CN108452780B - It is a kind of selectively to fix selenous adsorbed film and preparation method thereof - Google Patents
It is a kind of selectively to fix selenous adsorbed film and preparation method thereof Download PDFInfo
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- CN108452780B CN108452780B CN201810401744.2A CN201810401744A CN108452780B CN 108452780 B CN108452780 B CN 108452780B CN 201810401744 A CN201810401744 A CN 201810401744A CN 108452780 B CN108452780 B CN 108452780B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/106—Selenium compounds
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Abstract
The invention discloses fixed selenous adsorbed films of a kind of selectivity and preparation method thereof, belong to diffusion thin film technique field.The adsorbed film is the polyacrylamide gel film that the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino are evenly distributed with containing surface.The preparation method comprises the following steps: preparing the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino in acid condition；Crosslinking agent, pure water and acrylamide solution are mixed, polyacrylamide glue solution is obtained；After the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino are fully ground and glue solution is uniformly mixed so as to obtain glue solution, ultrasound；Ammonium persulfate solution and tetramethyl diethylamine solution are added into obtained mixed solution, mixes, mixed solution is slowly injected into the two glass sheets holes for accompany U-shaped Teflon material web and is formed a film, impregnated in pure water, obtain the adsorbed film.Adsorbed film preparation process of the present invention is simple, and distributing homogeneity is good, has good selectivity to tetravalence selenium.
Description
Technical field
The invention belongs to diffusion thin film technique fields, selenous more specifically to a kind of selectivity fixation
Adsorbed film and preparation method thereof.
Background technique
Necessary component of the selenium as activity of glutathione peroxidase site is micro- necessary to plant and animal
One of nutrient is measured, the mankind can be helped effectively to prevent cardiovascular disease, delaying cell aging.Studies have shown that the shortage of selenium
Difference between dosage and poisoning dose is very small.Selenium deficiency (40 μ g/day of <) will lead to Keshan disease and Kaschin-Beck disease, and excessive
Selenium intake (400 μ g/day of >) can equally cause the human bodies health disease such as alopecia, piptonychia.Selenium in Environment is mainly with inorganic tetravalence
Selenium and sexavalence Se form exist, and there were significant differences for migration, the toxicity of different valence state selenium.
Currently, mainly taking the initiative sample mode to the morphological analysis of selenium in water environment, i.e., live water sampling simultaneously takes back reality
Test room measurement.But in sampling, transport, preservation Forms Transformation easily occurs for the selenium between different valence state, causes error to result.By
British scientist Williams Davison and Zhang Hao is in the diffusion thin film technique (Diffusive of invention in 1994
Gradients in thin films, DGT), it is a kind of element analysis technology in situ, nondestructive, can more reflects biology
The heavy metal concentration that body is absorbed.With the invention of the materials such as iron-based, titanium-based, pick base, DGT technology measurement water body, soil and
It is widely applied in terms of nutritive salt, trace heavy metals, organic matter in deposit.
In recent years, DGT technology expands a series of researchs for the morphological analysis of heavy metal.Through retrieving, Chinese patent Shen
Please numbers 201510483125.9, publication number CN 105080519B discloses a kind of adsorbed film of fixed hexavalent chromium of selectivity
And preparation method thereof.The patent is prepared into adsorbed film using NMDG aminoglucose functional resin and bisacrylamide solution, realizes
The selective determination of Cr VI.Chinese Patent Application No. 201510780858.9, publication number 105289541B disclose one kind
The adsorbed film and preparation method thereof of fixed fluorine ion, using the adsorbed film in-site detecting multiple water environments of alumina powder preparation
In fluorine ion.But the material particle size that both the above method uses is larger, is unfavorable for material uniformly dividing on adsorbed film
Cloth.The bisacrylamide solution that the former uses does not contain crosslinking agent, and the absorption film toughness prepared is poor, and during glue
It needs to be then transferred in baking oven after N-METHYL-ALPHA-L-GLUCOSAMINE functional resin powder settles completely, process is relatively time-consuming, cumbersome.
Chinese Patent Application No. 200910070692.6, publication number CN 101664755A disclose a kind of copolycondensation method
The method for preparing heavy metal deactivator, comprising the following steps: mix water with methanol；Template cetyl trimethyl bromine is added
Change ammonium and sodium hydroxide；The mixture of TMOS and mercaptopropyl trimethoxysilane are added in above-mentioned alkaline solution and will be above-mentioned
Mixed solution continuously stirs 12h；It is heated in 96 DEG C of waters bath with thermostatic control；Then it by filtering, collects filter cake and dries to obtain white powder
End；It transfers them in Soxhlet extractor and is extracted with ethyl alcohol, collect sample and dry, can be prepared by after 80 DEG C of vacuum drying final
Product.In the prior art, use the mercapto-modified MCM-41 class mesoporous silicon material aperture of alkaline condition synthesis for 1.78nm,
Relatively small, certain to heavy metal ion being diffused in duct limitation.
