CN102908992A - Bifunctional material for detecting and adsorbing mercury ions as well as synthesizing method and application of same - Google Patents

Bifunctional material for detecting and adsorbing mercury ions as well as synthesizing method and application of same Download PDF

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CN102908992A
CN102908992A CN2012103965801A CN201210396580A CN102908992A CN 102908992 A CN102908992 A CN 102908992A CN 2012103965801 A CN2012103965801 A CN 2012103965801A CN 201210396580 A CN201210396580 A CN 201210396580A CN 102908992 A CN102908992 A CN 102908992A
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bifunctional material
solution
nano particle
sio
scattered
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CN102908992B (en
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吴爱国
汪竹青
赵新梅
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention discloses a synthesizing method of a bifunctional material for detecting and adsorbing mercury ions as well as a synthesizing method and application of the same. According to the invention, magnetic nanoparticles serve as carriers, SiO2 is coated or connected on surfaces of the magnetic nanoparticles, and rhodamine hydrazine is modified to surfaces of MxOy/SiO2 type composite magnetic nanoparticles in turn through silane hydrolyzation and schiff-base reaction so as to prepare the bifunctional material; the invention also discloses the bifunctional material and application of same, the bifunctional material can quickly detect Hg2+ in water body, has the characteristics of high sensibility, high adsorption rate and recyclability, is applicable to investigating quality of water in rivers and lakes, monitoring quality of sewage discharged from factories as well as detecting and treating domestic water, food, human and animal blood and various water samples obtained through the treatment of various solid samples, and therefore has wide application value.

Description

For detection of with bifunctional material and synthetic method and the application of Adsorption of Mercury ion
Technical field
The invention belongs to the mercury ion detecting field, be specifically related to a kind of for detection of with the bifunctional material of Adsorption of Mercury ion and synthetic method and application.
Background technology
Mercury is the human body non-essential element, will produce harm to human health when low concentration, causes the damage of brain injury and liver, kidney, GI hypofunction and central nervous system.The Mercury in Water Body ion is mainly derived from smelting, chlorine industry and the electrical equipment industry etc. of mercury ore and other metals.Exploitation can fast detecting and the functional material of Adsorption Mercury in Water Body ion significant.
At present, a lot of about the bibliographical information of Mercury in Water Body ion detection, mainly be by chemical sensitisation mechanism such as Photoinduced Electron transfer, intramolecular charge transfer and chemical reaction systems, realize the detection to mercury ion.The mercury ion chemical sensor of having reported mainly contains rhodamine derivative, crown ether compound, polyamine compounds etc., these mercury ion chemical sensing appliances have following shortcoming: (1) mostly belongs to organic molecule, poorly water-soluble, can only be applied to the mixed solution of organic solvent or organic solvent and water, for example: DMF/H 2O or CH 3CN/H 2Among the O etc., therefore reduced the practicality of material; (2) when detecting mercury ion, the mercury ion in can not the Adsorption water body; (3) reclaiming difficulty is unfavorable for recycling.At present, about for detection of and adsorbed water body in the report of bifunctional material of mercury ion less.
Summary of the invention
The invention provides a kind of for detection of with synthetic method and the application of the bifunctional material of Adsorption of Mercury ion, the bifunctional material that is synthesized be applicable to detect and adsorbed water body in Hg 2+, and be easy to reclaim, can be recycled.
A kind of for detection of with the synthetic method of the bifunctional material of Adsorption of Mercury ion, comprise the steps:
(1) magnetic nano-particle is scattered in the solution of second alcohol and water, under the stirring condition, adds tetraethoxysilane (TEOS) and ammoniacal liquor and react, after reacting completely, through Magnetic Isolation, washing, drying, obtain the composite magnetic nano particle;
(2) the composite magnetic nano particle that step (1) is made is scattered in the aqueous solution, under the stirring condition, adding N-aminoethyl-γ aminopropyl trimethoxysilane (TPED) reacts, after reacting completely, through Magnetic Isolation, washing, drying, make amido modified composite magnetic nano particle;
(3) the amido modified composite magnetic nano particle that step (2) is made is scattered in the aqueous solution, under the stirring condition, adding the twain-aldehyde compound compound reacts, after reacting completely, through Magnetic Isolation, washing, drying, make aldehyde radical (the composite magnetic nano particle of CHO) modifying;
(4) the aldehyde group modified composite magnetic nano particle that step (3) is made is scattered in the alcoholic solvent, under the stirring condition, add rhodamine hydrazine compound and react, after reacting completely, through Magnetic Isolation, washing, drying, obtain described bifunctional material.
Among the present invention, with magnetic nano-particle (M xO y) be carrier, SiO on its surface coats or connects 2, then by silane hydrolyzate, schiff base reaction rhodamine hydrazine compound (RH) is modified M successively xO y/ SiO 2The composite magnetic nanoparticle surface of type prepares the magnetic bifunctional material (M of tool xO y/ SiO 2/ RH).Described bifunctional material contains rhodamine lactams structure, Hg 2+Can optionally complexing occur and make this structure generation open loop with this structure, cause that fluorescence intensity strengthens, thus can be to Hg 2+Detect or adsorb; This bifunctional material is comprised of the particle of nano-scale, has larger surface area, easily be scattered in the aqueous solution, thereby realize in water body to Hg 2+Detection and absorption; This functional material has magnetic simultaneously, is easy to reclaim, and can be recycled after treatment.
Magnetic nano-particle described in the step (1) is magnetic by band, and the material that can adopt the Magnetic Isolation method to carry out separated and collected forms, and is preferably Fe 3O 4, γ-Fe 2O 3, MnFe 2O 4, ZnFe 2O 4And CoFe 2O 4At least a in the nano particle, these nano particle low prices, easily preparation; For so that described bifunctional material is easy to disperse in water body, the particle diameter of described magnetic nano-particle is unsuitable excessive, described magnetic nano-particle more preferably particle diameter less than 500nm Fe 3O 4Nano particle.
In the step (1), reaction temperature is 15～40 ℃, and with respect to magnetic nano-particle, the consumption of tetraethoxysilane and ammoniacal liquor is excessive to be got final product, without strict especially requirement.
In the step (2), reaction temperature is 45～80 ℃, and with respect to the composite magnetic nano particle, excessive the getting final product of consumption of described N-aminoethyl-γ aminopropyl trimethoxysilane is without strict especially requirement.
In the step (3), reaction temperature is 15～40 ℃, and described twain-aldehyde compound compound can be preferably glyoxal for aromatic series twain-aldehyde compound compound or aliphatic dialdehydes compounds, and cost is lower when selecting glyoxal.
In the step (4), reaction condition is for adding hot reflux, and temperature is controlled to be 70～120 ℃, is preferably 90 ℃, and the reaction time was preferably 6 hours greater than 4 hours, and described alcoholic solvent is preferably at least a in methyl alcohol and the ethanol.
