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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- 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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- 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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- 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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- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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 Heavy Metals in Water Environment detection technique fields, and in particular to the silicon dioxide modified magnetism of one kind is received
The preparation and its application in environmental water sample in heavy metal analysis of rice material.Invention also provides a kind of sensitive efficient
The detection method of Heavy Metals in Water Environment ion.
Background technique
With economic and manufacturing development, the heavy metals such as chromium, cobalt, nickel, copper, cadmium, lead, zinc are inevitably discharged into water
Body causes environment water pollution.Heavy metal be it is not biodegradable, human body can be entered by food chain, if it exceeds normally
Range will directly be detrimental to health.Therefore, one kind is developed quickly, sensitive, highly reliable analysis method is for determining environment
Content of beary metal in waters is of great significance.
Inductivity coupled plasma mass spectrometry (ICP-MS) is due to its highly sensitive and abundant detectability, it is considered to be measurement
One of the most effective means of ultratrace element in complex matrices.However, when analyte concentration to be treated is very low and sample
When matrix is relative complex, the trace level heavy metal being difficult in Accurate Determining authentic sample is horizontal.In these cases, analyte with
Compound separation is separated from matrix and is generally indispensable with pre-concentration analyte before ICP-MS measurement.Thus
Applied a variety of separation/pre-concentration methods, such as liquid-liquid extraction (LLE), Solid Phase Extraction (SPE), cloud point extraction (CPE), liquid
Phase extraction (LPM) and ion exchange (IE).In these techniques, Solid Phase Extraction (SPE) due to its enrichment factor is high, it is easy,
Quickly, cost is minimum, reagent consumption is low, the reusability of adsorbent and is easy to the advantages that automating, be for realizing
The most common technology of the analysis of heavy metal in actual sample with complex matrices.Obviously, adsorbent material determines analysis spirit
The selectivity of sensitivity and SPE technology is the key factor of adsorption process.
Graphene (G) is two dimension (2D) structure of the sp2 bonding carbon atom with an atomic thickness, is every other dimension
The basic building block of the graphite material of degree.Due to specific surface area (2630 m of theoretical value of its superelevation2·g-1) and its two sides all may be used
For the plane platelet structures of ionic adsorption, become the excellent of the suitable material for effectively adsorbing heavy metal ion from aqueous solution
Different candidate.Graphene oxide (GO) has the ability being easy to suitable functional group modification, and surface is rich in hydrophilic
Group, such as hydroxyl, carbonyl, epoxy group and carboxyl, are well dispersed in water it.However, due to its polymolecularity, hydrophily
And small particle, it is difficult to rapidly be separated GO with solution by traditional centrifugation and filter method.Thus, it is easy to magnetic field separation
Magnetic graphene adsorbent is since its high score is from the absorption for being applied to heavy metal ion with recovery efficiency.
Summary of the invention
The purpose of the present invention is intended to overcome prior art defect, a kind of New Magnetic Field Controlled solid phase extraction adsorbents is provided, for mentioning
Take the Cr(III in various environmental water samples (bottled mineral water, well water, sewage treatment plant's Inlet and outlet water)), Co(II), Ni(II) and, Cu
(II), Cd(II), Pb(II), Ag(I) and ion.
It is a further object to provide the methods for measuring 7 kinds of trace heavy metal ion contents in water environment simultaneously.
The present invention is achieved through the following technical solutions:
The present invention provides a kind of magnetic nanometer composite material, and the magnetic nanometer composite material is prepared via a method which:
(1) magnetic oxygenated graphite is prepared in alkaline solution by graphene oxide, ferric chloride hexahydrate, Iron dichloride tetrahydrate
Alkene；
(2) the silicon dioxide modified magnetic of magnetic solid phase extraction adsorbent is prepared by magnetic oxygenated graphene, silester in ethanol
Property graphene oxide；
Wherein,
Graphene oxide as described in step (1), ferric chloride hexahydrate, Iron dichloride tetrahydrate mass ratio are as follows: 1:1.50~
5.00:0.50~3.80, preferably are as follows: 1.00:2.16:0.80.
