CN109759034A - A kind of selective fixing means, adsorbed film and the application of trivalent antimony - Google Patents
A kind of selective fixing means, adsorbed film and the application of trivalent antimony Download PDFInfo
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- CN109759034A CN109759034A CN201910174830.9A CN201910174830A CN109759034A CN 109759034 A CN109759034 A CN 109759034A CN 201910174830 A CN201910174830 A CN 201910174830A CN 109759034 A CN109759034 A CN 109759034A
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- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 title claims abstract description 79
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000010703 silicon Substances 0.000 claims abstract description 57
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 57
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 40
- 239000011521 glass Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 26
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 9
- 239000000017 hydrogel Substances 0.000 claims abstract description 9
- NGWSAUQBWVWFCU-UHFFFAOYSA-N n-ethyl-2,3-dimethylbutan-2-amine Chemical compound CCNC(C)(C)C(C)C NGWSAUQBWVWFCU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002604 ultrasonography Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 86
- 238000002360 preparation method Methods 0.000 claims description 36
- 239000003292 glue Substances 0.000 claims description 27
- 238000005516 engineering process Methods 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 108010025899 gelatin film Proteins 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 125000006850 spacer group Chemical group 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000012263 liquid product Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 121
- 238000000034 method Methods 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 12
- 238000009792 diffusion process Methods 0.000 abstract description 11
- 239000000499 gel Substances 0.000 abstract description 6
- 239000010409 thin film Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000002210 silicon-based material Substances 0.000 abstract description 2
- 239000004809 Teflon Substances 0.000 abstract 1
- 229920006362 Teflon® Polymers 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 54
- 229910052787 antimony Inorganic materials 0.000 description 52
- 238000010521 absorption reaction Methods 0.000 description 23
- 238000001179 sorption measurement Methods 0.000 description 21
- 229910001439 antimony ion Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229960002510 mandelic acid Drugs 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- JCZPMGDSEAFWDY-SQOUGZDYSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanamide Chemical compound NC(=O)[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO JCZPMGDSEAFWDY-SQOUGZDYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- ZDINGUUTWDGGFF-UHFFFAOYSA-N antimony(5+) Chemical compound [Sb+5] ZDINGUUTWDGGFF-UHFFFAOYSA-N 0.000 description 1
- 238000000559 atomic spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003891 environmental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
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- 231100000701 toxic element Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses selective fixing means, adsorbed film and the applications of a kind of trivalent antimony, belong to diffusion thin film technique field.The polyacrylamide hydrogel film that the present invention is evenly distributed with sulfhydryl modified SBA-15 mesoporous silicon using surface carries out selectivity to trivalent antimony and fixes, firstly, synthesizing mercapto-modified SBA-15 mesoporous silicon material as adsorbed film；Then, SBA-15 mesoporous silicon obtained is mixed with polyacrylamide solution, ultrasound mixes, and ammonium persulfate solution and tetramethyl diethylamine solution is added, it is slowly injected into gel in the two glass sheets holes for accompany U-shaped Teflon material web after mixing evenly to form a film, pure water, which impregnates, to be made.Adsorbed film prepared by the present invention has good selectivity to trivalent antimony, and material distributing homogeneity is good, is remarkably improved the resolution ratio of diffusion thin film technique.
Description
Technical field
The invention belongs to diffusion thin film technique fields, fix more specifically to a kind of selectivity of trivalent antimony
Method, adsorbed film and application.
Background technique
In recent years, heavy metal pollution problem caused by industrial wastewater discharge becomes increasingly conspicuous, and effectively removes the heavy metal in water
Ion is always the research hotspot of water-treatment technology field.Antimony as it is a kind of can long distance delivery global toxic element, closely
Year over receive more and more attention, since antimony can be accumulated in animal and plant body and generate toxic action, additionally it is possible to grown away from
From migration, therefore U.S. EPA and European Union are classified as the pollutant that need to be given priority to.China is the big producer of antimony, accounts for generation
The 90% of boundary's antimony annual output, antimony is usually used in acid accumulator, fire retardant, glass and plastics etc., as the mankind are more next to antimonial
More extensive use, the pollution of antimony is increasingly severe in environment.If stibium-containing wastewater is not pocessed direct emission and finally flows into
River and the water that permeates the ground by food chain can all generate different degrees of harm to all living things body.Based on to antimony toxicity
Research, the maximum acceptable concentration that some scholars have obtained Antimony In The Soils is 3.5-5mg/kg.U.S.EPA is by antimony in drinking water
Limit value be set to 6 μ g/L, China " surface water environment quality mark " (GB3838-2002) and " Drinking Water hygienic practice " (are defended
Life portion, 2001) in the limit value of antimony is set to 5 μ g/L.