Among the present invention, the mol ratio of the twain-aldehyde compound compound that adds in the N-aminoethyl that adds in the step (2)-γ aminopropyl trimethoxysilane and the step (3) was less than 1: 2, and preferred molar ratio is 1: 4; The mol ratio of the rhodamine hydrazine compound that adds in the N-aminoethyl that adds in the step (2)-γ aminopropyl trimethoxysilane and the step (4) was greater than 1: 1 o'clock, can both obtain well described bifunctional material, consider from the cost aspect, preferred molar ratio is 1.5: 1.
The bifunctional material that the present invention also provides a kind of above-mentioned synthetic method to obtain.
The present invention also provides a kind of and has adopted above-mentioned bifunctional material to the method that the mercury ion in the solution to be measured detects, and comprising:
(1) described bifunctional material is scattered in the water, measures fluorescence intensity I 1
(2) add solution to be measured in the aqueous solution in the step (1), measure its fluorescence intensity I 2
(3) compare I 2With I 1If size is I 2＞I 1, then have mercury ion in the solution to be measured, and wherein the concentration of mercury ion 10 -8More than the mol/L.
During detection, the amount ranges of described bifunctional material is 1.5～5mg, and described water is generally selected distilled water, and consumption is 2～3mL, and it is 30～60 μ L that band detects the water sample consumption.
When measuring fluorescence intensity, the wave-length coverage of measuring emission peak is 530～650nm.
Described solution to be measured can be the water sample in the environment, also can be to swim in the blood of dust, food samples, human body or animal in the atmosphere and the aqueous solution that other body fluid obtains after treatment.For example, the water sample of river, lake water, from the water sample of industrial and mineral, electrical equipment, electroplating industry, the environmental water sample in the soil, and the water sample etc. of pellet in the atmosphere
Experimental result shows, in the step (2), adds quantitative different metal solion, records each sample fluorescence intensity level, and by relatively fluorescence intensity difference discovery, when adding other metal ion solutions, each fluorescence intensity level remains unchanged or reduces, when adding Hg 2+During solution, fluorescence intensity level strengthens, and illustrates that described bifunctional material is to Hg 2+Has high selectivity.
As preferably, in the step (2), add before the solution to be measured, the pH that regulates the described aqueous solution is 6.0～8.0, at this moment, not only can get rid of the interference of non-detection material, but also can improve detectability and sensitivity, preferentially select hydrochloric acid or NaOH to regulate the pH value.
The present invention also provides the detection method of the ion concentration of mercury in a kind of solution to be measured, comprising:
(1) under the condition that described bifunctional material exists, measures the fluorescence intensity of the titer that contains the variable concentrations mercury ion, the drawing standard curve;
(2) under the condition that described bifunctional material exists, measure the fluorescence intensity in the solution to be measured, utilize described calibration curve to calculate the concentration of mercury ion in the solution to be measured.
The concrete method for drafting of this calibration curve is as follows:
At first prepare the titer of variable concentrations mercury ion, take by weighing an amount of bifunctional material and be scattered in the aqueous solution, get respectively equal volume variable concentrations mercury ion titer and add in the magnetic bifunctional material dispersion liquid, record each solution fluorescence intensity level, take fluorescence intensity level as ordinate, Hg 2+Concentration is the abscissa mapping, namely obtains canonical plotting;
Found through experiments, when canonical plotting was drawn, the emission peak position of the fluorescence intensity level of described titer was preferably 550nm.
The present invention also provides a kind of adsorption method that contains mercury ion in the mercury solution, comprising: regulate the pH value to 6.0 contain mercury solution～8.0, add described bifunctional material and react, after reacting completely, carry out Magnetic Isolation, obtain the solution of mercury ion minimizing;
The described mercury solution that contains is the waste water that contains mercury ion.
Bifunctional material among the present invention can recycle, and detailed process is as follows, will adsorb Hg 2+Bifunctional material again be scattered in the distilled water, add organic base, described organic base comprises TMAH, tetraethyl ammonium hydroxide, TBAH, benzyltrimethylammonium hydroxide, be preferably TBAH, through separating washing, drying, can again obtain bifunctional material, experimental result shows, recycles 6 times, and described bifunctional material detects and absorption Hg 2+Performance is basicly stable.
Compare with prior art, beneficial effect of the present invention is embodied in:
(1) this invention is based on bifunctional material and Hg 2+Selective complexation, cause the open loop of rhodamine lactams structure, thereby cause fluorescence intensity to strengthen, therefore, utilize XRF to judge, can detect rapidly whether contain Hg in the solution 2+, realize Hg in the aqueous solution 2+Fast detecting and quantitative analysis;
(2) this bifunctional material has preferably magnetic, is easy to Separation of Solid and Liquid;
(3) this bifunctional material has sensitive selective response to mercury ion, energy Adsorption of Mercury ion;
(4) this bifunctional material is processed through organic base, can be recycled, and has wide prospects for commercial application.
Description of drawings
Fig. 1 is the synthetic route chart of bifunctional material among the embodiment 1;
Fig. 2 is the transmission electron microscope picture of bifunctional material among the embodiment 1;
Fig. 3 is that embodiment 18 draws the canonical plotting that obtains, and among the figure, ordinate is fluorescence intensity level, and abscissa is the ion concentration of mercury value.
The specific embodiment
Embodiment 1: synthetic bifunctional material (Fe 3O 4/ SiO 2/ RH)
Fig. 1 is synthetic bifunctional material (Fe in the present embodiment 3O 4/ SiO 2/ RH) chemical reaction route map, as shown in Figure 1, detailed process is as follows:
(1) takes by weighing 0.2g Fe 3O 4(particle diameter: 60～100nm) are scattered in (volume ratio 1: 1) in the 100mL ethanol/water mixed solution, under the stirring condition, add 4.5mL tetraethoxysilane (TEOS) and 9mL concentrated ammonia liquor, react 3h under the room temperature condition, Magnetic Isolation, distilled water washing, 60 ℃ of dryings make SiO 2Coat or the upper Fe of connection 3O 4Composite magnetic nano particle (Fe 3O 4/ SiO 2);
(2) the composite magnetic nano particle (Fe that step (1) is made 3O 4/ SiO 2) be scattered in the 100mL distilled water, under the stirring condition, add 3mLN-β aminoethyl-γ aminopropyl trimethoxysilane (TPED, cas number: 1760-24-3), react 3h, Magnetic Isolation under 50 ℃ of conditions, the distilled water washing, 60 ℃ of dryings make amido modified composite magnetic nano particle;
(3) the amido modified composite magnetic nano particle that step (2) is made is scattered in the 50mL distilled water, under the stirring condition, adds the 3mL glyoxal, react 2h under the room temperature condition, Magnetic Isolation, distilled water washing, 50 ℃ of dryings make aldehyde group modified composite magnetic nano particle;
(4) the aldehyde group modified composite magnetic nano particle that step (3) is made is scattered in the 60mL methyl alcohol, under the stirring condition, add 0.5g rhodamine hydrazine compound (the visible Fig. 1 of concrete structure), 90 ℃ of heating reflux reaction 6h, Magnetic Isolation, methanol wash, 50 ℃ of dryings make the magnetic bifunctional material (Fe of tool 3O 4/ SiO 2/ RH), this bifunctional material (Fe 3O 4/ SiO 2/ RH) transmission electron microscope picture as shown in Figure 2.
