CN108519370A - The analysis method of manganese, silicon and potassium element in a kind of measurement graphene oxide - Google Patents
The analysis method of manganese, silicon and potassium element in a kind of measurement graphene oxide Download PDFInfo
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- CN108519370A CN108519370A CN201810413315.7A CN201810413315A CN108519370A CN 108519370 A CN108519370 A CN 108519370A CN 201810413315 A CN201810413315 A CN 201810413315A CN 108519370 A CN108519370 A CN 108519370A
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
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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
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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
- G01N1/34—Purifying; Cleaning
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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
- G01N1/44—Sample treatment involving radiation, e.g. heat
Abstract
The invention belongs to graphene oxide impurity element quantitative analysis tech, are related to a kind of analysis method measuring manganese, silicon and potassium element in graphene oxide.The present invention uses the sample treatment of electric furnace staged heating Muffle furnace calcination acid soluble oxide, using inductively coupled plasma spectrometer measurement.The present invention is tested by dissolution conditions, and co-existing element interference experiment, working curve linear test determines optimal analytical line, improves the accuracy of measurement；Method measurement range is wide, manganese element detection range 0.10%~10.0%, element silicon detection range 0.05%~1.00%, potassium element detection range 0.01%~0.20%；Method is reproducible, and the rate of recovery, precision are preferable；Show that made fixed analysis method accuracy is good by analysis results comparisons such as the analyzing of standard sample, different instrument verifications, method is stablized, and the requirement of trace element analysis is complied fully with；The method of the present invention measurement is directly quick, easy to operate, has saved a large amount of man power and materials.
Description
Technical field
The invention belongs to graphene oxide impurity element quantitative analysis tech, be related to manganese in a kind of measurement graphene oxide,
The analysis method of silicon and potassium element.
Background technology
Graphene is the two-dimentional carbon atomic layer of monoatomic thickness, it is considered to be builds the basis of the isomer of other carbon
Unit.For graphene, in graphene oxide the presence of a large amount of oxygen-containing functional groups with excellent hydrophily and
The chemical coordinability of height, is easily compounded to form novel nanocomposite materials with other materials.Manganese, silicon and potassium element are as impurity
Element be present in graphite oxide it is dilute in, their presence can make graphene oxide reunite, its unique two-dimensional structure of dying, seriously
Product quality is influenced, huge hidden danger is brought to material application.Therefore, it establishes in quickly and accurately quantitative analysis graphene oxide
For the analysis method of manganese, silicon and potassium element to materials engineering, industrialization has great importance.At present both at home and abroad for aoxidizing stone
There has been no examination criteria method, the analysis method about manganese, silicon and potassium element that can be consulted is directed to mostly for the quantitative analysis of black alkene
Metal materials such as steel, high temperature alloy, aluminium alloy etc., above-mentioned material and the dilute physical property of graphite oxide, chemical property and poor activity
Different larger, the above method is not particularly suited for manganese, silicon and potassium element quantitative analysis in graphene oxide.
In recent years, inductively coupled plasma atomic emission technology (ICP-AES) is because it is with accurate, high sensitivity, ring
It protects, save the features such as manpower, be widely used in the fields such as material, geology, metallurgy, environment, food, be fixed in analytical chemistry profession
Measure the important means of analytical element content.Currently, being yet there are no both at home and abroad in relation to utilizing inductive coupling plasma emission spectrum technology
The report of constituent content in quantitative analysis graphene oxide.
Invention content
The purpose of the present invention is：Manganese in the graphene oxide that a kind of pre-treatment is easy, analyst coverage is wide, silicon and potassium member are provided
The quantitative analysis method of cellulose content solves the problems, such as quality evaluation in graphene oxide preparation process.
Technical scheme of the present invention：The analysis method of manganese, silicon and potassium in a kind of measurement graphene oxide, it is characterised in that：
Using platinum crucible as container, graphene oxide is warming up to 400 DEG C using electric furnace staged, is then existed using Muffle furnace
1000 ± 50 DEG C of calcinations obtain the residual oxide of removal carbon base body；After calcination oxide using hydrochloric acid, hydrofluoric acid 20:1
Mixed solution dissolves, the sample clear that dissolves after treatment, limpid, using inductively coupled plasma spectrometer, using Mn
257.610nm, Si 251.611nm, K 766.468nm are as analytical line, in the work item of instrument high frequency incident power 0.9kW
Part measures.
