CN102489256B - Preparation of composite material having enrichment effect on heavy metal ions - Google Patents
Preparation of composite material having enrichment effect on heavy metal ions Download PDFInfo
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- CN102489256B CN102489256B CN201110380254.7A CN201110380254A CN102489256B CN 102489256 B CN102489256 B CN 102489256B CN 201110380254 A CN201110380254 A CN 201110380254A CN 102489256 B CN102489256 B CN 102489256B
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 150000002500 ions Chemical class 0.000 title claims abstract description 48
- 230000000694 effects Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 62
- 238000004140 cleaning Methods 0.000 claims abstract description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 103
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- 235000019441 ethanol Nutrition 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 3
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 claims description 3
- XGIDEUICZZXBFQ-UHFFFAOYSA-N 1h-benzimidazol-2-ylmethanethiol Chemical compound C1=CC=C2NC(CS)=NC2=C1 XGIDEUICZZXBFQ-UHFFFAOYSA-N 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003463 sulfur Chemical class 0.000 claims description 3
- -1 2,2'-dipyridyl disulfides Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 3
- 238000006056 electrooxidation reaction Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 26
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 10
- VHJLVAABSRFDPM-QWWZWVQMSA-N dithiothreitol Chemical compound SC[C@@H](O)[C@H](O)CS VHJLVAABSRFDPM-QWWZWVQMSA-N 0.000 description 10
- 229910052793 cadmium Inorganic materials 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 8
- 230000000274 adsorptive effect Effects 0.000 description 6
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 230000004936 stimulating effect Effects 0.000 description 5
- 108010024636 Glutathione Proteins 0.000 description 4
- 229960003180 glutathione Drugs 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- RWPHLPTXMDOTHS-UHFFFAOYSA-N 1H-imidazole-4,5-dithiol Chemical class SC1=C(N=CN1)S RWPHLPTXMDOTHS-UHFFFAOYSA-N 0.000 description 1
- NYQWTKITKMJQSI-UHFFFAOYSA-N 2-phenyl-1h-imidazole-5-thiol Chemical compound N1C(S)=CN=C1C1=CC=CC=C1 NYQWTKITKMJQSI-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
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- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
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- 239000011133 lead Substances 0.000 description 1
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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Abstract
The invention provides a preparation method of a composite material having an enrichment effect on heavy metal ions. The method comprises the following steps: 1, pretreating a silicon chip, and carrying out electrochemical corrosion to obtain a porous silicon chip; 2, cleaning porous silicon chip; and 3, grafting disulfide bond grafted imidazole groupsto the surface of the porous silicon chip through adopting a multi-step organic synthesis reaction comprising mercapto group grafting, pyridine ring grafting and imidazole group grafting to obtain the composite material having an enrichment effect on the heavy metal ions. The organically modified porous silicon-based composite material provided in the invention has the to trace heavy metal cadmium ion selective adsorption characteristic, the enrichment capability of the composite material to the cadmium ions can reach above 10 times, and groups adsorbed with the metal cadmium ions can depart from the surface of the composite material under the action of a small amount of a reducing agent to reach a separation purpose. The method of the invention has the characteristics of simplicity, high efficiency and the like.
Description
Technical field
The present invention relates to a kind of preparation method heavy metal ion to the composite of enrichment.
Background technology
In recent decades, along with developing rapidly of modern industry, many pollutants containing heavy metal ion enter atmosphere, water and soil environment, cause serious environmental pollution.Heavy metal pollution in environment mainly contains mercury, cadmium, lead, copper, chromium, nickel etc.The heavy metal of discharging with waste water, even if concentration is minimum, also can in algae and bed mud, accumulate, by fish and shellfish body surface, adsorbed, generation food chain is concentrated, and heavy metal can not be by organism institute decomposition and inversion, so easily accumulation in vivo can directly threaten higher organism to comprise the mankind's health.In recent years, of common occurrence about heavy metal pollution event, Hunan Ferroalloy Group Co., Ltd causes pollution of chromium event, cadmium pollution event is caused in the Hunan of Liuyang and chemical plant, Fengxiang, Shaanxi, thousand children blood leads of Jiyuan, Henan event that exceeds standard, a series of heavy metal pollution events order whole nation shocks of the ground outbursts such as Shanghang, Fujian, Jiyuan, Henan, Yancheng, Jiangsu Province, Guangdong Qingyuan.More alarming, these events are only the tips of the iceberg of heavy metal pollution, and visible heavy metal pollution has had influence on our living environment.
