CN102626611A - Method for preparing metal ion imprinting adsorbent with underwater selective recognition performance - Google Patents
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Abstract
The invention provides a method for preparing a metal ion imprinting adsorbent with an underwater selective recognition performance. The method comprises the steps of: preparation of an amino functional material: dispersing a nuclear body material into a methanol solution, slowly adding 3-propylaminoethoxy silane, uniformly stirring, and then, continuously adding a cross-linking agent and a stabilizer to form the amino functional material; and preparation of the metal ion imprinting adsorbent: dispersing the amino functional material in the methanol solution, and exposing to ultrasound to obtain a solution A; dissolving isonicotinic acid and metal template ions in deionized water to form a solution B; dripping the solution B into the solution A, and reacting to obtain a white sol-like product; and eluting the metal template ions: performing Soxhlet extraction by using an acetic acid-methanol solution, then eluting the metal template ions by using a hydrochloric acid, and drying to obtain the metal ion imprinting adsorbent. The metal ion imprinting adsorbent disclosed by the invention can be widely applied to advanced treatment of drinking water as well as enrichment recovery or rapid analysis detection of metal ions in different water bodies, such as industrial waste water, aquaculture water and seawater.
Description
Technical field
What the present invention relates to is a metal ion species trace preparation of adsorbent method, belongs to the environment functional material technical applications.
Background technology
Heavy metal wastewater thereby is that environmental pollution the most seriously and to the mankind endangers maximum industrial wastewater.Heavy metal ion is of a great variety, intractability is big, chemical property is stablized, be not easy to be degraded by microorganisms, and is through the biological chain enrichment, big to vegeto-animal toxic action.Therefore, to the detection of heavy metal ions in wastewater with remove significant.
The technology that detects heavy metal ion at present mainly contains spectroscopic methodology and electrochemical process, comprising: atomic absorption spectrography (AAS), atomic emission spectrometry, atomic fluorescence method, mass spectrography etc., voltammetry, polarography, potentiometry, conductimetry etc.Spectroscopic methodology is the preliminary treatment trouble when detecting heavy metal ion, and most nonmetalloids can not directly be measured, the range of linearity of standard working curve narrow (generally in an one magnitude scope), and for complex sample, interference ratio is more serious, complicated operation, instrument is expensive.Electrochemical process can detect heavy metal ion in the water simply, fast, yet electrochemical process uses mercury electrode to be prone to cause secondary pollution in testing process.
Absorption method is one of most important method for treating water, and absorption method is widely used in the heavy metal containing wastewater treatment.The adsorbent kind is a lot of like active carbon, clay, flyash, peat, bark, chitin, liver moss, marine alga, rice husk etc.Wherein active carbon has special loose structure, and huge surface area and high-adsorption-capacity are to remove the most widely used adsorbent of heavy metal ion in the water; Yet its non-selective, high-quality, expensively limit its use.Therefore, develop a kind of high efficiency selected absorption property that in water, has, can be used for heavy metal ion and detect, the sorbing material that also can be used for removal of heavy metal ions is very important.