Antimony in water environment there are valence state and form are extremely complex, the valence state of antimony is usually+3 (Sb (III)) or 5 valences
(Sb (V)), high ten times of toxicity of the toxicity of trivalent antimony Sb (III) than quinquevalence antimony Sb (V).Studies have shown that heavy metal poison in environment
Property depends primarily on its occurrence patterns rather than total amount, and the free state concentration of heavy metal is frequently used to measure its biologically effective
Property, therefore the concentration for how effectively testing and analyzing Sb in water body (III) is the research purpose of this programme.And common antimony form
Analysis method has spectrophotometry, electrochemical methods, Raman spectrum (RS) technology and atomic spectroscopy etc..For example, middle promulgated by the State Council
Bright patent, application number: 201610264393.6, the applying date: 2016.04.26 discloses a kind of analysis method of antimony in water body,
The Au particle for having good dispersion and Raman-enhancing energy is prepared using reduction of sodium citrate method, and passes through mandelic acid table
The detection of face enhancing Raman signal is capable of forming complex, passes through inspection after mandelic acid is mixed with Sb (III), Sb (V)
The surface-enhanced Raman signals of complex are surveyed, it can be achieved that Sb (III), Sb (V) are detected indirectly.The above method had reached compared with
High-caliber measuring accuracy still mainly takes the initiative sample mode to the morphological analysis of antimony in water environment, i.e. scene water intaking
Sample simultaneously takes back experimental determination, and but the antimony between different valence state Forms Transformation easily occurs in sampling, transport, preservation, especially
It is easily to be converted into quinquevalence antimony Sb (V) for trivalent antimony Sb (III), impacted to testing result；And instrument
It is expensive, it is more demanding to sample pre-treatments.Therefore, the monitoring method of traditional dystopy analysis is difficult to ensure that antimony form is being protected
It deposits, change in transportational process, explore easy economic, antimony detection method rapidly and efficiently and have become current environmental analysis neck
One of the important research direction in domain.
And diffusion thin film technique (Diffusivegradients in thin films, DGT), it is a kind of original position
, nondestructive element analysis technology, can more reflect the heavy metal concentration that organism is absorbed, it is by Davison and Zhang
(1994) it is put forward for the first time.DGT technology can set enrichment sample time within the scope of certain time, by examining in sampling process
Determinand enriching quantity is surveyed to determine testing concentration, and can be in enrichment time with the wave of concentration of metal ions in bulk solution
It is dynamic, cumulant and mean intensity value are provided.DGT device is mainly formed by diffusion phase, in conjunction with phase with obturator；Obturator master
It plays the filter membrane of support, protection and fixed function thereon and primarily serves restriction by diameter of particle, while protecting internal expansion
Dephasing and combination be not mutually contaminated；Diffusion mutually be used to limit particle by speed, make itself and time, external solution and inside
Ion concentration is proportional, is a kind of hydrogel or semi-permeable membrane (hereinafter referred to as diffusion barrier)；It is then to realize ion selectivity in conjunction with phase
The key of absorption is divided into solid-state bond phase (hereinafter referred to as combining film) and liquid combination phase.
But due to the more complicated property of natural environment, and the extraction of heavy metal element available state in addition to water body environment,
The factors such as pH, extractant property, temperature have a close relationship, most important to will receive adsorbed metallic element type
It influences.Therefore, available combination film is still extremely limited DGT technology at present, and selectivity is seldom.Through retrieving, China is specially
Sharp application number 201510483125.9, publication number CN 105080519B disclose a kind of suction of fixed hexavalent chromium of selectivity
Membrane and preparation method thereof.The patent is prepared into adsorbed film using NMDG aminoglucose functional resin and bisacrylamide solution,
Realize the selective determination of Cr VI.Applicant, Chinese invention patent, application number: 201810401744.2, application
Day: 2018.04.28 discloses selenous adsorbed film of a kind of selectively fixation and preparation method thereof, which uses sulfydryl ammonia
The polyacrylamide gel film of the double modification SBA-15 mesoporous silicon materials of base, realizes selenous selective determination.More than but
Two kinds of materials can not achieve the selective absorption of trivalent antimony.
It other than above-mentioned factor, is found through retrieval, the fixed adsorbed film of the selectivity of metal ion, property (for example inhale
The stabilization of attached performance, film-strength, ductility and retain the shelf-life etc.) have direct relationship with adsorbent material property, it is general to select
The shelf-life of the fixed adsorbed film of selecting property only has 1~2 month, such as Luo et al. (Luo, et al., Analytical
Chemistry.2010,82,8903-8909) shelf-life of the precipitated iron film prepared is about 38 days；With regard to existing trivalent antimony ion
For adsorbed film, there is that absorption property is unstable, and film-strength is low mostly, easily broken, poor ductility and shelf-life be not long
Problem when applying it in DGT technology, not only will affect later period measurement effect；Also, in the preparation conjunctival process of DGT
In there are the problems such as not easy to be processed, easily broken.For example, 2016, Bennett et al. (Bennett, et al., Environ
Sci.:Processes Impacts, 2016,18,992-998) adsorbed film is made using commercially available sulfydryl silica gel, realizes water
The selective absorption of trivalent antimony in environment.But sulfydryl silica gel is not easy to form a film in preparation process, and in later period DGT technology measurement process
In, there are problems that being unevenly distributed on trivalent antimony adsorbed film (the combination film in DGT technology), is unfavorable for realizing that diffusion is thin
The high-resolution application of membrane technology.
In conclusion seek the efficient selective adsorption method of trivalent antimony, and prepare have to trivalent antimony it is highly selective,
Absorption profiles are uniform, and film-strength is high, and it is very important to be not only DGT technical field for the stable adsorbed film of absorption property (in conjunction with film)
Research emphasis and present patent application scheme research purpose.