Chinese Patent Application No. 201611265639.8, publication No. CN 106732461A disclose a kind of heavy metal adsorption
The synthesis technology of agent, comprising the following steps: with three embedding copolymer ps 123 be template, using ethyl orthosilicate as silicon source, in room temperature
Under acid medium in stir, then brilliant China, calcining, synthesizing ordered mesoporous material SBA-15；Then first on the SBA-15
Functional group compound is added, is once modified, amino and/or mercapto-modified SBA-15 are generated；Again in the primary modification
The compound of amino and/or sulfydryl reaction is added in SBA-15 afterwards, carries out secondary modification, obtains the SBA-15 of hydroxyl modification.
In the prior art, the functional group method of modifying of amino and/or mercapto-modified SBA-15 are rear grafting, that is, are being obtained orderly
After mesoporous material SBA-15 finished product, while being grafted sulfydryl and/or amino.But due to the property of amino and sulfydryl difference,
Using special reaction condition on SBA-15 primary sex modification amino and mercapto functional group, graft effect and amino and sulfydryl
On the surface SBA-15, the degree that is evenly distributed has certain limitation；Simultaneously as only in specification part in the prior art
It refers to and once being modified jointly containing amino and sulfydryl, and do not specifically give in embodiment and prepare amino and sulfydryl is jointly primary
The method for modifying SBA-15, also to amino and sulfydryl, once modification SBA-15 absorption heavy metal ion is not tested jointly.
At present about the morphological analysis research of selenium also in backward state, 2010, Bennett et al. (Bennett, et
Al., adsorbed film Anal.Chem.2010,82,7401-7407) is prepared using titanium dioxide as adsorbent material, is realized in environment
Selenous selectivity is fixed.But this method needs to be eluted with sodium hydroxide, influences instrument analysis measurement.And selectivity
Extension at any time is affected, unsuitable outer long-time application out of office.Therefore, find to tetravalence selenium have it is highly selective, be convenient for
The adsorbed film of elution, it has also become the research hotspot of DGT technical field.
Summary of the invention
1, it to solve the problems, such as
It is an object of the invention to overcome existing titanium dioxide adsorbed film poor selectivity, the cumbersome problem of elution process,
A kind of selenous adsorbed film of selectivity fixation and preparation method thereof applied to diffusion thin film technique is provided.The present invention adopts
Use the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino as adsorbent material, by being mixed and made into gel with polyacrylamide solution
Film applies to DGT technology.
2, technical solution
To solve the above problems, the present invention adopts the following technical scheme that.
A kind of preparation method of the fixed selenous adsorbed film of selectivity, comprising the following steps:
Step 1: preparing the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino: passing through copolycondensation in acid condition first
Method prepares mercapto-modified SBA-15, then modifies amino using rear grafting, and sulfhydryl amino pair is obtained after removing template agent removing and is repaired
Adorn SBA-15 mesoporous silicon material；
Step 2: preparing glue solution: crosslinking agent, pure water and acrylamide solution being mixed, polyacrylamide is obtained
Glue solution is saved backup in 4 DEG C of refrigerators；
Step 3: after the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino that step 1 is prepared are fully ground and walking
The rapid two glue solution being prepared mix, ultrasonic 3~5 minutes obtained mixed solutions；
Step 4: ammonium persulfate solution and tetramethyl diethylamine is added into the mixed solution that step 3 is prepared respectively
Solution mixes；
Step 5: the mixed solution that step 4 is prepared is slowly injected into the two panels for accompanying U-shaped Teflon material web
In glass plate hole, most bubble is caught up with, in the baking oven of horizontal transfer to 42~46 DEG C, to the solution gel film forming in glass plate,
It is impregnated 24 hours or more in pure water, is during which changed clothes 3~5 times with pure water, obtain the adsorbed film.
Preferably, the method for the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino is prepared described in step 1 specifically:
(1) copolycondensation method modifies sulfydryl: with P123 triblock copolymer, ethyl orthosilicate and mercaptopropyi trimethoxy silicon
Alkane is raw material, and the mercapto-modified SBA-15 containing template is prepared using copolycondensation method in acid condition；
(2) grafting modifies amino afterwards: using 3- TSL 8330 in step (1) in toluene solution
The mercapto-modified SBA-15 containing template is modified, and the SBA-15 of the sulfhydryl amino modification containing template is made；
(3) it removes template agent removing: the SBA-15 of the resulting sulfhydryl amino modification containing template of step (2) is returned in ethanol
Template agent removing is flowed away, the mesoporous silicon heavy metal absorbent of sulfydryl and the double modifications of amino is made.
Preferably, crosslinking agent described in step 2 is the DGT gel cross- that Britain DGT studies Co., Ltd's production
Linker crosslinking agent.
Preferably, the mass percent concentration of the acrylamide solution is 40%.
Preferably, crosslinking agent, pure water described in step 2 and acrylamide solution volume ratio are 1:(3.0~3.5):
(2.3~2.8).
Preferably, the quality volume of the double modification SBA-15 mesoporous silicon materials and glue solution of sulfhydryl amino described in step 3
Than for 1:(10~30).
