CN115779862A - Silver nanoparticle composite material and preparation method and application thereof - Google Patents
Silver nanoparticle composite material and preparation method and application thereof Download PDFInfo
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- CN115779862A CN115779862A CN202211711567.0A CN202211711567A CN115779862A CN 115779862 A CN115779862 A CN 115779862A CN 202211711567 A CN202211711567 A CN 202211711567A CN 115779862 A CN115779862 A CN 115779862A
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- aqueous solution
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 158
- 239000004332 silver Substances 0.000 title claims abstract description 158
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 156
- 239000002131 composite material Substances 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 135
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 109
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 70
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 56
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 48
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 25
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 15
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 15
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 10
- 239000012498 ultrapure water Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 20
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- 230000000274 adsorptive effect Effects 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 47
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 18
- 238000004020 luminiscence type Methods 0.000 description 18
- 238000001514 detection method Methods 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 16
- 238000001179 sorption measurement Methods 0.000 description 13
- 238000010791 quenching Methods 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 230000000171 quenching effect Effects 0.000 description 9
- 229910001960 metal nitrate Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- 239000011651 chromium Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
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- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
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- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- JVTMLBYYQYMFLV-UHFFFAOYSA-N 2-methyl-1h-imidazole;zinc Chemical compound [Zn].CC1=NC=CN1 JVTMLBYYQYMFLV-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- VSXQNMCMCVKLOI-UHFFFAOYSA-N CC1=NC=CN1.[Zn+2] Chemical compound CC1=NC=CN1.[Zn+2] VSXQNMCMCVKLOI-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a silver nanoparticle composite material and a preparation method and application thereof, wherein the preparation method of the silver nanoparticle composite material comprises the following steps: adding a diphenylamine aqueous solution and a silver nitrate aqueous solution into ultrapure water, and adding a sodium borohydride aqueous solution under stirring to react to form a silver nanoparticle aqueous solution; and mixing the silver nanoparticle aqueous solution with a zinc nitrate aqueous solution, and then adding a 2-methylimidazole aqueous solution to react to obtain the silver nanoparticle composite metal organic framework material. The technical scheme of the invention can detect the hexavalent chromium in the environment and efficiently remove the hexavalent chromium in the environment at the same time.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a silver nanoparticle composite material and a preparation method and application thereof.
Background
Hexavalent chromium is a swallowable poison/inhalant toxicant, and direct contact with human skin may cause allergies, more likely cause genetic defects, and direct inhalation may be carcinogenic and also pose a persistent risk to the environment. Therefore, the detection and removal of hexavalent chromium in the environment are of great significance.
The existing methods for detecting hexavalent chromium include spectrophotometry, fluorescence quenching, oscillography, atomic spectrometry and ion chromatography. The spectrophotometry is a detection method commonly used for element analysis, is a classical method, can be used for measuring the total amount of elements and can also be used for measuring the various morphological contents of the elements, but the method has poor reproducibility and not strong selectivity; the fluorescence quenching method has the capability of real-time, online, remote and automatic continuous monitoring, can be used for analyzing and monitoring dangerous zones and micro spaces which are difficult to be accessed by human beings, and provides an effective, convenient and quick monitoring means for realizing process analysis of environmental monitoring; the oscillography polarography is a polarography with electrolyte added rapidly, and has the advantages of low detection limit, good reproducibility, less reagent consumption, easy operation and high analysis speed; the atomic spectrometry has the characteristics of low detection limit, high analysis speed and the like, but the method can only measure the total amount of chromium and cannot directly measure the percentage mass of hexavalent chromium; the ion chromatography uses resin with small granularity and low exchange capacity, a separation column with small column diameter, a sample injection valve for sample injection, and a pump for conveying eluent, can continuously detect, and has the characteristics of rapidness, continuity, high efficiency, flexibility and the like. Thus, the above methods all have different advantages and disadvantages; however, the above methods are only applicable to detection or only to removal of hexavalent chromium.
Therefore, how to detect hexavalent chromium in the environment and remove hexavalent chromium in the environment is a problem that needs to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a silver nanoparticle composite material, a preparation method and application thereof, which can detect hexavalent chromium in an environment and efficiently remove the hexavalent chromium in the environment.
In order to solve the above technical problems, the present invention provides a method for preparing a silver nanoparticle composite material, comprising:
adding a diphenylamine aqueous solution and a silver nitrate aqueous solution into ultrapure water, and adding a sodium borohydride aqueous solution under stirring to react to form a silver nanoparticle aqueous solution;
and mixing the silver nanoparticle aqueous solution with a zinc nitrate aqueous solution, and then adding a 2-methylimidazole aqueous solution to react to obtain the silver nanoparticle composite metal organic framework material.