The graphene oxide sample sample quality can be referred to as 0.1000g to 0.5000g according to constituent content to be measured.
The electric furnace staged heating keeps keeping within 1 hour, 200 ± 10 DEG C 2 hours, 300 ± 10 DEG C of guarantors for 100 ± 10 DEG C
It holds 2 hours, 400 ± 10 DEG C and is kept for 2 hours.
The Muffle furnace can be increased to suitably 2 hours in 1000 ± 50 DEG C of calcinations at least 1 hour depending on sample oxidation situation.
The hydrochloric acid, hydrofluoric acid mixed solution be 5mL hydrochloric acid, 5 drop hydrofluoric acid.
The method have the advantages that：
1) one of the advantages of sample treatment technology is the invention has originality.The present invention using platinum crucible as container,
The heating of electric furnace staged removes the organic reagents such as the hydrazine hydrate of surface of graphene oxide absorption；Candidate agent is put into Muffle furnace after eliminating
1000 DEG C of calcinations 2 hours；After carbon base body oxidation completely, 5mL hydrochloric acid, 5 drop hydrofluoric acid are added.This processing method can be effectively
The interference of removal residual organic reagent and carbon base body to experimental result, is manganese, silicon and potassium in accurate quantitative analysis graphene oxide
The prerequisite of element；
2) it is tested by co-existing element interference, it is determined that best instrument operating condition and analytical line improve measurement knot
The accuracy of fruit and stability；
3) measurement range is wide, manganese element detection range 0.10%~10.0%, and element silicon detection range 0.05%~
1.00%, potassium element detection range 0.01%~0.20%；
4) hydrochloric acid, nitron use high-purity or MOS grades of reagent, are conducive to the measurement of low content potassium element；
5) low content potassium element is analyzed, and preferable analysis result can be obtained by directly measuring；
6) there is no interference for coexistence elements, using mixed configuration standard curve, disposably measure manganese, silicon and potassium element and contain
Amount, it is easy to operate quick；
7) synchronization process blank sample, and being deducted when calculating measurement result, reduce reagent and processing procedure introduce it is dry
It disturbs, improves precision of analysis；
8) it is reviewed by method and is compared with other unit analysis result, as a result compared and show that made fixed analysis method is accurate
Exactness is good, and method is stablized, and the requirement of material analysis is complied fully with；
9) the application method measures quick, easy to operate, has saved a large amount of man power and materials；
10) ICP-AES methods are applied widely, and use cost is cheap, easy to spread, have economic value.
Description of the drawings
Fig. 1 is the dilute sample pre-treatments temperature and time curve of graphite oxide
Specific implementation mode
Graphene oxide sample is used electric furnace ladder by the analysis method of manganese, silicon and potassium in a kind of measurement graphene oxide
Formula is warming up to 400 DEG C, then uses Muffle furnace in 1000 ± 50 DEG C of calcinations, obtains the residual oxide of removal carbon base body；Calcination
Afterwards oxide using hydrochloric acid, hydrofluoric acid 20:1 mixed solution dissolving, it is the sample clear that dissolves after treatment, limpid, it adopts
It is measured with inductance Coupled Plasma Spectroscopy instrument, in the operating condition of the instrument of high frequency incident power 0.9kW, using Mn
257.610nm, Si 251.611nm, K 766.468nm are as analytical line.Instrument operating condition is as shown in table 1：
1 instrument operating condition of table
| Project | Parameter | Project | Parameter |
| Higher frequency, MHz | 40.68 | Incident power, kW | 0.9 |
| Entrance slit, μm | 20 | Sheath throughput, L/min | 0.2 |
| Secondary air amount L/min | 0.3 | Sample lifting capacity, mL/min | 1.2 |
| The time of integration, s | 2 | Integral way | One-point type |
| Reflection power, W | ＜ 10 | - | - |
1. specific testing procedure is as follows：
(1), the reagent used in continuous mode is as follows：
(1.1), hydrochloric acid：It is prepared by ρ 1.19g/mL, high-purity or sub-boiling distillation；
(1.2), nitric acid：It is prepared by ρ 1.42g/mL, high-purity or sub-boiling distillation；
(1.3), hydrofluoric acid：ρ about 1.15g/mL；
(1.4), sodium hydroxide：100g/L.
(1.5), manganese standard solution A：1.00mg/mL.