Preferably, the mass percent concentration of ammonium persulfate solution described in step 4 is 10%, and matching while using, is prevented
Only ammonium persulfate failure effect solution film forming.
Preferably, polyacrylamide glue solution described in ammonium persulfate solution described in step 4 and step 2
Volume ratio is 1:(80~150).
Preferably, tetramethyl diethylamine solution described in step 4 and polyacrylamide glue described in step 2 are molten
The volume ratio of liquid is 1:(400~800).
Preferably, tetramethyl diethylamine solution described in step 4 and ammonium persulfate solution ratio are 1:(2.67~6).
Preferably, glass plate described in step 5 is the simple glass that main component is silica, cannot use and contain
There is the poly (methyl methacrylate) plate of polymethyl methacrylate, standing time is 40~60min in an oven.
The present invention also provides a kind of fixed selenous adsorbed films of selectivity, and the adsorbed film is using foregoing any
One the method is prepared.
The present invention also provides a kind of application of the fixed selenous adsorbed film of selectivity in fixed tetravalence selenium.
3, beneficial effect
Compared with the prior art, the invention has the benefit that
(1) the double modification SBA-15 mesoporous adsorption materials of sulfhydryl amino employed in the present invention, are to Chinese patent application
Number for 201611265639.8 the amino used in the prior art and/or sulfydryl by rear grafting modification SBA-15 method
(i.e. after obtaining ordered mesoporous material SBA-15 finished product, grafting sulfydryl and/or amino) has carried out further improvement；Due to
The mesoporous of SBA-15 is formed in acid condition, and traditional view is thought, proton easily occurs in acid condition for amino and sulfydryl
Change, will affect the formation in silicon skeleton and duct, reduces the load capacity of group usually to ensure the formation of meso-hole structure, therefore use
The SBA-15 material of amino and sulfydryl while modification should not be prepared using copolycondensation method；In order to make sulfydryl and amino more in the present invention
Be uniformly distributed in the mesoporous duct and surface of SBA-15, by debugging mercaptopropyi trimethoxy silane, ethyl orthosilicate and
The dosage of P123 when reaction condition, control in ethyl orthosilicate it is siliceous account for the 5% of P123 molal quantity, mercaptopropyi trimethoxy
In base silane it is siliceous account for 20%~30% of total silicon molal quantity in mixed solution, under the conditions of, stir, be first added dropwise just at room temperature
Mercaptopropyi trimethoxy silane is added dropwise after being spaced 45~90min in silester again, and it is good containing template to obtain mesoscopic structure
Mercapto-modified SBA-15, make mercaptopropyi trimethoxy silane in acid condition, pass through the cocondensation with ethyl orthosilicate
Poly- reaction forming is into SBA-15 skeleton, and skeleton is mesoporous does not collapse because of the connection of sulfydryl；After further using later
Grafting modifies amino, had both overcome sulfydryl and amino in traditional view while having passed through mesoporous collapsing caused by copolycondensation method is modified
Or the lesser problem of load capacity, in turn avoid the outer surface that group when two kinds of groups are all modified with rear grafting is distributed in mesoporous silicon
At aperture, it is difficult to the diffusion in duct of the problem being evenly distributed in duct, more conducively target contaminant and with activity
The reaction of group.
(2) the fixed selenous adsorbed film of a kind of selectivity of the invention is selectively superior to tetravalence selenium.The present invention is adopted
The double modification SBA-15 mesoporous silicon materials of adsorbent material sulfhydryl amino contain sulfydryl, exist between sulfydryl and tetravalence selenium and are bonded as follows
Reaction: 4RSH+H2SeO3→RSSeSR+RSSR+3H2O, thus realize selenous selective absorption, and hexavalent selenium and sulfydryl are not
This bonding reaction can occur, be based on this principle, the adsorbed film prepared by the material have to selenous absorption it is highly selective,
It is respectively placed in containing 0.01mol/L NaNO3In the tetravalence selenium or sexavalence selenium solution of 50 μ g/L, different time is vibrated, is surveyed
The densimeter of selenium calculates the amount (as shown in Figure 3) of selenium in adsorbed film in the solution of fixed absorption front and back, 95% or more tetravalence selenium quilt when 2h
Absorption, and to the adsorbance of hexavalent selenium only less than the 5% of total amount when for 24 hours, illustrating the adsorbed film, not only the rate of adsorption is fast, and
And the fixed tetravalence selenium of the property of can choose.
(3) the fixed selenous adsorbed film still property of can choose in DGT device of a kind of selectivity of the invention fixes four
Valence selenium optionally adsorbs tetravalence selenium in the water environment that sexavalence selenium concentration is ten times of tetravalence selenium concentration, the suction to hexavalent selenium
Attached amount is less than 5%, selenous absorption and analysis suitable for the surrounding mediums such as water body, soils and sediments.
(4) in the fixed selenous adsorbed film selectivity fixed environment of a kind of selectivity of the invention after tetravalence selenium, relatively
In the technical problem of titanium dioxide absorption membrane elution difficulty, elution process of the present invention is simple and easy to do, only with 1mol/L HNO3+
1%KIO3It can reach 97% elution efficiency.