The pH of alkaline solution as described in step (1) is 10~12, is adjusted by the way that ammonia solution or sodium hydroxide solution is added
pH。
The mass ratio of magnetic oxygenated graphene described in step (2), silester are as follows: 1:2.00~6.50, preferably are as follows:
1.00:3.92.Etoh solvent volume is 30~75mL, preferably 49.5mL.
Specifically, the magnetic nanometer composite material is prepared via a method which:
Graphene oxide is dispersed in water, be vigorously stirred under nitrogen protection while being warming up to 70~90 DEG C.Chlorine is hydrated by six
Change iron, Iron dichloride tetrahydrate are soluble in water to be made solution, and above-mentioned solution is added into system when reaching 70~90 DEG C for temperature.Add
Enter ammonia solution and system pH is adjusted to 12, continues 1~2h of mechanical stirring at 70~90 DEG C, obtain magnetic oxygenated graphene；
Silester is dispersed in water, stirs and is ultrasonically treated suspension is made.Magnetic oxygenated graphene is added in ethyl alcohol,
Silester suspension is added under 0~4 DEG C of ice bath, it is vigorously stirred 10~after twenty minutes, it is added dropwise under stiring into system
2.0~5.0mL ammonia solution continues to stir 8~12h under 0~4 DEG C of ice bath, obtains silicon dioxide modified magnetic oxygenated graphite
Alkene.
It is solid that the silicon dioxide modified magnetic oxygenated graphene of magnetic nanometer composite material prepared by the present invention can be used as magnetic
Mutually extraction adsorbent, the pretreatment technology using MSPE as environmental water sample, and using ICP-MS as detection instrument, to trace
It measures heavy metal and carries out content detection.Especially contents of many kinds of heavy metal ion detects simultaneously.Fe nanometer particles are overcome in application
In the problems such as easily being leached from graphene sheet, Cr(III in water environment can be detected simultaneously), Co(II), Ni(II), Cu(II),
Cd(II), Pb(II), Ag(I) and content, sample pretreatment is easy to operate, quickly, efficiently.
The silicon dioxide modified magnetic oxygenated graphene of the magnetic nanometer composite material that the present invention synthesizes extracts as magnetic solid phase
The method for taking adsorbent and inductivity coupled plasma mass spectrometry being combined to be used to detect Heavy Metals in Water Environment ion concentration is specific
Steps are as follows:
(1) it the pretreatment of water sample: collects water sample and filters；
(2) magnetic solid phase extraction is enriched with concentration process: magnetic nanometer composite material is added in the water sample of step (1) processing, ultrasound
Processing is vortexed, and separation discards supernatant liquid, obtains residue, nitric acid solution is added in the residue, is vortexed, and it is standby to obtain supernatant for separation
With；
(3) 7 kinds of trace heavy metal ions in inductively coupled plasma mass spectrometry (ICP-MS) measurement water environment；
In step (1), 0.45 μm of membrane filtration of water sample；
In step (2), sonication treatment time: 2~8min, vortex time: 2~8min；
In step (3), vortex time: 2~8min, nitric acid solution volume: 4~10mL.
Specifically, the present invention can be prepared with the following method:
(1) pretreatment of water sample: water sample is collected, and with 0.45 μm of membrane filtration.
(2) magnetic solid phase extraction is enriched with concentration process: filtered 50~200mL of water sample in step (1) is taken,
The silicon dioxide modified magnetic oxygenated graphene of 20~50mg is added, is ultrasonically treated 2~4min, be vortexed 4~8min, passes through
Using external magnets in centrifugation bottom of the tube separation material, supernatant is removed, addition 4~10mL nitric acid solution in residue, vortex 3~
5min, separation obtain supernatant, and sampling, which is introduced into ICP-MS, to be analyzed.
