WO2020113706A1

WO2020113706A1 - Application of semiconductor compound in benzaldehyde specificity detection and detection method therefor

Info

Publication number: WO2020113706A1
Application number: PCT/CN2018/123334
Authority: WO
Inventors: 赵志刚; 潘婷; 丛杉
Original assignee: 中国科学院苏州纳米技术与纳米仿生研究所
Priority date: 2018-12-06
Filing date: 2018-12-25
Publication date: 2020-06-11
Also published as: CN109596595B; CN109596595A

Abstract

Disclosed are an application of a semiconductor compound in the benzaldehyde specificity detection and a detection method therefor. The detection method comprises: using a semiconductor compound as an SERS active substrate material, contacting same with a detection sample that may contain benzaldehyde, then carrying out detection by means of a Raman spectrometer, and according to a specificity Raman enhancement effect generated between the semiconductor compound and the benzaldehyde, realizing the benzaldehyde specificity detection. Compared with a noble metal substrate material, the semiconductor compound as an SERS active substrate material is wide in selectable range, low in cost, simple in operation, and quick and effective. The semiconductor compound can generate the specificity Raman enhancement effect on the benzaldehyde, can realize the benzaldehyde specificity detection and can effectively distinguish benzyl alcohol from the benzaldehyde. A tiny quantity of benzaldehyde mixed into the common organic solvent benzyl alcohol of injection type medicines can be effectively identified, and the usage safety of medicines can be guaranteed to a certain degree.

Description

Application and detection method of semiconductor compound in benzaldehyde specific detection

Technical field

The present application relates to a method for specific detection of benzaldehyde based on SERS (Surface Enhanced Raman Scattering Spectroscopy) technology using semiconductor compound base materials, which belongs to the technical field of spectroscopy and molecular recognition.

Background technique

Benzaldehyde is an important chemical raw material, currently widely used in plasticizers, pharmaceutical intermediates, fragrances, dyes and cosmetics [Chemical Communications, 2010, 46, 5909-5911.], but also a volatile organic compound (VOC). The unreasonable use of benzaldehyde not only seriously threatens human health, but also causes serious environmental pollution [Dalton Transactions, 2015, 44, 4362-4369.], [Chemical Luminescence, 2008, 23, 376-380.], and even has a carcinogenic risk. In addition, benzaldehyde is the main toxic substance in benzyl alcohol, which is a common organic solvent for many injection drugs (such as spectidium hydrochloride, diclofenac sodium, etc.), because benzyl alcohol is easily oxidized in the air. Benzaldehyde. The existing methods for the detection of benzaldehyde include gas chromatography (GC), high performance liquid chromatography (HPLC), ultraviolet spectroscopy, polarographic analysis, and luminescence spectroscopy (Chemical Luminescence, 2008, 23(6 ): 376-380). However, these methods have some defects, such as high requirements for detection systems, poor detection sensitivity, and difficulty in specific detection, etc. [Chemistry, 2015, 21, 15854-15859.]. Therefore, it is of great significance to develop a method that is fast, efficient, simple to operate, and capable of directly detecting benzaldehyde directly.

Summary of the invention

The main purpose of the present application is to provide an application of semiconductor compound materials in the specific detection of benzaldehyde to overcome the deficiencies in the prior art.

Another object of the present application is to provide a method for specifically detecting benzaldehyde based on semiconductor compounds as SERS active substrate materials.

In order to achieve the above-mentioned invention purpose, the present application adopts the following technical solutions:

The embodiments of the present application provide an application of a semiconductor compound as a SERS active substrate material in the specific detection of benzaldehyde.

The embodiments of the present application also provide a SERS active substrate material for benzaldehyde specific detection, which includes a semiconductor compound, and a preparation method of the semiconductor compound includes:

Solvothermal method is used to subject the reaction system containing metal chloride, ammonium salt, metal organic reagent or metal oxide and solvent to alcoholysis and hydrolysis reaction at 160-200°C for 12-24 hours to directly obtain semiconductor compound base material; or, First, a solvothermal method is used to obtain a semiconductor compound precursor, and then annealed at 400 to 600°C for 4 to 6 hours to obtain semiconductor compound base materials with different stoichiometric ratios.