Embodiment 2: synthetic bifunctional material (γ-Fe 2O 3/ SiO 2/ RH)
(1) takes by weighing 0.2g γ-Fe 2O 3(particle diameter: 60～100nm) are scattered in (volume ratio 1: 1) in the 100mL ethanol/water mixed solution, under the stirring condition, add 4.5mL tetraethoxysilane (TEOS) and 9mL concentrated ammonia liquor, react 3h under the room temperature condition, Magnetic Isolation, distilled water washing, 70 ℃ of dryings make SiO 2Coat or the upper γ-Fe of connection 2O 3Composite magnetic nano particle (γ-Fe 2O 3/ SiO 2);
(2) the composite magnetic nano particle (γ-Fe that step (1) is made 2O 3/ SiO 2) be scattered in the 100mL distilled water, under the stirring condition, add 3mL N-aminoethyl-γ aminopropyl trimethoxysilane (TPED), react 3h under 50 ℃ of conditions, Magnetic Isolation, distilled water washing, 65 ℃ of dryings make amido modified composite magnetic nano particle;
(3) the amido modified composite magnetic nano particle that step (2) is made is scattered in the 50mL distilled water, under the stirring condition, adds the 3mL glyoxal, react 2h under the room temperature condition, Magnetic Isolation, distilled water washing, 60 ℃ of dryings make aldehyde group modified composite magnetic nano particle;
(4) the aldehyde group modified composite magnetic nano particle that step (3) is made is scattered in the 60mL methyl alcohol, under the stirring condition, add 0.5g rhodamine hydrazine compound, 95 ℃ of heating reflux reaction 6h, Magnetic Isolation, methanol wash, 60 ℃ of dryings make the magnetic bifunctional material (γ-Fe of tool 2O 3/ SiO 2/ RH).
Embodiment 3: synthetic bifunctional material (MnFe 2O 4/ SiO 2/ RH)
(1) takes by weighing 0.2gMnFe 2O 4(particle diameter: 60～100nm) are scattered in (volume ratio 1: 1) in the 100mL ethanol/water mixed solution, under the stirring condition, add 4.5mL tetraethoxysilane (TEOS) and 9mL concentrated ammonia liquor, react 3h under the room temperature condition, Magnetic Isolation, distilled water washing, 65 ℃ of dryings make SiO 2Coat or the upper MnFe of connection 2O 4Composite magnetic nano particle (MnFe 2O 4/ SiO 2);
(2) the composite magnetic nano particle (MnFe that step (1) is made 2O 4/ SiO 2) be scattered in the 100mL distilled water, under the stirring condition, add 3mLN-aminoethyl-γ aminopropyl trimethoxysilane (TPED), react 3h under 50 ℃ of conditions, Magnetic Isolation, the distilled water washing, 65 ℃ of dryings make amido modified composite magnetic nano particle;
(3) the amido modified composite magnetic nano particle that step (2) is made is scattered in the 50mL distilled water, under the stirring condition, adds the 3mL glyoxal, react 2h under the room temperature condition, Magnetic Isolation, distilled water washing, 55 ℃ of dryings make aldehyde group modified composite magnetic nano particle;
(4) the aldehyde group modified composite magnetic nano particle that step (3) is made is scattered in the 60mL methyl alcohol, under the stirring condition, adds 0.5g rhodamine hydrazine compound, 85 ℃ of heating reflux reaction 6h, Magnetic Isolation, methanol wash, 55 ℃ of dryings make the magnetic bifunctional material (MnFe of tool 2O 4/ SiO 2/ RH).
Embodiment 4: synthetic bifunctional material (ZnFe 2O 4/ SiO 2/ RH)
(1) takes by weighing 0.2gZnFe 2O 4(particle diameter: 60～100nm) are scattered in (volume ratio 1: 1) in the 100mL ethanol/water mixed solution, under the stirring condition, add 4.5mL tetraethoxysilane (TEOS) and 9mL concentrated ammonia liquor, react 3h under the room temperature condition, Magnetic Isolation, distilled water washing, 70 ℃ of dryings make SiO 2Coat or the upper ZnFe of connection 2O 4Composite magnetic nano particle (ZnFe 2O 4/ SiO 2);
(2) the composite magnetic nano particle (ZnFe that step (1) is made 2O 4/ SiO 2) be scattered in the 100mL distilled water, under the stirring condition, add 3mLN-aminoethyl-γ aminopropyl trimethoxysilane (TPED), react 3h under 50 ℃ of conditions, Magnetic Isolation, the distilled water washing, 70 ℃ of dryings make amido modified composite magnetic nano particle;
(3) the amido modified composite magnetic nano particle that step (2) is made is scattered in the 50mL distilled water, under the stirring condition, adds the 3mL glyoxal, react 2h under the room temperature condition, Magnetic Isolation, distilled water washing, 55 ℃ of dryings make aldehyde group modified composite magnetic nano particle;
(4) the aldehyde group modified composite magnetic nano particle that step (3) is made is scattered in the 60mL methyl alcohol, under the stirring condition, adds 0.5g rhodamine hydrazine compound, 90 ℃ of heating reflux reaction 6h, Magnetic Isolation, methanol wash, 55 ℃ of dryings make the magnetic bifunctional material (ZnFe of tool 2O 4/ SiO 2/ RH).
Embodiment 5: synthetic bifunctional material (CoFe 2O 4/ SiO 2/ RH)
(1) takes by weighing 0.2g CoFe 2O 4(particle diameter: 60～100nm) are scattered in (volume ratio 1: 1) in the 100mL ethanol/water mixed solution, under the stirring condition, add 4.5mL tetraethoxysilane (TEOS) and 9mL concentrated ammonia liquor, react 3h under the room temperature condition, Magnetic Isolation, distilled water washing, 70 ℃ of dryings make SiO 2Coat or the upper CoFe of connection 2O 4Composite magnetic nano particle (CoFe 2O 4/ SiO 2);
(2) the composite magnetic nano particle (CoFe that step (1) is made 2O 4/ SiO 2) be scattered in the 100mL distilled water, under the stirring condition, add 3mLN-aminoethyl-γ aminopropyl trimethoxysilane (TPED), react 3h under 50 ℃ of conditions, Magnetic Isolation, the distilled water washing, 70 ℃ of dryings make amido modified composite magnetic nano particle;
(3) the amido modified composite magnetic nano particle that step (2) is made is scattered in the 50mL distilled water, under the stirring condition, adds the 3mL glyoxal, react 2h under the room temperature condition, Magnetic Isolation, distilled water washing, 65 ℃ of dryings make aldehyde group modified composite magnetic nano particle;
4) the aldehyde group modified composite magnetic nano particle that step (3) is made is scattered in the 60mL methyl alcohol, under the stirring condition, adds 0.5g rhodamine hydrazine compound, 90 ℃ of heating reflux reaction 6h, Magnetic Isolation, methanol wash, 65 ℃ of dryings make the magnetic bifunctional material (CoFe of tool 2O 4/ SiO 2/ RH).