Recycling for the trace heavy metal ion in water body has important and actual meaning.But for now, the trace element in Accurate Determining geology, biology and environmental sample becomes in analytical chemistry the content of heavy metal ion in very important and challenging work, especially an environmental water sample and need do conventional monitoring.Often need that in this case sample is carried out to pretreatment-concentration and separation just can measure later accurately.Trace metal ion enrichment is more and more being paid close attention to and is being studied.
Summary of the invention
For solving the recovery problem of the trace heavy metal ion in water body, the invention provides a kind of preparation method heavy metal ion to the composite of enrichment, take porous silicon as substrate, prepare porous silicon surface, to realize the enrichment to heavy metal ion, by following technical proposal, realize.
Preparation method heavy metal ion to the composite of enrichment, following each step of process:
A. silicon chip is carried out to pretreatment;
B. hydrofluoric acid=0.5～2 ︰ 1～10 ︰ 0.5～5 that is 5～60% for Qu Li Shui ︰ Wu Shui Yi Chun ︰ mass concentration is by volume mixed with corrosive liquid;
C. using the pretreated silicon chip of steps A gained as anode, put into step B gained corrosive liquid, using platinized platinum as negative pole, two ends pass into 5～100mA/cm
2electric current, through the electrolytic corrosion effect of 5～80min, obtain aperture and be the porous silicon of 5～10 microns;
D. step C gained porous silicon is used successively absolute ethyl alcohol, deionized water ultrasonic lower cleaning 1～30 minute, then porous silicon is placed in to temperature is 5～60min or irradiate under low pressure mercury lamp 0.5～4 hour at 100～300 ℃;
E. go from sub-water ︰ ammonia water ︰ absolute ethyl alcohol=0.5～5 ︰ 1～10 ︰ 0.5～5 ︰ 10～100 to be mixed into mixed liquor I for 3-mercaptoalkyl triethoxysilane or 3-mercaptoalkyl three methoxy silane ︰ by volume, step D gained porous silicon is put into mixed liquor I, at 30～90 ℃, stir after 5～20 hours, use successively ethanol and deionized water at ultrasonic lower cleaning 1～10min porous silicon chip, finally with nitrogen, dry up;
F. by solid-to-liquid ratio, be that two pyridine two sulphur Yan Sheng Wu ︰ acetonitrile=0.01～0.5 ︰ 10～30 are mixed to get mixed liquor II, step e gained porous silicon is put into mixed liquor II, at 5～20 ℃, lucifuge stirred after 12～72 hours, use successively acetonitrile, ethanol and deionized water at ultrasonic lower cleaning 1～10min porous silicon, finally with nitrogen, dry up;
G. by solid-to-liquid ratio, be that dimercapto Mi Zuo Yan Sheng Wu ︰ absolute ethyl alcohol=0.05～1 ︰ 10～50 is mixed to get mixed liquor III, step F gained porous silicon is put into mixed liquor III, at room temperature lucifuge stirred after 12～48 hours, use successively ethanol and deionized water at ultrasonic lower cleaning 1～10min porous silicon, finally with nitrogen, dry up, obtain heavy metal ion to have the composite of enrichment.
The pretreatment of described step e is to use successively ethanol, deionized water ultrasonic lower cleaning 1～20 minute silicon chip, then the hydrofluoric acid dips that is 5～40% by mass concentration 1～10 minute.
Two pyridine two sulfur derivatives of described step F comprise 4,4 ' two pyridine two sulphur or 2,2 ' two pyridine two sulphur.