The embodiments of the present application also provide a benzaldehyde specific detection method, which includes:

Use semiconductor compounds as SERS active substrate materials; or provide the aforementioned SERS active substrate materials;

The SERS active substrate material is brought into contact with a detection sample that may contain benzaldehyde, and then a Raman spectrometer is used for detection to achieve specific detection of benzaldehyde.

The embodiment of the present application also provides a method for distinguishing and identifying benzyl alcohol and benzaldehyde, which includes:

Provide the aforementioned SERS active substrate material;

The SERS active substrate material is contacted with a mixture of benzyl alcohol and benzaldehyde, and then detected by a Raman spectrometer to realize the distinguishing identification of benzyl alcohol and benzaldehyde.

Compared with the prior art, the beneficial effects of this application are:

1) Compared with noble metal base materials, the semiconductor compounds provided in this application as SERS active base materials have a wide range of options, low cost, simple operation, fast and effective, and the semiconductor compounds can produce specific Raman enhancement effects on benzaldehyde. Realize the specific detection of benzaldehyde, which can effectively distinguish benzyl alcohol and benzaldehyde, and can efficiently identify benzaldehyde, which only has a good enhancement effect on benzaldehyde;

2) This application can also effectively identify and detect trace benzaldehyde mixed in benzyl alcohol, a common organic solvent for injection drugs, which can ensure the safety of drug use to a certain extent.

BRIEF DESCRIPTION

In order to more clearly explain the embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the drawings required in the embodiments or the description of the prior art. Obviously, the drawings in the following description are only These are the embodiments described in this application. For those of ordinary skill in the art, without paying any creative work, other drawings can be obtained based on these drawings.

FIG. 1 is an enhanced Raman spectrum diagram of the probe molecule benzaldehyde with tungsten oxide of different stoichiometric ratio as the SERS active substrate in Example 1 of the present application, and the excitation wavelength is 532 nm.

FIG. 2 is an enhanced Raman spectrum of the W ₁₈ O ₄₉ substrate and the Ag sol for benzyl alcohol, benzaldehyde, and two probe molecules in Example 2 of the present application, and the laser wavelength is 532 nm.

FIG. 3 is a comparison chart of infrared spectra of W ₁₈ O ₄₉ adsorbed by benzaldehyde and pure W ₁₈ O ₄₉ in Example 6 of the present application. FIG 500-1000cm ^-1 absorption peak is at the W ₁₈ O _49, and W = O OWO vibration absorption peak of 1622cm ^-1 characteristic absorption of water molecules to the sample surface.

detailed description

In view of the many shortcomings of the existing technology, the inventor of this case has been able to propose the technical solution of this application after long-term research and extensive practice. The technical solution, its implementation process and principle will be further explained as follows. However, it should be understood that within the scope of the present application, the above technical features of the present application and the technical features specifically described in the following (embodiments) can be combined with each other, thereby forming a new or preferred technical solution. Due to space limitations, I will not repeat them here.

Surface enhanced Raman spectroscopy (SERS) is a highly selective and ultra-sensitive rapid surface analysis technology, which lays a theoretical foundation for the rapid and specific detection of benzaldehyde. At the same time, in recent years, the use of semiconductor compounds as SERS active substrates has also made tremendous breakthroughs. As a SERS active substrate, semiconductor compound materials can effectively increase the enhancement factor and reduce the detection limit of target molecules; on the other hand, they also have good stability and biocompatibility, which lays the foundation for the specific detection of benzaldehyde .

As an aspect of the technical solution of the present application, it relates to the application of a semiconductor compound as a SERS active substrate material in the specific detection of benzaldehyde.

This application provides a new SERS technology based on semiconductor compounds as a SERS active substrate material for the specific detection of benzaldehyde, including first preparing a SERS active substrate material, and then directly mixing the substrate material with benzaldehyde to achieve adsorption equilibrium Raman optical spectrum analyzer for direct and rapid detection.