Embodiment 6: synthetic bifunctional material (Fe 3O 4/ SiO 2/ RH)
(1) takes by weighing 0.2g Fe 3O 4(particle diameter: 60～100nm) are scattered in (volume ratio 1: 1) in the 100mL ethanol/water mixed solution, under the stirring condition, add 4.5mL tetraethoxysilane (TEOS) and 9mL concentrated ammonia liquor, react 3h under the room temperature condition, Magnetic Isolation, distilled water washing, 60 ℃ of dryings make SiO 2Coat or the upper Fe of connection 3O 4Composite magnetic nano particle (Fe 3O 4/ SiO 2);
(2) the composite magnetic nano particle (Fe that step (1) is made 3O 4/ SiO 2) be scattered in the 100mL distilled water, under the stirring condition, add 3mLN-aminoethyl-γ aminopropyl trimethoxysilane (TPED), react 3h under 50 ℃ of conditions, Magnetic Isolation, the distilled water washing, 60 ℃ of dryings make amido modified composite magnetic nano particle;
(3) the amido modified composite magnetic nano particle that step (2) is made is scattered in the 50mL distilled water, under the stirring condition, adds the 3mL OPA, react 2h under the room temperature condition, Magnetic Isolation, distilled water washing, 50 ℃ of dryings make aldehyde group modified composite magnetic nano particle;
(4) the aldehyde group modified composite magnetic nano particle that step (3) is made is scattered in the 60mL methyl alcohol, under the stirring condition, adds 0.5g rhodamine hydrazine compound, 90 ℃ of heating reflux reaction 6h, Magnetic Isolation, methanol wash, 50 ℃ of dryings make the magnetic bifunctional material (Fe of tool 3O 4/ SiO 2/ RH).
The present embodiment has been investigated twain-aldehyde compound material in the synthetic bifunctional material process and has been changed impact on properties of product, and experimental result shows: glyoxal is replaced with OPA, synthetic bifunctional material (Fe 3O 4/ SiO 2/ RH) fast detecting and Adsorption Mercury in Water Body ionic nature keep stable, and adsorption rate is substantially constant.
Embodiment 7: synthetic bifunctional material (Fe 3O 4/ SiO 2/ RH)
(1) takes by weighing 0.2gFe 3O 4(particle diameter: 60～100nm) are scattered in (volume ratio 1: 1) in the 100mL ethanol/water mixed solution, under the stirring condition, add 4.5mL tetraethoxysilane (TEOS) and 9mL concentrated ammonia liquor, react 3h under the room temperature condition, Magnetic Isolation, distilled water washing, 70 ℃ of dryings make SiO 2Coat or the upper Fe of connection 3O 4Composite magnetic nano particle (Fe 3O 4/ SiO 2);
(2) the composite magnetic nano particle (Fe that step (1) is made 3O 4/ SiO 2) be scattered in the 100mL distilled water, under the stirring condition, add 3mL N-aminoethyl-γ aminopropyl trimethoxysilane (TPED), react 3h under 50 ℃ of conditions, Magnetic Isolation, distilled water washing, 70 ℃ of dryings make amido modified composite magnetic nano particle;
(3) the amido modified composite magnetic nano particle that step (2) is made is scattered in the 50mL distilled water, under the stirring condition, adds the 3mL glyoxal, react 2h under the room temperature condition, Magnetic Isolation, distilled water washing, 70 ℃ of dryings make aldehyde group modified composite magnetic nano particle;
(4) the aldehyde group modified composite magnetic nano particle that step (3) is made is scattered in the 60mL methyl alcohol, under the stirring condition, adds 0.5g rhodamine hydrazine compound, 80 ℃ of heating reflux reaction 6h, Magnetic Isolation, methanol wash, 50 ℃ of dryings make the magnetic bifunctional material (Fe of tool 3O 4/ SiO 2/ RH).
The present embodiment has been investigated the variation of step (4) reaction temperature in the synthetic bifunctional material process to the impact of properties of product, and experimental result shows: when the heating reflux temperature is set to 70 ℃ in the step (4), and synthetic bifunctional material (Fe 3O 4/ SiO 2/ RH, γ-Fe 2O 3/ SiO 2/ RH, MnFe 2O 4/ SiO 2/ RH, ZnFe 2O 4/ SiO 2/ RH, CoFe 2O 4/ SiO 2/ RH) fast detecting and absorption are removed the Mercury in Water Body ionic nature and are kept stable, and adsorption rate is substantially constant.
Embodiment 8: synthetic bifunctional material (Fe 3O 4/ SiO 2/ RH) the impact of step (4) reaction temperature in the process
(1) takes by weighing 0.2g Fe 3O 4(particle diameter: 60～100nm) are scattered in (volume ratio 1: 1) in the 100mL ethanol/water mixed solution, under the stirring condition, add 4.5mL tetraethoxysilane (TEOS) and 9mL concentrated ammonia liquor, react 3h under the room temperature condition, Magnetic Isolation, distilled water washing, 75 ℃ of dryings make SiO 2Coat or the upper Fe of connection 3O 4Composite magnetic nano particle (Fe 3O 4/ SiO 2);
(2) the composite magnetic nano particle (Fe that step (1) is made 3O 4/ SiO 2) be scattered in the 100mL distilled water, under the stirring condition, add 3mL N-aminoethyl-γ aminopropyl trimethoxysilane (TPED), react 3h under 50 ℃ of conditions, Magnetic Isolation, distilled water washing, 75 ℃ of dryings make amido modified composite magnetic nano particle;
(3) the amido modified composite magnetic nano particle that step (2) is made is scattered in the 50mL distilled water, under the stirring condition, adds the 3mL glyoxal, react 2h under the room temperature condition, Magnetic Isolation, distilled water washing, 50 ℃ of dryings make aldehyde group modified composite magnetic nano particle;
(4) the aldehyde group modified composite magnetic nano particle that step (3) is made is scattered in the 60mL methyl alcohol, under the stirring condition, adds 0.5g rhodamine hydrazine compound, 120 ℃ of heating reflux reaction 6h, Magnetic Isolation, methanol wash, 50 ℃ of dryings make the magnetic bifunctional material (Fe of tool 3O 4/ SiO 2/ RH).
The present embodiment has investigated that step (4) reaction temperature is on the impact of properties of product in the synthetic bifunctional material process, and experimental result shows: when the heating reflux temperature is set to 120 ℃ in the step (4), and synthetic bifunctional material (Fe 3O 4/ SiO 2/ RH, γ-Fe 2O 3/ SiO 2/ RH, MnFe 2O 4/ SiO 2/ RH, ZnFe 2O 4/ SiO 2/ RH, CoFe 2O 4/ SiO 2/ RH) fast detecting and absorption are removed the Mercury in Water Body ionic nature and are kept stable, and adsorption rate is substantially constant.