The polymer-function material that it is template that the metal ion imprinted polymer is meant with the metal ion, utilize engram technology to prepare to the selective absorption of templated metal ion.The metal ion engram technology is a branch direction of molecular imprinting research, is the cross discipline that together grows up with the organic molecule engram technology.The metal ion imprinted polymer has selectivity height, good stability, preparation cost is low and advantages of wide application range, is applied in aspects such as chromatographic isolation, film separation, SPE, chiral Recognition, biomimetic sensor in recent years widely.Existing metal ion imprinted polymer adopts traditional organic trace synthesizing mean mostly; The function monomer that uses is traditional organic functions monomers such as methacrylic acid, vinyl capric acid; Although adopt the metal ion imprinted polymer of traditional organic trace method preparation to have certain selection adsorptivity, its adsorption capacity is low, in the aqueous solution to the selection adsorptivity difference of metal ion and be difficult to reuse.Therefore, be badly in need of to improve the application that selection identity and the adsorption capacity of metal ion imprinted polymer in the aqueous solution improves the metal ion imprinted polymer.At present, there is the people once to adopt traditional metal ion blotting technology, prepared the metal ion imprinted polymer.Be that disclosed technical scheme is in the patent document of CN101735417A like publication number: adopt crosslinking technology to introduce polyacrylonitrile at silicon oxide surface, through trace rare earth ion after the amidoxim conversion, the rare earth ion imprinted polymer that obtains.Its clearance to metal ion improves than the metal ion imprinted polymer that traditional organic synthesis prepares; Yet its building-up process is complicated, cost is high, adopt traditional functions monomer metallic print ion still exist in aqueous phase to templated metal ion identification difficulty, under the situation that interfering ion exists to problems such as the selection separation property of templated metal ion are not ideal enough.Therefore, the needs exploitation is a kind of has good selection recognition performance, high, synthetic low, the simple metal ion trace of the building-up process adsorbent preparation method of cost of adsorption capacity to heavy metal ion in the aqueous solution.
Summary of the invention
The object of the present invention is to provide a kind of preparation technology simple; Cost of material is cheap; Metal form ion to trace in the water has very high adsorption capacity and special selection recognition performance; Have good physical chemistry and mechanical stability simultaneously, have the recognition performance of selection metal ion trace preparation of adsorbent method in the simple water of renovation process.
The objective of the invention is to realize like this:
(1) preparation of amino functional formed material: take by weighing 0.1～1.6g nucleome material and evenly spread in 5～80mL methanol solution; Slowly adding 1～20mL 3-, the third amino ethoxy silane stirs; Continue adding the crosslinking agent of 1～20mL and the stabilizing agent of 1～20mL then, is the amino functional formed material with the surface modification of nucleome;
(2) metal ion trace preparation of adsorbent: the amino functional formed material of 0.1～3.0mol is dispersed in 5～100mL methanol solution, and ultrasonic 15～120min forms uniform solution A; With ratio is that 1: 1～10: 1 isonicotinic acid and metal form ion is dissolved in the deionized water, and magnetic agitation reaction 2～3h forms homogeneous solution B; Under the state that stirs, solution B slowly is added dropwise in the solution A, react 10～18h down at 20～35 ℃, obtain leucosol shape product; With ethanol and deionized water leucosol shape product is washed repeatedly, dry down at 60～80 ℃ then;
(3) wash-out of metal form ion: using volume ratio is that acetate-methanol solution of 1: 1～1: 30 extracts 10～16h with the product Suo Shi of step (2); Use hydrochloric acid solution wash-out metal form ion 1～5h under magnetic agitation of 100mL 0.1～1.0mol/L then, make metal ion trace adsorbent after the drying.
The present invention can also comprise:
1, described nucleome material is the compound of metal oxide, two kinds of metal oxides or the compound of metal oxide and carbonaceous material, and said metal oxide is SiO
2, Fe
2O
3, TiO
2, V
2O
5, Co
3O
4, NiO, ZnO, MnO
2, Fe
3O
4, CuO, Zr
2O
3, Al
2O
3, CaO, MgO or BaO, said carbonaceous material is active carbon, CNT or graphene oxide.
2, described nucleome material is that general formula is MFe
2O
4The compound of ferrospinel, two kinds of said spinel ferrite nanocrystal composition or said ferrospinel and carbonaceous material; Wherein M is any one among metallic element Mn, Ni, Zn, Ti, Cu, Cr, Cd, Pb, Sn, Ba, Bi or the Al, and carbonaceous material is active carbon, CNT or graphene oxide.
3, described nucleome material is that general formula is MMn
2O
4Ferrospinel or two kinds of said spinel ferrite nanocrystal composition, M is any one among metallic element Fe, Ni, Zn, Ti, Cu, Cr, Cd, Pb, Sn, Ba, Bi, the Al.