In some embodiments, the method for preparing the semiconductor compound includes:

Using solvothermal method, metal chloride, ammonium salt, metal organic reagent or metal oxide can be selected as raw materials in anhydrous ethanol solvent, reacted at 160～200℃ for 12～24h, through alcoholysis and hydrolysis etc. The semiconductor compound base material is directly obtained through the process; or, the semiconductor compound precursor is first obtained by a solvothermal method, and then annealed at 400 to 600°C for 4 to 6 hours to obtain corresponding semiconductor compound base materials with different stoichiometric ratios.

In some embodiments, the preparation of semiconductor compound substrate materials with different oxygen defect concentrations using semiconductor compounds as SERS active substrate materials can have a wide range of choices, but can be but not limited to WO ₂ , W ₁₈ O ₄₉ , WO ₃ , MoO ₂ , Any one or a combination of two or more semiconductor compound materials such as MoO _3-x , MoO ₃ , ZnO, TiO ₂ and Cu ₂ O as precursors, or other stoichiometric or non-stoichiometric semiconductor compounds . In a mixed gas of one or several gases such as hydrogen, argon, and ammonia, annealing is performed at different temperatures and times.

In some embodiments, the annealing atmosphere of the annealing treatment may be a reducing atmosphere, such as hydrogen, argon, ammonia, or a mixture of several gases; or an oxidizing atmosphere, such as air, oxygen, etc., which The purpose is to obtain semiconductor compound SERS active substrate materials with different stoichiometric ratios.

As an aspect of the technical solution of the present application, it relates to a SERS active substrate material for benzaldehyde specific detection, which includes a semiconductor compound, and a preparation method of the semiconductor compound includes:

Solvothermal method is used to react metal chloride, ammonium salt, metal organic reagent or metal oxide directly to obtain semiconductor compound base material; or, first use solvothermal method to obtain semiconductor compound precursor, and then annealing treatment to obtain different stoichiometry Ratio of semiconductor compound base material.

Another aspect of the embodiments of the present application also provides a benzaldehyde specific detection method, which includes:

The SERS active substrate material is brought into contact with a detection sample that may contain benzaldehyde, and then detected by a Raman spectrometer, and a specific Raman enhancement effect is generated between the semiconductor compound and benzaldehyde to realize the specific detection of benzaldehyde.

In some embodiments, the benzaldehyde-specific detection method includes:

The solution in which a certain amount of semiconductor compound base material is dispersed is directly mixed with a certain concentration of benzaldehyde to achieve adsorption equilibrium. Then, after a certain amount of the mixed solution is dripped on a clean silicon wafer and dried, the Raman spectrometer can be used to directly detect benzaldehyde, and the benzaldehyde has a significant Raman enhancement effect, which can efficiently identify benzaldehyde.

Further, the prepared semiconductor compound material is dispersed into a certain amount of ethanol to obtain an ethanol solution of the semiconductor compound material. Then take a certain amount of this solution, add benzaldehyde ethanol solution of different concentrations, and let it stand in the dark. After reaching the adsorption equilibrium, take a certain amount of mixed solution and drop it on a clean Si/SiO ₂ substrate. After natural drying, in Raman Test on a spectrometer to collect data.

Further, the detection sample includes benzaldehyde, or a mixture of benzyl alcohol and benzaldehyde.

Among them, compared with precious metals, semiconductor compounds are specific for the detection of benzaldehyde, which can specifically detect benzaldehyde in complex systems, and precious metals are universal for the detection of molecules, which will have an enhanced effect on all molecules, so The peaks in the Raman spectrum detected by the complex system cannot be distinguished.

Further, the principle of the specific detection method of the present application is that the enhancement mechanism of the semiconductor compound to benzaldehyde is different from the enhancement mechanism of the semiconductor compound to other organic molecules. Semiconductor compounds generally produce Raman enhancement of organic molecules through energy band position matching mechanism, while semiconductor compounds produce specific Raman enhancement of benzaldehyde through special chemical action. Benzaldehyde can bond with the active site on the surface of the semiconductor compound to generate a new surface compound, which is beneficial to the charge transfer between the two and enhances the Raman scattering signal.