The dimercapto imdazole derivatives of described step G comprises 2-mercaptobenzimidazole, 2-mercaptoimidazole, 2-sulfydryl-1-methylimidazole, 2 mercaptomethyl benzimidazole or 2-sulfydryl-5-methoxyl group benzo imidazoles.
Described 3-mercaptoalkyl triethoxysilane, 3-mercaptoalkyl trimethoxy silane, ammoniacal liquor, absolute ethyl alcohol, acetonitrile, 4,4 ' two pyridine two sulphur, 2,2 ' two pyridine two sulphur, 2-mercaptobenzimidazole, 2-mercaptoimidazole, 2-sulfydryl-1-methylimidazole, 2 mercaptomethyl benzimidazole, that 2-sulfydryl-5-methoxyl group benzo imidazoles is commercial analysis is pure.
By preparing gained, heavy metal ion is there is to the composite of enrichment, adopt static adsorptive method to carry out enrichment to the heavy metal ion in water body, concrete steps are as follows: the composite that heavy metal ion is had to an enrichment preparing is put into 100mL conical flask, regulator solution pH value is 4～7, with pipette, pipetting concentration of heavy metal ion is that solution 10～100mL of 0.01～1ppm adds in conical flask, shake after 1～24 hour, composite is taken out and puts into small test tube, in small test tube, add again 1～5mL containing after the reductant solution of sulfydryl, standing 2～10 hours to guarantee that disulfide bond is as much as possible by under disconnected, finally take out composite, liquid remaining in small test tube is done to the concentration effect that Atomic absorption detects heavy metal.
The present invention receives porous silicon surface by Silanization reaction by thiohydroxy-containing group's ligand molecular, the porous silicon of sulfhydrylation can be by the disulfide bonds in two pyridine two sulfur derivatives, thereby pyridine ring grafting is got on, the ligand molecular of Yong Han imidazoles functional group (dimercapto imidazoles or Mercaptophenylimidazole) removes " attack " formed disulfide bond, and generate new disulfide bond, reached the object of imdazole derivatives substituted pyridines ring, shown in following synthetic route:
To the enrichment of trace heavy metal ion, be by composite being put into the solution of the more trace heavy metal ion of volume, after making it to adsorption of metal ions, from solution, take out, make again it in a small amount of strong reductant, disulfide bond be ruptured, metal ion is together ruptured in solution, reach like this object to metal ion enrichment, shown in following mechanism route:
The effect that the present invention possesses and advantage:
The organic decoration porous silicon-base composite relating in the present invention has the characteristic of selective absorption trace heavy metal cadmium ion, to the enrichment of cadmium ion, can reach more than 10 times, the group that absorption has a cadmium metal ion leaves composite material surface and reaches separated object under the effect of a small amount of strong reductant, and the method has the features such as simple, efficient.
The specific embodiment
Below in conjunction with embodiment, further illustrate content of the present invention, but these examples do not limit the scope of the invention.