Preferably, the concentration of the diphenylamine aqueous solution is 0.5-1.0 mol/L.
Preferably, the concentration of the silver nitrate aqueous solution is 0.1-0.5 mol/L.
Preferably, the molar ratio of diphenylamine in the aqueous diphenylamine solution to silver nitrate in the aqueous silver nitrate solution is 3.5.
Preferably, after the sodium borohydride solution is added, stirring is continued for 30-60 min, and standing reaction is carried out for 5-7 h.
Preferably, the molar ratio of 2-methylimidazole in the aqueous 2-methylimidazole solution to zinc nitrate in the aqueous zinc nitrate solution is 2.5.
Preferably, the molar ratio of the zinc nitrate in the zinc nitrate water solution to the silver nitrate in the silver nitrate water solution is 15 to 20.
Preferably, after the 2-methylimidazole aqueous solution is added, stirring at room temperature for 20-40 min, and then sequentially performing centrifugation, washing and vacuum drying to obtain the silver nanoparticle composite metal organic framework material.
The invention also provides a silver nanoparticle composite material, and the silver nanoparticle composite metal organic framework material is prepared by adopting the preparation method of the silver nanoparticle composite material.
In addition, the invention also provides an application of the silver nanoparticle composite material, which comprises the following steps: the silver nanoparticle composite metal organic framework material is used for detecting and adsorbing to remove hexavalent chromium.
Preferably, the step of detecting hexavalent chromium comprises:
mixing the aqueous solution of the silver nanoparticle composite metal organic framework material with an aqueous solution containing hexavalent chromium, and adjusting the pH of the mixed aqueous solution to 8.5;
and measuring the fluorescence intensity of the mixed aqueous solution at the emission wavelength of 730nm under the excitation wavelength of 420nm, and calculating to obtain the concentration of hexavalent chromium according to the fluorescence intensity.
Preferably, the step of adsorptive removal of hexavalent chromium comprises:
mixing the aqueous solution of the silver nanoparticle composite metal organic framework material with an aqueous solution containing hexavalent chromium, and standing for 8-12 hours; the pH value of the aqueous solution containing hexavalent chromium is 8.5, and the concentration range of the aqueous solution containing hexavalent chromium is 5-1000 mu mol/L;
and centrifuging the silver nanoparticle composite metal organic framework material adsorbed with hexavalent chromium to remove.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the preparation method of the silver nanoparticle composite material provided by the invention comprises the following steps: adding a diphenylamine aqueous solution and a silver nitrate aqueous solution into ultrapure water, and adding a sodium borohydride aqueous solution under stirring to react to form a silver nanoparticle aqueous solution; the silver nanoparticle aqueous solution and the zinc nitrate aqueous solution are mixed, and then the 2-methylimidazole aqueous solution is added to react to obtain the silver nanoparticle composite metal organic framework material, so that hexavalent chromium in the environment can be detected and can be efficiently removed.
2. According to the silver nanoparticle composite material provided by the invention, the silver nanoparticle composite metal organic framework material is prepared by adopting the preparation method of the silver nanoparticle composite material, so that hexavalent chromium in the environment can be detected and simultaneously can be efficiently removed.
3. The invention provides an application of a silver nanoparticle composite material, which comprises the following steps: the silver nanoparticle composite metal organic framework material is used for detecting and adsorbing hexavalent chromium, so that the hexavalent chromium in the environment can be detected and efficiently removed.
Drawings
Fig. 1 is a method for preparing a silver nanoparticle composite material according to an embodiment of the present invention;
fig. 2a is a schematic structural diagram of silver nanoparticles provided in an embodiment of the present invention;
fig. 2b is a schematic structural diagram of a silver nanoparticle composite material according to an embodiment of the present invention;
FIG. 2c is a schematic structural diagram of a silver nanoparticle composite adsorbing hexavalent chromium according to an embodiment of the present invention;
FIG. 3 is a photoluminescence spectrum of a silver nanoparticle composite at different concentrations of hexavalent chromium ions provided by an embodiment of the present invention;
FIG. 4 is a graph showing the variation of the luminescence quenching ratio of the silver nanoparticle composite material at different concentrations of hexavalent chromium ions according to an embodiment of the present invention;
FIG. 5 is a graph showing the variation of the luminescence quenching ratio of a silver nanoparticle composite material in the presence of different kinds of metal ions according to an embodiment of the present invention;
fig. 6 is an isotherm of adsorption of hexavalent chromium ions at 298K for a silver nanoparticle composite provided by an embodiment of the present invention.