Summary of the invention
1. to solve the problems, such as
For existing trivalent antimony measurement method vulnerable to quinquevalence antimony, water body pH and ionic strength affect, in DGT detection technique
Unstable in conjunction with film absorption property, the problems such as absorption profiles are uniform and film-strength is low, an object of the present invention is to provide one
The selective fixing means of kind trivalent antimony ion, the second object of the present invention is to provide a kind of trivalent antimony ion choosing of efficient stable
Selecting property fixes adsorbed film, and it is applied widely that the third object of the present invention is to provide a kind of pH, ionic strength, and efficient DGT knot
Close film.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
A kind of selective fixing means of trivalent antimony is evenly distributed with the poly- of sulfhydryl modified SBA-15 mesoporous silicon using surface
Acrylamide gel film carries out selectivity to trivalent antimony and fixes as adsorbed film.
Preferably, specific preparation process is as follows for the adsorbed film:
Step 1: the sulfhydryl modified SBA-15 mesoporous silicon and polyacrylamide sol solution after grinding is uniformly mixed so as to obtain glue
Solution；
Step 2: ammonium persulfate solution and tetramethyl diethylamine solution are sequentially added in glue solution, and mixed liquor is made；
Step 3: mixed liquor injection is accompanied in two glass sheets gaps of U-shaped plastic spacers piece, drives gas between glass plate out of
Bubble is impregnated 24 hours or more in pure water, is during which changed water 3~5 times to the solution gel film forming in glass plate, is obtained described
Adsorbed film.
Preferably, in the preparation step one of the adsorbed film, the addition quality A of sulfhydryl modified SBA-15 mesoporous silicon and poly-
The ratio of the addition volume B of acrylamide sol solution is 1~(12~25) g/mL, is uniformly mixed so as to obtain glue solution, ultrasound 15~20
Minute mixes well solution.
Preferably, in the preparation step two of the adsorbed film, the ammonium persulfate volume of addition is the 1/ of glue liquor capacity
90~1/200, the tetramethyl diethylamine solution volume of addition is the 1/500~1/600 of glue liquor capacity.
Preferably, in the preparation step three of the adsorbed film, the glass plate for being marked with mixed liquor is horizontally arranged, 42~46
Under conditions of DEG C, 15~50min is placed, the solution gel in glass plate is made to form a film.
Preferably, in the preparation step one of the adsorbed film, the preparation step of sulfhydryl modified SBA-15 mesoporous silicon is as follows:
(1) by polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), 2mol L-1Hydrochloric acid
It is added in conical flask, after P123 dissolution, ethyl orthosilicate (TEOS) and mercaptopropyi trimethoxy silane is successively added dropwise
(MPTMS), it is stirred 22 hours at 40 DEG C, the autoclave that temperature is 90-110 DEG C is then moved into, by product after 24 hours
It is cooling to filter, it washs, vacuum drying；
(2) in 95% ethyl alcohol, heating stirring simultaneously flows back 20-26 hours the product that step (1) is prepared, washing,
To get sulfhydryl modified SBA-15 mesoporous silicon after vacuum drying.
Preferably, in the preparation step (1) of the sulfhydryl modified SBA-15 mesoporous silicon, silicon contains in the TEOS of the dropwise addition
Amount is the 3~6% of P123 molal quantity, and silicone content in MPTMS is added dropwise and accounts for 10~30% of total silicon molal quantity in mixed liquor
Preferably, in the preparation step (1) of the sulfhydryl modified SBA-15 mesoporous silicon, ethyl orthosilicate and sulfydryl is added
The time interval of propyl trimethoxy silicane is 60-120min, is the abundant prehydrolysis of TEOS, improves yield, but needs to illustrate
Be also resulted in if interval is too long mesoporous material structure regularity decline.
Preferably, the adsorbed film is obtained using the preparation method of any of the above-described adsorbed film.
Preferably, using above-mentioned adsorbed film as film is combined, it is applied in DGT technology.
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) the selective fixing means of a kind of trivalent antimony provided by the present invention, by being evenly distributed with mercapto using surface
The polyacrylamide hydrogel film of the modified SBA-15 mesoporous silicon of base may be implemented solid to the selectivity of trivalent antimony as adsorbed film
It is fixed；Trivalent antimony is from water body with uncharged Sb (OH)3Actual conditions existing for form are set out, by adsorbed film sulfydryl with
Sb (III) generates chelation, and without reacting with the Sb (V) in water body, (SbV is with Sb (OH)6 -Oxo-anions shape
Formula presence), to achieve the purpose that fixed absorption Sb (III) of selectivity；Also, herein it is worth noting that, it is anti-through inventor
Multiple experimental verification, the adsorbent material surface for being used to fixed absorption Sb (III) of selectivity need to avoid that there are the higher bands of isoelectric point
Functional group's (such as amino) of positive electricity；In terms of specifically its advantage mainly has following two:
1. strong antijamming capability has good selectivity trivalent antimony, by the adsorbed film prepared be respectively placed in containing
0.01mol/L NaNO3In the trivalent antimony or quinquevalence antimony solution of 50 μ g/L, different time is vibrated, before and after measurement absorption in solution
The densimeter of antimony calculates the amount (as shown in Figure 3) of antimony in adsorbed film, and 95% or more trivalent antimony is adsorbed when 2h, and to quinquevalence antimony
Adsorbance is when for 24 hours only less than the 5% of total amount；
2. selective absorption is high-efficient, and in the prior art, Bennett et al. (Bennett, et al., Environ
Sci.:Processes Impacts, 2016,18,992-998) it is compared using adsorbed film made from commercially available sulfydryl silica gel,
Sulfhydryl modified SBA-15 mesoporous silicon in the application patent, density is low, and partial size is small and is evenly distributed, therefore manufactured adsorbed film contains
More adsorbent materials, the absorption point on monolithic membrane is more, is up to 98.5% to the adsorption efficiency of trivalent antimony.