Weigh 0.5000g manganese metals (w (Mn)>99.99%) it, is placed in 200mL beakers.3mL water and 3mL nitric acid is added
(1.2), it dissolves by heating completely, boils drive nitrogen oxides to the greatest extent.It is cooled to room temperature, moves into 500ml volumetric flasks, 40mL nitric acid is added
(1.2), it is diluted with water to scale.
(1.6), silicon standard solution A：0.50mg/mL；
Weigh 5.06g sodium metasilicate (Na2SiO3·9H2O), it is placed in 250mL polytetrafluoroethylene beakers, uses water dissolution.It is added
4mL sodium hydroxide solutions move into plastic bottle, are diluted with water to 800mL, place 72h, filter in 1000mL volumetric flasks, use
Water is diluted to after scale mixing and moves into immediately in dry plastic bottle.Its actual concentrations presses 4.9 progress in HB 5218.6-2004
Calibration.
(1.7), silicon standard solution A：0.10mg/mL；
50.00mL silicon standard solution A (1.7) are pipetted in 250mL volumetric flasks, 20mL hydrochloric acid is added, is diluted with water to quarter
Degree, mixing.
(1.8), potassium standard solution A：1.00mg/mL.
1.907g potassium chloride (in advance in 450 DEG C~500 DEG C calcination 2h) accurately is weighed, is placed in 300mL beakers, use is water-soluble
Solution moves into 1000 mL volumetric flasks, is diluted with water to scale, shakes up.
(1.9), potassium standard solution B：0.10mg/mL.
25.00mL potassium standard solution A (1.9) are pipetted in 250mL volumetric flasks, are diluted with water to scale, mixing.
(1.10), potassium standard solution C：0.01mg/mL.
25.00mL potassium standard solution B (1.10) are pipetted in 250mL volumetric flasks, are diluted with water to scale, mixing.
(2), sampling and sample preparation：The sample of analysis is sampled by systematic sampling method, i.e., each bag in a collection of product
Sample arranges in certain sequence, selects one bag to be sampled at random in product from the 1st bag to n-th bag, then every γ bags of pumpings one of n-
Bag is sampled, and sampling amount is identical in each bag, and samples taken is merged mixing, as the sample of this batch of product, total sampling amount
No less than 5g.
(3), sample solubility test
Graphene oxide activity is very high, but common inorganic acid cannot be allowed to clear up at normal temperatures and pressures, and sample is turned
Becoming fluid analysis has certain difficulty.Graphene oxide has the characteristics that large specific surface area, graphene are adsorbed in oxidation process
A large amount of hydrazine hydrate.Heating speed is too fast to cause vigorous reaction, sample splashing to cause to lose.It is determined after test of many times is groped
The organic reagents such as electric furnace low temperature step heating removal hydrazine hydrate；After through 1000 DEG C of high temperature sinterings of Muffle furnace, obtain removal carbon
The residual oxide of matrix；Oxide finally uses 5ml hydrochloric acid, 5 drop hydrofluoric acid dissolutions, the sample dissolved after treatment after calcination
Product are transparent, limpid, can meet requirement of the spectrum analysis for sample solution.
(4) co-existing element interference is tested
It prepares single-element and tests solution, near 2~4 analysis spectral line centre wavelengths of each analytical element
It is scanned in 0.1842nm window ranges, obtains single interference element solution, analytical element solution and blank reagent solution
Spectral scan figure is overlapped spectrogram, enhanced processing, studies its spectra1 interfer- situation.Finally use analytical line：
Mn257.610nm、Si 251.611nm、K 766.468nm
(5) working curve linear test
Mn 6.00mg, Si 0.30mg, K 0.15mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 6.00%Mn, 0.30%Si, 0.15%K, in standard
Peak is used as in curve.
Mn 4.00mg, Si 0.20mg, K 0.05mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 4.00%Mn, 0.20%Si, 0.05%K, in standard
Control point 1 is used as in curve.
Mn 2.00mg, Si 0.10mg, K 0.02mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 2.00%Mn, 0.10%Si, 0.02%K, in standard
Control point 2 is used as in curve.
Mn 1.00mg, Si 0.05mg, K 0.01mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 1.00%Mn, 0.05%Si, 0.01%K, in standard
Control point 3 is used as in curve.
Blank solution and series standard solution are carried out successively by selected instrument operating condition in instrument optimum state
Standard working curve, using least square fitting data, the standard curve number of the Mn, Si, K element that obtain is made in standardization
According to being shown in Table 2- tables 4.