Embodiment 1
A. the N-type silicon chip that by resistivity is 0.01 Ω cm carries out pretreatment, uses successively ethanol, deionized water ultrasonic lower cleaning 5 minutes silicon chip, then the hydrofluoric acid dips that is 10% by mass concentration 10 minutes;
B. for pure hydrofluoric acid=1 ︰ 1 ︰ 1 that is 50% Wu Shui Yi Chun ︰ mass concentration of the commercial analysis of Qu Li Shui ︰, be mixed with corrosive liquid by volume;
C. using the pretreated silicon chip of steps A gained as anode, put into step B gained corrosive liquid, using platinized platinum as negative pole, two ends pass into 20mA/cm
2electric current, through the electrolytic corrosion effect of 40min, obtain aperture and be the porous silicon of 5 microns;
D. step C gained porous silicon is used successively the pure absolute ethyl alcohol of commercial analysis, deionized water ultrasonic lower cleaning 30 minutes, then porous silicon is placed in to temperature is 40min at 200 ℃;
E. go from pure absolute ethyl alcohol=0.5 ︰ 5 ︰ 5 ︰ 20 of the commercial analysis of the commercial analysis of sub-water ︰ pure ammonia water ︰ to be mixed into mixed liquor I for commercial analysis pure 3-sulfydryl propyl-triethoxysilicane or the pure 3-mercaptoalkyl three methoxy silane ︰ of commercial analysis by volume, step D gained porous silicon is put into mixed liquor I, at 70 ℃, stir after 20 hours, use successively ethanol and deionized water at ultrasonic lower cleaning 5min porous silicon chip, finally with nitrogen, dry up;
F. by solid-to-liquid ratio, be commercial analysis pure 4, pure acetonitrile=0.1 ︰ 10 of 4 ' the two commercial analyses of Bi pyridine Er Liu ︰ is mixed to get mixed liquor II, step e gained porous silicon is put into mixed liquor II, at 20 ℃, lucifuge stirred after 48 hours, use successively acetonitrile, ethanol and deionized water at ultrasonic lower cleaning 5min porous silicon, finally with nitrogen, dry up;
G. by solid-to-liquid ratio, be that the pure 2-Qiu of commercial analysis base Ben Mi Zuo ︰ absolute ethyl alcohol=0.1 ︰ 20 are mixed to get mixed liquor III, step F gained porous silicon is put into mixed liquor III, at room temperature lucifuge stirred after 24 hours, use successively ethanol and deionized water at ultrasonic lower cleaning 5min porous silicon, finally with nitrogen, dry up, obtain heavy metal ion to have the composite of enrichment.
By preparing gained, heavy metal ion is there is to the composite of enrichment, adopt static adsorptive method to carry out enrichment to the heavy metal ion in water body, concrete steps are as follows: the composite that heavy metal ion is had to an enrichment preparing is put into 100mL conical flask, regulator solution pH value is 6, with pipette, pipetting concentration of heavy metal ion is that the solution 100mL of 0.05ppm adds in conical flask, shake after 24 hours, composite is taken out and puts into small test tube, after adding again 3mL concentration to be the glutathione of 5mM in small test tube, standing 5 hours to guarantee that disulfide bond is as much as possible by under disconnected, finally take out composite, liquid remaining in small test tube is done to the concentration effect that Atomic absorption detects heavy metal: the concentration of finding heavy metal ion cadmium becomes 0.62ppm, this value is compared with original concentration 0.05ppm, after enrichment, the concentration of cadmium has improved 12.4 times, this shows that porous silicon-base composite not only has characterization of adsorption to heavy metal cadmium ion, and under disulfide bond wherein is successfully broken by glutathione, absolutely prove that this porous silicon-base composite has stimulating responsive.
Embodiment 2
A. the P type silicon chip that by resistivity is 0.01～0.09 Ω cm carries out pretreatment, uses successively ethanol, deionized water ultrasonic lower cleaning 20 minutes silicon chip, then the hydrofluoric acid dips that is 5% by mass concentration 5 minutes;
B. for pure hydrofluoric acid=0.5 ︰ 3 ︰ 0.5 that are 5% Wu Shui Yi Chun ︰ mass concentration of the commercial analysis of Qu Li Shui ︰, be mixed with corrosive liquid by volume;
C. using the pretreated silicon chip of steps A gained as anode, put into step B gained corrosive liquid, using platinized platinum as negative pole, two ends pass into 5mA/cm
2electric current, through the electrolytic corrosion effect of 80min, obtain aperture and be the porous silicon of 10 microns;
D. step C gained porous silicon is used successively the pure absolute ethyl alcohol of commercial analysis, deionized water ultrasonic lower cleaning 5 minutes, then porous silicon is placed in to temperature is 60min at 100 ℃;
E. for pure 3-sulfydryl the third base three methoxy silane ︰ of commercial analysis, go from pure absolute ethyl alcohol=2 ︰ 10 ︰ 2 ︰ 10 of the commercial analysis of the commercial analysis of sub-water ︰ pure ammonia water ︰ to be mixed into mixed liquor I by volume, step D gained porous silicon is put into mixed liquor I, at 30 ℃, stir after 18 hours, use successively ethanol and deionized water at ultrasonic lower cleaning 1min porous silicon chip, finally with nitrogen, dry up;
F. by solid-to-liquid ratio, be commercial analysis pure 2, pure acetonitrile=0.5 ︰ 30 of 2 ' the two commercial analyses of Bi pyridine Er Liu ︰ is mixed to get mixed liquor II, step e gained porous silicon is put into mixed liquor II, at 10 ℃, lucifuge stirred after 24 hours, use successively acetonitrile, ethanol and deionized water at ultrasonic lower cleaning 10min porous silicon, finally with nitrogen, dry up;
G. by solid-to-liquid ratio, be that the pure 2-sulfydryl of commercial analysis Mi Zuo ︰ absolute ethyl alcohol=0.05 ︰ 10 is mixed to get mixed liquor III, step F gained porous silicon is put into mixed liquor III, at room temperature lucifuge stirred after 12 hours, use successively ethanol and deionized water at ultrasonic lower cleaning 10min porous silicon, finally with nitrogen, dry up, obtain heavy metal ion to have the composite of enrichment.
