CN110193345A - A kind of preparation method of magnetic nanometer composite material - Google Patents
A kind of preparation method of magnetic nanometer composite material Download PDFInfo
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- CN110193345A CN110193345A CN201910366120.6A CN201910366120A CN110193345A CN 110193345 A CN110193345 A CN 110193345A CN 201910366120 A CN201910366120 A CN 201910366120A CN 110193345 A CN110193345 A CN 110193345A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000002131 composite material Substances 0.000 title description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910001868 water Inorganic materials 0.000 claims abstract description 58
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000002114 nanocomposite Substances 0.000 claims abstract description 35
- 150000002500 ions Chemical class 0.000 claims abstract description 31
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 19
- 239000003463 adsorbent Substances 0.000 claims abstract description 16
- 238000001514 detection method Methods 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 45
- 229910021389 graphene Inorganic materials 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 6
- 229960002089 ferrous chloride Drugs 0.000 claims description 6
- 230000010354 integration Effects 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 238000010828 elution Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
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- 229910052738 indium Inorganic materials 0.000 claims description 3
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- LQERIDTXQFOHKA-UHFFFAOYSA-N nonadecane Chemical compound CCCCCCCCCCCCCCCCCCC LQERIDTXQFOHKA-UHFFFAOYSA-N 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- 230000003595 spectral effect Effects 0.000 claims description 3
- 239000002349 well water Substances 0.000 claims description 3
- 235000020681 well water Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims 2
- 230000000087 stabilizing effect Effects 0.000 claims 2
- 238000001179 sorption measurement Methods 0.000 abstract description 48
- 229910052681 coesite Inorganic materials 0.000 abstract description 28
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 28
- 229910052682 stishovite Inorganic materials 0.000 abstract description 28
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract 1
- 238000003795 desorption Methods 0.000 abstract 1
- 238000002203 pretreatment Methods 0.000 abstract 1
- 239000002594 sorbent Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 35
- 239000000523 sample Substances 0.000 description 17
- 239000011651 chromium Substances 0.000 description 12
- 239000011133 lead Substances 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
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- 239000000203 mixture Substances 0.000 description 8
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- 229910052802 copper Inorganic materials 0.000 description 5
- 229910052745 lead Inorganic materials 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000136 cloud-point extraction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012156 elution solvent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 238000001334 liquid-phase micro-extraction Methods 0.000 description 2
- 239000002122 magnetic nanoparticle Substances 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
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- 229910021642 ultra pure water Inorganic materials 0.000 description 2
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- 238000003260 vortexing Methods 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 101100001676 Emericella variicolor andK gene Proteins 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- 229910002589 Fe-O-Fe Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
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- 239000012488 sample solution Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
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- 238000003911 water pollution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- 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
- G01N1/40—Concentrating samples
- G01N1/405—Concentrating samples by adsorption or absorption
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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Abstract
The invention belongs to Heavy Metals in Water Environment detection technique field, it is related to 7 heavy metal species ions and the method for measuring content simultaneously in a kind of separation and concentration water environment.It is related to the preparation of the silicon dioxide modified magnetic Nano material of one kind and its application in environmental water sample in trace heavy metal detection.It has used and has prepared resulting Fe3O4‑GO @ SiO2Nanocomposite is as novel SPE sorbent material, pre-treatment is carried out to environmental water sample using magnetic solid phase extraction technology, ICP-MS is used to measure Cr(III in several true water samples simultaneously and delicately as detection method), Co(II), Ni(II), Cu(II), Cd(II), Pb(II), Ag(I) ion concentration.Optimize several extraction parameters and desorption condition, be successfully established it is a kind of simple, efficiently, quick MSPE-ICP-MS combined analysis method.It is compared with the traditional method, this method adsorption capacity with higher and lower detection limit, there is the advantages that high sensitivity, good linearity, rate of recovery height, organic solvent and few adsorbent consumption.
Description
Technical Field
The invention belongs to the technical field of heavy metal detection in water environment, and particularly relates to preparation of a magnetic nano material modified by silicon dioxide and application of the magnetic nano material in heavy metal detection in an environmental water sample. The invention also provides a sensitive and efficient detection method for heavy metal ions in the water environment.
