CN110327873A - A kind of magnetic graphite phase carbon nitride material and its preparation method and application - Google Patents
A kind of magnetic graphite phase carbon nitride material and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of magnetic graphite phase carbon nitride material, the material refer to using barium ions be Doped ions construct with stratiform, coplanar three s-triazine that aperture is 2 ~ 50nm cavity structure as the multi-cluster compound of basic structural unit.Meanwhile the invention also discloses the preparation method and application of the material.Large specific surface area of the present invention has to radionuclide210The good feature of Pb strong adsorption, selectivity.
Description
Technical field
The present invention relates to technical field of analysis and detection more particularly to a kind of magnetic graphite phase carbon nitride material and its preparation sides
Method and application.
Background technique
The development and utilization of mining site resource cause the natural radionuclide being present in mineral to spread to periphery.Wherein, it puts
Penetrating property nucleic210Pb is often discharged in surface drainage nearby in the form of waste water, and enters human body by drinking water and food chain, is made
It is endangered at interior irradiation, causes the damage and canceration of human inner cell.Therefore it realizes to food and the radioactivity for drinking underwater trace
Nucleic210The detection of Pb is of great significance.However, in the complex samples such as food, radionuclide210The concentration of Pb is lower,
It can not directly be measured.Therefore, before sample detection, to the radionuclide in sample210Pb is enriched with and is divided
From, can be improved instrument detection sensitivity, preci-sion and accuracy (Z. C. Huang,Nucl. Sci. Tech.,
2013, 36 (7): 070301-1-6) 。
Currently, to radionuclide in food samples210The method of Pb enrichment mainly has resin method, the precipitation method, solvent extraction
Method and ion-exchange etc., but these methods have safety poor, the disadvantages of disengaging time is long, poor selectivity, seriously affect sample
Radioactive element in product210Pb measurement result (Z. S. Chen,Chin. J. Radiol. Med. Prot., 1990, 10
(1):49−52; X. T. Yang, Chin. J. Radiol. Med. Prot., 1988, 8(4):254−256).Therefore,
Need to develop one kind simply, quickly, collection enrichment is located away from integrated sample-pretreating method.
It is revolutionary technology of the 21 century in separation and concentration field that Magnetic solid phases, which extract (MSPE), mainly with magnetism or can magnetic
A kind of dispersive solid-phase extraction technology of the material of change as adsorbent.During MSPE, magnetic adsorbent is added to sample
Solution or suspension in, target analytes are adsorbed onto the magnetic adsorbent surface of dispersion, under external magnetic fields, mesh
Mark analyte is migrated with adsorbent, measured matter is eluted eventually by suitable solvent, so that the matrix with sample separates
Come, have many advantages, such as easy to operate, extraction time is short, organic solvent usage amount is few, Solid-Liquid Separation speed it is fast (N. Li,
Anal. Chim. Acta, 2017, 949, 23-34; A. Amiri, Microchim. Acta, 2018, 185,
393.) 。
Graphite phase carbon nitride material (g-C3N4) be a kind of approximate graphene planar lamellar structure, because it is to environment
Close friend, it is without secondary pollution, have the characteristics that good thermal stability and chemical stability and favored, and metal ion is mixed
It is miscellaneous to make g-C3N4With special pore size distribution size, the specific adsorption to target metal ions is realized.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of pair of radionuclides210Pb strong adsorption, selectivity are good
Magnetic graphite phase carbon nitride material.
Another technical problem to be solved by this invention is to provide the preparation method of the magnetic graphite phase carbon nitride material.
Third technical problem to be solved by this invention is to provide the application of the magnetic graphite phase carbon nitride material.
To solve the above problems, a kind of magnetic graphite phase carbon nitride material of the present invention, it is characterised in that: the material
Refer to that the have stratiform, coplanar three s-triazine that aperture is 2 ~ 50nm cavity structure constructed by Doped ions of barium ions are basic
The multi-cluster compound of structural unit.