4, described nucleome material is that general formula is M
1-xN
xFe
2O
4The compound of the ferrospinel of 0＜x＜1, two kinds of said spinel ferrite nanocrystal composition or said ferrospinel and carbonaceous material wherein; M and N are the arbitrary elements among metallic element Ni, Mn, Zn, Cu, Cr, Pb, Ba or the Ca, and M is different elements with N; Carbonaceous material is active carbon, CNT or graphene oxide.
5, the ion of described metal form can be the ion of following metallic element formation: Li, Rb, Cs, Fr, Be, Ca, Mg, Sr, Ba, Ra, Sc, Ti, Zr, Nb, Ta, Mo, Cr, W, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Sn, Pb, Cu, Ag, Au, Zn, Cd, Hg, Bi, Al, Ga, In, Ge, Sb, As, Bi, Se, Te, Po, La, Ce, Eu, U or V.
6, described crosslinking agent is ethyl orthosilicate, lauryl sodium sulfate or softex kw.
7, described stabilizing agent is acetate or oleic acid solutions.
The preferred molar ratio example of amination functional material, isonicotinic acid and metal form ion is 1: 1: 1～8: 10: 1.The preparation feedback temperature of amino functional formed material, isonicotinic acid and templated metal ion is 25～30 ℃, and the reaction time is 12～16h.
With acetate-methanol solution of 1: 7～1: 9 of volume ratio above-mentioned product Suo Shi is extracted 12～15h earlier during wash-out metal form ion, use hydrochloric acid solution wash-out templated metal ion 2～3h under magnetic agitation of 0.2～0.4mol/L of 100mL then.
Adsorbent of the present invention is used for the method that underwater gold belongs to ion selectivity enrichment and identification: get 0.005～0.05g metal ion trace adsorbent and throw and join the water sample that 10～100mL contains templated metal ion 100～1000 μ mol/L; 20～40 ℃ shake 1～5h down; Supernatant is collected in centrifugal back, detects the wherein content of templated metal ion.
Adsorbent for heavy metal adsorption capacity in the prior art is low, in the aqueous solution, select absorption property poor, can not be used for problem such as fast detecting, the invention provides a kind of metal ion trace preparation of adsorbent method and application thereof that in water, has the high efficiency selected recognition performance.Adopt the surface imprinted method that combines with sol-gel technique to improve trace adsorbent selection recognition performance to heavy metal ion in the aqueous solution effectively; Realized in the aqueous solution selective absorption to heavy metal ion; Effectively avoided the interference of other materials in the aqueous solution, possibility is provided for from water, reclaiming and detect single heavy metal.The metal ion trace adsorbent of the present invention preparation has overcome that inorganic adsorbent hydrophobicity such as traditional active carbon is strong, poor with the heavy metal ion compatibility, adsorption capacity and select shortcoming such as recognition performance difference; Preparation technology is simple; Cost of material is cheap; Metal form ion to trace in the water has very high adsorption capacity and special selection recognition performance, has good physical chemistry and mechanical stability simultaneously, and renovation process is simple.In water, can substitute traditional adsorbent or extraction material, the enriching and recovering or the rapid analysis that can be widely used in metal ion in the different water bodys such as drinking water deep processing, industrial wastewater, aquaculture system and seawater detect.
Content of the present invention is to disclose a kind of metal ion trace adsorbent preparation method and application thereof that in water, has the high efficiency selected recognition performance; It is presoma that this preparation method adopts various oxide or two kinds of complex oxides or oxide and carbonaceous material compound; The 3-third amino ethoxy silane is the functionalization material, has prepared the amino functional formed material; Adopting the amino functional formed material is that trace supporter, isonicotinic acid are that function monomer, metal ion are imprinted templates, the method that adopts the sol-gel polymerization; Through steps such as trace polymerisation, wash-out templates, prepared in water the trace adsorbent that metal ion is had the high selectivity absorption property.