Background
With the development of economy and manufacturing industry, heavy metals such as chromium, cobalt, nickel, copper, cadmium, lead, zinc and the like are inevitably discharged into water bodies, and environmental water pollution is caused. Heavy metals are not biodegradable and can enter the human body through the food chain, and if exceeding the normal range, the heavy metals directly harm the human health. Therefore, the development of a rapid, sensitive and highly reliable analysis method is of great significance for determining the content of heavy metals in environmental water.
Inductively coupled plasma mass spectrometry (ICP-MS) is considered one of the most effective means for determining ultra trace elements in complex matrices due to its high sensitivity and abundant detection capability. However, it is difficult to accurately determine trace levels of heavy metals in authentic samples when the analyte concentration to be treated is very low and the sample matrix is relatively complex. In these cases, separation of the analyte from the complex is often necessary to separate and pre-concentrate the analyte from the matrix prior to ICP-MS measurement. Various separation/preconcentration methods have been applied for this purpose, such as liquid-liquid extraction (LLE), solid-phase extraction (SPE), cloud-point extraction (CPE), liquid-phase microextraction (LPM) and Ion Exchange (IE). Among these techniques, Solid Phase Extraction (SPE) is the most commonly used technique for realizing analysis of heavy metals in actual samples with complex matrices due to its advantages of high enrichment factor, simplicity, rapidity, lowest cost, low reagent consumption, reusability of adsorbents, and easy automation. Obviously, the adsorption material determines the analytical sensitivity and selectivity of the SPE technique, and is a key factor in the adsorption process.
Graphene (G) is a two-dimensional (2D) structure of sp2 bonded carbon atoms with one atomic thickness, and is the basic building block for graphitic materials in all other dimensions. Due to its ultra-high specific surface area (2630 m theoretical value)2·g-1) And planar sheet-like structures, both sides of which are useful for ion adsorption, are excellent candidates for suitable materials for the efficient adsorption of heavy metal ions from aqueous solutions. Graphene Oxide (GO) has the ability to be easily modified with suitable functional groups, and its surface contains abundant hydrophilic groups such as hydroxyl, carbonyl, epoxy and carboxyl groups, making it well dispersed in water. However, due to its high dispersibility, hydrophilicity and small particle size, it is difficult to quickly separate GO from solution by traditional centrifugation and filtration methods. Therefore, a magnetic graphene adsorbent that is easy to separate by a magnetic field is applied to adsorption of heavy metal ions due to its high separation and recovery efficiency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a novel magnetic solid phase extraction adsorbent which is used for extracting Cr (III), Co (II), Ni (II), Cu (II), Cd (II), Pb (II) and Ag (I) ions in various environmental water samples (bottled mineral water, well water, inlet and outlet water of a sewage treatment plant).
Another object of the present invention is to provide a method for simultaneously determining the content of 7 trace heavy metal ions in an aqueous environment.
The invention is realized by the following technical scheme:
the invention provides a magnetic nano composite material, which is prepared by the following method:
(1) preparing magnetic graphene oxide from graphene oxide, ferric chloride hexahydrate and ferrous chloride tetrahydrate in an alkaline solution;
(2) preparing magnetic graphene oxide modified by magnetic solid phase extraction adsorbent silicon dioxide from magnetic graphene oxide and ethyl silicate in ethanol;
wherein,
the mass ratio of the graphene oxide, the ferric chloride hexahydrate and the ferrous chloride tetrahydrate in the step (1) is as follows: 1: 1.50-5.00: 0.50 to 3.80, preferably: 1.00: 2.16: 0.80.
the pH value of the alkaline solution in the step (1) is 10-12, and the pH value is adjusted by adding an ammonia solution or a sodium hydroxide solution.
The mass ratio of the magnetic graphene oxide to the ethyl silicate in the step (2) is as follows: 1: 2.00-6.50, preferably: 1.00: 3.92. the volume of the solvent ethanol is 30-75 mL, preferably 49.5 mL.
Specifically, the magnetic nanocomposite material is prepared by the following method:
dispersing graphene oxide in water, and heating to 70-90 ℃ while violently stirring under the protection of nitrogen. Dissolving ferric chloride hexahydrate and ferrous chloride tetrahydrate in water to prepare a solution, and adding the solution into a system when the temperature reaches 70-90 ℃. Adding an ammonia solution to adjust the pH value of the system to 12, and continuously mechanically stirring for 1-2 hours at 70-90 ℃ to obtain magnetic graphene oxide;
ethyl silicate was dispersed in water, stirred and sonicated to make a suspension. Adding magnetic graphene oxide into ethanol, adding ethyl silicate suspension under ice bath at 0-4 ℃, violently stirring for 10-20 minutes, dropwise adding 2.0-5.0 mL of ammonia solution into the system under stirring, and continuously stirring for 8-12 hours under ice bath at 0-4 ℃ to obtain the magnetic graphene oxide modified by silicon dioxide.