(3) 7 kinds of trace heavy metal ions in inductively coupled plasma mass spectrometry (ICP-MS) measurement water environment；
(3.1) inductivity coupled plasma mass spectrometry measures
Operating condition:
| ICP-MS running parameter | Parameter value |
| Radio-frequency power | 1550 W |
| Plasma argon flow | 15 L·min-1 |
| Auxiliary argon flow | 1 L·min-1 |
| Atomizer argon gas flow velocity | 1 L·min-1 |
| Sampling depth | 7.0 mm |
| Sampler/skimming tool diametric hole | Nickel 1.0 mm/0.4 mm |
| Scan pattern | Peak-hopping |
| The time of integration/quality | 0.3 s |
| Sample soak time | 30 s |
| Stablize the time | 35 s |
| Integration mode | Peak area |
| The points of each spectrum peak | 3 |
| ISTD | Sc,Ge,In,Bi |
(3.2) supernatant obtained in step (2) icp ms are introduced as analyte to analyze；
This research successfully synthesizes a kind of novel Fe3O4-GO@SiO2Nanocomposite, and mentioned as a kind of effective heavy metal
Take adsorbent material.It establishes, optimize and demonstrates one kind simply, efficiently, quick MSPE combined analysis method is same using ICP-MS
When measurement drinking water and varying environment water sample in 7 heavy metal species.This method high sensitivity, good linearity, the rate of recovery is high, You Jirong
Agent and adsorbent consumption are minimum.To sum up, a kind of novel analysis method is thus developed, it is several true for delicately measuring
Seven kinds of target heavy metals in real environment water sample.Show novel nanocomposite materials extraction/removal trace in various environmental water samples
Measuring heavy metal has very big application potential.
Detailed description of the invention
Fig. 1 is graphene oxide (a), magnetic oxygenated graphene (b), silicon dioxide modified magnetic oxygenated graphene (c)
Scanning electron microscope (SEM) photograph；
Fig. 2 is the infrared spectrogram of graphene oxide, magnetic oxygenated graphene, silicon dioxide modified magnetic oxygenated graphene；
Fig. 3 is the hysteresis loop figure of magnetic oxygenated graphene and silicon dioxide modified magnetic oxygenated graphene；
Fig. 4 is for adsorption time to target metal ions in Fe3O4-GO@SiO2Upper absorption influence curve (cationic initial concentration:
100mg L-1, temperature: 25 DEG C)；
Magnetic oxygenated graphene Fig. 5 silicon dioxide modified when being 25 DEG C is to Cr(III), Co(II), Ni(II) and, Cu(II), Cd
(II), Pb(II), Ag(I) ion curve of adsorption kinetics；
Magnetic oxygenated graphene Fig. 6 silicon dioxide modified when being 25 DEG C is to Cr(III), Co(II), Ni(II) and, Cu(II), Cd
(II), Pb(II), Ag(I) ion experiment and theoretical adsorption isotherm；
Fig. 7 is adsorbent amount (a), extracting method (b), sample solution pH value (c), extraction time (d), eluting solvent concentration
(e), influence of eluting solvent volume (f) elution time (g) to the extraction efficiency of MSPE.
Fig. 8 is shadow of 6 circulating repetitions using silicon dioxide modified magnetic oxygenated graphene to the metal target rate of recovery
It rings.
Specific embodiment
The present invention establishes a kind of method for accurately and reliably analyzing 7 kinds of trace heavy metal ions in water environment.Firstly, two
The magnetic oxygenated graphene of silica modification is successfully prepared as magnetic solid phase extraction adsorbent, then, using magnetic solid phase extraction
Technology carries out pre-treatment to environmental water sample and using inductivity coupled plasma mass spectrometry to analyte accurate quantitative analysis, answers later
Analysis measurement for 7 kinds of trace heavy metal ions in true environment water sample.
