CN112834478B - Based on AgNPs/MOFs/g-C 3 N 4 Composite film and preparation method and application thereof - Google Patents
Based on AgNPs/MOFs/g-C 3 N 4 Composite film and preparation method and application thereof Download PDFInfo
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- CN112834478B CN112834478B CN202011489318.2A CN202011489318A CN112834478B CN 112834478 B CN112834478 B CN 112834478B CN 202011489318 A CN202011489318 A CN 202011489318A CN 112834478 B CN112834478 B CN 112834478B
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- 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
- G01N21/62—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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- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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Abstract
Based on AgNPs/MOFs/g-C 3 N 4 Mixing and stirring a methanol solution of cobalt nitrate hexahydrate and a methanol solution of 2-methylimidazole, transferring the mixture into a reaction kettle, and standing the mixture at room temperature to obtain a metal framework MOFs material a; dispersing the alpha in deionized water, adding a tannin water solution, centrifuging to obtain a dark color product b, and washing to remove excessive tannin; re-dispersing the b in deionized water, and adding a silver nitrate solution to obtain c; a monolayer of g-C 3 N 4 Placing into a centrifuge tube, adding concentrated hydrochloric acid to obtain protonated g-C 3 N 4 (ii) a C and g-C after protonation 3 N 4 Adding the mixture into a methanol solution, stirring the mixture at room temperature and standing the mixture for a period of time to form a solution d; vacuum-filtering the product d with polyethersulfone, washing with methanol, and drying to obtain AgNPs/MOFs/g-C 3 N 4 And (3) compounding the film. The invention mainly constructs AgNPs/MOFs/g-C by methods such as in-situ reduction, electrostatic interaction and the like 3 N 4 The preparation method of the composite film is green, environment-friendly and simple.
Description
Technical Field
The invention particularly relates to a method based on AgNPs/MOFs/g-C 3 N 4 The preparation method and the application of the composite film.
Background
Surface-enhanced Raman scattering (SERS) spectroscopy has become a spectroscopic tool for identifying and detecting biological and chemical species, has the advantages of fast detection speed, high sensitivity, in-situ analysis, small water interference and the like, and is widely used in the field of life analysis. Therefore, the preparation of the nano material with high SERS performance is an important aspect for realizing the wide application of the SERS technology. Wherein, noble metal nano-particles Ag and MOFs are compounded to prepare a nano composite structure, and the structure has the dual advantages of strong adsorption capacity of the MOFs and enhanced electromagnetic field of the gold nano-particles, and g-C 3 N 4 The composition of the compounds is beneficial to the formation of the membrane, thereby being hopeful to realize the rapid enrichment of the lung cancer marker exhaled aldehyde and the high-sensitivity SERS detection.
Disclosure of Invention
The invention aims to provide a method based on AgNPs/MOFs/g-C 3 N 4 The composite film and the preparation method and the application thereof improve the SERS sensitivity and the detection efficiency.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
based on AgNPs/MOFs/g-C 3 N 4 The preparation method of the composite film comprises the following steps:
s1: mixing and stirring a methanol solution of cobalt nitrate hexahydrate and a methanol solution of 2-methylimidazole, transferring the solution to a reaction kettle, standing for 24 hours at room temperature, centrifuging the solution, washing and drying to obtain an MOFs material a;
s2: dispersing a in deionized water, adding a tannin water solution under vigorous stirring, stirring for a period of time, obtaining a dark color product b by centrifugation, and washing with ultrapure water for a plurality of times to remove excessive tannin;
re-dispersing the b in deionized water, adding a silver nitrate solution under stirring at room temperature, continuing stirring for 1 hour, and centrifuging, washing and drying to obtain c;
s3: taking a certain mass of g-C 3 N 4 Placing into a centrifuge tube, adding concentrated hydrochloric acid, and performing ultrasonic treatment until g-C 3 N 4 From pale yellow to white to give protonated g-C 3 N 4 ；
S4: c and protonated g-C 3 N 4 Adding the mixture into a methanol solution, stirring the mixture at room temperature and standing the mixture for a period of time to form a solution d;
vacuum filtering d with polyethersulfone membrane (aperture of 0.22 μm, diameter of 47mm), washing with methanol, and drying to obtain final product based on AgNPs/MOFs/g-C 3 N 4 The composite film of (1).
Preferably, in step S1, the volume ratio of the methanol solution of cobalt nitrate hexahydrate to the methanol solution of 2-methylimidazole is 1: 20.
as a preferable technical solution, in the step S2, the volume ratio of the silver nitrate solution to the tannic acid solution is 19: 1.
preferably, in step S3, g-C is added 3 N 4 Protonation can be verified by testing its zeta potential to see if it has a positive charge to prove that it has been successfully protonated.
Preferably, in step S4, C and g-C 3 N 4 The reaction time was 24 hours.
The invention also provides a preparation method based on AgNPs/MOFs/g-C 3 N 4 And (3) compounding the film material.
The invention provides the above AgNPs/MOFs/g-C-based 3 N 4 The composite film is applied to SERS detection or preparation of an SERS detection device.
Compared with the prior art, the invention has the beneficial effects that:
the method takes MOFs material as a precursor, constructs AgNPs/MOFs nano material by in-situ reduction of silver nitrate, and then performs electrostatic interaction and g-C 3 N 4 And (4) adsorbing, and finally preparing the AgNPs/MOFs-based composite thin film material by means of vacuum filtration. The noble metal nano-particle Ag and the MOFs are compounded to prepare the nano composite structure, and the structure has the double advantages of strong adsorption capacity of the MOFs and enhanced electromagnetic field of the gold nano-particle. Second, g-C 3 N 4 Is advantageous for film formation once AgNPs/MOFs/g-C 3 N 4 The distance of the benzaldehyde molecule passing through the substrate is expanded due to the film formation, so that the contact time between the benzaldehyde molecule and the substrate is prolonged, and the reaction efficiency and the SERS detection sensitivity are improved.