Furthermore, noble metals are universal for the enhancement of molecules. For complex detection systems, the peaks in the Raman spectrum cannot specifically distinguish the substances, and the semiconductor compounds can produce a specific Raman enhancement effect on benzaldehyde. Under the same conditions, the semiconductor compound can efficiently and selectively identify benzaldehyde, and it only has a significant enhancement effect on benzaldehyde, and has almost no enhancement effect on benzyl alcohol. When a small amount of benzaldehyde is mixed in benzyl alcohol, it can also be effectively identified by this technology.

Further, the semiconductor compound material of the present application can specifically detect trace amounts of benzaldehyde contained in benzyl alcohol.

Another aspect of the embodiments of the present application also provides a method for distinguishing and identifying benzyl alcohol and benzaldehyde, which includes:

Provide the aforementioned SERS active substrate material;

The SERS active substrate material is contacted with a mixture of benzyl alcohol and benzaldehyde, and then detected by a Raman spectrometer, and a specific Raman enhancement effect is generated between the semiconductor compound and benzaldehyde to realize the discrimination between benzyl alcohol and benzaldehyde .

Further, benzyl alcohol was tested under the same conditions and methods, and the selected base material was the same as the base material used for benzaldehyde.

Further, benzaldehyde and benzyl alcohol are mixed in different proportions, and then a certain amount of mixed solution is added to the base material solution to specifically detect the benzaldehyde mixed in benzyl alcohol.

Among them, in this test method, benzyl alcohol and benzaldehyde can be directly mixed with the base material, and the sample can be directly tested after adsorption equilibrium.

In summary, through the above technical solutions, the present application can implement a method for direct and specific detection of benzaldehyde, a practical small molecule. The method has simple operation, fast and efficient and easy preparation of SERS active substrates, and a wide range of options specialty. In addition, it can effectively detect trace benzaldehyde mixed in benzyl alcohol, a common organic solvent for injectable drugs, which can ensure the safety of drug use to a certain extent.

The technical solutions of the present application will be further described in detail below in conjunction with several preferred embodiments and accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, but not all the embodiments. Based on the embodiments in this application, all other embodiments obtained by a person of ordinary skill in the art without making creative efforts fall within the scope of protection of this application. The implementation conditions adopted in the following examples can be further adjusted according to actual needs, and the implementation conditions not specified are usually the conditions in routine experiments.

Example 1

Dissolve a certain amount of WO ₃ in a certain amount of ethylenediamine, react at 180°C for 12h, and naturally cool to room temperature. Centrifuge, wash and vacuum dry to obtain WO ₃ -EDA precursor. Then, the precursor was annealed at 600°C and Ar for 5 hours to obtain WO ₂ -C material; a certain amount of WCl _{6 was} added to a certain amount of ethanol and dissolved at 160°C for 24 hours and naturally cooled to room temperature. Wash and dry to obtain W ₁₈ O ₄₉ ; W ₁₈ O ₄₉ is annealed in air at 400° C. for 6 hours to obtain WO ₃ . The same amount of benzaldehyde was added to 3 mL of ethanol solution of WO ₂ -C, W ₁₈ O ₄₉ and WO ₃ with a concentration of 0.2 mg/mL, and allowed to stand for 2 hours. After adsorption equilibrium, 20 μL of the mixed solution was taken separately Drop it on a clean Si/SiO ₂ substrate and dry it naturally to obtain the sample 1 to be tested.

As shown in FIG. 1, in this embodiment, tungsten oxide with different stoichiometric ratios is used as the SERS active substrate to enhance the Raman spectrum of the probe molecule benzaldehyde, and the excitation wavelength is 532 nm.

Example 2

A certain amount of WCl _{6 was} added to a certain amount of ethanol, and the reaction was carried out at 180°C for 12 hours, and then naturally cooled to room temperature. Wash and dry to obtain W ₁₈ O ₄₉ . The same amount of benzyl alcohol and benzaldehyde were added to 3mL W ₁₈ O ₄₉ ethanol solution and Ag sol, and allowed to stand for 2h. After adsorption equilibrium, 20μL of the mixed solution was dropped on a clean Si/SiO ₂ substrate, naturally Dry to get the sample 2 to be tested.