The magnetic graphene oxide modified by the magnetic nano composite material silicon dioxide, prepared by the invention, can be used as a magnetic solid phase extraction adsorbent, MSPE is used as a pretreatment technology of a water environment sample, and ICP-MS is used as a detection tool to detect the content of trace heavy metals. Especially the simultaneous detection of multiple heavy metal ions. The method overcomes the problems that iron nanoparticles are easy to leach from graphene sheets in the application process, and the like, can simultaneously detect the contents of Cr (III), Co (II), Ni (II), Cu (II), Cd (II), Pb (II) and Ag (I) in the water environment, and is simple, rapid and efficient in sample pretreatment operation.
The invention discloses a method for detecting the content of heavy metal ions in a water environment by using synthesized magnetic nano composite material silicon dioxide modified magnetic graphene oxide as a magnetic solid phase extraction adsorbent and combining inductively coupled plasma mass spectrometry, which comprises the following specific steps:
(1) pretreatment of a water sample: collecting and filtering a water sample;
(2) magnetic solid phase extraction, enrichment and concentration processes: adding a magnetic nano composite material into the water sample treated in the step (1), performing ultrasonic treatment, performing vortex separation, removing supernatant to obtain residue, adding a nitric acid solution into the residue, performing vortex separation, and obtaining supernatant for later use;
(3) inductively coupled plasma mass spectrometry (ICP-MS) is used for determining 7 trace heavy metal ions in the water environment;
in the step (1), a water sample is filtered by a 0.45-micron filter membrane;
in the step (2), the ultrasonic treatment time is as follows: 2-8 min, vortex time: 2-8 min;
in the step (3), the vortex time is as follows: 2-8 min, volume of nitric acid solution: 4-10 mL.
Specifically, the invention can be prepared by the following method:
(1) pretreatment of a water sample: the water samples were collected and filtered through a 0.45 μm filter.
(2) Magnetic solid phase extraction, enrichment and concentration processes: taking 50-200 mL of the water sample filtered in the step (1),
adding 20-50 mg of silicon dioxide modified magnetic graphene oxide, carrying out ultrasonic treatment for 2-4 min, carrying out vortex treatment for 4-8 min, separating materials at the bottom of a centrifugal tube by using an external magnet, removing supernatant, adding 4-10 mL of nitric acid solution into residues, carrying out vortex treatment for 3-5 min, separating to obtain supernatant, and sampling and introducing the supernatant into ICP-MS for analysis.
(3) Inductively coupled plasma mass spectrometry (ICP-MS) is used for determining 7 trace heavy metal ions in the water environment;
(3.1) inductively coupled plasma Mass Spectrometry
The operating conditions are as follows:
| ICP-MS working parameters | Parameter value |
| Radio frequency power | 1550 W |
| Plasma argon flow | 15 L·min-1 |
| Auxiliary argon flow | 1 L·min-1 |
| Argon flow velocity of atomizer | 1 L·min-1 |
| Depth of sampling | 7.0 mm |
| Sampler/skimmer diameter hole | Nickel 1.0 mm/0.4 mm |
| Scanning mode | Peak-hopping |
| Integration time/mass | 0.3 s |
| Time of absorption of sample | 30 s |
| Time of settling | 35 s |
| Integration mode | Peak area |
| Number of points per spectral peak | 3 |
| ISTD | Sc,Ge,In,Bi |
(3.2) introducing the supernatant obtained in the step (2) as an analyte into an inductively coupled plasma mass spectrometer for analysis;
the research successfully synthesizes novel Fe3O4-GO@SiO2The nano composite material is used as an effective heavy metal extraction and adsorption material. A simple, efficient and rapid MSPE combined analysis method is established, optimized and verified, and 7 heavy metals in drinking water and water samples in different environments are simultaneously determined by utilizing ICP-MS. The method has high sensitivity, good linearity, high recovery rate, and minimal consumption of organic solvent and adsorbent. In conclusion, a novel analytical method was thus developed for the sensitive determination of seven target heavy metals in several real-world water samples. The novel nano composite material has great application potential in extracting/removing trace heavy metals from various environmental water samples.