Detailed Description
In order to make the objects, advantages and features of the present invention more clear, the silver nanoparticle composite material and the preparation method and application thereof proposed by the present invention will be further described in detail with reference to the accompanying drawings and specific examples. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention. Further, the structures illustrated in the drawings are often part of actual structures. In particular, the drawings may have different emphasis points and may sometimes be scaled differently.
Referring to fig. 1, a method for preparing a silver nanoparticle composite material according to an embodiment of the present invention includes:
step S1, adding a diphenylamine aqueous solution and a silver nitrate aqueous solution into ultrapure water, and adding a sodium borohydride solution under stirring to react to form a silver nanoparticle aqueous solution;
and S2, mixing the silver nanoparticle aqueous solution with a zinc nitrate aqueous solution, and then adding a 2-methylimidazole aqueous solution to react to obtain the silver nanoparticle composite metal organic framework material.
The method of making the silver nanoparticle composite material provided in this example is described in more detail below.
According to step S1, diphenylamine (DPA) aqueous solution and silver nitrate (AgNO) 3 ) The aqueous solution was added to ultrapure water and sodium borohydride (NaBH) was added with stirring 4 ) An aqueous solution to form an aqueous silver nanoparticle solution by a redox reaction.
As shown in fig. 2a, diphenylamine is bonded to silver ions in silver nanoparticles (AgNPs) in the aqueous silver nanoparticle solution.
The step S1 may include: firstly, preparing diphenylamine aqueous solution and silver nitrate aqueous solution with certain concentrations respectively; then, respectively adding a certain volume of the diphenylamine aqueous solution and the silver nitrate aqueous solution into ultrapure water, and violently stirring to uniformly mix the diphenylamine aqueous solution and the silver nitrate aqueous solution; then, under the condition of continuous violent stirring, adding a certain concentration of sodium borohydride aqueous solution with a certain volume into the uniformly mixed solution for mixing to form a mixed solution, wherein the color of the mixed solution is changed from colorless transparency to brownish black immediately; then, continuously stirring the mixed solution at room temperature to ensure that the mixed solution can be fully and uniformly mixed, preferably stirring for 30-60 min, and gradually changing the color of the mixed solution from brown black to bright light yellow along with continuous stirring; and then, standing the mixed solution for reaction until the mixed solution is fully reacted to form a transparent yellow silver nanoparticle aqueous solution, preferably, the standing reaction time is 5-7 h, and the silver nanoparticles in the silver nanoparticle aqueous solution are a luminescence enhancer.
Wherein, preferably, the concentration of the diphenylamine aqueous solution is 0.5-1.0 mol/L, the concentration of the silver nitrate aqueous solution is 0.1-0.5 mol/L, and the concentration of the sodium borohydride aqueous solution is 0.5-0.8 mmol/L; preferably, the molar ratio of diphenylamine in the aqueous diphenylamine solution to silver nitrate in the aqueous silver nitrate solution is 3.5 to 1-4.5, and further preferably, the molar ratio of diphenylamine in the aqueous diphenylamine solution to silver nitrate in the aqueous silver nitrate solution is 4:1.
The silver nitrate aqueous solution is easily decomposed by light, so that the newly prepared silver nitrate aqueous solution is used for reaction in the preparation process. In addition, the sodium borohydride aqueous solution is unstable, so the newly prepared sodium borohydride aqueous solution is also used for reaction in the experiment, thereby avoiding influencing the reaction effect.
It should be noted that the concentrations, molar ratios, stirring times and standing reaction times of the respective aqueous solutions are not limited to the above-described ranges, and in other embodiments, may be adjusted according to the actual reaction effects of the diphenylamine aqueous solution, the silver nitrate aqueous solution and the sodium borohydride aqueous solution.
Mixing the silver nanoparticle aqueous solution with zinc nitrate (Zn (NO) according to step S2 3 ) And mixing the aqueous solutions, and then adding a 2-methylimidazole (2-MIM) aqueous solution to react to obtain the silver nanoparticle composite metal organic framework material.