As shown in FIG. 2, it is an enhanced Raman spectrogram of the W ₁₈ O ₄₉ substrate and the Ag sol for benzyl alcohol, benzaldehyde, and two probe molecules in this embodiment, and the laser wavelength is 532 nm.

Example 3

A certain amount of molybdenum acetylacetonate was added to dissolve in a certain amount of ethanol, and the reaction was carried out at 180°C for 20 hours, and naturally cooled to room temperature. Wash and dry to obtain MoO ₂ . A series of different amounts of benzaldehyde were added to 3mL of MoO ₂ ethanol solution, and allowed to stand for 2h. After adsorption equilibrium, 20μL of the mixed solution was dropped on clean Si/SiO ₂ substrates, and naturally dried to obtain the sample 3 to be tested.

Example 4

A certain amount of ammonium molybdate tetrahydrate and a certain amount of thiourea were dissolved in a certain amount of deionized water, and magnetically stirred for 30 minutes to form a uniform and stable solution. Then the solution was transferred to a 100 mL hydrothermal reactor and reacted at 200°C for 20 h, and naturally cooled to room temperature. Wash and dry to obtain MoS ₂ . A series of different amounts of benzaldehyde were added to 3mL of MoO ₂ ethanol solution, and allowed to stand for 2h. After adsorption equilibrium, 20μL of the mixed solution was dripped on a clean Si/SiO ₂ substrate, and naturally dried to obtain the sample 4 to be tested.

Example 5

Dissolve a certain amount of WO ₃ into a certain amount of ethylenediamine, and react at 180°C for 24 hours, then cool naturally to room temperature. Centrifuge, wash and vacuum dry to obtain WO ₃ -EDA precursor. Then, the precursor was annealed in Ar at 500°C for 4h to obtain WO ₂ -C material. A series of different amounts of benzaldehyde were added to 3mL of WO ₂ -C ethanol solution and allowed to stand for 2h. After adsorption equilibrium, 20μL of the mixed solution was dripped on a clean Si/SiO ₂ substrate and dried naturally to obtain the test Sample 5.

Example 6

A certain amount of benzaldehyde was dissolved in a certain amount of W ₁₀ O ₄₉ ethanol solution, and allowed to stand for 2 hours. After adsorption equilibrium, centrifugation, the resulting precipitate was naturally dried, and the obtained powder was detected by infrared spectrometer.

As shown in FIG. 3, it is a comparison chart of infrared spectra of W ₁₈ O ₄₉ adsorbed by benzaldehyde and pure W ₁₈ O ₄₉ in this embodiment. The absorption peak at 500-1000 cm ^-1 in the figure is W ₁₈ O ₄₉ W =O and OWO vibration absorption. 1622cm ^-1 is the characteristic peak of water molecules absorbed on the sample surface. When benzaldehyde adsorbed onto the W ₁₈ O ₄₉ surface, a new absorption peak appeared in the infrared spectrum. The peak at 1697 cm ^-1 is the stretching vibration of the C=O bond after the benzaldehyde binds to the Lewis active site on the surface of tungsten oxide. The 1455cm ^-1 corresponds to the vibration of the benzene ring, and the 1410cm ^-1 corresponds to the stretching vibration of the OCO in the benzoate.

This application mainly uses semiconductor compounds of various stoichiometric ratios and non-stoichiometric ratios as SERS active substrate materials to achieve direct and rapid specific detection of benzaldehyde. And semiconductor compound materials can greatly enhance the Raman response signal of benzaldehyde in Raman detection, which is quite comparable to the precious metal-based SERS chip, and can effectively distinguish benzyl alcohol from benzaldehyde. It makes up for the defects of precious metal-based SERS chips in practical applications, and promotes the practical application of semiconductor compound substrate materials in the field of SERS.

In addition, the inventors of the present case also used other process conditions listed in the foregoing to substitute the corresponding process conditions in Examples 1-6 to perform corresponding tests, and the contents to be verified are similar to the products of Examples 1-6. Therefore, the verification content of each embodiment is not described one by one here, and only the embodiments 1 to 6 are used as representatives to explain the advantages of the application of this application.