Drawings
Fig. 1 is a scanning electron microscope image of graphene oxide (a), magnetic graphene oxide (b), and magnetic graphene oxide modified with silica (c);
FIG. 2 is an infrared spectrum of graphene oxide, magnetic graphene oxide, and silicon dioxide-modified magnetic graphene oxide;
fig. 3 is a hysteresis loop diagram of magnetic graphene oxide and silicon dioxide modified magnetic graphene oxide;
FIG. 4 shows the adsorption time versus the target metal ion in Fe3O4-GO@SiO2Influence Curve of the Upper adsorption (initial concentration of cation: 100mg L)-1Temperature: 25 ℃);
FIG. 5 is a graph showing the adsorption kinetics of magnetic graphene oxide modified with silicon dioxide on Cr (III), Co (II), Ni (II), Cu (II), Cd (II), Pb (II), and Ag (I) ions at 25 ℃;
FIG. 6 is an experimental and theoretical adsorption isotherm of silica-modified magnetic graphene oxide on Cr (III), Co (II), Ni (II), Cu (II), Cd (II), Pb (II), Ag (I) ions at 25 ℃;
FIG. 7 is a graph of the effect of adsorbent usage (a), extraction method (b), sample solution pH (c), extraction time (d), elution solvent concentration (e), elution solvent volume (f) and elution time (g) on the extraction efficiency of MSPE.
Fig. 8 is a graph of the effect of 6 cycles of repeated use of silica-modified magnetic graphene oxide on target metal recovery.
Detailed Description
The invention establishes a method for accurately and reliably analyzing 7 trace heavy metal ions in a water environment. Firstly, magnetic graphene oxide modified by silicon dioxide is successfully prepared as a magnetic solid phase extraction adsorbent, then a water environment sample is pretreated by adopting a magnetic solid phase extraction technology, and then an analyte is accurately quantified by utilizing an inductively coupled plasma mass spectrometry, so that the method is applied to the analysis and determination of 7 trace heavy metal ions in a real environment water sample.
Example 1: analysis and determination of 7 trace heavy metal ions in water sample
(1) Synthesis of magnetic graphene oxide modified by silicon dioxide
(1.1) Synthesis of magnetic graphene oxide
0.5g GO powder and 100 ml distilled water were added to a three-neck round bottom flask, then mechanically stirred until the bath temperature rose to 70 ℃. FeCl was added in a total amount of 2.16g3·6H2O and 0.80g FeCl2·4H2O was dissolved in 40mL of distilled water in a beaker to give a clear solution. The mixture was then added to the dispersion with vigorous stirring at 70 ℃. Thereafter, the pH of the suspension was adjusted to 12 by adding ammonia solution to modify Fe on GO sheet3O4Nanoparticles. The mixture was mechanically stirred at 70 ℃ for 60 minutes. The reaction was protected with pure nitrogen throughout the process to prevent complete growth and oxidation of the nanoparticle crystals. After the reaction was completed, the magnetic material was separated from the mixture by a magnet. The resulting black material was washed three times with distilled water and ethanol, then dried under vacuum at 60 ℃ for 10 hours and ground in a mortar for the next step.
(1.2) Synthesis of silica-modified magnetic graphene oxide
First, 6.3mL of distilled water and 2.1mL of TEOS were added to the beaker. The mixture was stirred for 3 minutes and sonicated for an additional 1 minute to form a homogeneous suspension. Next, 0.5gFe3O4-GO was added to 49.5mL ethanol and then the homogeneous suspension was added at 0 ℃ in an ice bath. After vigorous stirring for 10 minutes, 2.0mL of ammonia solution was added dropwise to the mixture with stirring. Finally, the polymerization was continued at 0 ℃ for 10 hours. Fe collection by magnetic separation3O4-GO@SiO2With 2% (v/v) HNO respectively3Ultrapure water and ethanol were washed three times, and then vacuum dried at 70 ℃ for 8h for use.
(2) Pretreatment of water samples
Filtering bottled mineral water, well water, and inlet and outlet water of sewage treatment plant with 0.45 μm syringe filter membrane, acidifying with concentrated nitric acidTo a pH of less than 2 and then stored in PTFE plastic bottles in a refrigerator at around 4 ℃. Prior to extraction, 5% (v/v) HNO was used3And NH3·H2O adjusted the pH of the sample to 5.