(5) preparation method of the fixed selenous adsorbed film of a kind of selectivity of the invention, according to the double modifications of sulfhydryl amino
The property and particle size of SBA-15 mesoporous silicon material itself are used for the adsorbed film under different pH, under different tetravalence selenium concentrations
C in DGT deviceDGT/CsolnInfluence, obtain making the good (C of DGT device performanceDGT/CsolnRatio is in 1.0 ± 0.1 ranges)
The double modification SBA-15 mesoporous silicon material additive amounts of sulfhydryl amino, glue solution proportion, ratio of initiator and tetramethylethylenediamine
Ratio；Preparation process is easily-controllable, and different batches absorption film properties obtained are stablized, and film-strength is high, and ductility is good.
(6) in absorption membrane preparation method disclosed by the invention, and application No. is 201510780858.9 prior art phases
Than the alumina powder grain density used in the prior art is larger, and under equal volume glue solution, the present invention only needs more
The double modification SBA-15 mesoporous silicon materials of the sulfhydryl amino of low adding proportion can be realized the preparation of adsorbed film and reach corresponding effect
Fruit, more saving material.
(7) the fixed selenous adsorbed film of a kind of selectivity of the invention, film surface are uniformly distributed nanoscale sulfydryl
The double modification SBA-15 mesoporous silicon materials of amino can parse water body in submicron-scale high-resolution, tetravalence selenium in soils and sediments
Content and distribution；The adsorbed film is applied to DGT technology, can effectively measure heavy metal biological available state in nature,
Compared with other traditional form analytical technologies, the heavy metal that organism is absorbed can be preferably reacted.
Detailed description of the invention
Fig. 1 is the DGT apparatus structure schematic diagram for being assembled with the fixed selenous adsorbed film of selectivity prepared by the present invention；
Fig. 2 is a kind of scanning electron microscope diagram of the fixed selenous adsorbed film of selectivity of the invention；
Fig. 3 is adsorption dynamics adsorption kinetics of the adsorbed film prepared by the present invention to tetravalence selenium and hexavalent selenium；
Fig. 4 is to be assembled with the DGT device of adsorbed film prepared by the present invention to the adsorbance of tetravalence selenium and hexavalent selenium with placement
The variation of time, solid line is the Molded Line being calculated according to fick's first law of diffusion in figure；
Fig. 5 is adsorbent material in comparative example 1 and comparative example 2 to the adsorption efficiency of tetravalence selenium, hexavalent selenium；
In figure: 1, plastic wrapper；2, filter membrane；3, diffusion barrier；4, adsorbed film；5, plastic feet.
Specific embodiment
Present invention will now be described in detail with reference to the accompanying drawings..
Embodiment 1
Inventor obtains by theory analysis and multiple repetition test: if wanting to obtain to tetravalence selenium with highly selective and high
The adsorbed film of adsorption capacity not only needs to select new adsorbent, while needing to consider that adsorbent is molten with initiator ammonium persulfate
The proportion of liquid and tetramethylethylenediamine, only these aspect comprehensive considerations just can guarantee that adsorbed film obtains ideal absorption effect
Fruit.SBA-15 mesoporous silicon material is mainly used for the removal of the heavy metals such as copper in environment, lead, inhales as selenous selectivity
Enclosure material be applied to DGT technology adsorbed film there is not been reported.Meanwhile the preparation of adsorbed film, it is not that modified SBA-15 is situated between
Plastic is simply mixed in hole silicon materials and polyacrylamide solution, the intensity and absorption after needing to consider simultaneously operability, film forming
Capacity.When the SBA-15 quantity of material of addition is excessive, it may occur that reunite, SBA-15 material in mixed sol solution is caused to be distributed
Unevenly, it cannot smoothly inject in U-shaped glass plate crack, therefore not have operability；When ammonium persulfate solution and tetramethyl
When diethylamine solution ratio is too low, manufactured adsorbed film viscosity is big, intensity is low；When ratio is excessively high, solution can reunite rapidly, also not
It is able to satisfy the requirement of adsorbed film.In addition, the selection of glass plate also will have a direct impact on plastic effect, it is poly- according to main component
Methyl methacrylate poly (methyl methacrylate) plate replaces general silica glass plate to will affect glue solution generation polymerization reaction, due to
It reacts between polymethyl methacrylate and sol solution, will lead to polymerization reaction and be affected, cause solution can not plastic.
Our lot of experiments discovery, when the ratio of the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino and sol solution is controlled 1:
(10~30), tetramethyl diethylamine solution and mass percent concentration be 10% ammonium persulfate solution ratio control 1:(2~
6) when, film forming can be smoothly injected, the adsorbed film being prepared is but also with preferable toughness and adsorption effect.