By preparing gained, heavy metal ion is there is to the composite of enrichment, adopt static adsorptive method to carry out enrichment to the heavy metal ion in water body, concrete steps are as follows: the composite that heavy metal ion is had to an enrichment preparing is put into 100mL conical flask, regulator solution pH value is 7, with pipette, pipetting concentration of heavy metal ion is that the solution 100mL of 0.1ppm adds in conical flask, shake after 24 hours, composite is taken out and puts into small test tube, after the dithiothreitol (DTT) that the concentration that adds again 3mL in small test tube is 10mM, standing 5 hours to guarantee that disulfide bond is as much as possible by under disconnected, finally take out composite, liquid remaining in small test tube is done to the concentration effect that Atomic absorption detects heavy metal: the concentration of finding mercury ion becomes 1.45ppm, this value is compared with original concentration 0.1ppm, after enrichment, the concentration of cadmium has improved 14.5 times, this shows that porous silicon-base composite all has characterization of adsorption to cadmium ion and mercury ion, and under disulfide bond wherein is successfully broken by dithiothreitol (DTT), absolutely prove that this porous silicon-base composite has stimulating responsive.
Embodiment 3
A. the P type silicon chip that by resistivity is 0.01～0.09 Ω cm carries out pretreatment, uses successively ethanol, deionized water ultrasonic lower cleaning 1 minute silicon chip, then the hydrofluoric acid dips that is 40% by mass concentration 1 minute;
B. for pure hydrofluoric acid=2 ︰ 10 ︰ 5 that are 60% Wu Shui Yi Chun ︰ mass concentration of the commercial analysis of Qu Li Shui ︰, be mixed with corrosive liquid by volume;
C. using the pretreated silicon chip of steps A gained as anode, put into step B gained corrosive liquid, using platinized platinum as negative pole, two ends pass into 100mA/cm
2electric current, through the electrolytic corrosion effect of 5min, obtain aperture and be the porous silicon of 8 microns;
D. step C gained porous silicon is used successively the pure absolute ethyl alcohol of commercial analysis, deionized water ultrasonic lower cleaning 1 minute, then porous silicon is placed under low pressure mercury lamp and is irradiated 4 hours;
E. for the pure 3-sulfydryl of commercial analysis fourth ethyl triethoxy silicane alkane ︰, go from pure absolute ethyl alcohol=5 ︰ 1 ︰ 0.5 ︰ 100 of the commercial analysis of the commercial analysis of sub-water ︰ pure ammonia water ︰ to be mixed into mixed liquor I by volume, step D gained porous silicon is put into mixed liquor I, at 90 ℃, stir after 5 hours, use successively ethanol and deionized water at ultrasonic lower cleaning 10min porous silicon chip, finally with nitrogen, dry up;
F. by solid-to-liquid ratio, be commercial analysis pure 4, pure acetonitrile=0.01 ︰ 20 of 4 ' the two commercial analyses of Bi pyridine Er Liu ︰ is mixed to get mixed liquor II, step e gained porous silicon is put into mixed liquor II, at 5 ℃, lucifuge stirred after 12 hours, use successively acetonitrile, ethanol and deionized water at ultrasonic lower cleaning 1min porous silicon, finally with nitrogen, dry up;
G. by solid-to-liquid ratio, be that the pure 2-sulfydryl-1-of commercial analysis Jia base Mi Zuo ︰ absolute ethyl alcohol=1 ︰ 50 is mixed to get mixed liquor III, step F gained porous silicon is put into mixed liquor III, at room temperature lucifuge stirred after 48 hours, use successively ethanol and deionized water at ultrasonic lower cleaning 1min porous silicon, finally with nitrogen, dry up, obtain heavy metal ion to have the composite of enrichment.
