensional TiO 2 -Ag/AgCl composite material is used for detecting norfloxacin solution, the three-dimensional TiO 2 -Ag/AgCl composite material has high SERS detection activity on 10 -4～10-10 mol/L norfloxacin solution. Cutting the three-dimensional TiO 2 -Ag/AgCl composite material prepared in the same batch into 10 pieces, randomly numbering 1-10 pieces, storing in a glass container with room temperature, air atmosphere and 50% humidity, sequentially taking a sample substrate daily according to the number to carry out the same Raman detection on the newly prepared 10 -6 mol/L norfloxacin solution, testing the selected laser wavelength to be 633 nm, testing 20 points randomly for 20 times for each sample, and taking the average surface enhancement map, wherein the SERS activity of the three-dimensional TiO 2 -Ag/AgCl composite material on the norfloxacin solution has a certain long-term effect. Therefore, the three-dimensional TiO 2 -Ag/AgCl composite material prepared by the method can be used in the detection and identification fields of water pesticide residues, food additives, environmental analysis, pharmaceutical analysis, biochemistry and the like.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (7)
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