CN114736415A - Silver nanoparticle @ cellulose membrane and in-situ synthesis method and application thereof - Google Patents
Silver nanoparticle @ cellulose membrane and in-situ synthesis method and application thereof Download PDFInfo
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- 239000004332 silver Substances 0.000 title claims abstract description 49
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- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical group [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 11
- 229940038773 trisodium citrate Drugs 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
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Abstract
The invention relates to a silver nanoparticle @ cellulose membrane and an in-situ synthesis method and application thereof, and the method comprises the following steps: (1) soaking the cellulose membrane in 1-1000 mmol/L silver nitrate solution for 0.5-20 hours to obtain a cellulose membrane attached with silver ions; (2) and immersing the cellulose membrane attached with silver ions into a mixed solution containing a reducing agent and a polymerization inhibitor, stirring and reacting for 1-100 min, and cleaning to obtain the silver nanoparticle @ cellulose membrane. The invention uses cellulose as raw material, has wide source and low cost; AgNPs are synthesized by a simple in-situ synthesis method, and are fixed in micro-nano holes of a cellulose membrane, so that no impurity is introduced, silver nanoparticles are uniformly distributed, no agglomeration phenomenon is caused, and color development is uniformHomogenizing; the visual detection limit is as low as 5nM, and Hg can be efficiently completed2+The early warning and semi-quantitative detection.
Description
Technical Field
The invention relates to the field of mercury ion detection materials, and particularly relates to a silver nanoparticle @ cellulose membrane and an in-situ synthesis method and application thereof.
Background
Silver nano (AgNPs) is a metallic silver simple substance having a particle diameter of a nanometer order. The particle size of the nano silver is mostly about 25 nanometers, and the nano silver has strong inhibiting and killing effects on dozens of pathogenic microorganisms such as escherichia coli, gonococcus, chlamydia trachomatis and the like. The silver nanoparticles have an extremely important position in the field of microelectronics due to the good conductivity of the silver nanoparticles. The surface effect, quantum size effect, etc. of the nano silver particles make the nano silver particles have some special uses, such as surface enhanced Raman application, medical application, etc. However, various soluble impurities are easily generated in the production process, and are difficult to effectively remove.
Hg2+Is a heavy metal pollutant, not only pollutes the environment, but also can harm human health. In the industries of fossil fuel, oil refineries, paint, paper pulp, paper, batteries and the like, Hg is inevitably mixed2+Are released into the environment, thus polluting the environment. Hg is a mercury vapor2+Can threaten human health and even cause a series of diseases, such as developmental delay, damage of the nervous system, the kidney and the endocrine system, and the like. Thus, a simple, sensitive Hg source was developed2+The detection method has important application value to environmental detection。
To date, Hg has been detected2+The method of (3) includes a colorimetric method, a chemiluminescent method, an electrochemical method, a fluorescence probe method and the like. Wherein, the colorimetric method is used for detecting the heavy metal Hg2+The analysis method has the advantages of simple and convenient operation, low cost, no need of using complex and expensive instruments and the like, and is concerned by more and more scientific researchers. However, the preparation method is usually prepared by using filter paper and the like as a substrate, coating a silver-containing detection reagent on the substrate and drying the silver-containing detection reagent, and the preparation method is easy to introduce impurities, easily causes the phenomena of non-uniformity, agglomeration and the like of the generated silver particles, and further has the problems of non-uniform color development, unstable detection and the like.
Disclosure of Invention
The invention aims to overcome the technical defects, provides a silver nanoparticle @ cellulose membrane and an in-situ synthesis method and application thereof, and solves the technical problems that impurities are easily introduced and agglomeration occurs in the preparation of mercury ion detection test paper in the prior art.
In order to achieve the technical purpose, the technical scheme of the synthesis method is as follows:
the method comprises the following steps:
(1) soaking the cellulose membrane in 1-1000 mmol/L silver nitrate solution for 0.5-20 hours to obtain a cellulose membrane attached with silver ions;
(2) and immersing the cellulose membrane attached with silver ions into a mixed solution containing a reducing agent and a polymerization inhibitor, stirring and reacting for 1-100 min, and cleaning to obtain the silver nanoparticle @ cellulose membrane.