The specific embodiment
For example the present invention is made more detailed description below:
Embodiment 1
Take by weighing the 1.2g silica dioxide granule and be dispersed in the 20mL methyl alcohol,, make the amino functional silica dioxide granule behind the mechanical agitation 12h to the ethyl orthosilicate of the 3-that wherein the adds 20mL successively third amino ethoxy silane, 3mL, the 0.1mol/L acetate of 10mL.1.0g amino functional silica dioxide granule is dispersed in the 20mL methanol solution; Mixed solution to the sodium molybdate of isonicotinic acid that wherein adds 3mmol and 0.8mmol; Behind the mechanical agitation 18h product that obtains is washed 3 times with distilled water, the centrifugation back is dry.Methyl alcohol-acetic acid solution of getting volume ratio and being 1: 9 is with dried product wash-out 1h, and the hydrochloric acid solution with 100mL1mol/L continues wash-out imprinted templates 3h under the effect of magnetic agitation then.Promptly get molybdenum ion trace adsorbent after the drying.
Take by weighing the 0.1mol sodium molybdate and be dissolved in the sodium molybdate storing solution that is mixed with 1mol/L in the 100mL water.With the sodium molybdate storing solution dilution of 1mol/L is that 100,200,300,400,500,800,1000 μ mol/L sodium molybdates use solution.0.01g molybdenum ion trace adsorbent is dropped into 20mL concentration be respectively in 100,200,300,400,500,800, the 1000 μ mol/L sodium molybdates use liquid, centrifugal behind the vibration 3h under the room temperature.Detect molybdenum ion content in the centrifuged supernatant, calculate the adsorption capacity of molybdenum ion clearance and molybdenum ion trace adsorbent, draw adsorption isotherm calculating and learns, molybdenum ion trace adsorbent in the aqueous solution to the adsorption capacity of molybdenum ion up to 1096 μ mol/g.
Take by weighing 0.1mol sodium molybdate, copper chloride, plumbi nitras and separate sodium molybdate storing solution, copper chloride storing solution, the plumbi nitras storing solution that in 100mL water, is mixed with 1mol/L respectively.With sodium molybdate storing solution, copper chloride storing solution, the dilution of plumbi nitras storing solution is sodium molybdate-copper chloride-plumbi nitras mixed solution of 100,200,300,400,500,800,1000 μ mol/L; 0.01g molybdenum ion trace adsorbent is dropped in the above-mentioned solution of 20mL, centrifugal behind the vibration 3h under the room temperature.Detect the content of molybdenum ion, copper ion and lead ion in the centrifuged supernatant, the clearance of calculating molybdenum ion, copper ion and lead ion and molybdenum ion trace adsorbent are to the adsorption capacity of three metal ion species.Under the same concentrations; Molybdenum ion trace adsorbent is all higher more than 50% than its clearance to copper ion, lead ion to the clearance of molybdenum ion; Be in the mixed solution of 100～500 μ mol/L at other concentration of metal ions wherein, molybdenum ion trace adsorbent is higher more than 80% than its clearance to copper ion, lead ion to the clearance of molybdenum ion.Molybdenum ion trace adsorbent is respectively 1027 μ mol/L, 97.3 μ mol/L and 54.9 μ mol/L to the adsorption capacity of molybdenum ion, copper ion and lead ion.Calculation of distribution coefficient (K
d), select adsorption coefficient (K), adsorption coefficient (K relatively
r) find that contain at solution under the situation of interfering ion, molybdenum ion trace adsorbent is to the K of molybdenum ion
d=1.055, select adsorption coefficient K=21.1, relatively adsorption coefficient K
r=0.87.Can know that molybdenum ion trace adsorbent has very high selection recognition performance to molybdenum ion.
