CN110127665A - Multi-walled carbon nanotube/graphene aerogel and its method for detecting organophosphorus pesticide - Google Patents
Multi-walled carbon nanotube/graphene aerogel and its method for detecting organophosphorus pesticide Download PDFInfo
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- CN110127665A CN110127665A CN201910415802.1A CN201910415802A CN110127665A CN 110127665 A CN110127665 A CN 110127665A CN 201910415802 A CN201910415802 A CN 201910415802A CN 110127665 A CN110127665 A CN 110127665A
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- carbon nanotube
- walled carbon
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 49
- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000004964 aerogel Substances 0.000 title claims abstract description 32
- 239000003987 organophosphate pesticide Substances 0.000 title claims abstract description 7
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 14
- 238000001514 detection method Methods 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003463 adsorbent Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003480 eluent Substances 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 8
- 239000012491 analyte Substances 0.000 claims abstract description 7
- 238000002203 pretreatment Methods 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000000575 pesticide Substances 0.000 claims description 24
- 239000000017 hydrogel Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- XLNZEKHULJKQBA-UHFFFAOYSA-N terbufos Chemical compound CCOP(=S)(OCC)SCSC(C)(C)C XLNZEKHULJKQBA-UHFFFAOYSA-N 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- MEBQXILRKZHVCX-UHFFFAOYSA-N methidathion Chemical compound COC1=NN(CSP(=S)(OC)OC)C(=O)S1 MEBQXILRKZHVCX-UHFFFAOYSA-N 0.000 claims description 4
- XIUROWKZWPIAIB-UHFFFAOYSA-N sulfotep Chemical compound CCOP(=S)(OCC)OP(=S)(OCC)OCC XIUROWKZWPIAIB-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 238000013467 fragmentation Methods 0.000 claims description 3
- 238000006062 fragmentation reaction Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 239000005350 fused silica glass Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000004451 qualitative analysis Methods 0.000 claims description 3
- 238000004445 quantitative analysis Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 6
- 239000000447 pesticide residue Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract 2
- 239000008367 deionised water Substances 0.000 abstract 1
- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 23
- 238000004458 analytical method Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000000622 liquid--liquid extraction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000001334 liquid-phase micro-extraction Methods 0.000 description 2
- 238000004853 microextraction Methods 0.000 description 2
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NNKVPIKMPCQWCG-UHFFFAOYSA-N methamidophos Chemical compound COP(N)(=O)SC NNKVPIKMPCQWCG-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KRTSDMXIXPKRQR-AATRIKPKSA-N monocrotophos Chemical compound CNC(=O)\C=C(/C)OP(=O)(OC)OC KRTSDMXIXPKRQR-AATRIKPKSA-N 0.000 description 1
- RGCLLPNLLBQHPF-HJWRWDBZSA-N phosphamidon Chemical compound CCN(CC)C(=O)C(\Cl)=C(/C)OP(=O)(OC)OC RGCLLPNLLBQHPF-HJWRWDBZSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000000956 solid--liquid extraction Methods 0.000 description 1
- 238000002470 solid-phase micro-extraction Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G01N30/48—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/291—Gel sorbents
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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Abstract
The present invention relates to multi-walled carbon nanotube/graphene aerogel and its methods for detecting organophosphorus pesticide, the multi-walled carbon nanotube/graphene aerogel detection organophosphorus pesticide method are as follows: the preparation of solid-phase extraction column: multi-walled carbon nanotube/graphene aerogel is filled in solid-phase extraction column, load the lower sieve plate of solid-phase extraction column, multi-walled carbon nanotube/graphene aerogel is lightly packed into again, is gently compacted with upper sieve plate；Solid Phase Extraction pre-treatment: before extraction, methanol, acetone, acetonitrile, tetrahydrofuran and deionized water activated solid extraction column are used respectively；Take water sample to be measured with 1 mL/min flow velocity loading；The analyte being retained on solid phase extraction adsorbents is eluted with tetrahydrofuran；Eluent is collected, water-bath is dried with nitrogen at room temperature, after being redissolved with acetone, crosses 0.22 μm of miillpore filter；GC/MS analysis.When the present invention detects pesticide residue in water, time-saving and efficiency, organic solvent consumption are few.
