CN108421280A - A kind of sulfhydrylation organic-inorganic hybridization monolithic column and its preparation method and purposes - Google Patents
A kind of sulfhydrylation organic-inorganic hybridization monolithic column and its preparation method and purposes Download PDFInfo
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- CN108421280A CN108421280A CN201810149074.XA CN201810149074A CN108421280A CN 108421280 A CN108421280 A CN 108421280A CN 201810149074 A CN201810149074 A CN 201810149074A CN 108421280 A CN108421280 A CN 108421280A
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- 238000009396 hybridization Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 49
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000004458 analytical method Methods 0.000 claims abstract description 8
- 239000007790 solid phase Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000002470 solid-phase micro-extraction Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical class CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 238000004853 microextraction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000005259 measurement Methods 0.000 abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 4
- 239000001230 potassium iodate Substances 0.000 abstract description 4
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 abstract description 4
- 229940093930 potassium iodate Drugs 0.000 abstract description 4
- 235000006666 potassium iodate Nutrition 0.000 abstract description 4
- 238000002203 pretreatment Methods 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 16
- 239000012488 sample solution Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000003396 thiol group Chemical class [H]S* 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011490 mineral wool Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 238000000918 plasma mass spectrometry Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
A kind of sulfhydrylation organic inorganic hybridization integral post, it is the mercapto-functionalized organic inorganic hybridization capillary monolithic column synthesized by the method for a step copolycondensation.The sulfydryl on the integral material surface can selectively adsorb As (III), the pin type solid-phase micro-extracting device of the integral post can within the scope of wider pH selective extraction As (III), and the As (V) being not preserved directly is collected；The As (III) of absorption is then eluted and collected measurement with nitric acid/potassium iodate solution, realizes the separation analysis of two kinds of inorganic arsenic morphologies.Compared with other sulfydryl Monolithic Columns, this method simple, favorable reproducibility using " one-step method " preparation manipulation, and sulfydryl is made to be more evenly distributed, mechanical strength is good；Pin type solid-phase micro-extracting device is simple, is easy and fast to complete the acquisition separation analysis that sample pre-treatments can be used for live water sample.
Description
Technical field：
The present invention relates to a kind of mercapto-functionalized organic-inorganic hybridization monolithic columns for inorganic arsenium morphological analysis, specifically
Say it is a kind of novel mercapto functionalization integral post material to be obtained based on the synthesis of novel ternary weakly alkaline solution system " one-step method "
Separation of the solid-phase micro-extracting device of material and syringe needle solid phase micro-extraction device structure for As (III) and As (V) is analyzed.
Background introduction：
Arsenic can all cause the health of the entire ecosystem and the mankind serious as a kind of trace element being widely present
Destruction.It is currently, there are the arsenic pollution in soil, underground water and drinking water and has become a global problem.
Arsenic is mainly derived from deposit containing arsenic, metallurgy, pesticide, chemical fertilizer, coal combustion and industrial wastewater discharge etc..Research shows that the poison of arsenic
Behavior of science and its existing forms are closely related, it is generally the case that the toxicity of inorganic arsenic is more than organo-arsenic, and trivalent in inorganic arsenic
The toxicity of arsenic (As (III)) and significantly greater than pentavalent arsenic (As (V)).In environment water, most important arsenic morphology is inorganic arsenic,
It endangers maximum.The World Health Organization (World Health Organization, referred to as WHO) is for Arsenic in Drinking Water
Limit value is 10 μ g/L, and less than the detection limit value of existing conventional determination of trace element instrument, and the concentration of As (III) limits in drinking water
Value is then relatively lower, and most elements detecting instrument can only measure total amount can not distinguish its different form.Therefore, it develops
A kind of simple and practical method is of great significance for inorganic arsenic morphology in pre-separation enrichment water body.
As (III) and As (V) exists in nature and unstable, the two in oxidisability matrix or reproducibility matrix
It may occur mutually to convert.Lab analysis will be transported back by generally requiring at present after water sampling, sample transport and storage need
Longer time, and it is usually required for time-consuming pre-treatment, these processes increase the risk of arsenic morphology conversion.Therefore development one
The easy method of kind completes sample pre-treatments in sampling location and has great importance.