Embodiment 2
0.8g ferriferrous oxide particles, 3mL oleic acid, 1.5g lauryl sodium sulfate are dispersed in the mixed liquor of 100mL ethanol and water, in solution, add APTES 5mL, in 60 ℃ of constant temperature ageing 2h.Take out solution and place under the permanent magnet, with absolute ethanol washing three times, distilled water washs three times, the amino functional magnetic particles of ferroferric oxide is put into thermostatic drying chamber, 80 ℃ of dry 10h.The amino functional magnetic particles of ferroferric oxide is dispersed in the 20mL methanol solution; Sodium molybdate mixed solution to isonicotinic acid that wherein adds 0.2mmol and 0.3mmol; Behind the mechanical agitation 18h trace adsorbent that obtains is washed 3 times with distilled water, the centrifugation back is dry.Methyl alcohol-acetic acid solution of getting volume ratio and being 1: 9 is with dried trace adsorbent wash-out 14h, and the hydrochloric acid solution with 100mL 0.5mol/L continues wash-out imprinted templates 3h under the effect of magnetic agitation then.Promptly get molybdenum ion trace magnetic adsorbent after the drying.
Take by weighing the 0.1mol sodium molybdate and be dissolved in the sodium molybdate storing solution that is mixed with 1mol/L in the 100mL water.With the sodium molybdate storing solution dilution of 1mol/L is that 100,200,300,400,500,800,1000 μ mol/L sodium molybdates use solution.0.01g molybdenum ion trace adsorbent is dropped into 20mL concentration be respectively in 100,200,300,400,500,800, the 1000 μ mol/L sodium molybdates use liquid, centrifugal behind the vibration 3h under the room temperature.Detect molybdenum ion content in the centrifuged supernatant; Calculate the adsorption capacity of molybdenum ion clearance and molybdenum ion trace magnetic adsorbent; Draw adsorption isotherm and calculate and learns, molybdenum ion trace magnetic adsorbent in the aqueous solution to the adsorption capacity of molybdenum ion up to 1105 μ mol/g.
Under the same concentrations; Molybdenum ion trace magnetic adsorbent is all higher more than 60% than its clearance to copper ion, lead ion to the clearance of molybdenum ion; At other concentration of metal ions is in the mixed solution of 100～500 μ mol/L, and molybdenum ion trace magnetic adsorbent is higher more than 75% than its clearance to copper ion, lead ion to the clearance of molybdenum ion.Through calculation of distribution coefficient (K
d), select adsorption coefficient (K), adsorption coefficient (K relatively
r) find that contain at solution under the situation of interfering ion, molybdenum ion trace magnetic adsorbent is to the K of molybdenum ion
d=1.121, select adsorption coefficient K=22.3, relatively adsorption coefficient K
r=0.91.Can know that molybdenum ion trace magnetic adsorbent has very high selection recognition performance to molybdenum ion in the water.
Embodiment 3
Get the 0.6g silica dioxide granule and be dispersed in the 20mL methyl alcohol, to the acetate of the 0.1mol/L of the ethyl orthosilicate of the 3-that wherein the adds 4mL successively third amino ethoxy silane, 6mL, 1.5mL, mechanical agitation 12h makes the amino functional silica dioxide granule.The amino functional silica dioxide granule is dispersed in the 20mL methanol solution; Zirconyl chloride mixed solution to isonicotinic acid that wherein adds 2mmol and 0.3mmol; Behind the mechanical agitation 18h trace adsorbent that obtains is washed 3 times with distilled water, the centrifugation back is dry.Methyl alcohol-acetic acid solution of getting volume ratio and being 1: 8 is with dried trace adsorbent wash-out 14h, and the hydrochloric acid solution with 100mL 0.1mol/L continues wash-out imprinted templates 3h under the effect of magnetic agitation then.Promptly get zirconium ion trace adsorbent after the drying.