This example is to consider from above-mentioned several respects, and the preparation side of the fixed selenous adsorbed film of selectivity has finally been determined
Method, specific steps are as follows:
Step 1: preparing the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino:
(1) total with 1.9M dissolving with hydrochloric acid polyethylene oxide-polypropylene oxide-polyethylene oxide three block in conical flask
Reaction temperature is increased to 40 DEG C after completely dissolution to P123, is added dropwise ethyl orthosilicate (TEOS), additive amount is by polymers (P123)
It is siliceous account for the 5% of P123 molal quantity, after stirring 60min, then mercaptopropyi trimethoxy silane (MPTMS) is added dropwise, the two
Dropwise addition molar ratio is x=MPTMS/ ((TEOS+MPTMS)), and mixed solution is transferred to reaction under high pressure after stirring 20h by x=0.2
In kettle, 100 DEG C of ageings for 24 hours, by the cooling suction filtration of products therefrom, are washed, dry；
(2) by after the dehydration of material vacuum obtained in step (1), round-bottomed flask is moved into, and toluene and 3- aminopropan is added
Base trimethoxy silane (APTMS) stirs for 24 hours under the conditions of 110 DEG C, products therefrom is successively used to toluene, dehydrated alcohol, deionization
Water cleans 2~3 times, vacuum drying；
(3) the resulting material of step (2) and 95% ethyl alcohol are added in round-bottomed flask, heating stirring flows back for 24 hours, cooling
It filters, washing, vacuum drying, the SBA-15 mesoporous silicon heavy metal absorbent of the double modifications of sulfhydryl amino is made.
Step 2: the crosslinking agent DGT gel cross- for being 2% using the concentration of purchase from Britain DGT research Co., Ltd
The acrylamide solution by volume 15 of linker, MQ water and General Electric's Medical Group (GE Healthcare) production:
The ratio of 47.5:37.5 is mixed to get glue solution, and wherein the mass percent concentration of acrylamide solution is 40%, at 4 DEG C
It is saved backup in refrigerator；
Step 3: after the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino that step 1 is prepared are fully ground and walking
The rapid two glue solution being prepared are uniformly mixed so as to obtain glue solution, ultrasonic 3 minutes obtained mixed solutions by mass volume ratio 1:30；
Step 4: matter is added by the 1/150 of polyacrylamide solution volume into the mixed solution that step 3 is prepared
The ammonium persulfate solution that percent concentration is 10% is measured, tetramethyl diethylamine is added by the 1/800 of polyacrylamide solution volume
Solution is mixed evenly to obtain mixed solution；
Step 5: the mixed solution that step 4 is prepared is accompanied the U-shaped of 0.25mm thickness with the rate injection of 5mL/min
In two glass sheets holes of Teflon material web, most bubble is caught up with, places 40min in the baking oven of horizontal transfer to 42 DEG C, to
Solution gel film forming in glass plate, impregnates for 24 hours in pure water, is during which changed clothes 4 times with pure water, obtain the adsorbed film.
The selectively fixed tetravalence selenium experiment of adsorbed film: it is 2.51cm that adsorbed film made from this example, which is cut into area,2Circle
Piece is respectively placed in 10mL and contains 0.01mol/L NaNO3In the tetravalence selenium or sexavalence selenium solution of 50 μ g/L, different time is vibrated
(1min~for 24 hours), the densimeter of selenium calculates the amount (as shown in Figure 3) of selenium in adsorbed film in the solution of measurement absorption front and back, when 2h
95% or more tetravalence selenium is adsorbed, and to the adsorbance of hexavalent selenium only less than the 5% of total amount when for 24 hours, these results suggest that
Not only the rate of adsorption is fast for the adsorbed film, but also the fixed tetravalence selenium of the property of can choose.
Adsorbed film selectively fixed tetravalence selenium experiment in DGT device: adsorbed film made from this example, which is cut into area, is
2.51cm2Disk, by the adsorbed film cut, (thickness 0.78mm, preparation method are shown in document Zhang with polyacrylamide diffusion barrier
And Davison, Anal.Chem.1995,67 (19), 3391-3400.) and polyethersulfone membranes (thickness 0.14mm, aperture 0.45
μm, Pall Supor) according to the composition DGT device of attached drawing 1, it is respectively placed in 6L and contains 0.01mol/L NaNO3With the four of 50 μ g/L
In valence selenium or sexavalence selenium solution, the abundant magnetic agitation of solution.1mL solution and device are taken out in different time sections, using 3mL
1mol/L HNO3+ 1%KIO3Solution elutes adsorbed film for 24 hours, and Inductively coupled plasma-mass spectrometry measures in eluent and solution
Se content.Using tetravalence Se content fixed in adsorbed film as ordinate, the time is that abscissa is mapped (such as Fig. 4), selenous suction
Attached amount linearly increases at any time coincide with Molded Line, and the adsorbance of hexavalent selenium is held essentially constant, and illustrates that the adsorbed film can
Realize that selenous selectivity is fixed to be applied to DGT technology.
The fixed selenous adsorbed film (scanning electron microscope is as shown in Figure 2) of a kind of selectivity manufactured in the present embodiment is described
Adsorbed film is the polyacrylamide hydrogel film that surface is evenly distributed with the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino, right
Tetravalence selenium have it is highly selective, when also optionally adsorbing tetravalence selenium in the environment that tetravalence selenium and hexavalent selenium coexist, to sexavalence
The adsorbance of selenium is less than 5%, selenous absorption and analysis suitable for the surrounding mediums such as water body, soils and sediments.