(3) Magnetic Solid Phase Extraction (MSPE) enrichment and concentration process
Taking 50mL of the sample obtained in the step (2) to adjust the pH of the solution to 5.8. Mixing 30mg of Fe3O4-GO@SiO2Added to the previous solution, the mixture was then sonicated for 2 minutes and stirred by vortexing for an additional 4 minutes to ensure complete adsorption of the heavy metals on the adsorbent. The nanocomposite was separated at the bottom of the centrifuge tube by using an external magnet and the supernatant was discarded. Next, 6.0mL of 5% (v/v) HNO3Added to the nanocomposite and the mixture was vortexed vigorously for 3 minutes to elute heavy metals from the nanocomposite surface. Finally, Fe3O4-GO@SiO2The nanocomposite was magnetically separated from the solution while the supernatant was introduced into ICP-MS for subsequent analysis.
(4) Inductively coupled plasma mass spectrometry (ICP-MS) measurements
The operating conditions are as follows:
(5) verification method
Using Fe under optimized conditions3O4-GO@SiO2The analytical performance of the development process for extracting 7 target heavy metals from aqueous solutions using nanocomposites as adsorbents is shown in table 1. The calibration curve uses a series of mixed standard solutions with Cr, Co, Cd of 0.05-60 μ g.L-1The mixed standard solution of Ni, Cu, Pb and Ag is 0.1-60 mu g.L-1. All regression coefficients (R) were above 0.9998. The limit of detection (LODs, 3 σ) of this method, defined as three times the standard deviation of the blank signal intensity, is 2 each.776, 2.023, 7.668, 6.472, 3.79, 4.64 and 13.81 ng.L-1Corresponding to Cr, Co, Ni, Cu, Cd, Pb and Ag. By analyzing three concentration levels (1, 5 and 10. mu.g.L)-1) To evaluate the accuracy of the developed method. The Relative Standard Deviation (RSD) was determined to be below 8% (n = 5), indicating that the developed method may show a favorable analytical accuracy. In addition, under the optimal conditions, the enrichment coefficient of SPME to the target heavy metal ions is 10 times, the pre-enrichment time is 360s, and the elution time is 180 s.
The addition amount and recovery rate of the target heavy metals in the four water samples are shown in table 2.
TABLE 1 analytical Performance data for ICP-MS systems
Table 2 addition amount and recovery rate of target heavy metals in four water samples
aRelative recovery rate
bBDL: is lower than the detection limit
cMean. + -. standard deviation of
(6) Characterization of silica-modified magnetic graphene oxide
The size and morphology of the nanocomposites were characterized by Scanning Electron Microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and Vibrating Sample Magnetometer (VSM).
(6.1) Observation of GO, Fe3O4-GO and Fe3O4-The surface morphology of GO @ SiO2 is shown in fig. 1. Fig. 1a shows a sheet-like structure with a smooth, disordered fold in its surface morphology, which is typical of the GO structure. Fe shown in FIG. 1b3O4SEM images of GO have a rougher surface compared to GO due to Fe with a diameter of about 30nm3O4NPs are attached to the GO surface, and this also confirms the success of magnetic nanoparticle modification on the GO surface. According to Fe3O4-GO@SiO2SEM image (FIG. 1 c), Fe can be seen3O4The GO nanocomposite is clearly coated with silica nanoparticles, which can provide to some extent a larger surface area and more adsorption sites.
（6.2）GO，Fe3O4-GO，Fe3O4-GO@SiO2The FT-IR spectrum of (A) is shown in FIG. 2. FT-IR spectrum of GO (FIG. 2 a) is shown at 3436.6cm-1The most prominent peak, which is attributed to the O-H stretching vibration. At 1720.8, 1629.6, 1401.1 and 1052.1cm-1The characteristic peaks of GO appearing there correspond to C-O-C in carbonyl (C = O) stretching, sp2 carbon skeleton network, C-OH group stretching and epoxy group stretching vibration, respectively. According to Fe3O4Spectrum of GO (FIG. 2 b), visible at 1396.4cm-1There is an absorption peak, which is the presence of another vibration band, confirming the formation of a complex between carboxyl and Fe. Furthermore, 584.5cm-1The peak at (a) was due to Fe-O-Fe bond vibration, indicating successful formation of covalent bonds between the magnetic nanoparticles and the GO sheets. With Fe3O4-GO@SiO2In comparison with the spectrum of Fe3O4FT-IR of-GO (fig. 2 b) confirmed the functionalization of the nanocomposite with silica nanoparticles (fig. 2 c). In Fe3O4-GO@SiO2In the spectrum of (2), 1076.4cm-1The absorption peak at (A) was attributed to tensile vibration of Si-O-Si, indicating that Fe3O4GO was successfully coated with silica nanoparticles. Based on the above analysis, it is clear that Fe was successfully synthesized3O4-GO@SiO2A nanocomposite material. In addition, a silica shell structure is introduced to protect the magnetic core from acidic mediaOxidation and digestion, and improved reusability.