(2) the fixed adsorbed film of the selectivity of a kind of trivalent antimony provided by the present invention, has the advantage that
1. preparation process is easily-controllable, simple process, different batches absorption film properties obtained are stablized, film-strength height, ductility
It is good；
2. existing adsorbed film is prepared using commercially available sulfydryl silica gel (partial size is about 38-75 μm), and due to sulfydryl silicon
Glue particle is than heavier, therefore there are particles to be unevenly distributed on adsorbed film, and film toughness is poor easily broken, is not easy to subsequent operation
The problem of；And the SBA-15 particle size prepared in the present invention is between 500-600nm, and density of material is low, than sulfydryl silica gel
Small 100 times of partial size or so, and partial size is smaller, the manufactured adsorbed film uniformity is better, therefore the stability of adsorbed film is strong, toughness
Good, adsorption efficiency is high；
3. the shelf-life of the fixed adsorbed film of the selectivity of the trivalent antimony prepared in the present invention can reach 3 months, and in sulfydryl
If not using vacuum drying in the synthesis process of the SBA-15 mesoporous silicon of modification, the adsorbed film shelf-life being prepared can only reach
By 60 days or so, the shelf-life of adsorbed film and adsorbent material property had direct relationship.
(3) the fixed adsorbed film of the selectivity of a kind of trivalent antimony provided by the present invention is applied to DGT as film is combined
In technology, within the scope of different pH, different ionic strength, the good (C of device performanceDGT/CsolnRatio is in 1.0 ± 0.1 ranges
It is interior), it can use under different environmental conditions；Absorption film surface is evenly distributed with sulfydryl of the partial size between 500~600nm
Modified SBA-15 mesoporous silicon, water body can be parsed in submicron-scale high-resolution, in soils and sediments the content of trivalent antimony and point
Cloth.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of the adsorbent material of the fixed trivalent antimony of selectivity prepared by the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope diagram of the adsorbed film of the fixed trivalent antimony of selectivity prepared by the embodiment of the present invention 1；
Fig. 3 is adsorption dynamics adsorption kinetics of the adsorbed film to trivalent antimony and quinquevalence antimony of the preparation of the embodiment of the present invention 1；
Fig. 4 is to be assembled with the DGT apparatus structure of the adsorbed film of the fixed trivalent antimony of selectivity of the preparation of the embodiment of the present invention 1 to show
It is intended to；
The DGT device for the adsorbed film that Fig. 5 is prepared for the embodiment of the present invention 1 is to the adsorbance of trivalent antimony and quinquevalence antimony 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. 6 is pair of the adsorbed film prepared with commercially available sulfydryl silicon to antimony ion adsorption efficiency of the preparation of the embodiment of the present invention 1
Than figure；
Fig. 7 is the adsorbed film pair with the SBA-15 mesoporous silicon preparation of the double modifications of sulfhydryl amino prepared by the embodiment of the present invention 1
The comparison diagram of antimony ion adsorption efficiency；
In figure: 1, plastic wrapper；2, filter membrane；3, diffusion barrier；4, in conjunction with film；5, plastic feet.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Embodiment 1
As shown in Figure 1, Figure 2 and Figure 3, inventor obtains by theory analysis and multiple repetition test: if wanting to realize water body
The effective monitoring and detection of middle trivalent antimony ion, need to change the tradition fetched water sample and carry out analysis measurement behind laboratory again
Method, because, research shows that being easily converted into quinquevalence antimony Sb (V) for trivalent antimony Sb (III), being made to testing result
At influence；Therefore, there is highly selective and uniform adsorption film to obtain, not only needs to select new adsorbent, needs simultaneously
Consider the disturbing factor in quinquevalence antimony ion pair adsorption process, only these aspect comprehensive considerations, just can guarantee that adsorbed film obtains
Obtain ideal adsorption effect.In the present embodiment, sulfhydryl modified SBA-15 mesoporous silicon, density is low, and partial size is small and is evenly distributed, because
This manufactured adsorbed film contains more adsorbent materials, and the absorption point on monolithic membrane is more, high to the adsorption efficiency of trivalent antimony,
And to the adsorbance of pentavalent antimony ion only less than 5%.It is specific as follows:
A kind of adsorbed film and preparation method thereof of the fixed trivalent antimony of selectivity, specific steps are as follows:
One, sulfhydryl modified SBA-15 mesoporous silicon (particle size range 500-600nm) is prepared
(1) by polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), 2mol L-1Hydrochloric acid adds
Enter in conical flask, temperature is risen to 40 DEG C after P123 dissolution, ethyl orthosilicate (TEOS) and mercaptopropyi front three is successively added dropwise
Oxysilane (MPTMS) stirs 22 hours between the two every 65min；Wherein, silicone content is P123 molal quantity in the TEOS of dropwise addition
5%, be added dropwise MPTMS in silicone content account for 10% of total silicon molal quantity in mixed liquor, then by mixing precursor liquid immigration 100
DEG C autoclave is filtered product is cooling after 24 hours, is washed, vacuum drying；
(2) product that step (1) is prepared is in 95% ethyl alcohol, and heating stirring simultaneously flows back 24 hours, washing, vacuum
It is synthesized sulfhydryl modified SBA-15 mesoporous silicon after drying.