Description
Technical field
The present invention relates to detection of organic phosphorus pesticide technical fields, and in particular to be multi-walled carbon nanotube/graphene
Aeroge and its method for detecting organophosphorus pesticide.
Background technique
Organic phosphorus (OPPs) pesticide has many advantages, such as efficient, wide spectrum, and can be effective to bacterium, pest, weed growth etc.
Control action, and can boost agricultural yield, become China and use the maximum a kind of pesticide of most wide, dosage.But wherein 70%
OPPs pesticide is severe toxicity, hypertoxic type.The Ministry of Agriculture, China is forbidden to use acephatemet, parathion, methyl in the bulletin of publication in 2007
The OPPs insecticide such as parathion, Azodrin and phosphamidon.Recently as the extensive and unreasonable use of pesticide, agricultural product middle peasant
Medicine remains exceeded problem and becomes increasingly conspicuous, and it is exceeded serious to cause Residual Pesticides in Farm Produce, while causing sternly to environment water
It threatens again, causes the extensive concern of various circles of society, therefore it is very necessary to establish accurate, reliable qualitative and quantitative analysis method.
The method of detection OPPs pesticide mainly has gas chromatography (GC) at present, gas chromatography-mass spectrography (GC/MS), height
Effect liquid phase chromatogram method (HPLC), Liquid Chromatography-Tandem Mass Spectrometry (HPLC-MS/MS) etc..Gas chromatography-mass spectrography (GC-MS) because
With the advantages such as analysis speed is fast, qualitative ability is strong, it has also become the most commonly used method in current pesticide residue analysis.Sample is pre-
Processing, is most critical in analytic process, most important step, and Sample Pretreatment Technique Used often becomes the pass of analysis success or not
Key.It is liquid-liquid extraction, Solid Phase Extraction, solid phase microextraction, dispersion liquid that OPPs, which tests and analyzes pre-treatment main method, in water sample
Micro-extraction, molecular engram, liquid-phase micro-extraction, microwave abstracting, dispersive solid-phase extraction, doughnut liquid-phase micro-extraction, single drop are micro-
Extraction etc., it is big that liquid-liquid extraction consumes organic reagent amount, causes serious pollution to the environment, Solid Phase Extraction is that a kind of developed recently sample that gets up is pre-
Processing technique is mainly used for the separation, purifying and concentration of sample, more effectively by analyte compared with traditional liquid-liquid extraction method
It is separated with interfering component, improves the rate of recovery of analyte, reduce sample pretreatment process, it is easy to operate, time saving, laborsaving, extensively
Apply in fields such as food, environment, medicine, chemical industry.
Graphene, multi-walled carbon nanotube have that large specific surface area, adsorption capacity are strong, high mechanical strength, chemical stability are good
Etc. characteristics, be constantly subjected to the concern of numerous researchers, it has also become one of part to attract most attention in nanosecond science and technology.But Two-dimensional Carbon is received
Rice material is not easy to be separated from the water in production application, generally requires repeatedly to be centrifuged, and be easy to cause secondary pollution, also have
Research shows that graphene has been possible to potential bio-toxicity in environment, therefore limit its further answering in water pollution processing
With.
Summary of the invention
The object of the present invention is to provide the sides of a kind of multi-walled carbon nanotube/graphene aerogel and its detection organophosphorus pesticide
Method, for overcoming the problems, such as that existing traditional extraction technology is big using organic reagent amount.
The technical solution adopted by the present invention to solve the technical problems is: this multi-walled carbon nanotube/graphene aerogel
It is prepared by the following method:
One, 0.4g graphene oxide powder and 0.1g multi-walled carbon nanotube are taken, is distributed it in 100mL water, 1 h of ultrasonic disperse
Obtain dark brown dispersion liquid；
Two, the dark brown dispersion liquid of 5 mL is taken to be placed in the 25mL test tube that internal diameter is 11mm, adjusting solution ph with ammonium hydroxide is weak base
Property, adding 20 μ L concentration is 50mol/L ethylenediamine solution, slowly sufficiently shakes up, 24 h of water-bath at 80 DEG C, obtains
The reactant arrived is graphene hydrogel；
Three, multi-walled carbon nanotube/graphene hydrogel in test tube is taken out, 6h is impregnated with 20% ethanol water, removes multi wall carbon
Remaining soluble impurity and replacing section aqueous solution, prevent multi-walled carbon nanotube/graphene in nanotube/graphene hydrogel
Hydrogel occurs deforming in freezing dry process or fragmentation；
Four, multi-walled carbon nanotube/graphene hydrogel is taken out, is placed in surface plate, 48h is freeze-dried, obtains multi-wall carbon nano-tube
Pipe/graphene aerogel, multi-walled carbon nanotube/graphene aerogel are the porous cylindricality carbon material of three-dimensional black.