(6.3) study of Fe at room temperature with VSM3O4-GO and Fe3O4-GO@SiO2The magnetic property of (2) is shown in a hysteresis loop diagram of FIG. 3. Fe3O4-GO@SiO2And Fe3O4The magnetization hysteresis loop of GO is an S-like curve, which indicates that the synthesized nanocomposite has superparamagnetism. Fe3O4-GO having a saturation magnetization value of 31.42emu g-1，Fe3O4-GO@SiO2Has a saturation magnetization value of 22.58emu g-1。Fe3O4-GO@SiO2The magnetization of the composite material is reduced, which contributes to the SiO2The presence of a shell. However, measured Fe3O4-GO@SiO2Can be separated from the aqueous solution because of 16.3emu g-1Is sufficient for magnetic separation with conventional magnets.
(7) Research on adsorption performance of magnetic graphene oxide modified by silicon dioxide
(7.1) batch adsorption experiment
Standard solutions containing all seven heavy metals were prepared by diluting individual ion stock solutions of Cr (III), Co (II), Ni (II), Cu (II), Cd (II), Pb (II) and Ag (II). The solution was diluted with 5% (v/v) nitric acid to the concentration required for the experiment (100 mg. L)-110-150 mg-L for kinetic studies-1For isotherm studies). By adding 0.1 mol.L-1NaOH or HNO3The solution pH was adjusted to 5. Mixing 30mg of Fe3O4-GO@SiO2The nanocomposite was mixed with 30mL of the metal ion solution and shaken continuously at 180 rpm. In kinetic studies, samples were taken from the reaction mixture at regular intervals. For the isotherm study, the mixture was shaken continuously at room temperature for 1 hour to reach adsorption equilibrium. Subsequently, the adsorbent was magnetically separated from the solution, and the supernatant was collected and then sampled for analysis. Finally, by ICP-MS measures the concentration of the metal. The adsorption capacity of heavy metals was calculated according to the following equation (q t ，mg/g）：
Wherein,q t (mg/g) is the amount adsorbed over time t (min);C 0 （mg·L-1) AndC t （mg·L-1) Is the initial concentration and concentration of adsorbate after time t (min); m is the mass of the nanocomposite (g) and V is the volume of the heavy metal ion solution (L).
(7.2) adsorption kinetics
Using Fe3O4-GO@SiO2The kinetic study of the nanocomposite on adsorption experiments was to image the adsorption process. As can be seen from fig. 4, the adsorption of 7 heavy metal ions rapidly increased within 10min and reached adsorption equilibrium within 35 min. The initial adsorption capacity is high, the adsorption is fast, and the chemical adsorption and the inner ball surface complexation are the main interaction mechanism of the ions and the composite material. To further study the enucleated adsorption kinetics, first and second order-like equations were used to fit the experimental results. The linear equation is expressed as follows,
simulation to the first order:Ln(q e -q t ) = Lnq e - k 1 t
quasi-second order:
wherein k is1（min-1) Is a pseudo-first order adsorption rate constant; k is a radical of2（g·mg-1·min-1) Is the rate constant for pseudo-secondary adsorption;q e （mg·g-1) Andq t （mg·g-1) Respectively the amount of metal ions adsorbed per unit mass of adsorbent at equilibrium and at time t.
t/q t The linear relationship with t is shown in FIG. 5, and the kinetic parameters are shown in Table 3. Correlation coefficient (R) of pseudo second order model2) Are all greater than 0.999. Seven metal ions, and metal ion R of a pseudo first-order model2Between 0.311 and 0.825. Equilibrium adsorption value (q) calculated by a pseudo second order modelecal) also with the experimental adsorption results (q)eexp) fit well. It can be concluded that the pseudo-second order model is best suited to the experimental kinetic data of the target seven metal ions, which indicates that chemisorption is the rate-limiting step.