Further, the cellulose film preparation step in step (1) comprises: placing cotton linters in a NaOH/urea system, stirring at-12.5 ℃ to dissolve the cotton linters, preparing a crude cellulose membrane by a tape casting method, and washing with distilled water to be neutral to obtain a cellulose membrane; wherein the mass ratio of the cotton linters to the NaOH to the urea is 8:14:24, and the mass fraction of the NaOH in a NaOH/urea system is 7%; the thickness of the cellulose membrane is 0.5-2 mm.
Further, soaking in the step (1) at room temperature; the mass-to-volume ratio of the cellulose membrane to the silver nitrate solution is 1 g: 50 mL.
Further, the cellulose membrane attached with silver ions in the step (2) is washed by deionized water and then is immersed in the mixed solution.
Further, in the mixed solution in the step (2), the concentration of the reducing agent is 0.01-50 mmol/L, and the concentration of the polymerization inhibitor is 0.01-60 mmol/L; the molar volume ratio of the silver nitrate in the step (1) to the mixed solution in the step (2) is (0.05-50) mmol: 100 mL.
Further, in the step (2), the reducing agent is ascorbic acid, and the polymerization inhibitor is trisodium citrate.
Further, in the step (2), the temperature of the stirring reaction is 0-70 ℃.
Further, in the step (2), the stirring speed of the stirring reaction is 300-1000 rpm; and cleaning, namely placing a product of the stirring reaction in deionized water, and performing ultrasonic cleaning for 1-30 min at the ultrasonic power of 100W.
Silver nanoparticle @ cellulose film synthesized as above by the in situ synthesis method.
Such as the application of the silver nanoparticle @ cellulose membrane as mercury ion detection colorimetric test paper.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts cellulose as raw material, which is the most abundant natural biological polymer in the world, has wide sources and low cost; AgNPs are synthesized by a simple in-situ synthesis method, and are fixed in micro-nano holes of a cellulose membrane, so that no impurity is introduced, silver nanoparticles are uniformly distributed, no agglomeration phenomenon is caused, and color development is uniform; the silver nanoparticle/cellulose membrane (Ag @ CMs) synthesized by the method can be cleaned to remove various soluble impurities generated in the AgNPs synthesis process, and has high stability in 180 days; in addition, due to AgNPs and mercury ions (Hg)2+) The Ag @ CMs synthesized by the invention has excellent Hg2+Capacity for trapping Hg2+Colorimetric detection with visual detection limit as low as 5nM, can efficiently complete Hg2+The early warning and semi-quantitative detection.
Drawings
FIG. 1 is an SEM image of structural characterization of AgNPs generated in situ from a cellulose film of the present invention.
FIG. 2 is an EDS diagram of structural characterization of AgNPs generated in situ from a cellulose film of the present invention.
FIG. 3 is a Raman plot of in situ generation of AgNPs from a pure cellulose film and a cellulose film of the present invention.
FIG. 4 shows Hg detection by Ag @ CMs according to the present invention2+Experimental graphs of (2).
FIG. 5 is an experimental graph of the stability of Ag @ CMs of the present invention.
FIG. 6 is an appearance view of the sample obtained in comparative example 1.
FIG. 7 is an appearance diagram of a sample prepared in comparative example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a method for in-situ synthesis of silver nanoparticles on a porous cellulose membrane, which is simple, convenient and fast, can effectively remove various soluble impurities generated in the synthesis process of nanoparticles and has excellent stability. Which comprises the following steps:
s1, placing 8g of the dried cotton linters into a NaOH/urea system (NaOH:14 g; urea: 24 g: 162g of deionized water), rapidly stirring at-12.5 ℃ to dissolve the cotton linters, and preparing a cellulose film with the thickness of about 0.5-2 mm by a tape casting method. And finally, washing the cellulose membrane by using distilled water until the pH value of the washing solution is neutral, and preparing the pure cellulose membrane.