By preparing gained, heavy metal ion is there is to the composite of enrichment, adopt static adsorptive method to carry out enrichment to the heavy metal ion in water body, concrete steps are as follows: the composite that heavy metal ion is had to an enrichment preparing is put into 100mL conical flask, regulator solution pH value is 6, with pipette, pipetting concentration of heavy metal ion is that the solution 100mL of 0.05ppm adds in conical flask, shake after 20 hours, composite is taken out and puts into small test tube, after adding again 3mL concentration to be the glutathione of 5mM in small test tube, standing 5 hours to guarantee that disulfide bond is as much as possible by under disconnected, finally take out composite, liquid remaining in small test tube is done to the concentration effect that Atomic absorption detects heavy metal: the concentration of finding heavy metal ion cadmium becomes 0.68ppm, this value is compared with original concentration 0.05ppm, after enrichment, the concentration of cadmium has improved 13.6 times, this shows that porous silicon-base composite not only has characterization of adsorption to heavy metal cadmium ion, and under disulfide bond wherein is successfully broken by glutathione, absolutely prove that this porous silicon-base composite has stimulating responsive.
Embodiment 4
A. the P type silicon chip that by resistivity is 0.01～0.09 Ω cm carries out pretreatment, uses successively ethanol, deionized water ultrasonic lower cleaning 10 minutes silicon chip, then the hydrofluoric acid dips that is 20% by mass concentration 8 minutes;
B. hydrofluoric acid=1.5 ︰ 5 ︰ 2 that are 20% for Qu Li Shui ︰ Wu Shui Yi Chun ︰ mass concentration are by volume mixed with corrosive liquid;
C. using the pretreated silicon chip of steps A gained as anode, put into step B gained corrosive liquid, using platinized platinum as negative pole, two ends pass into 80mA/cm
2electric current, through the electrolytic corrosion effect of 60min, obtain aperture and be the porous silicon of 6 microns;
D. step C gained porous silicon is used successively absolute ethyl alcohol, deionized water ultrasonic lower cleaning 20 minutes, then porous silicon is placed in to temperature is 5min at 300 ℃;
E. for 3-mercapto methyl three methoxy silane ︰, go from sub-water ︰ ammonia water ︰ absolute ethyl alcohol=3 ︰ 8 ︰ 3 ︰ 50 to be mixed into mixed liquor I by volume, step D gained porous silicon is put into mixed liquor I, at 80 ℃, stir after 15 hours, use successively ethanol and deionized water at ultrasonic lower cleaning 8min porous silicon chip, finally with nitrogen, dry up;
F. by solid-to-liquid ratio, be 2,2 ' two Bi pyridine Er Liu ︰ acetonitrile=0.3 ︰ 15 are mixed to get mixed liquor II, step e gained porous silicon is put into mixed liquor II, at 15 ℃, lucifuge stirred after 72 hours, use successively acetonitrile, ethanol and deionized water at ultrasonic lower cleaning 8min porous silicon, finally with nitrogen, dry up;
G. by solid-to-liquid ratio, be that 2-mercapto methyl Ben Mi Zuo ︰ absolute ethyl alcohol=0.5 ︰ 30 are mixed to get mixed liquor III, step F gained porous silicon is put into mixed liquor III, at room temperature lucifuge stirred after 36 hours, use successively ethanol and deionized water at ultrasonic lower cleaning 8min porous silicon, finally with nitrogen, dry up, obtain heavy metal ion to have the composite of enrichment.