The deficiency of the existing method for preparing sulfydryl organic-inorganic hybridization monolithic column：Since mercapto reagent exists centainly
Faintly acid directly prepares the integral post containing sulfydryl there are certain difficulty, thus existing mercapto-functionalized hybrid inorganic-organic
There are two main classes for the preparation method of integral post：One is sulfydryl is introduced into the whole spinous process of the seventh cervical vertebra prepared by way of rear modification
Frame surface；Either the silane reagent containing sulfydryl is mixed with tetraethoxy/methoxy silane reagent, elder generation in acid condition into
Row hydrolysis is then added alkaline reagent and is polymerize to obtain.But there are still some problems for most common method at present for both：It is logical
Later the material that the method modified obtains, sulfydryl exist only in the surface of integral material, and can not the distribution of assurance function group
Uniformity, reproducibility is low.And in the second approach, after alkaline reagent is added, polymerization is very fast so that integral material
It is combined not enough securely between capillary wall, Monolithic Columns are easy to happen de- wall, influence service life.Meanwhile mesh first two
All there is the problems such as cumbersome, to take in method.
The deficiency of existing solid-phase extraction device：Existing solid-phase extraction device is typically to insert material in one section of blank pipe
(such as glass tube, polyfluortetraethylene pipe or stainless steel tube) needs in filling process the both ends of pipe to clog mineral wool by material
It is fixed.This preparation method has the following problems：First, the solid-phase extraction column column pressure of formation is very big, in particular by size compared with
When small packing material, larger flow velocity；Second, clogging the consistency of mineral wool can not ensure, lead to the Solid Phase Extraction prepared
Column is less reproducible.
Invention content：
The present invention provides a kind of new approaches preparing sulfhydrylation organic-inorganic hybridization monolithic column and for inorganic arsenic morphology
Quick separating is analyzed, specially a kind of preparation method preparing sulfydryl hydridization integral post by " one-step method "；One kind passing through pin type
The method that solid-phase micro-extracting device realizes the analysis of inorganic arsenic form fractionation.
Technical scheme is as follows：
A kind of sulfhydrylation organic-inorganic hybridization monolithic column, what it was prepared as follows：
130 μ L ethyl alcohol, 10% ammonium hydroxide of 173 μ L isopropanols and 152 μ L mixed liquor in be added 33.3mg cetyls
Trimethylammonium bromide (CTAB), vortex are completely dissolved to solid, then solution clear takes 300 μ L tetraethoxysilanes
(TEOS) it is added in above-mentioned clear solution with 100 μ L mercaptopropyl trimethoxysilanes (MPTMS), vortex mixing, in 0 DEG C of ice water
After middle ultrasound 30s, injection in activated capillary, after capillary sealing two ends, heats 20h in 45 DEG C of water-baths, cold
But it to after room temperature, uses methanol, water to rinse integral post successively, unreacted reagent and template CTAB is removed, later by sulfydryl
Change organic-inorganic hybridization monolithic column be stored in it is spare in 4 DEG C of refrigerators, reaction schematic diagram see Fig. 1.
The specific surface area of obtained sulfhydrylation organic-inorganic hybridization monolithic column material is 68.51m2/ g, average pore size are
7.124nm；Amount containing S is 3.31 ± 0.02mmol/g；It is 2.32 μ g/cm to trivalent arsenic adsorption capacity.
A kind of pin type solid phase micro-extraction device using above-mentioned sulfhydrylation organic-inorganic hybridization monolithic column, its following legal system
It is standby：The suitable syringe needle of size is chosen, metal needle is discarded, only retains base portion, intercepted length is the above-mentioned mercapto of 5cm
Base organic-inorganic hybridization monolithic column substitutes original metal needle and fixation, obtains pin type solid phase micro-extraction device, sees Fig. 2.
Application of the above-mentioned sulfhydrylation organic-inorganic hybridization monolithic column in the separation and concentration of inorganic arsenic.