Description of the drawings:
FIG. 1(a) Scanning Electron Micrograph (SEM) of MOF material a;
FIG. 2(a) Scanning Electron Micrograph (SEM) of the product of c;
FIG. 3(a) g-C 3 N 4 Transmission Electron Micrographs (TEMs); (b) d Transmission Electron Micrograph (TEM) of the product;
FIG. 4(a) an optical photograph of a composite film based on AgNPs/MOFs; (b) EDX element analysis of the surface of the composite film;
fig. 5 study of SERS performance of the composite film (a) limit of detection: detecting SERS spectra of rhodamine 6G with different concentrations; (b) uniformity: randomly collecting SERS spectra of 15 positions R6G; (c) based on the sensing of the composite film material to the lung cancer marker benzaldehyde.
The specific implementation mode is as follows:
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples
1. Based on AgNPs/MOFs/g-C 3 N 4 The preparation method of the composite film comprises the following steps:
10mL of Co (NO) 3 ) 2 ·6H 2 The O (4mM) methanol solution and 200mL of 2-methylimidazole (160mM) methanol solution were mixed by sonication. After stirring for 1h, the solution was transferred to a reaction kettle and allowed to stand at room temperature for 24h to obtain a purple product. The resulting product was collected by centrifugation, washed three times with ethanol and dried in an oven for use. Fig. 1 is a scanning electron micrograph of the product obtained under the above experimental conditions, which shows that the size and dimension of the obtained product are relatively uniform hexagonal structures.
Dispersing MOFs in 9.5mL H 2 O, tannic acid solution (0.5mL) was added rapidly, stirred for 20s, centrifuged to obtain dark colored product (tannic acid/MOFs), washed three times with ultrapure water, and excess tannic acid was removed. Redispersing tannic acid/MOFs in 9.5mL of water and adding AgNO 3 After stirring the solution (0.3M) at room temperature for 1h, the product was centrifuged, washed 3 times with water and dried in a dry box for future use. From fig. 2a, it can be seen that silver nanoparticles are densely distributed on the outer surface of the MOFs material.
Adding 1mg g-C into a centrifuge tube 3 N 4 Adding 3mL of concentrated hydrochloric acid, and carrying out ultrasonic treatment to g-C 3 N 4 Changing yellow to white, and showing g-C by transmission electron microscope 3 N 4 Presentation comparisonThin sheet state (fig. 3 a). 0.02g AgNPs/MOFs and 1mg g-C 3 N 4 Added to 5mL of methanol solution, stirred at room temperature for 1h, left to stand for 24h, then filtered through a polyethersulfone membrane (pore size 0.22 μm, diameter 47mm), washed several times with methanol and the product dried in a vacuum oven (40 ℃, 30 min) until ready for use (fig. 3 b). Fig. 4(a) is an optical photograph of the film, and EDX spectrum analysis shows that the distribution of each element is uniform (fig. 4 b). In FIG. 5(a), it can be seen that the composite film has higher sensitivity to the probe molecule rhodamine 6G and better uniformity (FIG. 5 b). FIG. 5c shows the detection of benzaldehyde, a lung cancer marker, with the detection limit reaching ppb level.
Claims (8)
1. Based on AgNPs/MOFs/g-C 3 N 4 The preparation method of the composite film is characterized by comprising the following steps:
s1: mixing and stirring a methanol solution of cobalt nitrate hexahydrate and a methanol solution of 2-methylimidazole, transferring the solution to a reaction kettle, standing for a period of time at room temperature, centrifuging the solution, washing and drying to obtain an MOFs material a;
s2: dispersing MOFs material a in deionized water, adding a tannin water solution under vigorous stirring, stirring for a period of time, obtaining a dark color product b through centrifugation, and washing with ultrapure water for several times to remove excessive tannin;
re-dispersing the product b in deionized water, adding a silver nitrate solution under stirring at room temperature, continuously stirring for a period of time, and centrifuging, washing and drying to obtain a product c;
s3: taking a certain mass of g-C 3 N 4 Placing into a centrifuge tube, adding concentrated hydrochloric acid, and performing ultrasonic treatment until g-C 3 N 4 From pale yellow to white to give protonated g-C 3 N 4 ；
S4: the product C and g-C after protonation 3 N 4 Adding the mixture into a methanol solution, stirring the mixture at room temperature and standing the mixture for a period of time to form a solution d;
and (4) carrying out vacuum filtration on the solution d through a polyether sulfone membrane, washing with methanol, and drying to obtain the Ag/MOF composite film.
2. The method according to claim 1, wherein the polyethersulfone membrane is 0.22 μm pore size, 47mm diameter.
3. The method according to claim 1, wherein in step S1, the volume ratio of the methanol solution of cobalt nitrate hexahydrate to the methanol solution of 2-methylimidazole is 1: 20.
4. the method as set forth in claim 1, wherein in the step S2, the volume ratio of the silver nitrate solution to the tannic acid solution is 19: 1.
5. the method according to claim 1, wherein the step S3 further comprises testing for g-C 3 N 4 Zeta potential of 3 N 4 Whether or not it has a positive charge.
6. The method of claim 1, wherein in step S4, products C and g-C 3 N 4 in a manner that The reaction time was 24 hours.
7. AgNPs/MOFs/g-C based process prepared by the process of any of the preceding claims 3 N 4 And (3) compounding the film.
8. The composition of claim 7 based on AgNPs/MOFs/g-C 3 N 4 The composite film is applied to SERS detection or preparation of an SERS detection device.
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