Embodiment 1: the analysis measurement of 7 kinds of trace heavy metal ions in water sample
(1) synthesis of silicon dioxide modified magnetic oxygenated graphene
(1.1) synthesis of magnetic oxygenated graphene
Three neck round bottom is added in 0.5 gram of GO powder and 100 milliliters of distilled water, then mechanical stirring is until bath temperature rises to 70
℃.The FeCl for being 2.16g by total amount3·6H2The FeCl of O and 0.80g2·4H2O is dissolved in 40mL distilled water in beaker, is obtained
To clear solution.Then, it is fed the mixture into dispersion under being vigorously stirred at 70 DEG C.Later, ammonia solution, which will be added, to suspend
The pH of liquid is adjusted to 12, to modify Fe on GO sheet material3O4Nanoparticle.By mixture at 70 DEG C mechanical stirring 60 minutes.
In the whole process, it is protected and is reacted with purity nitrogen, to prevent the complete growth and oxidation of nano particle crystal.After reaction, it uses
Magnet separates magnetic material with mixture.Three times by obtained atrament distilled water and ethanol washing, then at 60 DEG C
Lower vacuum drying 10 hours, and grind in mortar for using in next step.
(1.2) synthesis of silicon dioxide modified magnetic oxygenated graphene
Firstly, 6.3mL distilled water and 2.1mL TEOS are added in beaker.It stirs the mixture for 3 minutes and is then sonicated 1 point
Clock is to form uniform suspension.Next, by 0.5gFe3O4-GO is added in 49.5mL ethyl alcohol, is then added under 0 DEG C of ice bath
Enter above-mentioned unit for uniform suspension.It is vigorously stirred after ten minutes, 2.0mL ammonia solution is added dropwise into mixture under stiring.Finally, 0
Continue polymerization reaction 10 hours at DEG C.Fe is collected by magnetic separation3O4-GO@SiO2, 2%(v/v is used respectively) and HNO3, ultrapure water
Three times with ethanol washing, it is spare that 8h is then dried in vacuo at 70 DEG C.
(2) pretreatment of water sample
Bottled mineral water, well water, sewage treatment plant's Inlet and outlet water are used into 0.45 μm of syringe membrane filtration, are acidified to concentrated nitric acid
Then pH is stored in PTFE plastic bottle less than 2 in 4 DEG C or so of refrigerator.Before extraction, with 5%(v/v) HNO3With
NH3·H2The pH value of sample is adjusted to 5 by O.
(3) magnetic solid phase extraction (MSPE) is enriched with concentration process
Take step (2) resulting sample 50mL that the pH of solution is adjusted to 5.8.By 30mg Fe3O4-GO@SiO2It is added to previously
Solution in, then by mixture be ultrasonically treated 2 minutes and by be vortexed be stirred for 4 minutes to ensure that heavy metal is adsorbed on completely
On adsorbent.Nanocomposite is separated in the bottom of centrifuge tube by using external magnets, discards supernatant liquid.Next, will
The 5%(v/v of 6.0mL) HNO3It is added in nanocomposite, and mixture is acutely vortexed to 3 minutes with from nano combined material
Expect that surface elutes heavy metal.Finally, by Fe3O4-GO@SiO2Nanocomposite and solution Magneto separate, while supernatant being introduced
ICP-MS carries out subsequent analysis.
(4) inductivity coupled plasma mass spectrometry (ICP-MS) measures
Operating condition:
(5) verification method
Fe is used under optimal conditions3O4-GO@SiO2Nanocomposite extracts 7 kinds of target huge sum of moneys as adsorbent from aqueous solution
The analysis performance of the development approach of category is shown in Table 1.Calibration curve uses the Cr, Co, Cd 0.05-60 of a series of mixed standard solutions
μg·L-1, Ni, Cu, the mixed standard solution of Pb and Ag are 0.1-60 μ gL-1.All regression coefficients (R) are above 0.9998.