A kind of method of the separation of inorganic arsenic, enrichment and analysis, it includes the following steps：
Sample to be tested is adjusted to pH 4.0 by step 1 with 1% (v/v) dust technology, takes the sample solution (volume of certain volume
It is denoted as V), with 200 μ L min-1Flow velocity by sulfhydrylation organic-inorganic hybridization monolithic column, trivalent arsenic is selectively inhaled at this time
Be attached in sulfhydrylation organic-inorganic hybridization monolithic column, and pentavalent arsenic is then not preserved and flows directly out, collect efflux, then with
200μL min-1Flow velocity 200 μ L 3% (v/v) nitric acid (Potassiumiodate containing 0.01M) are whole by sulfhydrylation hybrid inorganic-organic
Scapus, at this time trivalent arsenic be eluted, collect eluent, enrichment times be V/200 μ L；
The measurement of step 2, pentavalent arsenic and trivalent arsenic
Select detecting instrument appropriate (such as：Inductivity coupled plasma mass spectrometry, inductively coupled plasma spectrometry, atom
Absorption spectrophotometer etc.) concentration of arsenic in above-mentioned sample solution, sample efflux and eluent is measured respectively, it is surveyed in eluent
Surely the arsenic concentration divided by enrichment times obtained is then the concentration of actual trivalent arsenic in sample, and the concentration of pentavalent arsenic can in sample
It is obtained by arsenic concentration in direct determination sample efflux, or trivalent is subtracted again by measuring total arsenic concentration in raw sample solution
Arsenic concentration obtains.
The innovation of the present invention is：
The first, ternary alkalescent solvent is used for the first time, and mercapto-functionalized hybrid inorganic-organic is synthesized by " one-step method "
Integral post, prepares simple, favorable reproducibility, the trivalent arsenic that gained integral material can be in selective enrichment solution.
The second, solid phase microextraction is carried out using homemade pin type solid phase micro-extraction device, this method is prepared simply, and column pressure is used
Small, adsorption efficiency is high.
Third, the As (III) being enriched with by nitric acid/Potassiumiodate elution, realize the separation and concentration of As (III) in sample, and
The concentration of As in sample (V) can be obtained by directly measuring the arsenic concentration after absorption in sample efflux, or utilize minusing
The concentration of As (V) is calculated.
Description of the drawings
The synthesis schematic diagram of Fig. 1 materials；
Fig. 2 pin type solid phase micro-extraction devices；
The Fourier transform infrared spectroscopy figure of Fig. 3 materials；
The Raman spectrogram of Fig. 4 materials；
The scanning electron microscope diagram of Fig. 5 materials；
Fig. 6 solid-phase extraction devices and morphological analysis step schematic diagram.
Specific implementation mode
Application example, by taking two kinds of actual environment water samples as an example, Yangtze River Water and rainwater pick up from Nanjing, cross 0.45 μm
After filter membrane, the concentration of inorganic arsenic morphology therein is measured, step is shown in Fig. 6.
1. materials synthesis
Raw material：Tetraethoxysilane (TEOS), mercaptopropyl trimethoxysilane (MPTMS), cetyl trimethyl bromination
Ammonium (CTAB)
Specific steps：First capillary is activated：The capillary of certain length is intercepted, uses 1M NaOH solutions successively
(12h), water (30min), 1M hydrochloric acid solutions (12h), water (30min), methanol (30min) rinse, and are dried up later with nitrogen, standby
With.To 130 μ L ethyl alcohol, 10% ammonium hydroxide of 173 μ L isopropanols and 152 μ L mixed liquor in 33.3mg CTAB are added, vortex makes
After solid is dissolved to solution clear, 300 μ LTEOS and 100 μ LMPTMS are added in above-mentioned clear solution, vortex 30s
After mixing, the ultrasound 30s in 0 DEG C of ice-water bath is passed through in activated capillary, after capillary sealing two ends, in 45 DEG C
20h is heated in water-bath.Be cooled to room temperature after reaction, successively use methanol, water rinse integral post, remove unreacted reagent with
And template CTAB, sulfhydrylation organic-inorganic hybridization monolithic column is stored in later spare in 4 DEG C of refrigerators.Obtained sulfydryl
The specific surface area for changing organic-inorganic hybridization monolithic column material is 68.51m2/ g, average pore size 7.124nm；Amount containing S is 3.31
±0.02mmol/g；It is 2.32 μ g/cm to trivalent arsenic adsorption capacity.The infrared spectrum of the material is shown in that Fig. 3, Raman spectrogram are shown in figure
4, scanning electron microscope diagram is shown in Fig. 5.
2. the structure of pin type solid phase micro-extraction device
The suitable syringe needle of size is chosen, metal needle is discarded, only retains base portion.Intercepted length is the mercapto of 5cm
Base organic-inorganic hybridization monolithic column substitutes original metal needle and fixation, you can.