A kind of preparation method of magnetic graphite phase carbon nitride material as described above, comprising the following steps:
(1), using triazine structure compound as presoma, after it is mixed with barium ions compound, the 1 ~ 3 of mixture quality is dissolved in
In ultrapure water again, stirring dissolves it sufficiently at room temperature, obtains the triazine structure compound solution containing barium ions；Before described
The mass ratio for driving body and the barium ions compound is 5:1 ~ 30:1；
(2) the triazine structure compound solution by described containing barium ions is dry to anhydrous in 60 ~ 80 DEG C, obtains white solid；
(3) the white solid is transferred in crucible, is placed in the calcining of Muffle furnace high temperature；It is cooled to room temperature, obtains after reaction
Flaxen solid powder；
(4) acid solution is added by the mass volume ratio of 1:5 ~ 20 in the flaxen solid powder, through 4000 W ultrasounds 10 ~ 20
4000 rpm are centrifuged 20min after min elution, obtain solid powder；
The solid powder through milli-Q water three times after in 60 ~ 80 DEG C of dry graphite adulterated to constant weights to get barium ions
Phase carbon nitride material；
(6) the graphite phase carbon nitride material of the barium ions doping is dissolved in alcohol-water mixing by the mass volume ratio of 1:60 ~ 120
In solution, and ultrasound 6h at room temperature, obtain suspension；
(7) by FeCl3∙6H2O and FeCl2∙4H2O is put into the suspension with the mass ratio of 1:1 ~ 1:3, heats and machinery stirs
It mixes, is gradually added into alkaline precipitating agent in 65 DEG C, makes the pH value of mixed solution to 10；Then in 70 ~ 90 DEG C of 30 min of back flow reaction ~
2 h, obtain product；
(8) the product is dried to constant weight in 45 ~ 80 DEG C to get magnetic respectively after dehydrated alcohol and ultrapure water successively wash three times
Property barium ions doping graphite phase carbon nitride material.
The step (1) in presoma refer to urea, melamine, cyanamide, thiocarbamide, any one in dicyandiamide.
The step (1) in barium ions compound refer to barium chloride (BaCl2), barium nitrate (Ba (NO3)2), barium acetate (Ba
(CH3COO)2) in any one.
The step (3) in high-temperature calcination condition refer to heating rate be 4 DEG C/min, temperature be 500 ~ 580 DEG C, the time
For 3 ~ 5h.
The step (4) in acid solution refer to concentration be the mol/L of 0.1 mol/L ~ 2.0 nitric acid, hydrochloric acid, phosphoric acid, vinegar
Any one in acid.
The step (6) in alcohol-water mixed solution to refer to that dehydrated alcohol and water are mixed by the volume ratio of 1:2 molten
Liquid.
(7) neutral and alkali precipitating reagent refers to ammonium hydroxide, sodium hydroxide, any one in potassium hydroxide to the step.
A kind of application of magnetic graphite phase carbon nitride material as described above, it is characterised in that: magnetism barium ions doping
Graphite phase carbon nitride material as adsorbent be applied to food in radioactivity210The fast enriching and trace detection of Pb.
A kind of application of magnetic graphite phase carbon nitride material as described above, comprising the following steps:
1. the graphite phase carbon nitride material that the mg magnetism barium ions of 1.0 mg ~ 10.0 adulterates is placed in 5 mL solution to be measured, ultrasound
20 min make material uniformly in being dispersed in solution to be measured, and mixed solution is put into 10 ~ 180 min of oscillation in oscillator therewith,
To reach extraction equilibrium；Magnetic Isolation is carried out using magnet, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase210Pb concentration is measured；
3. the adsorbent material after the separation is transferred in centrifuge tube, it is super that 0.5 mol/L nitric acid solution 200 μ L, 4000W is added
5 ~ 20min of sound, makes target species210Pb is desorbed from adsorbent；It repeats above operation 3 times, in 40 ~ 70 DEG C after merging stripping liquid
It is evaporated solution, then is dissolved with 0.5 mol/L nitric acid solution, 30 ~ 90 μ L, utilizes inductive coupling etc. according to GB5009.268-2016
Ion emission spectroscopy instrument measures its concentration, finally calculates target species in solution to be measured210The content of Pb.
Compared with the prior art, the present invention has the following advantages:
1, the present invention is eluted Doped ions by acid solution, is constructed and is nitrogenized with the graphite-phase that pore size is 2 ~ 50nm
Carbon material (referring to fig. 2 (b)), and being compared with blank graphite phase carbon nitride material (referring to fig. 2 (a)), it can be seen that barium from
The doped graphite phase carbon nitride material of son still has typical layer structure, and pleated structure occurs, can increase and compare table
Area.In addition, metal nanoparticle does not occur in the doped graphite phase carbon nitride surface in barium ions, illustrate Ba2+It is passing through
Complexing is learned to be doped in graphite phase carbon nitride.