Take by weighing the 0.1mol zirconium nitrate and be dissolved in the zirconium nitrate storing solution that is mixed with 1mol/L in the 100mL water.With the zirconium nitrate storing solution dilution of 1mol/L is that 100,200,300,400,500,800,1000 μ mol/L zirconium nitrates use solution.0.01g zirconium ion trace adsorbent is dropped into 20mL concentration be respectively in 100,200,300,400,500,800, the 1000 μ mol/L zirconium nitrates use liquid, centrifugal behind the vibration 3h under the room temperature.Detect zirconium ion content in the centrifuged supernatant, calculate the adsorption capacity of zirconium ion clearance and zirconium ion trace adsorbent, draw adsorption isotherm calculating and learns, zirconium ion trace adsorbent in the aqueous solution to the adsorption capacity of zirconium ion up to 1086 μ mol/g.
Under the same concentrations; Zirconium ion trace adsorbent is all higher more than 55% than its clearance to copper ion, lead ion to the clearance of zirconium ion; At other concentration of metal ions is in the mixed solution of 100～500 μ mol/L, and zirconium ion trace adsorbent is higher more than 75% than its clearance to copper ion, lead ion to the clearance of zirconium ion.Through calculation of distribution coefficient (K
d), select adsorption coefficient (K), adsorption coefficient (K relatively
r) find that contain at solution under the situation of interfering ion, zirconium ion trace adsorbent is to the K of zirconium ion
d=1.065, select adsorption coefficient K=21.5, relatively adsorption coefficient K
r=0.79.Can know that zirconium ion trace adsorbent has very high selection recognition performance to zirconium ion in the water.
Embodiment 4
0.2g ferriferrous oxide particles, 0.5mL oleic acid, 0.2g lauryl sodium sulfate are dispersed in the 100mL ethanol and the aqueous solution.In solution, add APTES 1mL, in 60 ℃ of constant temperature ageing 5h.Take out solution and place under the permanent magnet, with absolute ethanol washing three times, distilled water washs three times, will modify the amino functional magnetic particles of ferroferric oxide and put into thermostatic drying chamber, 80 ℃ of dry 10h.The amino functional magnetic particles of ferroferric oxide is dispersed in the 20mL methanol solution; Mixed potassium dichromate to isonicotinic acid that wherein adds 0.6mmol and 0.1mmol; Behind the mechanical agitation 18h trace adsorbent that obtains is washed 3 times with distilled water, the centrifugation back is dry.Methyl alcohol-acetic acid solution of getting volume ratio and being 1: 9 is with dried trace adsorbent wash-out 14h, and the hydrochloric acid solution with 100mL 0.3mol/L continues wash-out imprinted templates 3h under the effect of magnetic agitation then.Promptly get chromium ion trace magnetic adsorbent after the drying.
Take by weighing the 0.1mol potassium bichromate and be dissolved in the potassium bichromate storing solution that is mixed with 1mol/L in the 100mL water.With the potassium bichromate storing solution dilution of 1mol/L is that 100,200,300,400,500,800,1000 μ mol/L potassium bichromates use solution.0.01g chromium ion trace adsorbent is dropped into 20mL concentration be respectively in 100,200,300,400,500,800, the 1000 μ mol/L potassium bichromates use liquid, centrifugal behind the vibration 3h under the room temperature.Detect content of chromium ion in the centrifuged supernatant; Calculate the adsorption capacity of chromium ion clearance and chromium ion trace magnetic adsorbent; Draw adsorption isotherm and calculate and learns, chromium ion trace magnetic adsorbent in the aqueous solution to the adsorption capacity of chromium ion up to 1189 μ mol/g.
Under the same concentrations; Chromium ion trace magnetic adsorbent is all higher more than 60% than its clearance to copper ion, lead ion to the clearance of chromium ion; At other concentration of metal ions is in the mixed solution of 100～500 μ mol/L, and chromium ion trace magnetic adsorbent is higher more than 85% than its clearance to copper ion, lead ion to the clearance of chromium ion.Through calculation of distribution coefficient (K
d), select adsorption coefficient (K), adsorption coefficient (K relatively
r) find that contain at solution under the situation of interfering ion, molybdenum ion trace magnetic adsorbent is to the K of molybdenum ion
d=1.098, select adsorption coefficient K=21.3, relatively adsorption coefficient K
r=0.95.Can know that chromium ion trace magnetic adsorbent has very high selection recognition performance to chromium ion in the water.