The detection of this method limits (LODs, 3 σ), is defined as three times of blank signal intensity standard deviation, and respectively 2.776,2.023,
7.668,6.472,3.79,4.64 and 13.81ngL-1, corresponding Cr, Co, Ni, Cu, Cd, Pb and Ag.By analyzing three kinds of concentration
Level (1,5 and 10 μ gL-1) mark-on blank water sample development approach to assess accuracy.Determine relative standard deviation
(RSD) it is lower than 8%(n=5), show that developed method can show advantageous analysis precision.In addition, at optimum conditions,
SPME is 10 times to the concentration coefficient of target heavy metal ion, and the preenrichment time is 360s, elution time 180s.
The additive amount and the rate of recovery of target heavy metal in four kinds of water samples are shown in Table 2.
The analysis performance data of 1 ICP-MS system of table
The additive amount and the rate of recovery of target heavy metal in 2 four kinds of water samples of table
aRelative recovery
bBDL: lower than detection limit
cMean+SD
(6) to the characterization of silicon dioxide modified magnetic oxygenated graphene
By scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR) and vibrating specimen magnetometer (VSM) are right
The size and shape of nanocomposite is characterized.
(6.1) GO, the configuration of surface of Fe3O4-GO and Fe3O4-GO@SiO2 are observed by scanning electron microscope (SEM)
As shown in Figure 1.Fig. 1 a shows that its configuration of surface is smooth, the laminated structure of unordered folding, this is the typical structure of GO structure.Figure
Fe shown in 1b3O4The SEM image of-GO has rougher surface compared with GO, because diameter is the Fe of about 30nm3O4 NP
It is attached to the surface GO, and this point also confirms that the magnetic nanoparticle on the surface GO is modified successfully.According to Fe3O4-GO@SiO2
SEM image (Fig. 1 c), it can be seen that Fe3O4- GO nanocomposite is obviously coated by Nano particles of silicon dioxide, Ke Yi
Bigger surface area and more adsorption sites are provided to a certain extent.
(6.2) GO, Fe3O4- GO, Fe3O4-GO@SiO2FT-IR spectrum it is as shown in Figure 2.The FT-IR spectrum (Fig. 2 a) of GO
It is shown in 3436.6cm-1Locate peak most outstanding, this is attributed to O-H stretching vibration.In 1720.8,1629.6,1401.1 Hes
1052.1cm-1The characteristic peak for locating the GO occurred corresponds respectively to carbonyl (C=O) stretching, extension, sp2 carbon skeleton network, the stretching, extension of C-OH group
With the C-O-C in epoxy group stretching vibration.According to Fe3O4The spectrum (Fig. 2 b) of-GO, it can be seen that in 1396.4cm-1It deposits at place
In absorption peak, this is the presence of another vibration band, it was confirmed that the formation of compound between carboxyl and Fe.In addition,
584.5cm-1The peak value at place is attributed to Fe-O-Fe key chattering, shows the success of the covalent bond between magnetic nanoparticle and GO piece
It is formed.With Fe3O4-GO@SiO2Spectrum compare, Fe3O4FT-IR(Fig. 2 b of-GO) confirm nanocomposite and titanium dioxide
The functionalization (Fig. 2 c) of silicon nano.In Fe3O4-GO@SiO2Spectrum in, 1076.4cm-1The absorption peak at place is attributed to Si-
The stretching vibration of O-Si, shows Fe3O4- GO is successfully coated with Nano particles of silicon dioxide.Based on the above analysis, it is clear that success
Fe is synthesized3O4-GO@SiO2Nanocomposite.In addition, introducing silica shell structure to protect magnetic core to be situated between from acidity
Oxidation and digestion in matter, and improve its reusability.
(6.3) Fe at room temperature is studied using VSM3O4- GO and Fe3O4-GO@SiO2Magnetic property, hysteresis loop figure such as Fig. 3
It is shown.Fe3O4-GO@SiO2And Fe3O4The magnetization hysteresis loop line of-GO is S sample curve, shows that the nanocomposite of synthesis has
Superparamagnetism.Fe3O4The saturation magnetization value of-GO is 31.42emug-1, Fe3O4-GO@SiO2Saturation magnetization value
For 22.58emug-1。Fe3O4-GO@SiO2The intensity of magnetization of composite material reduces, this facilitates SiO2The presence of shell.However,
The Fe of measurement3O4-GO@SiO2Saturation magnetization can be separated with aqueous solution, because of 16.3emug-1Saturated magnetization it is strong
Degree is enough to carry out Magneto separate with conventional magnet.