Above-mentioned multi-walled carbon nanotube/graphene aerogel detection Organophosphorous in Water Samples pesticide method:
One, the preparation of solid-phase extraction column:
Multi-walled carbon nanotube/the graphene aerogel is filled in solid-phase extraction column, first by the lower sieve plate of solid-phase extraction column
In filling, then multi-walled carbon nanotube/graphene aerogel is lightly loaded in 3mL solid-phase extraction column, solid phase extraction is finally installed
Multi-walled carbon nanotube/graphene aerogel is gently compacted downwards by the upper sieve plate for taking column by upper sieve plate；
Two, Solid Phase Extraction pre-treatment:
Before extraction, it is activated respectively with 3 mL methanol, 3 mL acetone, 3 mL acetonitriles, 3 mL tetrahydrofurans and 10 mL deionized waters
Solid-phase extraction column；Take 40 mL water sample to be measured with 1 mL/min flow velocity loading；It is eluant, eluent with 5 mL tetrahydrofurans, elution retains
Analyte on solid phase extraction adsorbents；Eluent is collected, water-bath is dried with nitrogen at room temperature, after being redissolved with 1mL acetone, mistake
0.22 μm of miillpore filter；
Three, GC/MS is analyzed:
Organophosphorous in Water Samples pesticide after step 2 processing separate using GC/MS method and qualitative and quantitative analysis is carried out to it,
Detect 4 kinds of terbufos, sulfotep, Rogor, methidathion pesticides in water.
When above-mentioned GC/MS method is analyzed,
GC conditions: Rtx-50 fused-silica capillary column；Carrier gas: helium；Column temperature temperature program: 2 are kept by 70 DEG C
Min, rises to 160 DEG C with 15 DEG C/min rate, keeps 2 min, rises to 210 DEG C with 10 DEG C/min rate, 2 min is kept, with 5
DEG C/min rate rises to 220 DEG C, 2 min are kept, 270 DEG C is risen to 10 DEG C/min rate, keeps 14 min, sample injector temperature:
200℃；Sample injector mode: Splitless injecting samples, sample volume: 1 μ L；
Mass Spectrometry Conditions: EI electron bombardment ion source, 26.5 mL/min of total gas flow rate, column flow: 1.2 mL/ min, spray
220 DEG C, ionization energy 70eV of mist mouth temperature, ionization temperature is 260 DEG C, and interface temperature is 270 DEG C；Every kind of OPPs pesticide difference
1 quota ion is selected, 2 qualitative ions detect respectively at times according to peak sequence.
The invention has the following advantages:
1, the multi-walled carbon nanotube that the present invention establishes/graphene aerogel Solid Phase Extraction combination GC/MS method rate of recovery height, precision
Good, the wider range of linearity, it is simple to operate, reusable the advantages that, to OPPs pesticide residue in environment surface water
Detection provide a kind of new method, also can be used as the purification that a kind of solid phase extraction material is applied to complex matrices, it is more in pesticide
In retention analysis with good application prospect；The average recovery rate of this method is 92.8%~103.4%, relative standard deviation
(n=3) are 2.1%~7.6%.
2, traditional Sample Pretreatment Technique, such as liquid-liquid extraction, solid-liquid extraction, filtering, distillation, generally existing operation are numerous
Trivial time-consuming, the disadvantages of needing a large amount of use harmful to environment and human body organic solvent, in the present invention detection water when pesticide residue,
Time-saving and efficiency, organic solvent consumption are few.