As shown in fig. 2b, zinc nitrate reacts with 2-methylimidazole to generate 2-methylimidazolium salt (ZIF-8) as the metal organic framework, and the silver nanoparticles (AgNPs) in the silver nanoparticle aqueous solution or nanoclusters composed of silver nanoparticles (AgNP-NCs) and the 2-methylimidazolium salt undergo a self-assembly reaction, so that the silver nanoparticles or nanoclusters composed of silver nanoparticles are embedded in the metal organic framework, thereby obtaining the silver nanoparticle composite metal organic framework material (AgNP-NCs @ ZIF-8).
The step S2 may include: firstly, mixing a certain volume of silver nanoparticle aqueous solution and a certain volume of zinc nitrate aqueous solution, and uniformly stirring; then, adding a certain volume of 2-methylimidazole aqueous solution into the mixed solution, stirring the mixed solution at room temperature, wherein the stirring time is preferably 20-40 min, the mixed solution turns milky white after full reaction, and red luminescence can be observed under ultraviolet radiation; and then, sequentially centrifuging, washing and vacuum drying the mixed solution after the full reaction to obtain the light yellow powdery silver nanoparticle composite metal organic framework material.
Wherein, the molar ratio of 2-methylimidazole in the 2-methylimidazole aqueous solution to zinc nitrate in the zinc nitrate aqueous solution is preferably 2.5; the molar ratio of the zinc nitrate in the zinc nitrate water solution to the silver nitrate in the silver nitrate aqueous solution is 15 to 20, and more preferably, the molar ratio of the zinc nitrate in the zinc nitrate water solution to the silver nitrate in the silver nitrate aqueous solution is 17.75; the concentration of the zinc nitrate aqueous solution can be 20 mmol/L-30 mmol/L, and the concentration of the 2-methylimidazole aqueous solution can be 70 mmol/L-80 mmol/L. The molar ratio between the reactants and the concentration of the aqueous solution are not limited to the above ranges.
Preferably, the cleaning solution used for washing is ethanol, the washing times are at least three times, and the ethanol is used as an organic solvent, so that the excessive organic substances and other impurities on the surface of the centrifuged product can be effectively removed. Preferably, the time for vacuum drying is at least 12h.
In one embodiment, the step of preparing the silver nanoparticle composite metal organic framework material may comprise: firstly, mixing 0.4mL of prepared diphenylamine aqueous solution with the concentration of 0.5mol/L and 0.5mL of newly prepared silver nitrate aqueous solution with the concentration of 0.1 mol/L; subsequently, the mixed solution was added to 4.8mL of ultrapure water; subsequently, under vigorous stirring, adding 0.16mL of newly prepared sodium borohydride aqueous solution with the concentration of 0.625mmol/L into the mixture, immediately changing the mixture solution from a colorless transparent solution into a brownish black solution, keeping the mixture solution stirred for 30-60 min, and gradually changing the mixture solution from the brownish black solution into a bright light yellow solution along with the continuous stirring; then, after the mixture solution is subjected to standing reaction for 7 hours, stopping stirring when the mixture solution becomes a transparent yellow silver nanoparticle aqueous solution; then, mixing 1mL of the prepared silver nanoparticle aqueous solution with 6mL of 25mmol/L zinc nitrate aqueous solution (the zinc nitrate aqueous solution can be prepared by dissolving zinc nitrate hexahydrate in water); then, 6mL of 75 mmol/L2-methylimidazole aqueous solution was added to the mixed solution, and stirring was performed at room temperature for 20min until the mixture solution became a milky white solution and red luminescence could be observed under ultraviolet irradiation; and then, centrifuging the obtained milky white solution, washing with ethanol, and after three times of washing, vacuum-drying the product for 12 hours to obtain the silver nanoparticle composite metal organic framework material in a light yellow powder shape.
Wherein the formation of silver nanoparticles is confirmed by infrared detection of the aqueous silver nanoparticle solution; and detection shows that compared with the existing composite material, the luminous intensity of the silver nanoparticle composite metal organic framework material prepared by the invention is remarkably increased by (66 +/-5) times, and the luminous life is prolonged from nanosecond to microsecond, namely from (50.9 +/-1.8) ns to (15.9 +/-0.4) mus. Therefore, the silver nanoparticle composite metal organic framework material prepared by the invention has better luminescence performance and plays a certain role in luminescence detection of metal ions.
The silver nanoparticles in the silver nanoparticle composite metal organic framework material have large specific surface area, so that the silver nanoparticle composite metal organic framework material has very good adsorption effect on hexavalent chromium ions in the environment (such as in an aqueous solution); in addition, the silver nanoparticle composite metal organic framework material has a fluorescent light-emitting characteristic, and the hexavalent chromium ions adsorbed by the silver nanoparticle composite metal organic framework material can reduce the luminous intensity, so that the concentration of the hexavalent chromium ions in the environment can be known by detecting the change of the luminous intensity. Therefore, the silver nanoparticle composite metal organic framework material has the capability of simultaneously detecting and removing hexavalent chromium ions.