The standard working curve data of 2 Mn elements of table
The standard working curve data of 3 Si elements of table
The standard working curve data of 4 K element of table
(6) method detection limit is tested
Detection limit is the important indicator that analysis method and instrument carry out trace analysis, it shows that this method can be detected
The minimum concentration of element.Detection limit is defined as according to International Federation of Theoretical and Applied Chemistry (IUPAC)：" detection limit is with dense
Spend (or quality) indicate, refer to acquired by the minimum signal Analysis XL that specific analysis method can be detected reasonably it is minimum dense
Spend CL (or quality gL) ".In spectrum analysis, detection limit refers to that can generate one to confirm point that there is element to be measured in the sample
Analyse the minimum or Cmin of the required component of signal.Under conditions of measurement error Normal Distribution, detection limit
Referring to can be dense with the minimum of given confidence level (usually taking confidence level for 99.7%) detection component to be measured or minimum with this method
Degree.Can have and be exported by minimum detection signal and blank noise.
According to the recommendation of International Organization for standardization (ISO), when measuring the detection limit of analysis method, recommend with blank (examination
Agent blank or blank solution containing matrix) (concentration of component i.e. to be measured is attached in detection limit level with a sample close to blank
Close sample) enough times measurement is carried out, calculate Sb and b according to the data measured, you can according to formula (2.1), find out point
Analysis method measures the detection limit of certain component to be measured.
In formula：The average value for the signal Analysis that-analysis sample is measured in detection limit level；
- average value that secondary enough (this experiment is 12 times) measures measured blank signal is carried out to blank sample；
SbThe standard deviation of-measurement blank sample；
The slope of b-low concentration region calibration curve, when it indicates that component to be measured changes a unit, the change of signal Analysis
Amount, i.e. sensitivity；
K-constants related with confidence level, IUPAC suggest k=3,95%.
This experiment in defined conditions, according to the program that instrument is set, is pressed above-mentioned using curve zero as test solution
Method measures detection limit, and measurement result see the table below 5
5 detection limits table to be measured of table
(7), analytical procedure is as follows：
(7.1), sample：0.10g samples are weighed, 0.0001g is accurate to；
(7.2), sample solution is prepared：Sample after 7.1 weigh is placed in platinum crucible, crucible cover is removed, is placed in
Slowly heating is heated 12 hours on electric furnace.The organic reagents such as the hydrazine hydrate to sample surface remove, and remove slightly cold, cover crucible
Lid, takes out after being put into the calcination 2 hours of 1000 DEG C of Muffle furnace.5mL hydrochloric acid, 5 drop hydrofluoric acid are added.It is transferred to after solution is limpid
In 100mL plastics volumetric flasks, it is diluted with water to scale, mixing.Synchronization process blank sample.
(7.3), preparation work curve solution；
Using the curve solution prepared in step (5) preparation work；It is required that curve solution peak must cover in sample
Manganese, silicon and potassium element analyst coverage；
(7.4), the concentration of manganese, silicon and potassium in sample solution is measured；The work selected by inductively-coupled plasma spectrometer
Make condition and analytical line, instrument is standardized using standard curve, then, measures the dense of manganese in sample solution, silicon and potassium
Degree, subtracts blank sample concentration, the percentage composition ω being calculated as follows is indicated with %；
In formula：ρIt measuresTo measure manganese in graphene oxide, silicon and the mass concentration of potassium, unit mg/ml；
ρIt measuresTo measure manganese in blank, silicon and the mass concentration of potassium, unit mg/ml；
V is working curve liquor capacity, unit ml；
M is to weigh sample mass, unit g.
Embodiment one
It is used as sample using the graphite oxide of Hummers methods preparation is dilute, measures the dilute middle manganese of graphite oxide, silicon and potassium content,
Using inductively coupled plasma spectrometer, the operating condition and analytical line of instrument are as follows：Analytical line：Mn 257.610nm、Si
251.611nm、K 766.468nm；
2. 1 instrument operating condition of table
| Project | Parameter | Project | Parameter |
| Higher frequency, MHz | 40.68 | Incident power, kW | 0.9 |
| Entrance slit, μm | 20 | Sheath throughput, L/min | 0.2 |
| Secondary air amount L/min | 0.3 | Sample lifting capacity, mL/min | 1.2 |
| The time of integration, s | 2 | Integral way | One-point type |
| Reflection power, W | ＜ 10 | - | - |
(1), the reagent used in continuous mode is as follows：
(1.1), hydrochloric acid：It is prepared by ρ 1.19g/mL, high-purity or sub-boiling distillation；
(1.2), nitric acid：It is prepared by ρ 1.42g/mL, high-purity or sub-boiling distillation；
(1.3), hydrofluoric acid：ρ about 1.15g/mL；
(1.4), sodium hydroxide：100g/L.