2, the present invention by coprecipitation above-mentioned preparation graphite phase carbon nitride material surface carried magnetic nano particle,
The graphite phase carbon nitride material (referring to fig. 2 (c)) for preparing magnetic barium ions doping, in the graphite phase carbon nitride material of barium ions doping
Expect that there are a large amount of magnetic Fes on surface3O4Nano particle, it was demonstrated that the success of the graphite phase carbon nitride material of magnetic barium ions doping
Preparation.And graphite phase carbon nitride material and magnetic barium ions doping stone to blank graphite phase carbon nitride material, barium ions doping
Black phase carbon nitride material carries out IR Characterization (referring to fig. 2 (d)), if figure is in CN, CN-Ba and CN-Ba-Fe3O4Exist 1200 ~
1600cm-1Absorption peak, C=C/C=N/C-N group characteristic absorption of graphite phase carbon nitride can be belonged to；2188
cm-1Absorption peak be due to Ba2+Doping caused by；In CN-Ba-Fe3O4And Fe3O4There are 622 cm-1Absorption peak, be magnetic
The characteristic absorption of Fe-O in property nano particle.The above characterization proves the success of the graphite phase carbon nitride of magnetic barium ions doping
Preparation.
3, it is investigated by the specific surface area to the resulting magnetic graphite phase carbon nitride material of the present invention (referring to Fig. 3),
The specific surface area of the graphite phase carbon nitride material of blank is 6.602 m2The specific surface area of/g, magnetic graphite phase carbon nitride material is
109.606 m2/ g, therefore, the present invention is by increasing the specific surface area of composite material to graphite phase carbon nitride material functional.
4, it is investigated (referring to fig. 4) by the selectivity to the resulting magnetic graphite phase carbon nitride material of the present invention,
The magnetic graphite phase carbon nitride material of preparation is respectively placed in 5 mL, 30 μ g/mL, 10 kinds of metal ion [Co to be measured2+, Cs+,
Ca2+, Ce2+, Ba2+,Cu2+, Mg2+, Sr2+, Mn2+, Zn2+] in solution, ultrasonic 20min vibrates 60 min to reach extraction
It makes even weighing apparatus.Subsequent Magnetic Isolation is measured the concentration of each metal ion in water phase.Statistics indicate that, the magnetism is multiple in figure
Condensation material is to radioactivity210Pb has good selectivity adsorption capacity, is conducive to the composite material answering in analysis testing field
With.
5, the method for the present invention is simple, low in cost, raw material is green, pollution-free, resulting magnetic graphite phase carbon nitride material
The graphite phase carbon nitride material of large specific surface area, resulting magnetism barium ions doping is radionuclide210The sample pre-treatments of Pb
New theoretical foundation is provided with analysis detection, the status that such current material is completely dependent on external import is changed, fills up
The vacancy of domestic market.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 is the preparation flow schematic diagram of magnetic graphite phase carbon nitride material of the present invention.
Fig. 2 is the pattern and structural characterization map of magnetic graphite phase carbon nitride material of the present invention.Wherein, (a) is blank stone
The transmission electron microscope phenogram of black phase carbon nitride material；(b) the transmission electron microscope characterization of the graphite phase carbon nitride material of barium ions doping
Figure；(c) the transmission electron microscope phenogram of the graphite phase carbon nitride material of magnetic barium ions doping.(d) blank graphite phase carbon nitride, barium
The graphite phase carbon nitride of ion doping, the graphite phase carbon nitride and Fe of magnetic barium ions doping3O4The infrared characterization chart of nano particle
Spectrum.
Fig. 3 is the graphite phase carbon nitride material of the magnetic barium ions doping of the present invention and the specific surface of blank graphite phase carbon nitride
Product measurement map.
Fig. 4 is the measurement of the selective absorption performance of the graphite phase carbon nitride material of the magnetic barium ions doping of the present invention.
Specific embodiment
A kind of magnetic graphite phase carbon nitride material, the material refer to using barium ions as Doped ions construct have stratiform,
Aperture is that coplanar three s-triazine of 2 ~ 50nm cavity structure is the multi-cluster compound of basic structural unit.
Embodiment 1 is as shown in Figure 1, a kind of preparation method of magnetic graphite phase carbon nitride material, comprising the following steps:
(1) by 30g urea and 1g BaCl2It after mixing, is dissolved in 1 times of ultrapure water of mixture quality, stirring makes at room temperature
It is sufficiently dissolved, and obtains the triazine structure compound solution containing barium ions.
(2) the triazine structure compound solution containing barium ions is placed in a vacuum drying oven dry to anhydrous in 60 DEG C, obtained
To white solid.