Embodiment 2
Fixed selenous adsorbed film of a kind of selectivity of the present embodiment and preparation method thereof, it is different substantially with embodiment 1
Place is that the present embodiment is during preparation selectivity fixed selenous adsorbed film:
Bought in step 2 from Britain DGT research crosslinking agent DGT gel cross-linker of Co., Ltd, MQ water and
The acrylamide solution that the mass percent concentration of General Electric's Medical Group (GE Healthcare) production is 40% is according to body
Product is than being that the ratio of 1:3.0:2.3 is mixed to get glue solution.
The glue solution that will be prepared in the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino and step 2 in step 3
Mixed solution is mixed to prepare by mass volume ratio 1:15.
Matter is added by the 1/100 of polyacrylamide solution volume into the mixed solution that step 3 is prepared in step 4
The ammonium persulfate solution that percent concentration is 10% is measured, tetramethyl diethylamine is added by the 1/600 of polyacrylamide solution volume
Solution is mixed evenly to obtain mixed solution；
The mixed solution that step 4 is prepared is injected to the U for accompanying 0.3mm thickness in step 5 with the rate of 15mL/min
In two glass sheets hole of type Teflon material web, most bubble is caught up with, places 50min in the baking oven of horizontal transfer to 45 DEG C,
To the solution gel film forming in glass plate, 18h is impregnated in pure water, is during which changed clothes 3 times with pure water, obtains the adsorbed film.
It is 2.51cm that adsorbed film made from this example, which is cut into area,2Former piece, dress up DGT device with example 1 group.
Laboratory configuration 2L contains 0.01mol/L NaNO3With the tetravalence selenium solution of 50 μ g/L, it is arranged five groups of difference pH's
Comparative test, adjusting pH using the nitric acid and sodium hydroxide of 1mol/L is respectively 3.6,4.2,5.5,7.5,8.0.The abundant magnetic of solution
Power is stirred, and is put into the organic glass frame that card has the round DGT device based on the present embodiment adsorbed film, DGT dress is taken out after 4h
It sets, using 3mL 1mol/L HNO3+ 1%KIO3Solution elutes adsorbed film for 24 hours, and takes out 1mL before and after the 4h for placing DGT device
Solution measures the selenium in eluent and solution with inductance coupled plasma.Calculate the concentration that DGT is measured under different pH values
(CDGT) and solution concentration (Csoln) ratio (CDGT/Csoln), this ratio illustrates DGT device performance in 1.0 ± 0.1 ranges
Well, corresponding adsorbed film can effectively adsorb tetravalence selenium.Calculated result is referring to table 1, the corresponding C of different pH value in table 1DGT/Csoln
In 0.9~1.1 range, illustrate that adsorbed film manufactured in the present embodiment can effectively measure selenous concentration.
Selenous C in the solution of 1 difference pH of tableDGT/CsolnRatio is referring to table
Laboratory configuration 2L contains the tetravalence selenium solution of 50 μ g/L, and the comparative test of five groups of different ionic strengths, benefit is arranged
The nitrate radical content that solution is adjusted with sodium nitrate is respectively 0.1,1,10,50,100,200mmol/L.The abundant magnetic agitation of solution
Mixing is put into the organic glass frame that card has the round DGT device based on the present embodiment adsorbed film, takes out DGT device after 4h, use
3mL 1mol/L HNO3+ 1%KIO3Solution elutes adsorbed film for 24 hours, and 1mL solution is taken out before and after the 4h for placing DGT device, uses
Inductively coupled plasma body measures the selenium in eluent and solution.Calculate the concentration that DGT is measured under different nitrate radical contents
(CDGT) and solution concentration (Csoln) ratio (CDGT/Csoln), this ratio illustrates DGT device performance in 1.0 ± 0.1 ranges
Well, corresponding adsorbed film can effectively adsorb tetravalence selenium.Calculated result is referring to table 2, and different nitrate radical contents are corresponding in table 2
CDGT/CsolnIn 0.9~1.1 range, illustrate that adsorbed film manufactured in the present embodiment can effectively measure selenous concentration.
Selenous C in 2 different ionic strength solution of tableDGT/CsolnRatio is referring to table
Embodiment 3
Fixed selenous adsorbed film of a kind of selectivity of the present embodiment and preparation method thereof, it is different substantially with embodiment 1
Place is that the present embodiment is during preparation selectivity fixed selenous adsorbed film:
Bought in step 2 from Britain DGT research crosslinking agent DGT gel cross-linker of Co., Ltd, MQ water and
The acrylamide solution that the mass percent concentration of General Electric's Medical Group (GE Healthcare) production is 40% is according to body
Product is than being that the ratio of 1:3.5:2.8 is mixed to get glue solution.
The glue solution that will be prepared in the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino and step 2 in step 3
Mixed solution is mixed to prepare by mass volume ratio 1:10.