Table 3: parameters of the pseudo-primary and pseudo-secondary kinetic models were calculated from experimental data.
(7.3) adsorption isotherm
In this study, Langmuir and Freundlich isothermal models were used to simulate adsorption data to study adsorption isotherms. The Langmuir isotherm model is based on a monolayer of adsorption sites uniformly distributed on a uniform surface, while the Freundlich isotherm model is used to understand adsorption on a heterogeneous surface with multiple adsorption layers.
The Langmuir model can be represented as follows:
whereinq m (mg/g) is the maximum amount of metal ions adsorbed per unit weight of the adsorbent;Q e (mg/g) is the equilibrium adsorption capacity;C e （mg·L-1) Is the equilibrium concentration of the water in the aqueous medium,K L （L·mg-1) Is a constant of the Langmuir adsorption isotherm model.
The Freundlich model can be expressed as follows,
wherein n andK F is the Freundlich isotherm constant associated with adsorption capacity and adsorption strength and spontaneity.
The parameters fitted to the adsorption isotherms for the 7 metal ions are listed in table 4. R of all metal ions in Langmuir equation in comparison to Freundlich equation2The values are all higher than 0.97, and the experimental data described by the Langmuir isotherm is proved to be better than the Freundlich isotherm. Obtained by two modelsQ e The comparison of the experimental values and the theoretical values of (A) is shown in FIG. 6. Therefore, the Langmuir isotherm is more suitable for simulating the adsorption process, indicating that the target metal ion is in Fe3O4-GO@SiO2The nanocomposite material is advantageously provided with a single adsorption surface.
TABLE 4 Langmuir and Freundlich isotherm parameters for Fe3O4-GO@SiO2Influence of adsorption isotherms of 7 target heavy metal ions on nanocomposite
Fe at 25 ℃3O4-GO@SiO2The experimental and theoretical adsorption isotherms for Cr, Co, Ni, Cu, Cd, Pb, Ag are shown in FIG. 6.
The adsorption process is accurately simulated by a Langmuir isotherm, and the calculated maximum adsorption capacity is 182.98mg g-1，116.35mg·g-1And 226.08mg g-1，149.59mg·g-1，9001.81mg·g-1，168.55mg g-1，141.09mg·g-1Corresponding to Cr (III), Co (II), Ni (II), Cu (II), Cd (II), Pb (II) and Ag (II) ions, respectively.
（8）Fe3O4-GO@SiO2Reusability of the nanocomposite.
It is important for a nanocomposite not only to have a high metal adsorption capacity but also to be reusable. In this work, Fe was used in the magnetic solid phase extraction process3O4-GO@SiO2With 5mL 5% (v/v) HNO3Washed twice by vortexing and then rinsed with ultra pure water. Subsequently, the above nanocomposite was vacuum dried at 60 ℃ for 8 hours, and then the next extraction cycle was used. Determination of recovery of target Metal to evaluate Fe3O4-GO@SiO2The results are shown in fig. 8. After five consecutive extraction and elution cycles, no significant decrease in recovery was observed, indicating Fe3O4-GO@SiO2SiO when adsorbing Cr, Co, Ni, Cu, Cd, Pb and Ag2Can be reused at least 5 times. From this, it was found that the recovery rates of Cr and Pb were hardly decreased even after the fifth elution cycle.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A magnetic nanocomposite material, characterized by being prepared by a method comprising:
(1) preparing magnetic graphene oxide from graphene oxide, ferric chloride hexahydrate and ferrous chloride tetrahydrate in an alkaline solution;
(2) magnetic solid phase extraction adsorbent silicon dioxide modified magnetic graphene oxide is prepared from magnetic graphene oxide and ethyl silicate in ethanol.
2. The magnetic nanocomposite material of claim 1, wherein the mass ratio of graphene oxide, ferric chloride hexahydrate, and ferrous chloride tetrahydrate is: 1: 1.50-5.00: 0.50-3.80.
3. The magnetic nanocomposite material according to claim 1, wherein the alkaline solution in step (1) has a pH of 10 to 12, and the pH is adjusted by adding an ammonia solution or a sodium hydroxide solution.