(1.5), manganese standard solution A：1.00mg/mL.
Weigh 0.5000g manganese metals (w (Mn)>99.99%) it, is placed in 200mL beakers.3mL water and 3mL nitric acid is added,
It dissolves by heating completely, boils drive nitrogen oxides to the greatest extent.It is cooled to room temperature, moves into 500ml volumetric flasks, 40mL nitric acid is added, uses water
It is diluted to scale.
(1.6), silicon standard solution A：0.50mg/mL；
5.06g sodium metasilicate (Na2SiO39H2O) is weighed, is placed in 250mL polytetrafluoroethylene beakers, uses water dissolution.Add
Enter 4mL sodium hydroxide solutions, move into plastic bottle, be diluted with water to 800mL, place 72h, filters in 1000mL volumetric flasks,
It is diluted with water to scale, is moved into immediately in dry plastic bottle after mixing.Its actual concentrations press HB 5218.6-2004 in 4.9 into
Rower is fixed.
(1.7), silicon standard solution A：0.10mg/mL；
50.00mL silicon standard solution A are pipetted in 250mL volumetric flasks, 20mL hydrochloric acid is added, is diluted with water to scale, are mixed
It is even.
(1.8), potassium standard solution A：1.00mg/mL.
1.907g potassium chloride (in advance in 450 DEG C~500 DEG C calcination 2h) accurately is weighed, is placed in 300mL beakers, use is water-soluble
Solution moves into 1000mL volumetric flasks, is diluted with water to scale, shakes up.
(1.9), potassium standard solution B：0.10mg/mL.
25.00mL potassium standard solution A are pipetted in 250mL volumetric flasks, are diluted with water to scale, mixing.
(1.10), potassium standard solution C：0.01mg/mL.
25.00mL potassium standard solution B are pipetted in 250mL volumetric flasks, are diluted with water to scale, mixing.
(2), sampling and sample preparation：The sample of analysis is sampled by systematic sampling method, i.e., each bag in a collection of product
Sample arranges in certain sequence, selects one bag to be sampled at random in product from the 1st bag to n-th bag, then every γ bags of pumpings one of n-
Bag is sampled, and sampling amount is identical in each bag, and samples taken is merged mixing, as the sample of this batch of product, total sampling amount
No less than 5g.
(3), sample solubility test
Graphene oxide activity is very high, but common inorganic acid cannot be allowed to clear up at normal temperatures and pressures, and sample is turned
Becoming fluid analysis has certain difficulty.Graphene oxide has the characteristics that large specific surface area, graphene are adsorbed in oxidation process
A large amount of hydrazine hydrate.Heating speed is too fast to cause vigorous reaction, sample splashing to cause to lose.It is determined after test of many times is groped
The organic reagents such as electric furnace low temperature step heating removal hydrazine hydrate；After through 1000 DEG C of high temperature sinterings of Muffle furnace, obtain removal carbon
The residual oxide of matrix；Oxide finally uses 5ml hydrochloric acid, 5 drop hydrofluoric acid dissolutions, the sample dissolved after treatment after calcination
Product are transparent, limpid, can meet requirement of the spectrum analysis for sample solution.
(4) co-existing element interference is tested
It is configured to single-element test solution, near 2~4 analysis spectral line centre wavelengths of each analytical element
It is scanned in 0.1842nm window ranges, obtains single interference element solution, analytical element solution and blank reagent solution
Spectral scan figure is overlapped spectrogram, enhanced processing, studies its spectra1 interfer- situation.Finally use analytical line：
Mn257.610nm、Si 251.611nm、K 766.468nm
(5) working curve linear test
Mn 6.00mg, Si 0.30mg, K 0.15mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 6.00%Mn, 0.30%Si, 0.15%K, in standard
Peak is used as in curve.
Mn 4.00mg, Si 0.20mg, K 0.05mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 4.00%Mn, 0.20%Si, 0.05%K, in standard
Control point 1 is used as in curve.
Mn 2.00mg, Si 0.10mg, K 0.02mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 2.00%Mn, 0.10%Si, 0.02%K, in standard
Control point 2 is used as in curve.