(3) white solid is transferred in crucible, is placed in Muffle furnace, heating rate is 4 DEG C/min, temperature is 500 DEG C
Under conditions of high-temperature calcination 5h, prepared by way of thermal polycondensation barium ions doping graphite phase carbon nitride material；Reaction terminates
After be cooled to room temperature, obtain flaxen solid powder.
(4) the nitric acid solution of 0.1 mol/L, warp are added in flaxen solid powder by the mass volume ratio of 1g:5mL
4000 rpm are centrifuged 20 min after 4000W 20 min of ultrasound elution, discard supernatant liquid, and this process was repeated three times, remove barium ions
Doped ions (Ba in the graphite phase carbon nitride material of doping2+), obtain solid powder.
Solid powder through milli-Q water three times, removal is dry to perseverance in 80 DEG C after the acid solution of solid powder surfaces
The graphite phase carbon nitride material that weight adulterates to get barium ions.
(6) the graphite phase carbon nitride material of barium ions doping is dissolved in alcohol-water mixing by the mass volume ratio of 1g:60mL
In solution, and ultrasound 6h at room temperature, obtain suspension.
Wherein: it is molten that alcohol-water mixed solution refers to that dehydrated alcohol and water are mixed by the volume ratio (mL/mL) of 1:2
Liquid.
(7) by 0.3g FeCl3∙6H2O and 0.3g FeCl2∙4H2O is put into suspension, simultaneously mechanical stirring is heated, in 65
DEG C it is gradually added into ammonium hydroxide, makes the pH value of mixed solution to 10；Then in 70 DEG C of 2 h of back flow reaction, product is obtained.
(8) product is put into vacuum oven and dries extremely in 60 DEG C respectively after dehydrated alcohol and ultrapure water successively wash three times
The graphite phase carbon nitride material that constant weight is adulterated to get magnetic barium ions.
The graphite phase carbon nitride material of magnetism barium ions doping is applied to radioactivity in food as adsorbent210Pb's
Fast enriching and trace detection.The specific method is as follows:
1. testing sample solution will be obtained through the pretreated food samples such as dry and ashing, preparation.
The graphite phase carbon nitride material that 1.0 mg magnetism barium ions adulterate is placed in 5 mL solution to be measured, ultrasound 20
Min makes material uniformly in being dispersed in solution to be measured, mixed solution is put into oscillator vibrates 10 min therewith, to reach
Extraction equilibrium；Magnetic Isolation is carried out by magnet, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase210Pb concentration is measured；
3. the adsorbent material after separation is transferred in centrifuge tube, 0.5 mol/L nitric acid solution, 200 μ L, 4000W ultrasound 5 is added
Min makes target species210Pb is desorbed from adsorbent；It repeats above operation 3 times, is evaporated solution in 40 DEG C after merging stripping liquid,
It is dissolved again with 0.5 mol/L nitric acid solution, 30 μ L, utilizes inductive coupling plasma emission spectrum according to GB5009.268-2016
Instrument (ICP-OES) measures its concentration, finally calculates target species in solution to be measured210The content of Pb.
A kind of preparation method of the magnetic graphite phase carbon nitride material of embodiment 2, comprising the following steps:
(1) by 5g melamine and 1g Ba (NO3)2After mixing, it is dissolved in 3 times of ultrapure water of mixture quality, at room temperature
Stirring dissolves it sufficiently, obtains the triazine structure compound solution containing barium ions.
(2) the triazine structure compound solution containing barium ions is placed in a vacuum drying oven dry to anhydrous in 80 DEG C, obtained
To white solid.
(3) white solid is transferred in crucible, is placed in Muffle furnace, heating rate is 4 DEG C/min, temperature is 580 DEG C
Under conditions of high-temperature calcination 3h, prepared by way of thermal polycondensation barium ions doping graphite phase carbon nitride material；Reaction terminates
After be cooled to room temperature, obtain flaxen solid powder.
(4) the nitric acid solution of 2.0 mol/L, warp are added in flaxen solid powder by the mass volume ratio of 1g:20mL
4000 rpm are centrifuged 20 min after 4000W 10 min of ultrasound elution, discard supernatant liquid, and this process was repeated three times, remove barium ions
Doped ions (Ba in the graphite phase carbon nitride material of doping2+), obtain solid powder.
Solid powder through milli-Q water three times, removal is dry to perseverance in 60 DEG C after the acid solution of solid powder surfaces
The graphite phase carbon nitride material that weight adulterates to get barium ions.