Embodiment 9: synthetic bifunctional material (Fe 3O 4/ SiO 2/ RH)
(1) takes by weighing 0.2gFe 3O 4(particle diameter: 60～100nm) are scattered in (volume ratio 1: 1) in the 100mL ethanol/water mixed solution, under the stirring condition, add 4.5mL tetraethoxysilane (TEOS) and 9mL concentrated ammonia liquor, react 3h under the room temperature condition, Magnetic Isolation, distilled water washing, 60 ℃ of dryings make SiO 2Coat or the upper Fe of connection 3O 4Composite magnetic nano particle (Fe 3O 4/ SiO 2);
(2) the composite magnetic nano particle (Fe that step (1) is made 3O 4/ SiO 2) be scattered in the 100mL distilled water, under the stirring condition, add 3mL N-aminoethyl-γ aminopropyl trimethoxysilane (TPED), react 3h under 50 ℃ of conditions, Magnetic Isolation, distilled water washing, 60 ℃ of dryings make amido modified composite magnetic nano particle;
(3) the amido modified composite magnetic nano particle that step (2) is made is scattered in the 50mL distilled water, under the stirring condition, adds the 6mL glyoxal, react 2h under the room temperature condition, Magnetic Isolation, distilled water washing, 50 ℃ of dryings make aldehyde group modified composite magnetic nano particle;
(4) the aldehyde group modified composite magnetic nano particle that step (3) is made is scattered in the 60mL methyl alcohol, under the stirring condition, adds 0.5g rhodamine hydrazine compound, 120 ℃ of heating reflux reaction 6h, Magnetic Isolation, methanol wash, 50 ℃ of dryings make the magnetic bifunctional material (Fe of tool 3O 4/ SiO 2/ RH).
The present embodiment has investigated that step (3) reactant molar ratio is on the impact of properties of product in the synthetic bifunctional material process, and experimental result shows: the amount of substance of glyoxal doubles in the step (3), synthetic bifunctional material (Fe 3O 4/ SiO 2/ RH, γ-Fe 2O 3/ SiO 2/ RH, MnFe 2O 4/ SiO 2/ RH, ZnFe 2O 4/ SiO 2/ RH, CoFe 2O 4/ SiO 2/ RH) fast detecting and absorption are removed the Mercury in Water Body ionic nature and are kept stable, and adsorption rate is substantially constant.
Embodiment 10: synthetic bifunctional material (Fe 3O 4/ SiO 2/ RH)
(1) takes by weighing 0.2gFe 3O 4(particle diameter: 60～100nm) are scattered in (volume ratio 1: 1) in the 100mL ethanol/water mixed solution, under the stirring condition, add 4.5mL tetraethoxysilane (TEOS) and 9mL concentrated ammonia liquor, react 3h under the room temperature condition, Magnetic Isolation, distilled water washing, 80 ℃ of dryings make SiO 2Coat or the upper Fe of connection 3O 4Composite magnetic nano particle (Fe 3O 4/ SiO 2);
(2) the composite magnetic nano particle (Fe that step (1) is made 3O 4/ SiO 2) be scattered in the 100mL distilled water, under the stirring condition, add 3mL N-aminoethyl-γ aminopropyl trimethoxysilane (TPED), react 3h under 50 ℃ of conditions, Magnetic Isolation, distilled water washing, 80 ℃ of dryings make amido modified composite magnetic nano particle;
(3) the amido modified composite magnetic nano particle that step (2) is made is scattered in the 50mL distilled water, under the stirring condition, adds the 3mL glyoxal, react 2h under the room temperature condition, Magnetic Isolation, distilled water washing, 50 ℃ of dryings make aldehyde group modified composite magnetic nano particle;
(4) the aldehyde group modified composite magnetic nano particle that step (3) is made is scattered in the 60mL methyl alcohol, under the stirring condition, adds 0.25g rhodamine hydrazine compound, 120 ℃ of heating reflux reaction 6h, Magnetic Isolation, methanol wash, 50 ℃ of dryings make the magnetic bifunctional material (Fe of tool 3O 4/ SiO 2/ RH).
The present embodiment has been investigated the variation of step (4) reactant molar ratio in the synthetic bifunctional material process to the impact of properties of product, experimental result shows: rhodamine hydrazine compound amount of substance reduces half in the step (4), synthetic bifunctional material (Fe 3O 4/ SiO 2/ RH, γ-Fe 2O 3/ SiO 2/ RH, MnFe 2O 4/ SiO 2/ RH, ZnFe 2O 4/ SiO 2/ RH, CoFe 2O 4/ SiO 2/ RH) can fast detecting mercury ion in the water-outlet body, but Adsorption Mercury in Water Body ion ability descends, adsorption rate descends.
Embodiment 11: bifunctional material (Fe 3O 4/ SiO 2/ RH) to Hg 2+Selective
(1) compound concentration is 10 -4Each metal ion standard reserving solution (Ag of mol/L +, Ba 2+, Ca 2+, Cd 2+, Co 2+, Cu 2+, K +, Mg 2+, Mn 2+, Ni 2+, Pb 2+, Zn 2+, Fe 2+, Fe 3+, Cr 3+, Cr 6+), compound concentration is 10 -5The Hg of mol/L 2+Standard reserving solution;
(2) take by weighing the bifunctional material (Fe that 1.5mg embodiment 1 makes 3O 4/ SiO 2/ RH) be scattered in the 3mL distilled water, measure its fluorescence intensity level with XRF and (be designated as blank value I o, I o=51.3), add respectively the metal ion standard reserving solution of 30 μ L steps (1) preparation, after 2 minutes, measure its fluorescence intensity level (excitation wavelength 520nm, record emission peak 550nm place fluorescence intensity level) with XRF;
(3) by the data obtained (I Ag+=50.5, I Ba2+=51.1, I Ca2+=50.2, I Cd2+=51.3, I Co2+=49.2, I Cu2+=51.2, I K+=50.0, I Mg2+=48.4, I Mn2+=50.1, I Ni2+=49.2, I Pb2+=50.1, I Zn2+=47.9, I Fe2+=48.7, I Fe3+=48.9, I Cr3+=50.1, I Cr6+=49.5, I Hg2+=106.8) as can be known, when adding other metal ion solutions, each fluorescence intensity level and blank value I oRelatively, fluorescence intensity level remains unchanged or reduces, when adding Hg 2+During solution, fluorescence intensity level obviously strengthens, and bifunctional material is to Hg 2+Has high selectivity.