Mn 1.00mg, Si 0.05mg, K 0.01mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 1.00%Mn, 0.05%Si, 0.01%K, in standard
Control point 3 is used as in curve.
Configuration is in instrument optimum state, by selected instrument operating condition, successively by blank solution and series standard solution
It is standardized, standard working curve is made, using least square fitting data, the standard of the Mn, Si, K element that obtain are bent
Line number evidence.
(6) method detection limit is tested
Detection limit is the important indicator that analysis method and instrument carry out trace analysis, it shows that this method can be detected
The minimum concentration of element.Detection limit is defined as according to International Federation of Theoretical and Applied Chemistry (IUPAC)：" detection limit is with dense
Spend (or quality) indicate, refer to acquired by the minimum signal Analysis XL that specific analysis method can be detected reasonably it is minimum dense
Spend CL (or quality gL) ".In spectrum analysis, detection limit refers to that can generate one to confirm point that there is element to be measured in the sample
Analyse the minimum or Cmin of the required component of signal.Under conditions of measurement error Normal Distribution, detection limit
Referring to can be dense with the minimum of given confidence level (usually taking confidence level for 99.7%) detection component to be measured or minimum with this method
Degree.Can have and be exported by minimum detection signal and blank noise.
According to the recommendation of International Organization for standardization (ISO), when measuring the detection limit of analysis method, recommend with blank (examination
Agent blank or blank solution containing matrix) (concentration of component i.e. to be measured is attached in detection limit level with a sample close to blank
Close sample) enough times measurement is carried out, calculate Sb and b according to the data measured, you can according to formula (2.1), find out point
Analysis method measures the detection limit of certain component to be measured.
In formula：The average value for the signal Analysis that-analysis sample is measured in detection limit level；
- average value that secondary enough (this experiment is 12 times) measures measured blank signal is carried out to blank sample；
SbThe standard deviation of-measurement blank sample；
The slope of b-low concentration region calibration curve, when it indicates that component to be measured changes a unit, the change of signal Analysis
Amount, i.e. sensitivity；
K-constants related with confidence level, IUPAC suggest k=3,95%.
This experiment in defined conditions, according to the program that instrument is set, is pressed above-mentioned using curve zero as test solution
Method measures detection limit.
5 detection limits table to be measured of table
(7), analytical procedure is as follows：
(7.1), sample：0.1000g samples are weighed, 0.0001g is accurate to；
(7.2), sample solution is prepared：The sample of 7.1 processing is placed in platinum crucible, crucible cover is removed, is placed in electric furnace
Upper 100 DEG C keep keeping within 1 hour, 200 DEG C keeping within 2 hours, 300 DEG C 2 hours, 400 DEG C being kept for 2 hours, remove slightly cold, cover earthenware
Crucible lid, after through 1050 DEG C of high temperature sinterings of Muffle furnace, obtain the residual oxide of removal carbon base body；Oxide is finally adopted after calcination
It is the sample clear dissolved after treatment, limpid with 5ml hydrochloric acid, 5 drop hydrofluoric acid dissolutions, spectrum analysis can be met for sample
The requirement of solution.It is transferred to after solution is limpid in 100mL plastics volumetric flasks, is diluted with water to scale, mixing.Synchronization process blank
Sample.
(7.3), preparation work curve solution；
Using solution in (5) preparation work curve；It is required that curve solution peak must cover manganese in sample, silicon and potassium member
Plain analyst coverage；
(7.4), the concentration of manganese, silicon and potassium in sample solution is measured；The work selected by inductively-coupled plasma spectrometer
Make condition and analytical line, instrument is standardized using standard curve, then, measures the dense of manganese in sample solution, silicon and potassium
Degree, subtracts blank sample concentration, the percentage composition ω being calculated as follows is indicated with %；
In formula：ρIt measuresTo measure manganese in graphene oxide, silicon and the mass concentration of potassium, unit mg/ml；
ρIt measuresTo measure manganese in blank, silicon and the mass concentration of potassium, unit mg/ml；
V is working curve liquor capacity, unit ml；
M is to weigh sample mass, unit g.
Obtained manganese content 5.25%, silicone content 0.15%, potassium content 0.05%；
Embodiment two
It is used as sample using the graphite oxide of Hummers methods preparation is dilute, measures the dilute middle manganese of graphite oxide, silicon and potassium content,
Instrument operating condition, analytical line such as embodiment one.