Two, preparation surface is evenly distributed with the polyacrylamide hydrogel film of sulfhydryl modified SBA-15 mesoporous silicon as suction
Membrane
Step 1: the above-mentioned sulfhydryl modified SBA-15 mesoporous silicon being prepared is fully ground rear and polyacrylamide gel
Solution (ratio of the addition volume B of the addition quality A and polyacrylamide sol solution of sulfhydryl modified SBA-15 mesoporous silicon is 1:
It 15g/mL) is uniformly mixed so as to obtain glue solution, ultrasound mixes well solution in 18 minutes；
Step 2: ammonium persulfate solution and tetramethyl diethylamine solution are sequentially added the glue solution that step 1 obtains
In, mixed liquor is made；The ammonium persulfate volume being wherein added is the 1/150 of glue liquor capacity, the tetramethyl diethylamine of addition
Liquor capacity is the 1/550 of glue liquor capacity；
Step 3: the mixed liquor injection that step 2 is prepared to be accompanied to two glass sheets gaps of U-shaped plastic spacers piece
In, drive bubble between glass plate out of, glass plate be placed horizontally at 30min in 45 DEG C of baking ovens, to the solution gel in glass plate at
Film impregnates 24 hours or more in pure water, during which changes water 5 times, obtains the adsorbed film.
The selectively fixed trivalent antimony 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 50 μ g/L trivalent antimonies or quinquevalence antimony solution, different time is vibrated
(3min~for 24 hours), the concentration of antimony obtains the adsorption efficiency (as shown in Figure 3) of antimony in the solution of measurement absorption front and back, when 2h 95% with
Upper trivalent antimony is adsorbed, and to the adsorbance of quinquevalence antimony only less than the 5% of total amount when for 24 hours, these results suggest that the absorption
Not only the rate of adsorption is fast for film, but also the fixed trivalent antimony of the property of can choose, and the disturbing factor of quinquevalence antimony is discharged.
Adsorbed film selectively fixed trivalent antimony experiment in DGT device: adsorbed film made from this example, which is cut into area, is
2.51cm2Disk (as combine film), by the adsorbed film cut and polyacrylamide diffusion barrier (thickness 0.78mm, preparation side
Method is shown in document Zhang and Davison, Anal.Chem.1995,67 (19), 3391-3400.) and polyethersulfone membranes (thickness
0.14mm, 0.45 μm of aperture, Pall Supor) according to the composition DGT device of attached drawing 4, it is respectively placed in 6L and contains 0.01mol/L
NaNO3In the trivalent antimony or quinquevalence antimony solution of 50 μ g/L, the abundant magnetic agitation of solution.1mL solution is taken out in different time sections
And device, using 3mL 1mol/L HNO3+ 1%KIO3Solution elutes adsorbed film for 24 hours, and Inductively coupled plasma-mass spectrometry measurement is washed
Antimony content in de- liquid and solution.Using antimony content fixed in adsorbed film as ordinate, the time is that abscissa maps (such as Fig. 5),
The adsorbance of trivalent antimony linearly increases at any time coincide with Molded Line, and the adsorbance of quinquevalence antimony is held essentially constant, explanation
The adsorbed film can be applied to DGT technology and realize that the selectivity of trivalent antimony is fixed.
The adsorbent material (transmission electron microscope picture is as shown in Figure 1) of the fixed trivalent antimony of a kind of selectivity of the present embodiment, vertical
In the two-dimentional hexagonal structure that ordered arrangement in the plane in duct, can be observed；In the plane for being parallel to duct, it can be observed to put down
The tubular structure in row arrangement duct illustrates that sulfhydryl modified SBA-15 mesoporous silicon obtained has good Jie and sees order.Described
Adsorbed film is the polyacrylamide hydrogel film (as shown in Figure 2) that surface is evenly distributed with sulfhydryl modified SBA-15 mesoporous silicon,
Have to the absorption of trivalent antimony highly selective.