3, in the analysis process, the separation, purifying of sample are all essential pre-treatment steps.Sample pre-treatments it is good
The bad result that will directly affect analysis.The present invention is replaced using multi-walled carbon nanotube/graphene aerogel Solid Phase Extraction of preparation
Traditional liquid-phase extraction keeps sample more environmentally-friendly in pretreatment process and reduces the usage amount of organic reagent, and the standard of method
Exactness is high, precision is high, favorable reproducibility.
4, multi-walled carbon nanotube/graphene aerogel prepared by the present invention is applied to complexity as a kind of solid phase extraction material
The purification of matrix, in Multi-residue analysis with good application prospect.
Detailed description of the invention
Fig. 1 is multi-walled carbon nanotube prepared by the present invention/graphene aerogel figure；
Fig. 2 is that solid-phase extraction column prepares schematic diagram in the present invention；
Fig. 3 is Solid Phase Extraction pretreatment process schematic diagram in the present invention；
Fig. 4 is terbufos, sulfotep, Rogor, methidathion standard solution chromatogram, and 1 is terbufos in figure, and 2 be sulfotep,
3 be Rogor, and 4 be methidathion.
Specific embodiment
The present invention will be further described below with reference to the drawings:
This multi-walled carbon nanotube/graphene aerogel is prepared by the following method:
0.4 g graphene oxide powder and 0.1g multi-walled carbon nanotube are taken, is distributed it in 100 mL water, 1 h of ultrasonic disperse
Dark brown dispersion liquid is obtained, dispersion liquid is obtained.5 mL dispersion liquids are taken to be placed in the 25 mL test tubes that internal diameter is 11 mm, with ammonium hydroxide tune
Section solution ph is alkalescent, is 50 mol/L ethylenediamine solutions 20 μ L concentration are added, slowly sufficiently shakes up, at 80 DEG C
Lower 24 h of water-bath takes out reaction in test tube object, impregnates 6 h with the ethanol water (20%, v/v) of 20 %, removes multi wall
Remaining soluble impurity and replacing section aqueous solution, prevent multi-walled carbon nanotube/graphite in carbon nano tube/graphene hydrogel
Alkene hydrogel occurs deforming in freezing dry process or fragmentation etc. is existing.Multi-walled carbon nanotube/graphene hydrogel is taken out,
It is placed in surface plate, is freeze-dried 48 h, obtaining the three-dimensional porous cylindricality carbon material of black is multi-walled carbon nanotube/graphene gas
Gel (refering to fig. 1).
Three-dimensional carbon material remains the advantages of two-dimensional graphene carbon material, the physics and chemistry for not only having two-dimentional carbon material intrinsic
Property, and huge specific surface area and cellular structure effectively increase with the contact area of pollutant, enhance pollution
The diffusion of object, and material has Ke Xunhuanliyong equal good characteristics.
Above-mentioned multi-walled carbon nanotube/graphene aerogel detection Organophosphorous in Water Samples pesticide method:
One, the preparation of solid-phase extraction column:
Referring to Fig.2, multi-walled carbon nanotube/the graphene aerogel that the 25 mL test tubes that internal diameter is 11 mm will be used to prepare, filling
In the 3 mL solid-phase extraction columns for being 9 mm to internal diameter, first by the filling of the lower sieve plate of solid-phase extraction column it is upper after, by multi-walled carbon nanotube/
Graphene aerogel solid phase extraction adsorbents gently loaded in 3mL solid-phase extraction column, the upper sieve of solid-phase extraction column is finally installed
Multi-walled carbon nanotube/graphene aerogel is gently compacted downwards, improves the extraction adsorption efficiency of adsorbent by plate by upper sieve plate.
Two, Solid Phase Extraction pre-treatment:
Refering to Fig. 3, before extraction, respectively with 3 mL methanol, 3 mL acetone, 3 mL acetonitriles, 3 mL tetrahydrofurans and 10 mL go from
Sub- water activates pillar.Take 40 mL water sample to be measured with 1 mL/min flow velocity loading.5 mL tetrahydrofurans are eluant, eluent, and elution retains
Analyte on solid phase extraction adsorbents.Eluent is collected, water-bath is dried with nitrogen at room temperature.After 1mL acetone redissolves, mistake
0.22 μm of miillpore filter, for going to GC/MS analysis.