S2, soaking the cellulose membrane (1g) in the step S1 in 50mL of silver nitrate solution with the concentration of 1-1000 mM for 0.5-20 hours at room temperature, and repeatedly washing the cellulose membrane with deionized water for three times (removing the redundant silver nitrate solution on the surface) to obtain the cellulose membrane attached with silver ions. Wherein the mass molar ratio of the cellulose membrane to the silver nitrate is 1 g: (0.05 to 50) mmol, preferably 1 g: (0.1-5) mmol; that is, the concentration of the silver nitrate solution is preferably 2 to 100 mM.
S3, immersing the cellulose membrane attached with silver ions in the step S2 into 100mL of mixed solution containing 0.01-50 mM reducing agent and 0.01-60 mM polymerization inhibitor at 0-70 ℃, continuously stirring for 1-100 minutes at a stirring speed of 300-1000 rpm to obtain a silver nanoparticle/cellulose membrane (Ag @ CMs) crude product, placing the obtained Ag @ CMs crude product into deionized water, and removing various soluble impurities generated in the nanoparticle synthesis process by ultrasonic cleaning for 1-30 min at an ultrasonic power of 100W. The molar ratio of the silver nitrate to the ascorbic acid to the trisodium citrate is preferably (0.05-50): (0.001-5): (0.001-6).
Among them, the reducing agent is preferably ascorbic acid; the polymerization inhibitor is preferably trisodium citrate, the mixed solution is prepared by mixing an ascorbic acid solution and a trisodium citrate solution with water, and the volume ratio of the ascorbic acid solution to the trisodium citrate solution is 5 mL: 5mL of: 90 mL; in the resulting mixed solution, the final concentration of ascorbic acid is preferably 0.012M, and the final concentration of trisodium citrate is preferably 0.06M.
Ag @ CM prepared by the invention is used for detecting Hg2+Application of colorimetric test paper. The obtained test paper has the advantages of easily obtained raw materials, convenient modification, low cost, simple and convenient use, naked eye detection, high sensitivity and the like.
The invention is described in further detail below with reference to the attached drawings and specific examples.
Example 1
A method for in-situ synthesis of silver nanoparticles on a porous cellulose membrane specifically comprises the following steps:
s1, placing 8g of the dried cotton linters into a NaOH/urea system (NaOH:14 g; urea: 24 g: 162g of deionized water), rapidly stirring at-12.5 ℃ to dissolve the cotton linters, and preparing a cellulose film with the thickness of about 1mm by a tape casting method. And finally, washing the cellulose membrane by using distilled water until the pH value of the washing solution is neutral, and preparing the pure cellulose membrane.
S2, soaking the cellulose membrane (1g) in the step S1 in 50mL of silver nitrate solution with the concentration of 10mM for 3 hours at room temperature, and repeatedly washing the cellulose membrane with deionized water for three times to obtain the cellulose membrane attached with silver ions.
S3, immersing the cellulose membrane attached with silver ions in the step S2 into 100mL of mixed solution containing 12mM ascorbic acid and 60mM trisodium citrate at 25 ℃, continuously stirring for 30 minutes to obtain a silver nano/cellulose membrane (Ag @ CMs) crude product, and removing various soluble impurities generated in the nanoparticle synthesis process from the obtained Ag @ CMs crude product by ultrasonic cleaning for 10min to obtain the Ag @ CMs.
The resulting Ag @ CMs structures were characterized by SEM/EDS.
As shown in figure 1, silver nanoparticles (AgNPs) in the Ag @ CMs prepared by the invention are uniformly distributed on the surface and in pores of a cellulose membrane, and the average particle size of the silver nanoparticles is 30-60 nm.
As shown in figure 2, the Ag @ CMs prepared by the invention has the silver mass fraction of 22.4% and the atomic percentage of 3.6%.
The Raman spectra of the cellulose membrane obtained in example 1 (product of step S1) and of Ag @ CMs (product of step S3) were determined. The measurement results are shown in FIG. 3.
As can be seen from FIG. 3, with the generation of AgNPs on the cellulose membrane, the Raman spectrum of Ag @ CMs is obviously enhanced compared with the Raman spectrum of a pure cellulose membrane, and the successful synthesis of AgNPs on the cellulose membrane is strongly proved by the invention.
Application example 1
Determination of Ag @ CMs vs Hg as obtained in example 12+The response effect of (2).