(7) Study on adsorption properties is carried out to silicon dioxide modified magnetic oxygenated graphene
(7.1) batch adsorption experiment
Pass through dilution Cr(III), Co(II), Ni(II), Cu(II), Cd(II), Pb(II) and single ion stock Ag(II)
Solution preparation contains the standard solution of all seven heavy metal species.Use concentration needed for being diluted to experiment with 5%(v/v) nitric acid
(100mgL-1For dynamics research, and 10~150mgL-1It is studied for thermoisopleth).By adding 0.1molL-1
NaOH or HNO3PH value of solution is adjusted to 5.By 30mg Fe3O4-GO@SiO2Nanocomposite and 30mL metal ion solution are mixed
It closes, and is continuously shaken with the speed of 180 rpm.In dynamics research, periodically sampled from reaction mixture.Thermoisopleth is ground
Study carefully, mixture is continuously shaken to 1 hour at room temperature to reach adsorption equilibrium.Then, it by adsorbent and solution Magnetic Isolation, receives
Collect supernatant, then sampling is analyzed.Finally, measuring the concentration of metal by ICP-MS.A huge sum of money is calculated according to following equation
Category adsorption capacity (q t , mg/g):
Wherein,q t (mg/g) be time t(min) absorption amount；C 0 (mgL-1) andC t (mgL-1) be time t(min) inhale afterwards
The initial concentration and concentration of addendum；M is the quality of nanocomposite (g), and V is the volume of heavy metal ion solution (L).
(7.2) adsorption dynamics adsorption kinetics
Use Fe3O4-GO@SiO2The dynamics research that nanocomposite carries out adsorption experiment is to carry out to adsorption process
Imaging.From fig. 4, it can be seen that 7 being adsorbed in 10min for heavy metal species ion increase sharply, and reaches absorption in 35min and put down
Weighing apparatus.Initial adsorption capacity is high, and absorption is fast, show chemisorption and the complexing of interior ball surface be ion and composite material it is main mutually
Mechanism of action.In order to further study stoning adsorption dynamics adsorption kinetics, experimental result is fitted using quasi- single order and quasi- second-order equation.Line
Property equation is expressed as follows,
Quasi- single order:Ln(q e -q t ) = Lnq e - k 1 t
Quasi- second order:
Wherein, k1(min-1) it is quasi- single order adsorbing filament technique；k2(gmg-1·min-1) be quasi- secondary absorption rate it is normal
Number；q e (mgg-1) andq t (mgg-1) be respectively balance when and when time t the adsorbent metal of per unit mass from
The amount of son.
t/q t With linear relationship chart such as Fig. 5 of t, kinetic parameter is shown in Table 3.Related coefficient (the R of quasi- second-order model2) big
In 0.999.Seven metal ion species, and the metal ion R of quasi- first order modeling2Between 0.311~0.825.By intending second order mode
Equilibrium adsorption value (the q that type calculateseCal) also with experiment absorption result (qeExp) meet good.It may be concluded that quasi- second order mode
Type is most suitable for the experimental dynamics data of seven metal ion species of target, this shows that chemisorption is rate-limiting step.
Table 3: the parameter of the quasi- level-one and quasi- second order dynamic model that are calculated from experimental data.
(7.3) adsorption isotherm
During this investigation it turned out, Langmuir and Freundlich Isothermal Model is used to simulate adsorpting data, to study adsorption isotherm
Line.Langmuir isotherm model is based on monolayer adsorption equally distributed adsorption site on uniform outer surface, and Freundlich
Isotherm model is used to understand the absorption on the Heterogeneous surface with multiple adsorption layers.