(6) the graphite phase carbon nitride material of barium ions doping is dissolved in alcohol-water mixing by the mass volume ratio of 1g:120mL
In solution, and ultrasound 6h at room temperature, obtain suspension.
Wherein alcohol-water mixed solution is the same as embodiment 1.
(7) by 0.3g FeCl3∙6H2O and 0.9g FeCl2∙4H2O is put into suspension, simultaneously mechanical stirring is heated, in 65
DEG C it is gradually added into sodium hydroxide, makes the pH value of mixed solution to 10；Then in 90 DEG C of 30 min of back flow reaction, product is obtained.
(8) product is put into vacuum oven and dries extremely in 80 DEG C respectively after dehydrated alcohol and ultrapure water successively wash three times
The graphite phase carbon nitride material that constant weight is adulterated to get magnetic barium ions.
The graphite phase carbon nitride material of magnetism barium ions doping is applied to radioactivity in food as adsorbent210Pb's
Fast enriching and trace detection.The specific method is as follows:
1. testing sample solution will be obtained through the pretreated food samples such as dry and ashing, preparation.
The graphite phase carbon nitride material that 10.0 mg magnetism barium ions adulterate is placed in 5 mL solution to be measured, ultrasound 20
Min makes material uniformly in being dispersed in solution to be measured, mixed solution is put into oscillator vibrates 180 min therewith, to reach
Extraction equilibrium；Magnetic Isolation is carried out by magnet, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase210Pb concentration is measured；
3. the adsorbent material after separation is transferred in centrifuge tube, 0.5 mol/L nitric acid solution, 200 μ L, 4000W ultrasound is added
10min makes target species210Pb is desorbed from adsorbent；It repeats above operation 3 times, is evaporated after merging stripping liquid in 60 DEG C molten
Liquid, then dissolved with 0.5 mol/L nitric acid solution, 90 μ L, emit light using inductively coupled plasma according to GB5009.268-2016
Spectrometer (ICP-OES) measures its concentration, finally calculates target species in solution to be measured210The content of Pb.
A kind of preparation method of the magnetic graphite phase carbon nitride material of embodiment 3, comprising the following steps:
(1) by 10g cyanamide and 0.5g Ba (CH3COO)2After mixing, it is dissolved in 2 times of ultrapure water of mixture quality, room temperature
Lower stirring dissolves it sufficiently, obtains the triazine structure compound solution containing barium ions.
(2) the triazine structure compound solution containing barium ions is placed in a vacuum drying oven dry to anhydrous in 70 DEG C, obtained
To white solid.
(3) white solid is transferred in crucible, is placed in Muffle furnace, heating rate is 4 DEG C/min, temperature is 520 DEG C
Under conditions of high-temperature calcination 4h, prepared by way of thermal polycondensation barium ions doping graphite phase carbon nitride material；Reaction terminates
After be cooled to room temperature, obtain flaxen solid powder.
(4) the acetum of 1.0 mol/L, warp are added in flaxen solid powder by the mass volume ratio of 1g:10mL
4000 rpm are centrifuged 20min after 4000W 15 min of ultrasound elution, discard supernatant liquid, and this process was repeated three times, and removal barium ions is mixed
Doped ions (Ba in miscellaneous graphite phase carbon nitride material2+), obtain solid powder.
Solid powder through milli-Q water three times, removal is dry to perseverance in 70 DEG C after the acid solution of solid powder surfaces
The graphite phase carbon nitride material that weight adulterates to get barium ions.
(6) the graphite phase carbon nitride material of barium ions doping is dissolved in alcohol-water mixing by the mass volume ratio of 1g:80mL
In solution, and ultrasound 6h at room temperature, obtain suspension.
Wherein alcohol-water mixed solution is the same as embodiment 1.
(7) by 0.3g FeCl3∙6H2O and 0.6g FeCl2∙4H2O is put into suspension, simultaneously mechanical stirring is heated, in 65
DEG C it is gradually added into potassium hydroxide, makes the pH value of mixed solution to 10；Then in 80 DEG C of back flow reaction 1h, product is obtained.
(8) product is put into vacuum oven and dries extremely in 50 DEG C respectively after dehydrated alcohol and ultrapure water successively wash three times
The graphite phase carbon nitride material that constant weight is adulterated to get magnetic barium ions.
The graphite phase carbon nitride material of magnetism barium ions doping is applied to radioactivity in food as adsorbent210Pb's
Fast enriching and trace detection.The specific method is as follows:
1. testing sample solution will be obtained through the pretreated food samples such as dry and ashing, preparation.