The Ag @ CMs prepared in example 1 was immersed in 200. mu.M Hg2+In solution, after 15 minutes incubation, the Ag @ CMs was observed for color change as shown in figure 4.
As can be seen in FIG. 4, the change from grayish green to white for Ag @ CMs indicates that Ag @ CMs can detect Hg with the naked eye2+。
Hg is mixed2+The concentration of the solution was adjusted to 5nM and the Ag @ CMs changed from grayish green to white after 15min under the same test conditions.
The stability of the Ag @ CMs obtained in example 1 was determined.
The Ag @ CMs prepared in example 1 was immersed in distilled water and stored in a sealed state, and color change thereof was observed at different time periods, respectively, and the experimental results are shown in fig. 5.
As can be seen from FIG. 5, the color of the Ag @ CMs is basically unchanged with the increase of the storage time, and the Ag @ CMs obtained by the invention is proved to have excellent stability.
Example 2
The concentrations of the silver nitrate solutions in step S2 were changed to 2mM, 50mM, 100mM and 1000mM in this order, and the other conditions were the same as in example 1, and the resulting Ag @ CMs were numbered as samples A to E, respectively, in terms of the change in concentration.
From the apparent color of each sample, the Ag @ CMs sample A prepared at 2mM is slightly lighter than the sample B prepared in example 1, and the samples C and D prepared at 50mM and 100mM are gradually darker than the sample B prepared in example 1, and the colors of the sample E (1000mM) and the sample D (100mM) are not obviously different, which shows that the content of the silver nanoparticles loaded on the obtained samples is gradually increased along with the increase of the silver nitrate concentration, and the EDS characterization also confirms the point, and the specific test results are shown in the following table 1.
TABLE 1 analysis of Ag @ CMs samples made with different silver nitrate concentrations
| Condition | Silver nitrate concentration (mM) | Ag(wt％) |
| |
2 | 18.7 |
| |
10 | 22.4 |
| Sample C | 50 | 25.4 |
| Sample D | 100 | 29.9 |
| |
1000 | 32.1 |
As can be seen from Table 1 and the apparent color of each sample, the loading of the silver nanoparticles on the cellulose membrane gradually increases with the increase of the silver nitrate concentration, the increase rate decreases when the concentration exceeds 100mM, and the loading of the silver nanoparticles does not increase in direct proportion with the increase of the silver nitrate concentration due to the action of the polymerization inhibitor, and the silver nitrate concentration is preferably 2-100 mM in combination with the factors in the aspect of cost.
The Ag @ CMs sample prepared in the embodiment is adopted to detect the mercury ion-containing solution, the concentration of the mercury ion-containing solution is 5nM and 500nM respectively, and the method is as in application example 1; tests show that under two mercury ion concentrations, the samples A to C can be changed from gray green to white, the samples D and E can be changed from gray green to white when testing 500nM mercury ion solution, and the color is lightened but not completely whitened when testing 5nM mercury ion solution; thus, the naked eye colorimetric detection limit of the present invention is as low as 5 nM.
Example 3
S1, a pure cellulose film having a thickness of about 1.5mm was obtained in the same manner as in example 1.
S2, soaking the cellulose membrane (1g) in the step S1 in 50mL of silver nitrate solution with the concentration of 50mM for 0.5 hour at room temperature, and repeatedly washing the cellulose membrane with deionized water for three times to obtain the cellulose membrane attached with silver ions.
S3, immersing the cellulose membrane with silver ions attached in the step S2 into 100mL of mixed solution containing 20mM ascorbic acid and 50mM trisodium citrate at the temperature of 20 ℃, continuously stirring for 10 minutes to obtain a silver nano/cellulose membrane (Ag @ CMs) crude product, and removing various soluble impurities generated in the nanoparticle synthesis process from the obtained Ag @ CMs crude product by ultrasonic cleaning for 20min to obtain Ag @ CMs, wherein the Ag @ CMs can be used for mercury ion detection and has a detection limit of 5 nM.
Example 4
S1, a pure cellulose film having a thickness of about 0.8mm was obtained in the same manner as in example 1.