As shown in fig. 2c, hexavalent chromium Cr (vi) is adsorbed in the metal-organic framework of the silver nanoparticle composite metal-organic framework material.
In summary, the preparation method of the silver nanoparticle composite material provided by the invention comprises the following steps: adding a diphenylamine aqueous solution and a silver nitrate aqueous solution into ultrapure water, and adding a sodium borohydride aqueous solution under stirring to react to form a silver nanoparticle aqueous solution; the silver nanoparticle aqueous solution and the zinc nitrate aqueous solution are mixed, and then the 2-methylimidazole aqueous solution is added to react to obtain the silver nanoparticle composite metal organic framework material, so that hexavalent chromium in the environment can be detected and can be efficiently removed.
An embodiment of the invention also provides a silver nanoparticle composite material, and the silver nanoparticle composite metal organic framework material is prepared by adopting the preparation method of the silver nanoparticle composite material.
The silver nanoparticle composite material provided in this example will be described in detail with reference to fig. 2.
The preparation method of the silver nanoparticle composite material is described in the above description, and is not described in detail herein. In the preparation process of the silver nanoparticle composite material, silver nitrate in a silver nitrate aqueous solution is used as a source of silver ions, and is mixed with diphenylamine in a diphenylamine aqueous solution to carry out a reduction reaction, so that silver nanoparticles (AgNPs) in the silver nanoparticle aqueous solution are obtained. Subsequently, the silver nanoparticle aqueous solution and the zinc nitrate aqueous solution were mixed, and 2-methylimidazole aqueous solution was added thereto with stirring. In the process, zinc nitrate reacts with 2-methylimidazole to generate 2-methylimidazole zinc salt (ZIF-8) serving as a metal organic framework. Subsequently, the silver nanoparticles or nanoclusters (AgNP-NCs) consisting of the silver nanoparticles in the silver nanoparticle aqueous solution and 2-methylimidazolium zinc salt undergo a self-assembly reaction, so that the silver nanoparticles or nanoclusters consisting of the silver nanoparticles are embedded in a metal organic framework, and further the silver nanoparticle composite metal organic framework material (AgNP-NCs @ ZIF-8) is obtained.
The silver nanoparticles in the silver nanoparticle composite metal organic framework material have large specific surface area, so that the silver nanoparticle composite metal organic framework material has very good adsorption effect on hexavalent chromium ions in the environment (such as in an aqueous solution); in addition, the silver nanoparticle composite metal organic framework material has a fluorescent light-emitting characteristic, and the hexavalent chromium ions adsorbed by the silver nanoparticle composite metal organic framework material can reduce the luminous intensity, so that the concentration of the hexavalent chromium ions in the environment can be known by detecting the change of the luminous intensity. Therefore, the silver nanoparticle composite metal organic framework material has the capability of simultaneously detecting and removing hexavalent chromium ions.
In conclusion, the invention also provides a silver nanoparticle composite material, and the silver nanoparticle composite metal organic framework material is prepared by adopting the preparation method of the silver nanoparticle composite material, so that hexavalent chromium in the environment can be detected and simultaneously can be efficiently removed.
In addition, the invention also provides an application of the silver nanoparticle composite material, which comprises the following steps: the silver nanoparticle composite metal organic framework material is used for detecting and adsorbing to remove hexavalent chromium.
The application of the silver nanoparticle composite material provided by the present invention will be described in detail with reference to fig. 3 to 6.
Preferably, the step of detecting hexavalent chromium may include: firstly, mixing the aqueous solution of the silver nanoparticle composite metal organic framework material with an aqueous solution containing hexavalent chromium, and adjusting the pH value of the mixed aqueous solution to 8.5 so that the pH value of the mixed aqueous solution is consistent with the pH value of the aqueous solution of the silver nanoparticle composite metal organic framework material; and then, measuring the fluorescence intensity of the mixed aqueous solution at the emission wavelength of 730nm under the excitation wavelength of 420nm, and calculating to obtain the concentration of hexavalent chromium according to the fluorescence intensity.