Embodiment 12: bifunctional material (γ-Fe 2O 3/ SiO 2/ RH) to Hg 2+Selective
(1) compound concentration is 10 -4Each metal ion standard reserving solution (Ag of mol/L +, Ba 2+, Ca 2+, Cd 2+, Co 2+, Cu 2+, K +, Mg 2+, Mn 2+, Ni 2+, Pb 2+, Zn 2+, Fe 2+, Fe 3+, Cr 3+, Cr 6+), compound concentration is 10 -5The Hg of mol/L 2+Standard reserving solution;
(2) take by weighing bifunctional material (γ-Fe that 1.5mg embodiment 2 makes 2O 3/ SiO 2/ RH) be scattered in the 3mL distilled water, measure its fluorescence intensity level with XRF and (be designated as blank value I o, I o=51.2), add respectively the metal ion standard reserving solution of 30 μ L steps (1) preparation, after 2 minutes, measure its fluorescence intensity level (excitation wavelength 520nm, record emission peak 550nm place fluorescence intensity level) with XRF;
(3) by the data obtained (I Ag+=50.3, I Ba2+=50.7, I Ca2+=50.3, I Cd2+=51.1, I Co2+=49.7, I Cu2+=51.2, I K+=49.6, I Mg2+=48.4, I Mn2+=50.3, I Ni2+=49.6, I Pb2+=50.1, I Zn2+=48.9, I Fe2+=48.7, I Fe3+=48.7, I Cr3+=50.3, I Cr6+=49.7, I Hg2+=106.8) as can be known, when adding other metal ion solutions, each fluorescence intensity level and blank value I oRelatively, fluorescence intensity level remains unchanged or reduces, when adding Hg 2+During solution, fluorescence intensity level obviously strengthens, and bifunctional material is to Hg 2+Has high selectivity.
Embodiment 13: bifunctional material (MnFe 2O 4/ SiO 2/ RH) to Hg 2+Selective
(1) compound concentration is 10 -4Each metal ion standard reserving solution (Ag of mol/L +, Ba 2+, Ca 2+, Cd 2+, Co 2+, Cu 2+, K +, Mg 2+, Mn 2+, Ni 2+, Pb 2+, Zn 2+, Fe 2+, Fe 3+, Cr 3+, Cr 6+), compound concentration is 10 -5The Hg of mol/L 2+Standard reserving solution;
(2) take by weighing the bifunctional material (MnFe that 1.5mg embodiment 3 makes 2O 4/ SiO 2/ RH) be scattered in the 3mL distilled water, measure its fluorescence intensity level with XRF and (be designated as blank value I o, I o=51.3), add respectively the metal ion standard reserving solution of 30 μ L steps (1) preparation, after 2 minutes, measure its fluorescence intensity level (excitation wavelength 520nm, record emission peak 550nm place fluorescence intensity level) with XRF;
(3) by the data obtained (I Ag+=49.9, I Ba2+=51.3, I Ca2+=50.7, I Cd2+=51.2, I Co2+=49.4, I Cu2+=51.1, I K+=50.7, I Mg2+=48.6, I Mn2+=50.6, I Ni2+=49.6, I Pb2+=51.1, I Zn2+=48.3, I Fe2+=48.9, I Fe3+=49.5, I Cr3+=50.3, I Cr6+=49.6, I Hg2+=106.7) as can be known, when adding other metal ion solutions, each fluorescence intensity level and blank value I oRelatively, fluorescence intensity level remains unchanged or reduces, when adding Hg 2+During solution, fluorescence intensity level obviously strengthens, and bifunctional material is to Hg 2+Has high selectivity.
Embodiment 14: bifunctional material (ZnFe 2O 4/ SiO 2/ RH) to Hg 2+Selective
(1) compound concentration is 10 -4Each metal ion standard reserving solution (Ag of mol/L +, Ba 2+, Ca 2+, Cd 2+, Co 2+, Cu 2+, K +, Mg 2+, Mn 2+, Ni 2+, Pb 2+, Zn 2+, Fe 2+, Fe 3+, Cr 3+, Cr 6+), compound concentration is 10 -5The Hg of mol/L 2+Standard reserving solution;
(2) take by weighing the bifunctional material (ZnFe that 1.5mg embodiment 4 makes 2O 4/ SiO 2/ RH) be scattered in the 3mL distilled water, measure its fluorescence intensity level with XRF and (be designated as blank value I o, I o=51.2), add respectively the metal ion standard reserving solution of 30 μ L steps (1) preparation, after 2 minutes, measure its fluorescence intensity level (excitation wavelength 520nm, record emission peak 550nm place fluorescence intensity level) with XRF;
(3) by the data obtained (I Ag+=49.7, I Ba2+=50.8, I Ca+=50.3, I Cd2+=51.1, I Co2+=49.3, I Cu2+=51.2, I K+=50.2, I Mg2+=49.1, I Mn2+=50.5, I Ni2+=49.5, I Pb2+=51.1, I Zn2+=48.9, I Fe2+=48.5, I Fe3+=49.9, I Cr3+=50.4, I Cr6+=49.9, I Hg2+=106.8) as can be known, when adding other metal ion solutions, each fluorescence intensity level and blank value I oRelatively, fluorescence intensity level remains unchanged or reduces, when adding Hg 2+During solution, fluorescence intensity level obviously strengthens, and bifunctional material is to Hg 2+Has high selectivity.
Embodiment 15: bifunctional material (CoFe 2O 4/ SiO 2/ RH) to Hg 2+Selective
(1) compound concentration is 10 -4Each metal ion standard reserving solution (Ag of mol/L +, Ba 2+, Ca 2+, Cd 2+, Co 2+, Cu 2+, K +, Mg 2+, Mn 2+, Ni 2+, Pb 2+, Zn 2+, Fe 2+, Fe 3+, Cr 3+, Cr 6+), compound concentration is 10 -5The Hg of mol/L 2+Standard reserving solution;
(2) take by weighing the bifunctional material (CoFe that 1.5mg embodiment 5 makes 2O 4/ SiO 2/ RH) be scattered in the 3mL distilled water, measure its fluorescence intensity level with XRF and (be designated as blank value I o, I o=51.3), add respectively the metal ion standard reserving solution of 30 μ L steps (1) preparation, after 2 minutes, measure its fluorescence intensity level (excitation wavelength 520nm, record emission peak 550nm place fluorescence intensity level) with XRF;
(3) by the data obtained (I Ag+=50.3, I Ba2+=51.1, I Ca2+=50.2, I Cd2+=51.1, I Co2+=50.1, I Cu2+=51.3, I K+=50.3, I Mg2+=48.9, I Mn2+=50.2, I Ni2+=50.2, I Pb2+=50.5, I Zn2+=49.8, I Fe2+=48.8, I Fe3+=48.3, I Cr3+=50.3, I Cr6+=50.1, I Hg2+=106.8) as can be known, when adding other metal ion solutions, each fluorescence intensity level and blank value I oRelatively, fluorescence intensity level remains unchanged or reduces, when adding Hg 2+During solution, fluorescence intensity level obviously strengthens, and bifunctional material is to Hg 2+Has high selectivity.