S2, soaking the cellulose membrane (1g) in the step S1 in 50mL of silver nitrate solution with the concentration of 20mM for 10 hours at room temperature, and repeatedly washing the cellulose membrane with deionized water for three times to obtain the cellulose membrane attached with silver ions.
S3, immersing the cellulose membrane with silver ions attached in the step S2 into 100mL of mixed solution containing 30mM ascorbic acid and 55mM trisodium citrate at 15 ℃, continuously stirring for 20 minutes to obtain a silver nano/cellulose membrane (Ag @ CMs) crude product, and removing various soluble impurities generated in the nanoparticle synthesis process by using the obtained Ag @ CMs crude product through ultrasonic cleaning for 5min to obtain Ag @ CMs, wherein the Ag @ CMs can be used for mercury ion detection and has a detection limit of 5 nM.
Comparative example 1
And (4) directly soaking the pure cellulose membrane prepared in the step (S1) in a 0.1M nano silver solution, continuously stirring for 3 hours, and then carrying out ultrasonic cleaning for 10 minutes to obtain a first sample, wherein the appearance of the first sample is as shown in figure 6, the color of the first sample is uneven, the first sample is mainly grey white and brownish red, and the first sample cannot be used for mercury ion detection.
Comparative example 2
The pure cellulose membrane was replaced with filter paper under the same conditions as in example 1, and it was found that the filter paper was dissolved after soaking and stirring.
Comparative example 3
And replacing the pure cellulose membrane with filter paper, adopting the same soaking step as in example 1, and not stirring (standing and soaking) to obtain a second sample, wherein the appearance of the second sample is shown in figure 7, and the second sample is uneven in color and cannot be used as test paper for mercury ion detection.
Comparative example 4
The polymerization inhibitor trisodium citrate is not added, and the other conditions are the same as in example 1. Because of the existence of no polymerization inhibitor, silver nanoparticles are excessively generated, agglomeration is generated, and the appearance color of the prepared finished product is uneven.
Comparative example 5
The procedure of example 1 was otherwise the same as in example 1, except that ascorbic acid was not added as a reducing agent. Because no reducing agent exists, silver nanoparticles cannot be generated, and the prepared finished product has no obvious change.
Comparative example 6
The same conditions as in example 1 were used except that 100mM ascorbic acid was used. Due to the fact that the concentration of the reducing agent is too high, part of silver nano particles are excessively generated, agglomeration is generated, and the appearance color of the prepared finished product is uneven.
The invention provides a method for simply, conveniently and rapidly synthesizing silver nanoparticles (AgNPs) in situ on a porous cellulose membrane and application thereof, wherein the preparation method comprises the following steps: s1, dissolving cotton linters to prepare a pure cellulose membrane; s2, soaking the obtained pure cellulose membrane in a silver nitrate solution to obtain a cellulose membrane attached with silver ions; s3, immersing the cellulose membrane attached with the silver ions into a mixed solution of ascorbic acid and trinsodium citrate, and stirring and heating to obtain the AgNPs/cellulose membrane (Ag @ CMs). The obtained Ag @ CMs is cleaned by ultrasonic waves to remove various soluble impurities generated in the process of synthesizing the nano particles, and has high stability within at least 180 days. The Ag @ CMs synthesized by the method has excellent mercury ions (Hg)2+) Capacity for trapping Hg2+Colorimetric detection of (1). The invention relates to a cellulose membrane-based method for detecting Hg2+The lowest detection line of the colorimetric test paper is 5nM, and the rapid and effective naked eye detection of Hg in the solution can be realized2+。
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. An in-situ synthesis method of a silver nanoparticle @ cellulose membrane is characterized by comprising the following steps:
(1) soaking the cellulose membrane in 1-1000 mmol/L silver nitrate solution for 0.5-20 hours to obtain a cellulose membrane attached with silver ions;
(2) and immersing the cellulose membrane attached with silver ions into a mixed solution containing a reducing agent and a polymerization inhibitor, stirring and reacting for 1-100 min, and cleaning to obtain the silver nanoparticle @ cellulose membrane.