3. the separation and concentration of inorganic arsenic
Sample to be tested is adjusted to pH 4.0 with dust technology first, takes 4mL sample solutions, with 200 μ L min-1Flow velocity pass through
Integral post.Trivalent arsenic can be selectively adsorbed on sulfydryl integral material at this time, and pentavalent arsenic is then not preserved and flows directly out,
Sample efflux is collected, then with 200 μ L min-1Flow velocity 200 μ L 3% (v/v) nitric acid (Potassiumiodate containing 0.01M) are passed through
Integral post, at this time trivalent arsenic be eluted, collect eluent.Enrichment times are 4mL/200 μ L=20 times.
4. the measurement of pentavalent arsenic and trivalent arsenic
By the eluent inductivity coupled plasma mass spectrometry after above-mentioned sample solution, sample efflux and separation and concentration
(ICP-MS) it analyzes, selection measures75As.The concentration of pentavalent arsenic and trivalent arsenic in sample solution is obtained respectively.(remarks explanation：It is rich
Collection multiple and detection means can suitably increase enrichment times according to itself experiment condition if detecting instrument sensitivity is inadequate；
If detecting instrument sensitivity is enough, then enrichment times can be suitably reduced.)
1. sample measurement result tables of data of table
As can be seen from the above table, the concentration accuracy height for two kinds of arsenic morphologies that this method measures, the rate of recovery are preferable.
Sulfhydrylation organic-inorganic hybridization monolithic column, easy to operate, favorable reproducibility, sulfydryl distribution are prepared using " one-step method "
Evenly, mechanical strength is good；Sulfhydrylation organic-inorganic hybridization monolithic column can be in selective absorption water body trivalent arsenic, realize
The quick separating of inorganic arsenic morphology and enrichment in water body；Simultaneously needed for equipment it is easy to use, disclosure satisfy that it is various under the conditions of sample
Product pre-treatment, it can be achieved that in water sample arsenic morphology live separation and concentration.
Claims (3)
1. a kind of sulfhydrylation organic-inorganic hybridization monolithic column, it is characterized in that：What it was prepared as follows：
33.3mg cetyl front threes are added in the mixed liquor of 130 μ L ethyl alcohol, 173 μ L isopropanols and 152 μ L10% ammonium hydroxide
Base ammonium bromide (CTAB), vortex are completely dissolved to solid, then solution clear takes 300 μ L tetraethoxysilanes (TEOS)
It is added in above-mentioned clear solution with 100 μ L mercaptopropyl trimethoxysilanes (MPTMS), vortex mixing, it is ultrasonic in 0 DEG C of ice water
After 30s, injection in activated capillary, after capillary sealing two ends, heats 20h in 45 DEG C of water-baths, is cooled to room
Wen Hou, successively use methanol, water rinse integral post, remove unreacted reagent and template CTAB, later by sulfhydrylation it is organic-
Inorganic hybridization integral post is stored in spare in 4 DEG C of refrigerators.
2. a kind of pin type solid phase micro-extraction device using sulfhydrylation organic-inorganic hybridization monolithic column described in claim 1, special
Sign is prepared by its following method：The suitable syringe needle of size is chosen, metal needle is discarded, only retains base portion, intercepted length
For the above-mentioned sulfhydrylation organic-inorganic hybridization monolithic column of 5cm, original metal needle and fixation are substituted, pin type solid phase is obtained
Micro-extraction apparatus.
3. sulfhydrylation organic-inorganic hybridization monolithic column described in claim 1 answering in the separation, enrichment and analysis of inorganic arsenic
With.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112934199A (en) * | 2021-02-01 | 2021-06-11 | 南京大学 | Copper ion imprinted organic-inorganic hybrid monolithic column and preparation method and application thereof |
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| CN112934199A (en) * | 2021-02-01 | 2021-06-11 | 南京大学 | Copper ion imprinted organic-inorganic hybrid monolithic column and preparation method and application thereof |
| WO2023023968A1 (en) * | 2021-08-25 | 2023-03-02 | 宁德时代新能源科技股份有限公司 | Organic-inorganic hybrid porous material and preparation method therefor, membrane, electrochemical device, and electrical device |
| US11944954B2 (en) | 2021-08-25 | 2024-04-02 | Contemporary Amperex Technology Co., Limited | Organic-inorganic hybrid porous material and preparation method thereof, separator, electrochemical device, and electrical device |
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| CN108421280B (en) | 2020-08-04 |
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