Langmuir model is represented by following formula:
Whereinq m (mg/g) be the adsorbent metal ion of per unit weight maximum；Q e It (mg/g) is that equilibrium adsorption is held
Amount；C e (mgL-1) it is equilibrium concentration,K L (Lmg-1) be Langmuir adsorption isotherm line model constant.
Freundlich model is represented by following formula,
Wherein n andK F It is and adsorption capacity and adsorption strength and spontaneous relevant Freundlich isothermal constant.
The fitting parameter of 7 metal ion species adsorption isotherms is listed in Table 4 below.Compared with Freundlich equation,
The R of all metal ions in Langmuir equation2Value is above 0.97, it was demonstrated that the experimental data of Langmuir thermoisopleth description is excellent
In Freundlich thermoisopleth.What two kinds of models obtainedQ e Experiment value and theoretical value comparison it is as shown in Figure 6.Therefore,
Langmuir thermoisopleth is more suitable for simulating adsorption process, shows target metal ions in Fe3O4-GO@SiO2On nanocomposite
Be conducive to monolayer adsorption surface.
4 Langmuir and Freundlich thermoisopleth parameter of table is to Fe3O4-GO@SiO27 kinds of targets on nanocomposite
The influence of the adsorption isotherm of heavy metal ion
The Fe at 25 DEG C3O4-GO@SiO2Fig. 6 is shown in experiment and theoretical adsorption isotherm to Cr, Co, Ni, Cu, Cd, Pb, Ag.
Adsorption process is accurately simulated by Langmuir thermoisopleth, calculated maximum adsorption capacity is 182.98mgg-1, 116.35mgg-1And 226.08mgg-1, 149.59mgg-1, 9001.81mgg-1, 168.55mg g-1,
141.09mg·g-1, respectively correspond Cr(III), Co(II), Ni(II), Cu(II), Cd(II), Pb(II), Ag(II) ion.
(8) Fe3O4-GO@SiO2The reusability of nanocomposite.
For a kind of nanocomposite, it is important that not only there is high metal adsorption capacity, but also can repeat
It uses.In this work, Fe used in Magnetic solid phases extraction process3O4-GO@SiO2With 5mL5%(v/v) HNO3Pass through
Vortex method is rinsed twice, and ultrapure water is then used.Then, above-mentioned nanocomposite is dried in vacuo 8 hours at 60 DEG C,
Then it is recycled using next extraction.Determine the rate of recovery of metal target to evaluate Fe3O4-GO@SiO2Reusability,
As a result as shown in Figure 8.After continuous five times extractions and elution cycles, the significant decline of the rate of recovery is not observed, this shows Fe3O4-
GO@SiO2When adsorbing Cr, Co, Ni, Cu, Cd, Pb and Ag, SiO2It may be reused at least 5 times.It follows that even if
After five elution cycles, the rate of recovery of Cr and Pb are almost without reduction.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of magnetic nanometer composite material, which is characterized in that be prepared by the following method:
(1) magnetic oxygenated graphite is prepared in alkaline solution by graphene oxide, ferric chloride hexahydrate, Iron dichloride tetrahydrate
Alkene；
(2) the silicon dioxide modified magnetic of magnetic solid phase extraction adsorbent is prepared by magnetic oxygenated graphene, silester in ethanol
Property graphene oxide.
2. magnetic nanometer composite material as described in claim 1, which is characterized in that graphene oxide, ferric chloride hexahydrate, four
The mass ratio of chloride hydrate ferrous iron are as follows: 1: 1.50~5.00: 0.50~3.80.
3. magnetic nanometer composite material as described in claim 1, which is characterized in that the pH of alkaline solution described in step (1)
It is 10~12, adjusts pH by the way that ammonia solution or sodium hydroxide solution is added.
4. magnetic nanometer composite material as described in claim 1, which is characterized in that magnetic oxygenated graphene, silester
Mass ratio are as follows: 1: 2.00~6.50, etoh solvent volume is 30~75mL.