(1), the reagent used in continuous mode and embodiment 1 are consistent；
(2), sampling and sample preparation and embodiment 1 are consistent；
(3), sample solubility test and embodiment 1 are consistent；
(4), co-existing element interference experiment is consistent with embodiment 1；
(5), working curve linear test
Mn 8.00mg, Si 0.50mg, K 0.20mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 8.00%Mn, 0.50%Si, 0.20%K, in standard
Peak is used as in curve.
Mn 6.00mg, Si 0.30mg, K 0.10mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 6.00%Mn, 0.30%Si, 0.10%K, in standard
Control point 1 is used as in curve.
Mn 4.00mg, Si 0.20mg, K 0.05mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 4.00%Mn, 0.20%Si, 0.05%K, in standard
Control point 2 is used as in curve.
Mn 2.00mg, Si 0.10mg, K 0.02mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 2.00%Mn, 0.10%Si, 0.02%K, in standard
Control point 3 is used as in curve.
Configuration is in instrument optimum state, by selected instrument operating condition, successively by blank solution and series standard solution
It is standardized, standard working curve is made, using least square fitting data, the standard of the Mn, Si, K element that obtain are bent
Line number evidence.
(6), the experiment of method detection limit is consistent with embodiment 1；
(7), analytical procedure is as follows：
(7.1), sample：Weigh 0.2000g samples；
(7.2), sample solution is prepared：The sample of 7.1 processing is placed in platinum crucible, crucible cover is removed, is placed in electric furnace
Upper 100 DEG C keep keeping within 1.5 hours, 200 DEG C keeping within 2 hours, 300 DEG C 2 hours, 400 DEG C being kept for 2 hours, remove slightly cold, lid
Upper crucible cover, after through 1000 DEG C of high temperature sinterings of Muffle furnace, obtain the residual oxide of removal carbon base body；Oxide after calcination
It is the sample clear dissolved after treatment, limpid finally using 5ml hydrochloric acid, 5 drop hydrofluoric acid dissolutions, spectrum analysis pair can be met
In the requirement of sample solution.It is transferred to after solution is limpid in 100mL plastics volumetric flasks, is diluted with water to scale, mixing.At synchronous
Manage blank sample.
(7.3), preparation work curve solution；
Using solution in (5) preparation work curve；It is required that curve solution peak must cover manganese in sample, silicon and potassium member
Plain analyst coverage；
(7.4), the concentration of manganese, silicon and potassium in sample solution is measured；The work selected by inductively-coupled plasma spectrometer
Make condition and analytical line, instrument is standardized using standard curve, then, measures the dense of manganese in sample solution, silicon and potassium
Degree, subtracts blank sample concentration, the percentage composition ω being calculated as follows is indicated with %；
In formula：ρIt measuresTo measure manganese in graphene oxide, silicon and the mass concentration of potassium, unit mg/ml；
ρIt measuresTo measure manganese in blank, silicon and the mass concentration of potassium, unit mg/ml；
V is working curve liquor capacity, unit ml；
M is to weigh sample mass, unit g.
Obtained manganese content 5.22%, silicone content 0.16%, potassium content 0.06%；；
Embodiment three
It is used as sample using the graphite oxide of Hummers methods preparation is dilute, measures the dilute middle manganese of graphite oxide, silicon and potassium content,
Instrument operating condition and analytical line such as embodiment one.
(1), the reagent used in continuous mode and embodiment 1 are consistent；
(2), sampling and sample preparation and embodiment 1 are consistent；
(3), sample solubility test and embodiment 1 are consistent；
(4), co-existing element interference experiment is consistent with embodiment 1；
(5), working curve linear test
Mn 8.00mg, Si 0.50mg, K 0.20mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 8.00%Mn, 0.50%Si, 0.20%K, in standard
Peak is used as in curve.
Mn 6.00mg, Si 0.30mg, K 0.10mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 6.00%Mn, 0.30%Si, 0.10%K, in standard
Control point 1 is used as in curve.
Mn 4.00mg, Si 0.20mg, K 0.05mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 4.00%Mn, 0.20%Si, 0.05%K, in standard
Control point 2 is used as in curve.
Mn 2.00mg, Si 0.10mg, K 0.02mg are pipetted respectively in 100mL volumetric flasks, add 10mL hydrochloric acid, 5 drops
Hydrofluoric acid is diluted with water to scale, shakes up.This mixed standard solution contains 2.00%Mn, 0.10%Si, 0.02%K, in standard
Control point 3 is used as in curve.