2. The process for the in situ synthesis of silver nanoparticle @ cellulose film as claimed in claim 1, wherein the preparation step of the cellulose film in step (1) comprises: placing cotton linters in a NaOH/urea system, stirring at-12.5 ℃ to dissolve the cotton linters, preparing a crude cellulose membrane by a tape casting method, and washing with distilled water to be neutral to obtain a cellulose membrane; wherein the mass ratio of the cotton linters to the NaOH to the urea is 8:14:24, and the mass fraction of the NaOH in a NaOH/urea system is 7%; the thickness of the cellulose membrane is 0.5-2 mm.
3. The process for the in situ synthesis of silver nanoparticle @ cellulose film as claimed in claim 1, wherein in step (1) soaking is performed at room temperature; the mass-to-volume ratio of the cellulose membrane to the silver nitrate solution is 1 g: 50 mL.
4. The method for the in situ synthesis of silver nanoparticle @ cellulose film as defined in claim 1, wherein the cellulose film with silver ions attached thereto in step (2) is rinsed with deionized water and then immersed in the mixed solution.
5. The in-situ synthesis method of silver nanoparticle @ cellulose membrane as claimed in claim 1, wherein in the mixed solution of step (2), the concentration of the reducing agent is 0.01-50 mmol/L, and the concentration of the polymerization inhibitor is 0.01-60 mmol/L; the molar volume ratio of the silver nitrate in the step (1) to the mixed solution in the step (2) is (0.05-50) mmol: 100 mL.
6. The process for the in situ synthesis of silver nanoparticle @ cellulose film as claimed in claim 1, wherein in step (2), the reducing agent is ascorbic acid and the polymerization inhibitor is trisodium citrate.
7. The in-situ synthesis method of silver nanoparticle @ cellulose membrane as claimed in claim 1, wherein in the step (2), the temperature of the stirring reaction is 0-70 ℃.
8. The in-situ synthesis method of silver nanoparticle @ cellulose membrane as claimed in claim 1, wherein in the step (2), the stirring rate of the stirring reaction is 300-1000 rpm; and the cleaning is to place the product of the stirring reaction in deionized water, and ultrasonically clean for 1-30 min at the ultrasonic power of 100W.
9. Silver nanoparticle @ cellulose film synthesized according to the in situ synthesis method of any one of claims 1 to 8.
10. Use of the silver nanoparticle @ cellulose film of claim 9 as a mercury ion detection colorimetric test paper.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105778138A (en) * | 2014-12-13 | 2016-07-20 | 广东轻工职业技术学院 | Nano-silver composite antibacterial cellulose membrane, and preparation method and application thereof |
| CN109900692A (en) * | 2019-04-04 | 2019-06-18 | 青岛大学 | Green high-efficient detects the preparation method of the gel of mercury ion and the application of the gel |
| CN109900691A (en) * | 2019-04-04 | 2019-06-18 | 青岛大学 | The test paper of rapid mercury detection ion, preparation method and applications |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778138A (en) * | 2014-12-13 | 2016-07-20 | 广东轻工职业技术学院 | Nano-silver composite antibacterial cellulose membrane, and preparation method and application thereof |
| CN109900692A (en) * | 2019-04-04 | 2019-06-18 | 青岛大学 | Green high-efficient detects the preparation method of the gel of mercury ion and the application of the gel |
| CN109900691A (en) * | 2019-04-04 | 2019-06-18 | 青岛大学 | The test paper of rapid mercury detection ion, preparation method and applications |
Non-Patent Citations (3)
| Title |
|---|
| CHINNADURAI SHANMUGAM ET.AL.: "Antimicrobial and Free Radical Scavenging Activities of CelluloseSilver-Nanocomposites with In Situ Generated Silver Nanoparticles Using Cissampelos Pareira Leaf Extract", 《JOURNAL OF CLUSTER SCIENCE》, vol. 33, pages 1728 - 1729 * |
| INMACULADA DE LA CALLE ET.AL.: "Solid-phase extraction of Hg(II) using cellulose filters modified with silver nanoparticles followed by pyrolysis and detection by a direct mercury analyzer", vol. 161, pages 1 - 9 * |
| 詹益兴主编: "《现代化工小商品制法大全 第5集》", vol. 1, 上海科学技术文献出版社, pages: 325 * |
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