Embodiment 5
Get the MnFe of 0.5g
2O
4Particle is dispersed in the 40mL methyl alcohol, and to the acetate of the 0.1mol/L of the ethyl orthosilicate of the 3-that wherein the adds 5mL successively third amino ethoxy silane, 1mL, 5.0mL, mechanical agitation 12h makes amino functional MnFe
2O
4Particle.With amino functional MnFe
2O
4Uniform particles is dispersed in the 20mL methanol solution, to the copper chloride mixed solution of isonicotinic acid that wherein adds 3mmol and 0.2mmol, behind the mechanical agitation 18h trace adsorbent that obtains is washed 3 times with distilled water, and the centrifugation back is dry.Methyl alcohol-acetic acid solution of getting volume ratio and being 1: 8 is with dried trace adsorbent wash-out 14h, and the hydrochloric acid solution with 100mL 0.1mol/L continues wash-out imprinted templates 3h under the effect of magnetic agitation then.Promptly get copper ion trace adsorbent after the drying.
Take by weighing the 0.1mol copper nitrate and be dissolved in the copper nitrate storing solution that is mixed with 1mol/L in the 100mL water.With the copper nitrate storing solution dilution of 1mol/L is that 100,200,300,400,500,800,1000 μ mol/L copper nitrates use solution.With 0.01g copper ion trace adsorbent (MnFe
2O
4Particle is nuclear) drop into 20mL concentration and be respectively 100,200,300,400,500,800,1000 μ mol/L copper nitrates and use in the liquid, centrifugal behind the vibration 3h under the room temperature.Detect content of copper ion in the centrifuged supernatant, calculate the adsorption capacity of copper ion clearance and copper ion trace adsorbent, draw adsorption isotherm calculating and learns, copper ion trace adsorbent in the aqueous solution to the adsorption capacity of copper ion up to 1086 μ mol/g.
Under the same concentrations; Copper ion trace adsorbent is all higher more than 55% than its clearance to zinc ion, lead ion to the clearance of copper ion; At other concentration of metal ions is in the mixed solution of 100～500 μ mol/L, and copper ion trace adsorbent is higher more than 75% than its clearance to zinc ion, lead ion to the clearance of copper ion.Through calculation of distribution coefficient (K
d), select adsorption coefficient (K), adsorption coefficient (K relatively
r) find that contain at solution under the situation of interfering ion, copper ion trace adsorbent is to the K of copper ion
d=1.121, select adsorption coefficient K=20.5, relatively adsorption coefficient K
r=0.74.Can know that copper ion trace adsorbent has very high selection recognition performance to copper ion in the water.
Claims (10)
1. have the recognition performance of selection metal ion trace preparation of adsorbent method in a water, it is characterized in that comprising the steps:
(1) preparation of amino functional formed material: take by weighing 0.1～1.6g nucleome material and evenly spread in 5～80mL methanol solution; Slowly adding 1～20mL 3-, the third amino ethoxy silane stirs; Continue adding the crosslinking agent of 1～20mL and the stabilizing agent of 1～20mL then, is the amino functional formed material with the surface modification of nucleome;
(2) metal ion trace preparation of adsorbent: the amino functional formed material of 0.1～3.0mol is dispersed in 5～100mL methanol solution, and ultrasonic 15～120min forms uniform solution A; With ratio is that 1: 1～10: 1 isonicotinic acid and metal form ion is dissolved in the deionized water, and magnetic agitation reaction 2～3h forms homogeneous solution B; Under the state that stirs, solution B slowly is added dropwise in the solution A, react 10～18h down at 20～35 ℃, obtain leucosol shape product; With ethanol and deionized water leucosol shape product is washed repeatedly, dry down at 60～80 ℃ then;
(3) wash-out of metal form ion: using volume ratio is that acetate-methanol solution of 1: 1～1: 30 extracts 10～16h with the product Suo Shi of step (2); Use hydrochloric acid solution wash-out metal form ion 1～5h under magnetic agitation of 100mL 0.1～1.0mol/L then, make metal ion trace adsorbent after the drying.