In one embodiment, the step of detecting hexavalent chromium may include: firstly, taking 1mg/mL of newly prepared colloidal aqueous solution of the silver nanoparticle composite metal organic framework material and 300 mu L of potassium dichromate (K) with different concentrations 2 Cr 2 O 7 ) Mixing the solutions to obtain 1mL of solution; subsequently, the mixed solution was diluted to 3mL with ultrapure water; then, adjusting the pH value of the diluted solution by using a sodium hydroxide solution to enable the pH value of the solution to be equal to that of the colloidal aqueous solution, wherein the pH value of the colloidal aqueous solution is 8.5; then, the photoluminescence spectrum and fluorescence intensity (PL intensity) of the pH-adjusted solution at an emission wavelength of 730nm were measured at an excitation wavelength of 420nm, based on the optimal excitation and emission wavelengths.
Fig. 3 is a photoluminescence spectrum of a silver nanoparticle composite material under different hexavalent chromium ion concentrations, the abscissa is an emission wavelength, the ordinate is a fluorescence intensity of the silver nanoparticle composite material, and different curves represent different hexavalent chromium ion concentrations, where L1 is 0 μmol/L, L2 is 2 μmol/L, L3 is 10 μmol/L, L4 is 20 μmol/L, L5 is 30 μmol/L, L6 is 40 μmol/L, L7 is 50 μmol/L, L8 is 100 μmol/L, L9 is 150 μmol/L, L10 is 200 μmol/L, L11 is 400 μmol/L, L12 is 1000 μmol/L, and L13 is 2000 μmol/L. As can be seen from fig. 3, the silver nanoparticle composite material has the highest fluorescence intensity at the emission wavelength of 730nm, i.e., the best luminescence performance; and, since hexavalent chromium ions are adsorbed by the silver nanoparticle composite material to quench the luminescence of the nano silver, the fluorescence intensity of the silver nanoparticle composite material is continuously decreased as the concentration of hexavalent chromium ions increases.
Fig. 4 is a variation curve of the luminescence quenching ratio of the silver nanoparticle composite material under different concentrations of hexavalent chromium ions, the abscissa is the concentration of hexavalent chromium ions, the ordinate is the luminescence quenching ratio of the silver nanoparticle composite material (i.e., 1-I/I0), and I/I0 is the ratio of the presence of hexavalent chromium ions in the solution to the fluorescence intensity of the silver nanoparticle composite material in the absence of hexavalent chromium ions. As can be seen from FIG. 4, the hexavalent chromium content is in the range of 0. Mu. Mol/L to 2000. Mu. Mol/LIn the concentration range of the chromium ions, as the concentration of the hexavalent chromium ions increases, the hexavalent chromium ions are adsorbed by the silver nanoparticle composite material to quench the luminescence of the nano silver, so that the luminescence intensity of the silver nanoparticle composite material is reduced; in addition, in the concentration range of hexavalent chromium ions of 40 to 400 μmol/L, a good linear relation can be observed, wherein the linear equation is y =0.00212x +0.14408, and the correlation coefficient (R) is 2 ) 0.99858, the lowest concentration of hexavalent chromium ions, i.e., (23.5 ± 0.8) μmol/L, was detected with a detection Limit (LOD) of (23.5 ± 0.8) μmol/L calculated from D =3 σ/k (σ is the standard deviation, and k is the slope of the calibration curve).
In addition, a selectivity experiment is also carried out by using a metal nitrate solution instead of a hexavalent chromium solution to test the adsorption selectivity of the silver nanoparticle composite material on hexavalent chromium ions; and moreover, carrying out an anti-interference test on the hexavalent chromium ions so as to detect whether the silver nanoparticle composite material has good anti-interference performance on the hexavalent chromium ions.
Wherein, in the selective experiment, the metal nitrate solution (the metal ion can be Na for example) + 、Ca 2+ 、Zn 2+ 、Cr 3+ 、Co 2+ 、Cd 2+ 、Ni 2+ 、Pb 2+ ,Cu 2+ , K+ 、Mg 2+ 、Mn 2+ 、Fe 3+ 、Ag + And Hg 2+ ) The selectivity experiments were performed in place of hexavalent chromium, and the ion concentration of all solutions could be 25 μmol/L. Fig. 5 is a graph showing the change in luminescence quenching ratio of the silver nanoparticle composite material in the presence of different kinds of metal ions, and the excitation wavelength was 420nm, the emission wavelength was 730nm, the abscissa is different kinds of metal ions, and the ordinate is the luminescence quenching ratio of the silver nanoparticle composite material (i.e., 1-I/I0). As shown in fig. 5, the luminescence quenching ratio of the silver nanoparticle composite material in the nitrate solution of hexavalent chromium ions is significantly greater than that of other types of metal nitrate solutions, which indicates that the detection signal of the silver nanoparticle composite material in the nitrate solution of hexavalent chromium ions is significantly better than that of other types of metal nitrate solutions, and further indicates that the silver nanoparticle composite material is doped with a metal nitrate solution of hexavalent chromium ions, such that the detection signal of the silver nanoparticle composite material in the nitrate solution of hexavalent chromium ions is significantly better than that of the other types of metal nitrate solutions, and the detection signal of the silver nanoparticle composite material in the nitrate solution of hexavalent chromium ions is significantly better than that of the other types of metal nitrate solutions, thereby indicating that the silver nanoparticle composite material is doped with a metal nitrate solution of hexavalent chromium ionsThe rice particle composite material has good selectivity for hexavalent chromium ions.