It should be noted that, in this article, in general, the elements defined by the sentence "including..." do not exclude that there are other identical elements in the steps, processes, methods, or experimental equipment that include the elements.

It should be understood that the above examples are only to illustrate the technical concept and characteristics of this application, and its purpose is to allow those familiar with this technology to understand the content of this application and implement it accordingly, and should not limit the scope of protection of this application . All equivalent changes or modifications made according to the spirit of this application should be covered within the scope of protection of this application.

Claims

The application of semiconductor compounds as SERS active substrate materials in the specific detection of benzaldehyde.
The application according to claim 1, wherein the preparation method of the semiconductor compound comprises:

Solvothermal method is used to subject the reaction system containing metal chloride, ammonium salt, metal organic reagent or metal oxide and solvent to alcoholysis and hydrolysis reaction at 160-200°C for 12-24 hours to directly obtain semiconductor compound base material; or, First, a solvothermal method is used to obtain a semiconductor compound precursor, and then annealed at 400 to 600°C for 4 to 6 hours to obtain semiconductor compound base materials with different stoichiometric ratios.
The application according to claim 1, characterized in that: the semiconductor compound includes a stoichiometric or non-stoichiometric ratio of the semiconductor compound; preferably, the semiconductor compound precursor includes WO 2 , W 18 O 49 , WO 3 , MoO 2 , MoO 3 , ZnO, TiO 2 , Cu 2 O, or any combination of two or more.
The application according to claim 2, characterized in that: the atmosphere used for the annealing treatment includes a reducing atmosphere or an oxidizing atmosphere; preferably, the reducing atmosphere includes any one of hydrogen, argon, and ammonia Or a combination of two or more; preferably, the oxidizing atmosphere includes an air atmosphere and/or an oxygen atmosphere.
A SERS active substrate material for benzaldehyde specific detection, which is characterized by containing a semiconductor compound, and a preparation method of the semiconductor compound includes:

Solvothermal method is used to subject the reaction system containing metal chloride, ammonium salt, metal organic reagent or metal oxide and solvent to alcoholysis and hydrolysis reaction at 160-200°C for 12-24 hours to directly obtain semiconductor compound base material; or, First, a solvothermal method is used to obtain a semiconductor compound precursor, and then annealed at 400 to 600°C for 4 to 6 hours to obtain semiconductor compound base materials with different stoichiometric ratios.
The SERS active substrate material for benzaldehyde specific detection according to claim 5, characterized in that the semiconductor compound includes a stoichiometric or non-stoichiometric ratio of the semiconductor compound; preferably, the semiconductor compound precursor includes WO 2. Any one or a combination of two or more of W 18 O 49 , WO 3 , MoO 2 , MoO 3 , ZnO, TiO 2 , and Cu 2 O.
The SERS active substrate material for benzaldehyde specific detection according to claim 5, characterized in that: the atmosphere used for the annealing treatment includes a reducing atmosphere or an oxidizing atmosphere; preferably, the reducing atmosphere includes hydrogen, argon Any one or a combination of two or more of gas and ammonia; preferably, the oxidizing atmosphere includes an air atmosphere and/or an oxygen atmosphere.
A benzaldehyde specific detection method, which is characterized by:

Using a semiconductor compound as the SERS active substrate material; or providing the SERS active substrate material according to any one of claims 5-7;

The SERS active substrate material is brought into contact with a detection sample that may contain benzaldehyde, and then a Raman spectrometer is used for detection to achieve specific detection of benzaldehyde.
The benzaldehyde specific detection method according to claim 8, wherein the detection sample comprises benzaldehyde, or a mixture of benzyl alcohol and benzaldehyde.
A method for distinguishing between benzyl alcohol and benzaldehyde, which is characterized by:

Providing the SERS active substrate material according to any one of claims 5-7;

The SERS active substrate material is contacted with a mixture of benzyl alcohol and benzaldehyde, and then detected by a Raman spectrometer to realize the distinguishing identification of benzyl alcohol and benzaldehyde.