2. has the recognition performance of selection metal ion trace preparation of adsorbent method in the water according to claim 1; It is characterized in that: described nucleome material is the compound of metal oxide, two kinds of metal oxides or the compound of metal oxide and carbonaceous material, and said metal oxide is SiO
2, Fe
2O
3, TiO
2, V
2O
5, Co
3O
4, NiO, ZnO, MnO
2, Fe
3O
4, CuO, Zr
2O
3, Al
2O
3, CaO, MgO or BaO, said carbonaceous material is active carbon, CNT or graphene oxide.
3. have the recognition performance of selection metal ion trace preparation of adsorbent method in the water according to claim 1, it is characterized in that: described nucleome material is that general formula is MFe
2O
4The compound of ferrospinel, two kinds of said spinel ferrite nanocrystal composition or said ferrospinel and carbonaceous material; Wherein M is any one among metallic element Mn, Ni, Zn, Ti, Cu, Cr, Cd, Pb, Sn, Ba, Bi or the Al, and carbonaceous material is active carbon, CNT or graphene oxide.
4. have the recognition performance of selection metal ion trace preparation of adsorbent method in the water according to claim 1, it is characterized in that: described nucleome material is that general formula is MMn
2O
4Ferrospinel or two kinds of said spinel ferrite nanocrystal composition, M is any one among metallic element Fe, Ni, Zn, Ti, Cu, Cr, Cd, Pb, Sn, Ba, Bi, the Al.
5. have the recognition performance of selection metal ion trace preparation of adsorbent method in the water according to claim 1, it is characterized in that: described nucleome material is that general formula is M
1-xN
xFe
2O
4The compound of the ferrospinel of 0＜x＜1, two kinds of said spinel ferrite nanocrystal composition or said ferrospinel and carbonaceous material wherein; M and N are the arbitrary elements among metallic element Ni, Mn, Zn, Cu, Cr, Pb, Ba or the Ca, and M is different elements with N; Carbonaceous material is active carbon, CNT or graphene oxide.
6. according to having the recognition performance of selection metal ion trace preparation of adsorbent method in any one described water of claim 1-5, it is characterized in that: the ion of described metal form can be the ion of following metallic element formation: Li, Rb, Cs, Fr, Be, Ca, Mg, Sr, Ba, Ra, Sc, Ti, Zr, Nb, Ia, Mo, Cr, W, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Sn, Pb, Cu, Ag, Au, Zn, Cd, Hg, Bi, Al, Ga, In, Ge, Sb, As, Bi, Se, Te, Po, La, Ce, Eu, U or V.
7. according to having the recognition performance of selection metal ion trace preparation of adsorbent method in any one described water of claim 1-5, it is characterized in that: described crosslinking agent is ethyl orthosilicate, lauryl sodium sulfate or softex kw.
8. have the recognition performance of selection metal ion trace preparation of adsorbent method in the water according to claim 6, it is characterized in that: the ion of described metal form can be the ion of following metallic element formation: Li, Rb, Cs, Fr, Be, Ca, Mg, Sr, Ba, Ra, Sc, Ti, Zr, Nb, Ta, Mo, Cr, W, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Sn, Pb, Cu, Ag, Au, Zn, Cd, Hg, Bi, Al, Ga, In, Ge, Sb, As, Bi, Se, Te, Po, La, Ce, Eu, U or V.
9. according to having the recognition performance of selection metal ion trace preparation of adsorbent method in any one described water of claim 1-5, it is characterized in that: described stabilizing agent is acetate or oleic acid solutions.
10. have the recognition performance of selection metal ion trace preparation of adsorbent method in the water according to claim 6, it is characterized in that: described stabilizing agent is acetate or oleic acid solutions.
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