5. magnetic nanometer composite material as described in claim 1, which is characterized in that the preparation method is that:
(1) graphene oxide is dispersed in water, is vigorously stirred under nitrogen protection while is warming up to 70~90 DEG C；By six hydrations
Iron chloride, Iron dichloride tetrahydrate are soluble in water to be made solution, and above-mentioned solution is added into system when reaching 70~90 DEG C for temperature；
Ammonia solution is added, system pH is adjusted to 12, continues 1~2h of mechanical stirring at 70~90 DEG C, obtain magnetic oxygenated graphene；
(2) silester is dispersed in water, stirs and be ultrasonically treated suspension is made；Ethyl alcohol is added in magnetic oxygenated graphene
In, silester suspension is added under 0~4 DEG C of ice bath, is vigorously stirred 10~after twenty minutes, under stiring into system dropwise plus
Enter 2.0~5.0mL ammonia solution, continues to stir 8~12h under 0~4 DEG C of ice bath, obtain silicon dioxide modified magnetic oxygenated stone
Black alkene.
6. magnetic nanometer composite material described in claim 1~6 any one is in water environment in trace heavy metal detection
Using.
7. application as claimed in claim 6, which comprises the steps of:
(1) it the pretreatment of water sample: collects water sample and filters；
(2) magnetic solid phase extraction is enriched with concentration process: magnetic nanometer composite material is added in the water sample of step (1) processing, ultrasound
Processing is vortexed, and separation discards supernatant liquid, obtains residue, and 4~10mL nitric acid solution is added in the residue, is vortexed, and separation obtains
Clear liquid is spare；
(3) 7 kinds of trace heavy metal ions in inductively coupled plasma mass spectrometry measurement water environment；ICP-MS operating parameter values:
Radio-frequency power: 1550W；Plasma argon flow: 15Lmin-1；Auxiliary argon flow: 1Lmin-1；Atomizer argon gas flow velocity:
1L·min-1；Sampling depth: 7.0mm；Sampler/skimming tool diametric hole: 1.0 mm/0.4mm of Nickel；Scan pattern:
Peak-hopping；The time of integration/quality: 0.3s；Sample soak time: 30s；Stablize the time: 35s；Integration mode: Peak
area；The points of each spectrum peak: 3；ISTD:Sc, Ge, In, Bi；
The calculating of (4) 7 kinds of trace detection of heavy metal ion results.
8. the use as claimed in claim 7, which is characterized in that the trace heavy metal ion is Cr (III), Co (II), Ni
(II), Cu (II), Cd (II), Pb (II), one or more of Ag (I).
9. a kind of method for measuring 7 kinds of trace heavy metal ion contents in water environment simultaneously, which is characterized in that including walking as follows
It is rapid:
(1) it the pretreatment of water sample: collects water sample and filters；
(2) magnetic solid phase extraction is enriched with concentration process: magnetic nanometer composite material is added in the water sample of step (1) processing, ultrasound
Processing is vortexed, and separation discards supernatant liquid, it is spare to obtain residue；
(3) heavy metal ion elution process: being added 4~10mL nitric acid solution in the residue obtained in step (2), is vortexed, point
From it is spare to obtain supernatant；
(4) 7 kinds of trace heavy metal ions in inductively coupled plasma mass spectrometry measurement water environment, ICP-MS operating parameter values:
Radio-frequency power: 1550W；Plasma argon flow: 15Lmin-1；Auxiliary argon flow: 1Lmin-1；Atomizer argon gas flow velocity:
1L·min-1；Sampling depth: 7.0mm；Sampler/skimming tool diametric hole: Nickel 1.0mm/0.4mm；Scan pattern: Peak-
hopping；The time of integration/quality: 0.3s；Sample soak time: 30s；Stablize the time: 35s；Integration mode: Peak area；
The points of each spectrum peak: 3；ISTD:Sc, Ge, In, Bi.
The calculating of (5) 7 kinds of trace detection of heavy metal ion results.
10. method as claimed in claim 9, which is characterized in that the water environment refers to bottled mineral water, well water, sewage
Treatment plant's Inlet and outlet water.
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