Matter is added by the 1/80 of polyacrylamide solution volume into the mixed solution that step 3 is prepared in step 4
The ammonium persulfate solution that percent concentration is 10% is measured, tetramethyl diethylamine is added by the 1/400 of polyacrylamide solution volume
Solution is mixed evenly to obtain mixed solution；
The mixed solution that step 4 is prepared is injected to the U for accompanying 0.25mm thickness in step 5 with the rate of 10mL/min
In two glass sheets hole of type Teflon material web, most bubble is caught up with, places 60min in the baking oven of horizontal transfer to 46 DEG C,
To the solution gel film forming in glass plate, is impregnated 36 hours in pure water, during which changed clothes 5 times with pure water, obtain the absorption
Film.
It is 2.51cm that adsorbed film made from this example, which is cut into area,2Former piece, dress up DGT device with example 1 group.
Laboratory, which configures, is mixed with manual simulation's fresh water of tetravalence selenium and hexavalent selenium, and wherein tetravalence selenium concentration is 50 μ g/L, and six
Valence selenium concentration is set to 50 μ g/L and 500 μ g/L.Simulation fresh water total volume is 2L, and sodium nitrate, which is added, keeps final ion dense
Degree is 0.01mol/L.Solution sufficiently stirs evenly, and being put into card has the organic glass frame based on this example DGT device size, takes afterwards for 24 hours
DGT device out, with 3mL 1mol/L HNO3+ 1%KIO3Solution elutes adsorbed film.Inductively coupled plasma-mass spectrometry is surveyed
The concentration of selenium in eluent, the combination of High performance liquid chromatography-inductively coupled plasma mass spectrometry method measure in manual simulation's fresh water
Tetravalence selenium.And calculate selenous DGT measurement concentration (CDGT) and manual simulation's fresh water concentration (Csoln) ratio, this ratio exists
Illustrate that DGT device performance is good in 1.0 ± 0.1 ranges, corresponding adsorbed film can effectively adsorb tetravalence selenium.Calculated result referring to
Table 3, C under the conditions of different proportion in table 3DGT/CsolnIn 0.9~1.1 range, illustrate that the present embodiment adsorbed film is alternative
Measure tetravalence selenium.
The selenous DGT of table 3 measures concentration proportion reference table in concentration and manual simulation's fresh water
Embodiment 4
Selectively fixed selenous adsorbed film of one of the present embodiment and preparation method thereof, substantially with embodiment 1, no
It is with place, the present embodiment is during preparation selectivity fixed selenous adsorbed film:
Step 4: matter is added by the 1/150 of polyacrylamide solution volume into the mixed solution that step 3 is prepared
The ammonium persulfate solution that percent concentration is 10% is measured, tetramethyl diethylamine is added by the 1/400 of polyacrylamide solution volume
Solution is mixed evenly to obtain mixed solution.
The selectively fixed tetravalence selenium experiment of the adsorbed film finally prepared: adsorbed film made from this example, which is cut into area, is
2.51cm2Disk, be respectively placed in 10mL and contain 0.01mol/L NaNO3In the tetravalence selenium or sexavalence selenium solution of 50 μ g/L, vibration
Swinging 2h, the densimeter of selenium calculates the amount of selenium in adsorbed film in the solution of measurement absorption front and back, and 95% or more tetravalence selenium is adsorbed when 2h,
And to the adsorbance of hexavalent selenium only less than the 5% of total amount when for 24 hours, these results suggest that the adsorbed film rate of adsorption is fast, and
The property of can choose fixes tetravalence selenium.
Comparative example 1
This comparative example is the double modification SBA- of the amino mercapto being not added into film prepared using 1 method of the embodiment of the present invention
Adsorption experiment of 15 materials to tetravalence selenium, hexavalent selenium.
Tetravalence selenium and sexavalence selenium solution under different pH is respectively configured in laboratory, and concentration is 50 μ g/L.Take above-mentioned water sample
10mL, is added adsorbent material 0.1g prepared by the present invention, and oscillation measures the concentration of selenium in the solution of absorption front and back afterwards for 24 hours, calculates and inhale
Attached efficiency.The result shows that the double modification SBA-15 materials of amino prepared by the present invention, sulfydryl are to selenous adsorption efficiency
The adsorbed film formed after embodiment 1 is added in film in 98%, with the present invention is to selenous adsorption efficiency (95%)
It compares, the adsorption efficiency of the double modification SBA-15 materials of simple amino mercapto is slightly above adsorbed film, this is because in preparation process
It joined polyacrylamide sol solution, material has been fixed in adsorbed film, and tetravalence selenium needs to be diffused into film and then by material
Absorption, the process can have certain influence to adsorption effect, but have no effect on fixed to selenous selectivity.