By way of comparison, this example also investigated the selectivity of pure silver nanoparticles to hexavalent chromium. By using Mn 2+ 、Cu 2+ 、Mg 2+ 、Co 2+ And metal ions such as Cr (VI) quench the luminescence of the pure silver nano-particles, and the experimental result shows that the sensitivity of the silver nano-particles to hexavalent chromium is far lower than that of the silver nano-particle composite material.
The step of performing an anti-interference test on the hexavalent chromium ions may include: four groups of interfering metal ions were added to the solution of hexavalent chromium ions: m1: na (Na) + /Ca 2+ /Fe 3+ ，m2：K + /Co 2+ /Mn 2+ ，m3：Mg 2+ /Ag + /Pb 2+ ，m4：Zn 2+ /Ni 2+ /Cd 2+ And testing the luminescence performance of the silver nanoparticle composite material in a hexavalent chromium solution added with different mixed metal ions so as to judge whether the silver nanoparticle composite material has anti-interference performance on detection of hexavalent chromium ions. Wherein the concentration of hexavalent chromium ions is 100 mu mol/L, and the concentration of all interference metal ions is 100 mu mol/L. The experimental result shows that the silver nanoparticle composite material has good anti-interference performance on the detection of hexavalent chromium ions.
In addition, the application of the silver nanoparticle composite material further comprises: and (3) detecting the luminescence of hexavalent chromium in an actual sample. Collecting drinking water and tap water, adjusting the pH value of all water samples to 8.5 by a sodium hydroxide solution, adding detection water samples into 3 hexavalent chromium solutions with different concentrations (50 mu mol/L, 100 mu mol/L and 200 mu mol/L) by using the silver nanoparticle composite material as a fluorescence sensor, testing the fluorescence intensity of each sample, and judging whether hexavalent chromium ions exist in an actual sample or not by comparing experimental data, thereby judging whether hexavalent chromium ion detection has actual applicability in the actual sample or not.
Preferably, the step of adsorptive removal of hexavalent chromium comprises: firstly, mixing an aqueous solution of the silver nanoparticle composite metal organic framework material with an aqueous solution containing hexavalent chromium, and standing for 8-12 hours; the pH value of the aqueous solution containing hexavalent chromium is 8.5, and the concentration range of the aqueous solution containing hexavalent chromium can be 5-1000 mu mol/L; and then, centrifuging and removing the silver nanoparticle composite metal organic framework material adsorbed with hexavalent chromium.
In one embodiment, the prepared silver nanoparticle composite colloidal aqueous solution and hexavalent chromium solutions with different concentrations can be mixed for adsorption, wherein the pH of the hexavalent chromium solution is adjusted to 8.5 in advance; after adsorbing for 10 hours, the mixed solution was centrifuged, and the supernatant was taken and absorbance was measured at 370nm to measure the concentration of hexavalent chromium ions in the adsorbed solution, whereby the adsorption capacity of the silver nanoparticle composite material was calculated by equation 1.
Wherein Q is e Is the adsorption capacity of the silver nanoparticle composite; c 0 And C 1 The concentrations of the hexavalent chromium ions before and after adsorption are respectively obtained; m is the weight of the adsorbent (in this example, the adsorbent is the silver nanoparticle composite); v solution Is the volume of the solution.
Referring to fig. 6, fig. 6 is an isotherm of the adsorption of hexavalent chromium by the silver nanoparticle composite at 298K, with the abscissa being the equilibrium concentration of hexavalent chromium ions and the ordinate being the adsorption capacity of the silver nanoparticle composite. The results shown in fig. 6 confirm that the silver nanoparticle composite material has a good adsorption capacity for hexavalent chromium.