Embodiment 16: Hg in river, the lake water water sample 2+Detection
(1) preparation detects liquid: take by weighing 1.5mg bifunctional material (Fe 3O 4/ SiO 2/ RH) be scattered in the 3mL distilled water, namely obtain containing the detection liquid of bifunctional material, after 2 minutes, measure its fluorescence intensity level with XRF and (be designated as I o, I o=51.3);
(2) water sampling to be detected: with the water sample collecting bottle in the river, (20～50cm) locate to gather water sample, then regulate its pH to 6.0～8.0 with hydrochloric acid or NaOH, obtain water sample to be detected for the certain depth of three different locations, lake;
(3) measure step (2) water sample 30 μ L to be detected and add in the detection liquid of step (1) preparation, after 2 minutes, measure its fluorescence intensity level (I Lake water=57.2, I River=50.8) the fluorescence intensity level I that, measures with step (1) oRelatively, if fluorescence intensity level increases, then judge in the water sample to be detected and contain Hg 2+, and contained Hg in the solution 2+Concentration is more than or equal to 10 -8Mol/L; If fluorescence intensity level is constant or reduce, then judges and do not contain Hg in the water sample to be detected 2+Or Hg 2+Concentration is less than 10 -8Mol/L.
Embodiment 17: Hg in industrial and mineral, electrical equipment, the Electroplate Factory's water sample 2+Detection
(1) preparation detects liquid: take by weighing 1.5mg bifunctional material (Fe 3O 4/ SiO 2/ RH) be scattered in the 3mL distilled water, namely obtain containing the detection liquid of bifunctional material, after 2 minutes, measure its fluorescence intensity level with XRF and (be designated as I o, I o=51.3);
(2) water sampling to be detected: at the sample location of discharge of wastewater mouth at set intervals (such as 1h, 2h...) the collection water sample, then mixed in equal amounts becomes biased sample, regulates its pH to 6.0～8.0 with hydrochloric acid or NaOH afterwards, obtains water sample to be detected;
(3) get 30 μ L water sample to be detected and add in the detection liquid of step (1) preparation, after 2 minutes, measure its fluorescence intensity level (I Industrial and mineral=91.0, I Electrical equipment=116.2, I Electroplate Factory=50.7) the fluorescence intensity level I that, measures with step (1) oRelatively, if fluorescence intensity level increases, then judge in the water sample to be detected and contain Hg 2+, and contained Hg in the solution 2+Concentration is more than or equal to 10 -8Mol/L; If fluorescence intensity level is constant or reduce, then judges and do not contain Hg in the water sample to be detected 2+
Embodiment 18: the drawing standard curve
(1) draws respectively 10 -6The mercury standard reserving solution 0.00,1.00,3.00,5.00,7.00,9.00,11.00,13.00,15.00,17.00 of mol/L, 20.00mL to 100mL volumetric flask, adding distil water is diluted to scale, shakes up, and leaves standstill;
(2) take by weighing the bifunctional material (Fe that 1.5mg embodiment 1 makes 3O 4/ SiO 2/ RH) be scattered in the 3mL distilled water, add respectively the mercury ion titer of 30 μ L steps (1) preparation, after 2 minutes, measure its fluorescence intensity level (excitation wavelength 520nm, record emission peak 550nm place fluorescence intensity level) with XRF;
(3) take fluorescence intensity level as ordinate, ion concentration of mercury is that abscissa is drawn out calibration curve, referring to Fig. 3.
Embodiment 19: Hg in the water sample 2+The mensuration of concentration
(1) water sampling to be detected: with the water sample collecting bottle in the river, (20～50cm) locate to gather water sample, then regulate its pH to 6.0～8.0 with hydrochloric acid or NaOH, obtain water sample to be detected for the certain depth of three different locations, lake;
(2) take by weighing the bifunctional material (Fe that 1.5mg embodiment 1 makes 3O 4/ SiO 2/ RH) be scattered in the 3mL distilled water, add 30 μ L steps (1) water sample to be detected, after 2 minutes, measure its fluorescence intensity level (I with XRF Lake water=57.2, I River=50.8);
(3) with the measured fluorescence intensity level substitution of step (2) calibration curve equation, thereby calculate Hg in the water sample to be measured 2+Concentration (Hg in the lake water 2+Concentration is 1.1 * 10 -8Mol/L does not contain Hg in the river 2+Or Hg 2+Concentration is lower than 1 * 10 -8Mol/L).
Embodiment 20: Hg in the absorption water sample 2+
(1) water sampling upon adsorption: (20～50cm) locate to gather water sample, then regulate its pH to 6.0 with hydrochloric acid, obtain water sample upon adsorption with the certain depth of water sample collecting bottle in three different locations of Dong Qianhu (Ningbo of Zhejiang);
(2) measure Hg in the water sample upon adsorption by the atom fluorescent luminosity method 2+Concentration is 1.75 * 10 -7Mol/L;
(3) take by weighing the bifunctional material (Fe that 1.5mg embodiment 1 makes 3O 4/ SiO 2/ RH) be scattered in 3mL step (1) water sample upon adsorption, after 2 minutes, by remaining Hg in the atom fluorescent luminosity method mensuration solution 2+Concentration is 8.57 * 10 -9Mol/L, thus calculate bifunctional material (Fe 3O 4/ SiO 2/ RH) to Hg 2+Adsorption rate, adsorption rate is 95.1%.
Embodiment 21: Hg in the absorption water sample 2+
(1) water sampling upon adsorption: (20～50cm) locate to gather water sample, then regulate its pH to 7.0 with NaOH, obtain water sample upon adsorption with the certain depth of water sample collecting bottle in three different locations of Dong Qianhu (Ningbo of Zhejiang);
(2) measure Hg in the water sample upon adsorption by the atom fluorescent luminosity method 2+Concentration is 1.75 * 10 -7Mol/L;
(3) take by weighing the bifunctional material (Fe that 1.5mg embodiment 1 makes 3O 4/ SiO 2/ RH) be scattered in 3mL step (1) water sample upon adsorption, after 2 minutes, by remaining Hg in the atom fluorescent luminosity method mensuration solution 2+Concentration is 8.23 * 10 -9Mol/L, thus calculate bifunctional material (Fe 3O 4/ SiO 2/ RH) to Hg 2+Adsorption rate, adsorption rate is 95.3%.
Embodiment 22: Hg in the absorption water sample 2+
(1) water sampling upon adsorption: (20～50cm) locate to gather water sample, then regulate its pH to 8.0 with NaOH, obtain water sample upon adsorption with the certain depth of water sample collecting bottle in three different locations of Dong Qianhu (Ningbo of Zhejiang);
(2) measure Hg in the water sample upon adsorption by the atom fluorescent luminosity method 2+Concentration is 1.75 * 10 -7Mol/L;
(3) take by weighing the bifunctional material (Fe that 1.5mg embodiment 1 makes 3O 4/ SiO 2/ RH) be scattered in 3mL step (1) water sample upon adsorption, after 2 minutes, by remaining Hg in the atom fluorescent luminosity method mensuration solution 2+Concentration is 8.4 * 10 -9Mol/L, thus calculate bifunctional material (Fe 3O 4/ SiO 2/ RH) to Hg 2+Adsorption rate, adsorption rate is 95.2%.