Embodiment 2
Compared with Example 1 compared with the present embodiment the difference is that only:
The present embodiment is during preparing sulfhydryl modified SBA-15 mesoporous silicon:
Ethyl orthosilicate (TEOS) and mercaptopropyi trimethoxy silane (MPTMS) are successively added dropwise in step (1), is added dropwise just
Silicone content is in the interval 60min of silester (TEOS) and mercaptopropyi trimethoxy silane (MPTMS), the TEOS of dropwise addition
The 3% of P123 molal quantity is added dropwise silicone content in MPTMS and accounts for 20% of total silicon molal quantity in mixed liquor；Then, by gained mixed liquor
Autoclave at a temperature of 90 °C is moved into, by the cooling suction filtration of product after 24 hours, is washed, vacuum drying；
In 95% ethyl alcohol, heating stirring simultaneously flows back 20 hours the product that step (1) is prepared in step (2), washes
It washs, to get sulfhydryl modified SBA-15 mesoporous silicon after vacuum drying.
The present embodiment is thin in the polyacrylamide hydrogel that preparation surface is evenly distributed with sulfhydryl modified SBA-15 mesoporous silicon
During film is as adsorbed film:
Step 1: the above-mentioned sulfhydryl modified SBA-15 mesoporous silicon being prepared is fully ground rear and polyacrylamide gel
Solution (ratio of the addition volume B of the addition quality A and polyacrylamide sol solution of sulfhydryl modified SBA-15 mesoporous silicon is 1:
It 12g/mL) is uniformly mixed so as to obtain glue solution, ultrasound mixes well solution in 15 minutes；
Step 2: quality hundred is added by the 1/90 of polyacrylamide solution volume into the mixed liquor that step 1 is prepared
Dividing specific concentration is 10% ammonium persulfate solution, and tetramethyl diethylamine solution is added by the 1/500 of polyacrylamide solution volume,
It is mixed evenly to obtain mixed liquor；
Step 3: the mixed liquor that step 2 is prepared is slowly injected into two glass sheets for accompanying U-shaped plastic spacers piece
In gap, bubble between glass plate is driven out of, glass plate is placed horizontally at 15min in 42 DEG C of baking ovens, it is solidifying to the solution in glass plate
Glue film forming, impregnates 26 hours in pure water, during which changes water 3 times, obtain the adsorbed film.
Embodiment 3
Compared with Example 1 compared with, the present embodiment the difference is that:
The present embodiment is during preparing sulfhydryl modified SBA-15 mesoporous silicon:
Ethyl orthosilicate (TEOS) and mercaptopropyi trimethoxy silane (MPTMS) are successively added dropwise in step (1), is added dropwise just
Silicone content is in the interval 90min of silester (TEOS) and mercaptopropyi trimethoxy silane (MPTMS), the TEOS of dropwise addition
The 6% of P123 molal quantity is added dropwise silicone content in MPTMS and accounts for 30% of total silicon molal quantity in mixed liquor；Then, by gained mixed liquor
The autoclave that temperature is 110 DEG C is moved into, by the cooling suction filtration of product after 30 hours, is washed, vacuum drying；
In 95% ethyl alcohol, heating stirring simultaneously flows back 20 hours the product that step (1) is prepared in step (2), washes
It washs, to get sulfhydryl modified SBA-15 mesoporous silicon after vacuum drying.
The present embodiment is thin in the polyacrylamide hydrogel that preparation surface is evenly distributed with sulfhydryl modified SBA-15 mesoporous silicon
During film is as adsorbed film:
Step 1: the above-mentioned sulfhydryl modified SBA-15 mesoporous silicon being prepared is fully ground rear and polyacrylamide gel
Solution (ratio of the addition volume B of the addition quality A and polyacrylamide sol solution of sulfhydryl modified SBA-15 mesoporous silicon is 1:
It 25g/mL) is uniformly mixed so as to obtain glue solution, ultrasound mixes well solution in 20 minutes；
Step 2: quality is added by the 1/200 of polyacrylamide solution volume into the mixed liquor that step 1 is prepared
It is molten that tetramethyl diethylamine is added by the 1/600 of polyacrylamide solution volume in the ammonium persulfate solution that percent concentration is 10%
Liquid is mixed evenly to obtain mixed liquor；
Step 3: the mixed liquor that step 2 is prepared is slowly injected into two glass sheets for accompanying U-shaped plastic spacers piece
In gap, bubble between glass plate is driven out of, glass plate is placed horizontally at 50min in 46 DEG C of baking ovens, it is solidifying to the solution in glass plate
Glue film forming, impregnates 30 hours in pure water, during which changes water 4 times, obtain the adsorbed film.
It is 2.51cm that adsorbed film made from this example, which is cut into area,2Former piece (as combine film), remaining is the same as embodiment 1
It is assembled into DGT device.Laboratory configuration 2L contains 0.01mol/L NaNO3With the trivalent antimony solution of 50 μ g/L, six groups are set altogether not
With the comparative test of pH, adjusting pH using the nitric acid and sodium hydroxide of 1mol/L is respectively 3.2,4.2,5.3,6.6,8.2,8.8.
Solution abundant magnetic agitation mixing, is put into the organic glass frame that card has the round DGT device based on the present embodiment adsorbed film, after 4h
DGT device is taken out, using 3mL 1mol/L HNO3+ 1%KIO3Solution elutes adsorbed film for 24 hours, and before the 4h for placing DGT device
1mL solution is taken out afterwards, measures the antimony in eluent and solution with inductance coupled plasma.Calculate DGT under different pH values
Concentration (the C of measurementDGT) and solution concentration (Csoln) ratio (CDGT/Csoln), this ratio is explanation in 1.0 ± 0.1 ranges
DGT device performance is good, and corresponding adsorbed film can effectively adsorb trivalent antimony.Calculated result is referring to table 1, different pH value pair in table 1
The C answeredDGT/CsolnIn 0.9~1.1 range, illustrate that adsorbed film manufactured in the present embodiment can effectively measure the dense of trivalent antimony
Degree.