In addition, the practical application of the silver nanoparticle composite material in detecting hexavalent chromium is tested in the embodiment. Adding hexavalent chromium ion solutions with known concentrations into drinking water and tap water respectively, adding the silver nanoparticle composite material for adsorption, and testing the application effect of the silver nanoparticle composite material by testing the concentrations of hexavalent chromium ions before and after adsorption in an actual water sample. The experimental result shows that the recovery rate of hexavalent chromium ions in drinking water and tap water can reach 92% at most, and the relative deviation (RSD) is less than 13.36%, which indicates that the samples have small interference on the detection of the hexavalent chromium ions, and simultaneously proves that the silver nanoparticle composite material has a good effect in practical application.
In summary, an application provided by the present invention includes: the silver nanoparticle composite metal organic framework material is used for detecting and adsorbing hexavalent chromium, so that hexavalent chromium in the environment can be detected and efficiently removed.
The above description is only for the purpose of describing the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and any variations and modifications made by those skilled in the art based on the above disclosure are intended to fall within the scope of the appended claims.
Claims (12)
1. A method of preparing a silver nanoparticle composite material, comprising:
adding a diphenylamine aqueous solution and a silver nitrate aqueous solution into ultrapure water, and adding a sodium borohydride aqueous solution under stirring to react to form a silver nanoparticle aqueous solution;
and mixing the silver nanoparticle aqueous solution with a zinc nitrate aqueous solution, and then adding a 2-methylimidazole aqueous solution to react to obtain the silver nanoparticle composite metal organic framework material.
2. The method of preparing a silver nanoparticle composite material according to claim 1, wherein the concentration of the diphenylamine aqueous solution is 0.5 to 1.0mol/L.
3. The method for preparing a silver nanoparticle composite material according to claim 1, wherein the concentration of the silver nitrate aqueous solution is 0.1mol/L to 0.5mol/L.
4. The method of preparing a silver nanoparticle composite material according to claim 1, wherein the molar ratio of diphenylamine in the diphenylamine aqueous solution to silver nitrate in the silver nitrate aqueous solution is 3.5 to 4.5.
5. The method for preparing a silver nanoparticle composite material according to claim 1, wherein after the sodium borohydride solution is added, stirring is continued for 30min to 60min, and standing reaction is performed for 5h to 7h.
6. The method of preparing a silver nanoparticle composite material according to claim 1, wherein the molar ratio of 2-methylimidazole in the aqueous 2-methylimidazole solution to zinc nitrate in the aqueous zinc nitrate solution is 2.5 to 3.5.
7. The method for preparing a silver nanoparticle composite material according to claim 1, wherein the molar ratio of the zinc nitrate in the zinc nitrate aqueous solution to the silver nitrate in the silver nitrate aqueous solution is 15 to 20.
8. The method for preparing the silver nanoparticle composite material according to claim 1, wherein the silver nanoparticle composite metal organic framework material is obtained by stirring at room temperature for 20 to 40min after adding the 2-methylimidazole aqueous solution, and then sequentially performing centrifugation, washing and vacuum drying.
9. A silver nanoparticle composite material characterized by being produced by the production method of the silver nanoparticle composite material according to any one of claims 1 to 8.
10. Use of the silver nanoparticle composite material of claim 9, comprising: the silver nanoparticle composite metal organic framework material is used for detecting and adsorbing to remove hexavalent chromium.
11. Use of the silver nanoparticle composite of claim 10, wherein the step of detecting hexavalent chromium comprises:
mixing the aqueous solution of the silver nanoparticle composite metal organic framework material with an aqueous solution containing hexavalent chromium, and adjusting the pH of the mixed aqueous solution to 8.5;
and measuring the fluorescence intensity of the mixed aqueous solution at the emission wavelength of 730nm under the excitation wavelength of 420nm, and calculating to obtain the concentration of hexavalent chromium according to the fluorescence intensity.
12. Use of the silver nanoparticle composite of claim 10 wherein the step of adsorptive removal of hexavalent chromium comprises:
mixing the aqueous solution of the silver nanoparticle composite metal organic framework material with an aqueous solution containing hexavalent chromium, and standing for 8-12 hours; the pH value of the aqueous solution containing hexavalent chromium is 8.5, and the concentration range of the aqueous solution containing hexavalent chromium is 5-1000 mu mol/L;
and centrifuging the silver nanoparticle composite metal organic framework material adsorbed with hexavalent chromium to remove.
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