(1) it activates, remove the impurity in column and creates certain solvent environment.First with solvent appropriate by solid absorption
Agent activation, then again with activating solvent identical with sample solvent.This step can soak solid absorbent in column, and high-ranking military officer
Solvation can be rolled into a ball, the impurity on solid absorbent and filler is removed.
(2) loading, by sample in certain solvent solution transfer column, selective retention component is on column.
Sample solution carries out reservation absorption by solid-phase adsorbent, and flow velocity is it is ensured that solid absorbent can be adsorbed effectively
Target compound.
(3) it elutes, utmostly removes chaff interferent.Optimum and the eluant, eluent with eluting power are selected, solid is cleaned
Adsorbent, elution removes sample matrix components on solid-phase adsorbent, while ensuring that target analytes are unaffected.
Three, GC/MS is analyzed:
GC conditions: Rtx-50 fused-silica capillary column (0.25 μm of the μ m of 30 m × 250)；Carrier gas: helium (purity
≥ 99.999 %)；Column temperature temperature program: by 70 DEG C of 2 min of holding, rising to 160 DEG C with 15 DEG C/min rate, keep 2 min,
Rise to 210 DEG C with 10 DEG C/min rate, keep 2 min, rise to 220 DEG C with 5 DEG C/min rate, keep 2 min, with 10 DEG C/
Min rate rises to 270 DEG C, keeps 14 min, sample injector temperature: 200 DEG C；Sample injector mode: Splitless injecting samples, sample volume: 1 μ
L。
Mass Spectrometry Conditions: EI (lectron impact) electron bombardment ion source, 26.5 mL/min of total gas flow rate,
Column flow: 1.2 mL/ min, 220 DEG C of spray nozzle temperature, ionization energy is 70 eV, and ionization temperature is 260 DEG C, and interface temperature is
270℃.Every kind of OPPs pesticide selects 1 quota ion respectively, and 2 qualitative ions are examined respectively at times according to peak sequence
It surveys, is specifically shown in Table 1.
The retention time of 14 kinds of OPPs pesticides of table, quota ion, qualitative ion
Four, the range of linearity, quantitative limit and detection limit
Under optimal experiment condition, GC/MS analysis is carried out with bare substrate matching mixed standard solution, with the quality of each analyte
Concentration (μ g L-1) it is abscissa, matrix matching standard working curve is drawn to corresponding peak area, obtains the range of linearity and correlation
Coefficient.LOD and LOQ are calculated separately with 3 times (S/N=3) and 10 times of (S/N=10) signal-to-noise ratio, the results are shown in Table 2.By table
2 it is found that 4 kinds of OPPs insecticides in 0.5-500 μ g L-1In range, linear relationship is good, related coefficient 0.9993
-0.9998.The LOD of 4 kinds of OPPs insecticides is 0.28-0.52 μ g L-1, LOQ is 0.96-1.64 μ g L-1,
Method sensitivity can satisfy the requirement of actual water sample quantitative detecting analysis.
The range of linearity, related coefficient, quantitative limit, detection limit and the relative standard deviation (n=3) of 24 kinds of OPPs pesticides of table
Five, veracity and precision
Under optimal experiment condition, the matrix matching standard working curve of different water samples is prepared, to 4 kinds of OPPs pesticides in difference
Recovery of standard addition in blank water sample is investigated.In 2,5,10 μ g L-1Under 3 spiked levels are horizontal, each concentration level
Replication 3 times, experimental result is shown in Table 3.As shown in Table 3: the average recovery rate of 4 kinds of OPPs pesticides be 92.8%~
103.4%, opposite mark deviation (RSD) is 2.1%~7.6%.The accuracy of this method and precision data meet pesticide in water
Residue detection requirement.
The recovery of standard addition (n=3) of 34 kinds of OPPs pesticides of table in water
The average recovery rate of detection method provided by the invention is 92.8%~103.4%, and relative standard deviation (n=3) is 2.1%
~7.6%, have many advantages, such as that the rate of recovery is high, precision is good, the wider range of linearity, simple to operate, reusable.