The C of trivalent antimony in the solution of 1 difference pH of tableDGT/CsolnRatio is referring to table
Laboratory configuration 2L contains the trivalent antimony 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 0.1,1,10,100,200mmol/L.The abundant magnetic agitation of solution is mixed
It closes, 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 antimony 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 trivalent antimony.
Calculated result is referring to table 2, the corresponding C of different nitrate radical contents in table 2DGT/CsolnIn 0.9~1.1 range,
Illustrate that adsorbed film manufactured in the present embodiment can effectively measure the concentration of trivalent antimony.
The C of trivalent antimony in 2 different ionic strength solution of tableDGT/CsolnRatio is referring to table
Embodiment 4
Compared with Example 1 compared with, the present embodiment the difference is that:
It is 2.51cm that adsorbed film made from this example, which is cut into area,2Former piece (as combine film), with example 1 group fill
At DGT device.
Laboratory configures the simulation fresh water for being mixed with trivalent antimony and quinquevalence antimony, and DGT device is then placed on 2L and is contained
0.01mol L-1NaNO3In the different proportion mixed liquor being sufficiently stirred, wherein trivalent antimony concentration is 30 μ g/L, quinquevalence antimony concentration point
It is not set as 30 μ g/L and 300 μ g/L.Being put into card has the organic glass frame based on this example DGT device size, takes out DGT afterwards for 24 hours
Device elutes adsorbed film with 3mL 1mol/L HNO3+1%KIO3 solution.
Inductively coupled plasma-mass spectrometry surveys the concentration of antimony in eluent, high performance liquid chromatography-inductively coupled plasma body
Trivalent antimony in mass spectrography combination measurement water.And count DGT measurement concentration (CDGT) with the ratio of water body actual concentrations (Csoln), if
Ratio illustrates that DGT device performance is good in 1.0 ± 0.1 ranges, to the strong antijamming capability of quinquevalence antimony.Calculated result referring to
Table 3, C under the conditions of different proportion in table 3DGT/ Csoln illustrates that the present embodiment adsorbed film is alternative in 0.9~1.1 range
Measure trivalent antimony.
The C of trivalent antimony and quinquevalence antimony in 3 same solution of tableDGT/CsolnRatio is referring to table
Comparative example 1
This comparative example is compared with Example 1 compared with distinctive points are only that:
This comparative example is thin in the polyacrylamide hydrogel that preparation surface is evenly distributed with sulfhydryl modified SBA-15 mesoporous silicon
During film is as adsorbed film:
After being fully ground in step 1 using commercially available sulfydryl silica gel and polyacrylamide sol solution is uniformly mixed so as to obtain glue solution,
Ultrasound mixes well solution in 15 minutes；
Remaining is the same as embodiment 1.
The adsorbed film (being expressed as in Fig. 6) and commercially available mercapto that embodiment 1 is prepared using sulfhydryl modified SBA-15 mesoporous silicon
The adsorbed film (dredging base silica gel) of base silicon preparation has carried out the comparative experiments of the fixed absorption of trivalent antimony ion selectivity, specific experiment step
It is rapid as follows:
By adsorbed film prepared by sulfhydryl modified SBA-15 mesoporous silicon (indicating in Fig. 6 are as follows: SBA glue) and commercially available sulfydryl silicon
It is 2.51cm that the adsorbed film (indicating in Fig. 6 are as follows: sulfydryl silica gel) of preparation is cut into area respectively2Disk (as combine film),
Then, it is respectively placed in 10mL and contains 0.01mol/L NaNO3In 100 μ g/L trivalent antimonies or quinquevalence antimony solution, 4h, measurement are vibrated
The concentration of antimony obtains the adsorption efficiency (as shown in Figure 6) of antimony in the solution of absorption front and back.Although suction of two kinds of adsorbed films to quinquevalence antimony
Attached efficiency is below 5%, but the adsorbed film of SBA-15 mesoporous silicon preparation is up to 98.5% to the adsorption efficiency of trivalent antimony ion,
Much higher than the preparation of commercially available sulfydryl silicon adsorbed film to the adsorption efficiency of trivalent antimony ion.The reason is that the suction of SBA-15 mesoporous silicon preparation
Membrane has more absorption points on monolithic membrane.These results suggest that the absorption prepared using sulfydryl modification SBA-15 material
Film is substantially better than the adsorbed film prepared using sulfydryl silica gel to the adsorption effect of trivalent antimony.
Comparative example 2
Embodiment 1 is compared, and distinctive points are only that:
This comparative example is during preparing trivalent selectivity antimony adsorbed film:
Rear and polyacrylamide sol solution is fully ground using the SBA-15 mesoporous silicon of the double modifications of sulfhydryl amino in step 1
It is uniformly mixed so as to obtain glue solution, ultrasound mixes well solution in 15 minutes；
Remaining is the same as embodiment 1.