By preparing gained, heavy metal ion is there is to the composite of enrichment, adopt static adsorptive method to carry out enrichment to the heavy metal ion in water body, concrete steps are as follows: the composite that heavy metal ion is had to an enrichment preparing is put into 100mL conical flask, regulator solution pH value is 7, with pipette, pipetting concentration of heavy metal ion is that the solution 100mL of 0.1ppm adds in conical flask, shake after 24 hours, composite is taken out and puts into small test tube, in small test tube, add again 3mL containing after the reductant solution of sulfydryl, standing 5 hours to guarantee that disulfide bond is as much as possible by under disconnected, finally take out composite, liquid remaining in small test tube is done to the concentration effect that Atomic absorption detects heavy metal: the concentration of finding mercury ion becomes 1.57ppm, this value is compared with original concentration 0.1ppm, after enrichment, the concentration of cadmium has improved 15.7 times, this shows that porous silicon-base composite all has characterization of adsorption to cadmium ion and mercury ion, and under disulfide bond wherein is successfully broken by dithiothreitol (DTT), absolutely prove that this porous silicon-base composite has stimulating responsive.
Embodiment 5
A. the N-type silicon chip that by resistivity is 0.01 Ω cm carries out pretreatment, uses successively ethanol, deionized water ultrasonic lower cleaning 12 minutes silicon chip, then the hydrofluoric acid dips that is 30% by mass concentration 8 minutes;
B. hydrofluoric acid=0.8 ︰ 8 ︰ 4 that are 55% for Qu Li Shui ︰ Wu Shui Yi Chun ︰ mass concentration are by volume mixed with corrosive liquid;
C. using the pretreated silicon chip of steps A gained as anode, put into step B gained corrosive liquid, using platinized platinum as negative pole, two ends pass into 90mA/cm
2electric current, through the electrolytic corrosion effect of 70min, obtain aperture and be the porous silicon of 9 microns;
D. step C gained porous silicon is used successively absolute ethyl alcohol, deionized water ultrasonic lower cleaning 25 minutes, then porous silicon is placed under low pressure mercury lamp and is irradiated 0.5 hour;
E. for 3-sulfydryl the third base three methoxy silane ︰, go from sub-water ︰ ammonia water ︰ absolute ethyl alcohol=3 ︰ 8 ︰ 3 ︰ 40 to be mixed into mixed liquor I by volume, step D gained porous silicon is put into mixed liquor I, at 80 ℃, stir after 9 hours, use successively ethanol and deionized water at ultrasonic lower cleaning 8min porous silicon chip, finally with nitrogen, dry up;
F. by solid-to-liquid ratio, be 2,2 ' two Bi pyridine Er Liu ︰ acetonitrile=0.3 ︰ 30 are mixed to get mixed liquor II, step e gained porous silicon is put into mixed liquor II, at 16 ℃, lucifuge stirred after 60 hours, use successively acetonitrile, ethanol and deionized water at ultrasonic lower cleaning 8min porous silicon, finally with nitrogen, dry up;
G. by solid-to-liquid ratio, be that 2-sulfydryl-5-methoxyl group benzo miaow azoles ︰ absolute ethyl alcohol=0.8 ︰ 30 is mixed to get mixed liquor III, step F gained porous silicon is put into mixed liquor III, at room temperature lucifuge stirred after 30 hours, use successively ethanol and deionized water at ultrasonic lower cleaning 10min porous silicon, finally with nitrogen, dry up, obtain heavy metal ion to have the composite of enrichment.