Comparative example 2
This comparative example 2 is double using the hydroxyl amino of grafting preparation rear in Chinese Patent Application No. 201611265639.8
SBA-15 material is modified to the adsorption experiment of tetravalence selenium, hexavalent selenium.Tetravalence selenium and sexavalence under different pH is respectively configured in laboratory
Selenium solution, concentration are 50 μ g/L.It takes above-mentioned water sample 10mL, is added according to after in Chinese Patent Application No. 201611265639.8
The double modification SBA-15 material 0.1g of the amino mercapto of grafting preparation, oscillation measure the concentration of selenium in the solution of absorption front and back afterwards for 24 hours,
It calculates adsorption efficiency (Fig. 5).The result shows that once being prepared according to grafting rear in Chinese Patent Application No. 201611265639.8
The double modification SBA-15 materials of hydroxyl amino, selectivity is not shown to tetravalence selenium.Simultaneously, though it is foreseeable that even if adopting
The double modification SBA-15 of amino mercapto are prepared with the rear grafting mentioned in the prior art, due in material preparation process, directly
When connecing using rear grafting modification amino and sulfydryl, amino and sulfydryl are not easy to be evenly distributed on the duct SBA-15 inner wall, but
It gets lodged at mesoporous mouth or SBA-15 outer wall, leads to that actual sulfhydryl amino distribution is concentrated and grafting amount is small, while metal ion is not
It is easily diffused into mesoporous inside to be reacted, the double modification SBA-15 materials of amino that rear grafting is once prepared, sulfydryl can not be right
Tetravalence selenium does not show very high selectivity.In contrast, pass through copolycondensation method first using the method for the present invention for sulfydryl
It is connected in SBA-15 skeleton, then selenous selective absorption may be implemented by the amino that rear grafting is modified.
Claims (10)
1. a kind of preparation method of the fixed selenous adsorbed film of selectivity, it is characterised in that the following steps are included:
Step 1: preparing the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino: first in acid condition by copolycondensation legal system
Standby mercapto-modified SBA-15, then amino is modified using rear grafting, the double modifications of sulfhydryl amino are obtained after removing template agent removing
SBA-15 mesoporous silicon material；
Step 2: crosslinking agent, pure water and acrylamide solution are mixed, polyacrylamide glue solution is obtained；
Step 3: the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino that step 1 is prepared are fully ground rear and step 2
The glue solution mixes the obtained mixed solution of ultrasound；
Step 4: ammonium persulfate solution and tetramethyl diethylamine solution is added into mixed solution described in step 3 respectively, mix；
Step 5: the mixed solution that step 4 is prepared is slowly injected into two sheet glass for accompanying U-shaped Teflon material web
In plate hole gap, the adsorbed film is made after drying, washing.
2. a kind of preparation method of the fixed selenous adsorbed film of selectivity according to claim 1, which is characterized in that step
Crosslinking agent described in rapid two is the DGT gelcross-linker crosslinking agent that Britain DGT studies Co., Ltd's production.
3. a kind of preparation method of the fixed selenous adsorbed film of selectivity according to claim 2, which is characterized in that step
Crosslinking agent described in rapid two, pure water and acrylamide solution volume ratio are 1:(3.0~3.5): (2.3~2.8).
4. a kind of preparation method of the fixed selenous adsorbed film of selectivity according to claim 3, which is characterized in that step
The mass volume ratio of the double modification SBA-15 mesoporous silicon materials of sulfhydryl amino described in rapid three and glue solution is 1:(10~30).
5. a kind of preparation method of the fixed selenous adsorbed film of selectivity according to claim 4, which is characterized in that step
The mass percent concentration of ammonium persulfate solution described in rapid four is 10%, and is matching while using.
6. a kind of preparation method of the fixed selenous adsorbed film of selectivity according to claim 5, which is characterized in that step
The volume ratio of polyacrylamide glue solution described in ammonium persulfate solution described in rapid four and step 2 be 1:(80~
150)。
7. a kind of preparation method of the fixed selenous adsorbed film of selectivity according to claim 6, which is characterized in that step
The volume ratio of polyacrylamide glue solution described in tetramethyl diethylamine solution described in rapid four and step 2 is 1:
(400~800).
8. a kind of preparation method of the fixed selenous adsorbed film of selectivity according to claim 7, which is characterized in that step
Tetramethyl diethylamine solution described in rapid four and ammonium persulfate solution ratio are 1:(2.67~6).
9. a kind of fixed selenous adsorbed film of selectivity, which is characterized in that the adsorbed film is used as in claim 1~8
Any one the method is prepared.
10. a kind of application of fixed selenous adsorbed film of selectivity as claimed in claim 9 in fixed tetravalence selenium.
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| CN111359597A (en) * | 2020-03-23 | 2020-07-03 | 南京大学 | Adsorption film for selectively fixing trivalent arsenic, trivalent antimony and quadrivalent selenium and preparation method thereof |
| CN114477223B (en) * | 2020-10-23 | 2023-09-08 | 中国石油化工股份有限公司 | Preparation method and application of sulfhydryl-functionalized SBA molecular sieve |
| WO2022252217A1 (en) * | 2021-06-04 | 2022-12-08 | 山东省科学院生态研究所(山东省科学院中日友好生物技术研究中心) | Polycyclic aromatic hydrocarbon passive sampling device based on thin-film diffusion gradient technology and application thereof |
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