4. The magnetic nanocomposite material of claim 1, wherein the mass ratio of the magnetic graphene oxide to the ethyl silicate is: 1: 2.00-6.50, and the volume of the solvent ethanol is 30-75 mL.
5. The magnetic nanocomposite material of claim 1, wherein the preparation method comprises:
(1) dispersing graphene oxide in water, and heating to 70-90 ℃ while violently stirring under the protection of nitrogen; dissolving ferric chloride hexahydrate and ferrous chloride tetrahydrate in water to prepare a solution, and adding the solution into a system when the temperature reaches 70-90 ℃; adding an ammonia solution to adjust the pH value of the system to 12, and continuously mechanically stirring for 1-2 hours at 70-90 ℃ to obtain magnetic graphene oxide;
(2) dispersing ethyl silicate in water, stirring and carrying out ultrasonic treatment to prepare a suspension; adding magnetic graphene oxide into ethanol, adding ethyl silicate suspension under ice bath at 0-4 ℃, violently stirring for 10-20 minutes, dropwise adding 2.0-5.0 mL of ammonia solution into the system under stirring, and continuously stirring for 8-12 hours under ice bath at 0-4 ℃ to obtain the magnetic graphene oxide modified by silicon dioxide.
6. The use of the magnetic nanocomposite material according to any one of claims 1 to 6 for trace heavy metal detection in an aqueous environment.
7. The use according to claim 6, comprising the steps of:
(1) pretreatment of a water sample: collecting and filtering a water sample;
(2) magnetic solid phase extraction, enrichment and concentration processes: adding a magnetic nano composite material into the water sample treated in the step (1), performing ultrasonic treatment, performing vortex separation, removing supernatant to obtain residues, adding 4-10 mL of nitric acid solution into the residues, performing vortex separation, and obtaining supernatant for later use;
(3) measuring 7 trace heavy metal ions in the water environment by using an inductively coupled plasma mass spectrometry method; ICP-MS working parameter values: radio frequency power: 1550W; plasma argon flow: 15 L.min-1(ii) a Auxiliary argon flow: 1 L.min-1(ii) a Atomizer argon flow rate: 1 L.min-1(ii) a Sampling depth: 7.0 mm; sampler/skimmer diameter hole: nickel 1.0mm/0.4 mm; scanning mode: peak-hopping; integration time/mass: 0.3 s; sample absorption time: 30 s; the stabilizing time is as follows: 35 s; an integration mode: peakarea; number of points per spectral peak: 3; and (3) ISTD: sc, Ge, In, Bi;
(4) and (4) calculating detection results of 7 kinds of trace heavy metal ions.
8. The use according to claim 7, wherein the trace heavy metal ions are one or more of Cr (III), Co (II), Ni (II), Cu (II), Cd (II), Pb (II) and Ag (I).
9. A method for simultaneously measuring the content of 7 trace heavy metal ions in a water environment is characterized by comprising the following steps:
(1) pretreatment of a water sample: collecting and filtering a water sample;
(2) magnetic solid phase extraction, enrichment and concentration processes: adding a magnetic nano composite material into the water sample treated in the step (1), performing ultrasonic treatment, performing vortex separation, and removing supernatant to obtain residues for later use;
(3) and (3) heavy metal ion elution process: adding 4-10 mL of nitric acid solution into the residue obtained in the step (2), and performing vortex separation to obtain a supernatant for later use;
(4) the inductively coupled plasma mass spectrometry is used for determining 7 trace heavy metal ions in water environment, and ICP-MS working parameter values are as follows: radio frequency power: 1550W; plasma argon flow: 15 L.min-1(ii) a Auxiliary argon flow: 1 L.min-1(ii) a Atomizer argon flow rate: 1 L.min-1(ii) a Sampling depth: 7.0 mm; sampler/skimmer diameter hole: nickel 1.0mm/0.4 mm; scanning mode: peak-hopping; integration time/mass: 0.3 s; sample absorption time: 30 s; the stabilizing time is as follows: 35 s; an integration mode: peak area; number of points per spectral peak: 3; and (3) ISTD: sc, Ge, In and Bi.
(5) And (4) calculating detection results of 7 kinds of trace heavy metal ions.
10. The method of claim 9, wherein the water environment is bottled mineral water, well water, sewage treatment plant inlet and outlet water.
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