By preparing gained, heavy metal ion is there is to the composite of enrichment, adopt static adsorptive method to carry out enrichment to the heavy metal ion in water body, concrete steps are as follows: the composite that heavy metal ion is had to an enrichment preparing is put into 100mL conical flask, regulator solution pH value is 7, with pipette, pipetting concentration of heavy metal ion is that the solution 100mL of 0.1ppm adds in conical flask, shake after 24 hours, composite is taken out and puts into small test tube, after the dithiothreitol (DTT) that the concentration that adds again 3mL in small test tube is 10mM, standing 5 hours to guarantee that disulfide bond is as much as possible by under disconnected, finally take out composite, liquid remaining in small test tube is done to the concentration effect that Atomic absorption detects heavy metal: the concentration of finding mercury ion becomes 1.52ppm, this value is compared with original concentration 0.1ppm, after enrichment, the concentration of cadmium has improved 15.2 times, this shows that porous silicon-base composite all has characterization of adsorption to cadmium ion and mercury ion, and under disulfide bond wherein is successfully broken by dithiothreitol (DTT), absolutely prove that this porous silicon-base composite has stimulating responsive.
Claims (2)
1. heavy metal ion is there is to a preparation method for the composite of enrichment, it is characterized in that through following each step:
A. silicon chip is carried out to pretreatment: use successively ethanol, deionized water ultrasonic lower cleaning 1～20 minute silicon chip, then the hydrofluoric acid dips that is 5～40% by mass concentration 1～10 minute;
B. hydrofluoric acid=0.5～2 ︰ 1～10 ︰ 0.5～5 that is 5～60% for Qu Li Shui ︰ Wu Shui Yi Chun ︰ mass concentration is by volume mixed with corrosive liquid;
C. using the pretreated silicon chip of steps A gained as anode, put into step B gained corrosive liquid, using platinized platinum as negative pole, two ends pass into 5～100mA/cm
2electric current, the electrolytic corrosion effect through 5～80min, obtains porous silicon chip;
D. step C gained porous silicon chip is used successively absolute ethyl alcohol, deionized water ultrasonic lower cleaning 1～30 minute, then porous silicon chip is placed at 100～300 ℃ to 5～60min or under low pressure mercury lamp, irradiates 0.5～4 hour;
E. go from sub-water ︰ ammonia water ︰ absolute ethyl alcohol=0.5～5 ︰ 1～10 ︰ 0.5～5 ︰ 10～100 to be mixed into mixed liquor I for 3-mercaptoalkyl triethoxysilane or 3-mercaptoalkyl three methoxy silane ︰ by volume, step D gained porous silicon chip is put into mixed liquor I, at 30～90 ℃, stir after 5～20 hours, use successively ethanol and deionized water at ultrasonic lower cleaning 1～10min porous silicon chip, finally with nitrogen, dry up;
F. by solid-to-liquid ratio, be that two pyridine two sulphur Yan Sheng Wu ︰ acetonitrile=0.01～0.5 ︰ 10～30 are mixed to get mixed liquor II, step e gained porous silicon chip is put into mixed liquor II, at 5～20 ℃, lucifuge stirred after 12～72 hours, use successively acetonitrile, ethanol and deionized water at ultrasonic lower cleaning 1～10min porous silicon chip, finally with nitrogen, dry up;
G. by solid-to-liquid ratio, be that material A ︰ absolute ethyl alcohol=0.05～1 ︰ 10～50 is mixed to get mixed liquor III, wherein substance A comprises 2-mercaptobenzimidazole, 2-mercaptoimidazole, 2-sulfydryl-1-methylimidazole, 2 mercaptomethyl benzimidazole or 2-sulfydryl-5-methoxyl group benzo imidazoles, again step F gained porous silicon chip is put into mixed liquor III, at room temperature lucifuge stirred after 12～48 hours, use successively ethanol and deionized water at ultrasonic lower cleaning 1～10min porous silicon chip, finally with nitrogen, dry up, obtain heavy metal ion to have the composite of enrichment.
2. preparation method according to claim 1, is characterized in that: two pyridine two sulfur derivatives of described step F comprise 4,4 '-bis-pyridine two sulphur or 2,2'-dipyridyl disulfides.
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