Claims (3)
1. a kind of multi-walled carbon nanotube/graphene aerogel, it is characterised in that: this multi-walled carbon nanotube/graphene aerogel
It is prepared by the following method:
One, 0.4g graphene oxide powder and 0.1g multi-walled carbon nanotube are taken, is distributed it in 100mL water, 1 h of ultrasonic disperse
Obtain dark brown dispersion liquid；
Two, the dark brown dispersion liquid of 5 mL is taken to be placed in the 25mL test tube that internal diameter is 11mm, adjusting solution ph with ammonium hydroxide is weak base
Property, adding 20 μ L concentration is 50mol/L ethylenediamine solution, slowly sufficiently shakes up, 24 h of water-bath at 80 DEG C, obtains
The reactant arrived is multi-walled carbon nanotube/graphene hydrogel；
Three, multi-walled carbon nanotube/graphene hydrogel in test tube is taken out, 6h is impregnated with 20% ethanol water, removes multi wall carbon
Remaining soluble impurity and replacing section aqueous solution, prevent multi-walled carbon nanotube/graphene in nanotube/graphene hydrogel
Hydrogel occurs deforming in freezing dry process or fragmentation；
Four, multi-walled carbon nanotube/graphene hydrogel is taken out, is placed in surface plate, 48h is freeze-dried, obtains multi-wall carbon nano-tube
Pipe/graphene aerogel, multi-walled carbon nanotube/graphene aerogel are the porous cylindricality carbon material of three-dimensional black.
2. a kind of multi-walled carbon nanotube described in claim 1/graphene aerogel detection Organophosphorous in Water Samples pesticide method,
It is characterized by:
One, the preparation of solid-phase extraction column:
Multi-walled carbon nanotube/the graphene aerogel is filled in solid-phase extraction column, first by the lower sieve plate of solid-phase extraction column
In filling, then multi-walled carbon nanotube/graphene aerogel is lightly loaded in 3mL solid-phase extraction column, solid phase extraction is finally installed
Multi-walled carbon nanotube/graphene aerogel is gently compacted downwards by the upper sieve plate for taking column by upper sieve plate；
Two, Solid Phase Extraction pre-treatment:
Before extraction, it is activated respectively with 3 mL methanol, 3 mL acetone, 3 mL acetonitriles, 3 mL tetrahydrofurans and 10 mL deionized waters
Solid-phase extraction column；Take 40 mL water sample to be measured with 1 mL/min flow velocity loading；It is eluant, eluent with 5 mL tetrahydrofurans, elution retains
Analyte on solid phase extraction adsorbents；Eluent is collected, water-bath is dried with nitrogen at room temperature, after being redissolved with 1mL acetone, mistake
0.22 μm of miillpore filter；
Three, GC/MS is analyzed:
Organophosphorous in Water Samples pesticide after step 2 processing separate using GC/MS method and qualitative and quantitative analysis is carried out to it,
Detect 4 kinds of terbufos, sulfotep, Rogor, methidathion pesticides in water.
3. multi-walled carbon nanotube according to claim 2/graphene aerogel Solid Phase Extraction combination GC/MS method detects water sample
Middle organophosphorus pesticide, it is characterised in that: when the GC/MS method is analyzed,
GC conditions: Rtx-50 fused-silica capillary column；Carrier gas: helium；Column temperature temperature program: it is kept by 70 DEG C
2min, rises to 160 DEG C with 15 DEG C/min rate, keeps 2min, rises to 210 DEG C with 10 DEG C/min rate, keeps 2min, with 5 DEG C/
Min rate rises to 220 DEG C, keeps 2min, rises to 270 DEG C with 10 DEG C/min rate, keeps 14 min, sample injector temperature: 200
℃；Sample injector mode: Splitless injecting samples, sample volume: 1 μ L；
Mass Spectrometry Conditions: EI electron bombardment ion source, 26.5 mL/min of total gas flow rate, column flow: 1.2 mL/ min, spray
220 DEG C, ionization energy 70eV of mist mouth temperature, ionization temperature is 260 DEG C, and interface temperature is 270 DEG C；Every kind of OPPs pesticide difference
1 quota ion is selected, 2 qualitative ions detect respectively at times according to peak sequence.
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