In this comparative example, the adsorbed film of SBA-15 mesoporous silicon preparation sulfhydryl modified in embodiment 1 (is indicated in Fig. 7
For SBA glue) it (is expressed as in Fig. 7 with the adsorbed film of the SBA-15 mesoporous silicons preparation of the double modifications of sulfhydryl amino in this comparative example
NSBA glue) area is cut into as 2.51cm2Disk (as combine film), then, be respectively placed in 10mL and contain 0.01mol/L
NaNO3In trivalent antimony or quinquevalence antimony solution, solution concentration is 50 μ g/L, measures the concentration for adsorbing antimony in the solution of front and back after vibrating 4h
The adsorption efficiency (such as Fig. 7) of antimony is obtained, two kinds of adsorbed films are above 95% to the adsorption efficiency of trivalent antimony, good can adsorb
Trivalent antimony.But NSBA glue is up to 20%, significantly larger than adsorption efficiency of the SBA glue to quinquevalence antimony to the adsorption efficiency of quinquevalence antimony
(being lower than 5%), therefore, NSBA glue cannot achieve the purpose of the fixed trivalent antimony of selectivity.
Claims (10)
1. a kind of selective fixing means of trivalent antimony, it is characterised in that: be evenly distributed with sulfhydryl modified SBA-15 using surface
The polyacrylamide hydrogel film of mesoporous silicon carries out selectivity to trivalent antimony and fixes as adsorbed film.
2. a kind of selective fixing means of trivalent antimony according to claim 1, it is characterised in that: the tool of the adsorbed film
Preparation step is as follows:
Step 1: it is molten that the sulfhydryl modified SBA-15 mesoporous silicon and polyacrylamide sol solution after grinding is uniformly mixed so as to obtain glue
Liquid；
Step 2: ammonium persulfate solution and tetramethyl diethylamine solution are sequentially added in glue solution, and mixed liquor is made；
Step 3: mixed liquor injection being accompanied in two glass sheets gaps of U-shaped plastic spacers piece, drives bubble between glass plate out of,
To the solution gel film forming in glass plate, is impregnated 24 hours or more in pure water, during which change water 3~5 times, obtain the suction
Membrane.
3. a kind of selective fixing means of trivalent antimony according to claim 2, it is characterised in that: the system of the adsorbed film
In standby step 1, the ratio of the addition volume B of the addition quality A and polyacrylamide sol solution of sulfhydryl modified SBA-15 mesoporous silicon
Value is 1:(12~25) g/mL, it is uniformly mixed so as to obtain glue solution, ultrasound mixes well solution in 15~20 minutes.
4. a kind of selective fixing means of trivalent antimony according to claim 2, it is characterised in that: the system of the adsorbed film
In standby step 2, the ammonium persulfate volume of addition is the 1/90~1/200 of glue liquor capacity, and the tetramethyl diethylamine of addition is molten
Liquid product is the 1/500~1/600 of glue liquor capacity.
5. a kind of selective fixing means of trivalent antimony according to claim 1, it is characterised in that: the system of the adsorbed film
In standby step 3, the glass plate for being marked with mixed liquor is horizontally arranged, under conditions of 42~46 DEG C, 15~50min is placed, makes glass
Solution gel film forming in glass plate.
6. a kind of selective fixing means of trivalent antimony according to claim 1, it is characterised in that: the system of the adsorbed film
In standby step 1, the preparation step of sulfhydryl modified SBA-15 mesoporous silicon is as follows:
(1) by polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, 2mol L-1Hydrochloric acid be added conical flask
In, after the dissolution of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, be successively added dropwise ethyl orthosilicate and
Mercaptopropyi trimethoxy silane stirs 22 hours at 40 DEG C, then moves into the autoclave that temperature is 90~110 DEG C,
By the cooling suction filtration of product after 24 hours, wash, vacuum drying；
(2) product that step (1) is prepared is in 95% ethyl alcohol, and heating stirring simultaneously flows back 20~26 hours, washing, vacuum
To get sulfhydryl modified SBA-15 mesoporous silicon after drying.
7. a kind of selective fixing means of trivalent antimony according to claim 6, it is characterised in that: described sulfhydryl modified
In the preparation step (1) of SBA-15 mesoporous silicon, silicone content is polyethylene oxide-polycyclic oxygen third in the ethyl orthosilicate of the dropwise addition
Alkane-polyethylene oxide triblock copolymer molal quantity 3~6%, be added dropwise mercaptopropyi trimethoxy silane in silicone content account for it is mixed
Close 10~30% of total silicon molal quantity in liquid.
8. a kind of selective fixing means of trivalent antimony according to claim 6, it is characterised in that: described sulfhydryl modified
In the preparation step (1) of SBA-15 mesoporous silicon, the time interval that ethyl orthosilicate and mercaptopropyi trimethoxy silane is added is
60~120min.
9. a kind of fixed adsorbed film of the selectivity of trivalent antimony, it is characterised in that: the adsorbed film is any using claim 2 to 8
The preparation method of adsorbed film described in obtains.
10. a kind of fixed adsorbed film of selectivity as claimed in claim 9, it is characterised in that: as film is combined, be applied to
In DGT technology.
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