Embodiment 23: bifunctional material (Fe 3O 4/ SiO 2/ recycling RH)
(1) takes by weighing 1.5mg bifunctional material (Fe 3O 4/ SiO 2/ RH) be scattered in the 3mL distilled water, add 30 μ L and contain Hg 2+Water sample to be detected stirred 10 minutes;
(2) Magnetic Isolation goes out in the step (1) to have adsorbed Hg 2+Bifunctional material, again be scattered in the 3mL distilled water;
(3) add 30 μ L 0.1mol/L TBAH solution, Magnetic Isolation after 10 minutes, distilled water washing 3 times, drying can obtain bifunctional material again, recycles its detection and absorption Hg 6 times 2+Performance is basicly stable.
Embodiment 24: bifunctional material (Fe 3O 4/ SiO 2/ recycling RH)
(1) takes by weighing 1.5mg bifunctional material (Fe 3O 4/ SiO 2/ RH) be scattered in the 3mL distilled water, add 30 μ L and contain Hg 2+Water sample to be detected stirred 10 minutes;
(2) Magnetic Isolation goes out in the step (1) to have adsorbed Hg 2+Bifunctional material, again be scattered in the 3mL distilled water;
(3) add 30 μ L 0.1mol/L tetramethyl ammonium hydroxide solutions, Magnetic Isolation after 10 minutes, distilled water washing 3 times, drying can obtain bifunctional material again, recycles its detection and absorption Hg 6 times 2+Performance is basicly stable.
Embodiment 25: bifunctional material (Fe 3O 4/ SiO 2/ recycling RH)
(1) takes by weighing 1.5mg bifunctional material (Fe 3O 4/ SiO 2/ RH) be scattered in the 3mL distilled water, add 30 μ L and contain Hg 2+Water sample to be detected stirred 10 minutes;
(2) Magnetic Isolation goes out in the step (1) to have adsorbed Hg 2+Bifunctional material, again be scattered in the 3mL distilled water;
(3) add 30 μ L0.1mol/L tetraethyl ammonium hydroxide solution, Magnetic Isolation after 10 minutes, distilled water washing 3 times, drying can obtain bifunctional material again, recycles its detection and absorption Hg 6 times 2+Performance is basicly stable.
Embodiment 26: bifunctional material (Fe 3O 4/ SiO 2/ recycling RH)
(1) takes by weighing 1.5mg bifunctional material (Fe 3O 4/ SiO 2/ RH) be scattered in the 3mL distilled water, add 30 μ L and contain Hg 2+Water sample to be detected stirred 10 minutes;
(2) Magnetic Isolation goes out in the step (1) to have adsorbed Hg 2+Bifunctional material, again be scattered in the 3mL distilled water;
(3) add 30 μ L 0.1mol/L benzyltrimethylammonium hydroxide solution, Magnetic Isolation after 10 minutes, distilled water washing 3 times, drying can obtain bifunctional material again, recycles its detection and absorption Hg 6 times 2+Performance is basicly stable.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that the above only is specific embodiments of the invention; be not limited to the present invention; all any modifications of making in principle scope of the present invention and improvement etc. all should be included within protection scope of the present invention.

Claims (10)

  1. One kind for detection of with the synthetic method of the bifunctional material of Adsorption of Mercury ion, it is characterized in that, comprise the steps:
    (1) magnetic nano-particle is scattered in the mixed solution of second alcohol and water, under the stirring condition, adds tetraethoxysilane and ammoniacal liquor and react, after reacting completely, through Magnetic Isolation, washing, drying, obtain the composite magnetic nano particle;
    (2) the composite magnetic nano particle that step (1) is made is scattered in the aqueous solution, under the stirring condition, add N-aminoethyl-γ aminopropyl trimethoxysilane and react, after reacting completely, through Magnetic Isolation, washing, drying, make amido modified composite magnetic nano particle;
    (3) the amido modified composite magnetic nano particle that step (2) is made is scattered in the aqueous solution, under the stirring condition, add the twain-aldehyde compound compound and react, after reacting completely, through Magnetic Isolation, washing, drying, make aldehyde group modified composite magnetic nano particle;
    (4) the aldehyde group modified composite magnetic nano particle that step (3) is made is scattered in the alcoholic solvent, under the stirring condition, add rhodamine hydrazine compound and react, after reacting completely, through Magnetic Isolation, washing, drying, obtain described bifunctional material.
  2. According to claim 1 for detection of with the synthetic method of the bifunctional material of Adsorption of Mercury ion, it is characterized in that, the magnetic nano-particle described in the step (1) is Fe 3O 4, γ-Fe 2O 3, MnFe 2O 4, ZnFe 2O 4And CoFe 2O 4At least a in the nano particle.
  3. According to claim 2 for detection of with the synthetic method of the bifunctional material of Adsorption of Mercury ion, it is characterized in that, described magnetic nano-particle is that particle diameter is less than 500nm Fe 3O 4Nano particle.
  4. According to claim 1 for detection of with the synthetic method of the bifunctional material of Adsorption of Mercury ion, it is characterized in that, the twain-aldehyde compound compound described in the step (3) is glyoxal.
  5. According to claim 1 for detection of with the synthetic method of the bifunctional material of Adsorption of Mercury ion, it is characterized in that, the described alcoholic solvent of step (4) is at least a in methyl alcohol and the ethanol.
  6. 6. bifunctional material that is obtained by each described synthetic method of claim 1～5.
  7. 7. the detection method of the mercury ion in the solution to be measured is characterized in that, comprising:
    (1) bifunctional material claimed in claim 6 is scattered in the water, measures fluorescence intensity I 1
    (2) add solution to be measured in the aqueous solution in the step (1), measure its fluorescence intensity I 2
    (3) compare I 2With I 1If size is I 2＞I 1, then have mercury ion in the solution to be measured.
  8. 8. the detection method of mercury ion according to claim 7 is characterized in that, in the step (2), adds before the solution to be measured, and the pH that regulates the described aqueous solution is 6.0～8.0.
  9. 9. the detection method of the ion concentration of mercury in the solution to be measured is characterized in that, comprising:
    (1) under the condition that bifunctional material claimed in claim 6 exists, measures the fluorescence intensity of the titer that contains the variable concentrations mercury ion, the drawing standard curve;
    (2) under the condition that bifunctional material claimed in claim 6 exists, measure the fluorescence intensity in the solution to be measured, utilize described calibration curve to calculate the concentration of mercury ion in the solution to be measured.
  10. 10. an adsorption method that contains mercury ion in the mercury solution is characterized in that, comprising: regulate the pH value to 6.0 contain mercury solution～8.0, adding bifunctional material claimed in claim 6 reacts, after reacting completely, carry out Magnetic Isolation, obtain the solution that mercury ion reduces.
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