Configuration is in instrument optimum state, by selected instrument operating condition, successively by blank solution and series standard solution
It is standardized, standard working curve is made, using least square fitting data, the standard of the Mn, Si, K element that obtain are bent
Line number evidence.
(6), the experiment of method detection limit is consistent with embodiment 1；
(7), analytical procedure is as follows：
(7.1), sample：Weigh 0.1000g samples；
(7.2), sample solution is prepared：The sample of 7.1 processing is placed in platinum crucible, crucible cover is removed, is placed in electric furnace
Upper 100 DEG C keep keeping within 2 hours, 200 DEG C keeping within 2 hours, 300 DEG C 2 hours, 400 DEG C being kept for 2 hours, remove slightly cold, cover earthenware
Crucible lid, after through 980 DEG C of high temperature sinterings of Muffle furnace, obtain the residual oxide of removal carbon base body；Oxide is finally adopted after calcination
It is dissolved with 5ml hydrochloric acid (1.1), 5 drop hydrofluoric acid (1.3), it is the sample clear that dissolves after treatment, limpid, spectrum point can be met
Analyse the requirement for sample solution.It is transferred to after solution is limpid in 100 mL plastics volumetric flasks, is diluted with water to scale, mixing.
Synchronization process blank sample.
(7.3), preparation work curve solution；
Using solution in (5) preparation work curve；It is required that curve solution peak must cover manganese in sample, silicon and potassium member
Plain analyst coverage；
(7.4), the concentration of manganese, silicon and potassium in sample solution is measured；The work selected by inductively-coupled plasma spectrometer
Make condition and analytical line, instrument is standardized using standard curve, then, measures the dense of manganese in sample solution, silicon and potassium
Degree, subtracts blank sample concentration, the percentage composition ω being calculated as follows is indicated with %；
In formula：ρIt measuresTo measure manganese in graphene oxide, silicon and the mass concentration of potassium, unit mg/ml；
ρIt measuresTo measure manganese in blank, silicon and the mass concentration of potassium, unit mg/ml；
V is working curve liquor capacity, unit ml；
M is to weigh sample mass, unit g.
Obtained manganese content 5.25%, silicone content 0.14%, potassium content 0.05%.
Claims (6)
1. a kind of analysis method measuring manganese, silicon and potassium in graphene oxide, it is characterised in that：Using platinum crucible as appearance
Graphene oxide is warming up to 400 DEG C by device using electric furnace staged, is then used Muffle furnace in 1000 ± 50 DEG C of calcinations, is obtained
Remove the residual oxide of carbon base body；After calcination oxide using hydrochloric acid, hydrofluoric acid 20:1 mixed solution dissolving, by place
It is the sample clear that is dissolved after reason, limpid, using inductively coupled plasma spectrometer, using Mn 257.610nm, Si
251.611nm, K 766.468nm are measured as analytical line in the operating condition of instrument high frequency incident power 0.9kW.
2. measuring the analysis method of manganese, silicon and potassium in graphene oxide as described in claim 1, it is characterised in that：The oxygen
Graphite alkene sample sample quality can be referred to as 0.1000g to 0.5000g according to constituent content to be measured.
3. measuring the analysis method of manganese, silicon and potassium in graphene oxide as claimed in claim 2, it is characterised in that：The electricity
Stove staged heating for 100 ± 10 DEG C keep 1 hour, 200 ± 10 DEG C keep 2 hours, 300 ± 10 DEG C keep 2 hours, 400 ±
10 DEG C are kept for 2 hours.
4. measuring the analysis method of manganese, silicon and potassium in graphene oxide as claimed in claim 3, it is characterised in that：The horse
Not stove can be increased to suitably 2 hours in 1000 ± 50 DEG C of calcinations at least 1 hour depending on sample oxidation situation.
5. the analysis method for measuring manganese, silicon and potassium in graphene oxide as described in claim 1-4 any one, feature exist
In：The hydrochloric acid, hydrofluoric acid mixed solution be 5mL hydrochloric acid, 5 drop hydrofluoric acid.
6. measuring the analysis method of manganese, silicon and potassium in graphene oxide as claimed in claim 5, it is characterised in that：The oxygen
Graphite alkene sample manganese element detection range 0.10%~10.0%, element silicon detection range 0.05%~1.00%, potassium element
Detection range 0.01%~0.20%.
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