The graphite phase carbon nitride material that 5.0 mg magnetism barium ions adulterate is placed in 5 mL solution to be measured, ultrasound 20
Min makes material uniformly in being dispersed in solution to be measured, mixed solution is put into oscillator vibrates 100 min therewith, to reach
Extraction equilibrium；Magnetic Isolation is carried out by magnet, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase210Pb concentration is measured；
3. the adsorbent material after separation is transferred in centrifuge tube, 0.5 mol/L nitric acid solution, 200 μ L, 4000W ultrasound is added
10min makes target species210Pb is desorbed from adsorbent；It repeats above operation 3 times, is evaporated after merging stripping liquid in 45 DEG C molten
Liquid, then dissolved with 0.5 mol/L nitric acid solution, 60 μ L, emit light using inductively coupled plasma according to GB5009.268-2016
Spectrometer (ICP-OES) measures its concentration, finally calculates target species in solution to be measured210The content of Pb.
A kind of preparation method of the magnetic graphite phase carbon nitride material of embodiment 4, comprising the following steps:
(1) by 15g thiocarbamide and 1g BaCl2It after mixing, is dissolved in 2 times of ultrapure water of mixture quality, stirring makes at room temperature
It is sufficiently dissolved, and obtains the triazine structure compound solution containing barium ions.
(2) the triazine structure compound solution containing barium ions is placed in a vacuum drying oven dry to anhydrous in 65 DEG C, obtained
To white solid.
(3) white solid is transferred in crucible, is placed in Muffle furnace, heating rate is 4 DEG C/min, temperature is 540 DEG C
Under conditions of high-temperature calcination 4.5h, prepared by way of thermal polycondensation barium ions doping graphite phase carbon nitride material；Reaction knot
It is cooled to room temperature after beam, obtains flaxen solid powder.
(4) 0.1 mol/L hydrochloric acid solution, warp are added by the mass volume ratio of 1g:15mL in flaxen solid powder
4000 rpm are centrifuged 20 min after 4000W 12 min of ultrasound elution, discard supernatant liquid, and this process was repeated three times, remove barium ions
Doped ions (Ba in the graphite phase carbon nitride material of doping2+), obtain solid powder.
Solid powder through milli-Q water three times, removal is dry to perseverance in 65 DEG C after the acid solution of solid powder surfaces
The graphite phase carbon nitride material that weight adulterates to get barium ions.
(6) the graphite phase carbon nitride material of barium ions doping is dissolved in alcohol-water mixing by the mass volume ratio of 1g:100mL
In solution, and ultrasound 6h at room temperature, obtain suspension.
Wherein alcohol-water mixed solution is the same as embodiment 1.
(7) by 0.3g FeCl3∙6H2O and 0.3g FeCl2∙4H2O is put into suspension with the mass ratio (g/g) of 1:1,
Simultaneously mechanical stirring is heated, ammonium hydroxide is gradually added into 65 DEG C, makes the pH value of mixed solution to 10；Then in 75 DEG C of back flow reactions 30
Min obtains product.
(8) product is put into vacuum oven and dries extremely in 45 DEG C respectively after dehydrated alcohol and ultrapure water successively wash three times
The graphite phase carbon nitride material that constant weight is adulterated to get magnetic barium ions.
The graphite phase carbon nitride material of magnetism barium ions doping is applied to radioactivity in food as adsorbent210Pb's
Fast enriching and trace detection.The specific method is as follows:
1. testing sample solution will be obtained through the pretreated food samples such as dry and ashing, preparation.
The graphite phase carbon nitride material that 5.0 mg magnetism barium ions adulterate is placed in 5 mL solution to be measured, ultrasound 20
Min makes material uniformly in being dispersed in solution to be measured, mixed solution is put into oscillator vibrates 60 min therewith, to reach
Extraction equilibrium；Magnetic Isolation is carried out by magnet, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase210Pb concentration is measured；
3. the adsorbent material after separation is transferred in centrifuge tube, 0.5 mol/L nitric acid solution, 200 μ L, 4000W ultrasound is added
10min makes target species210Pb is desorbed from adsorbent；It repeats above operation 3 times, is evaporated after merging stripping liquid in 55 DEG C molten
Liquid, then dissolved with 0.5 mol/L nitric acid solution, 40 μ L, emit light using inductively coupled plasma according to GB5009.268-2016
Spectrometer (ICP-OES) measures its concentration, finally calculates target species in solution to be measured210The content of Pb.
A kind of preparation method of the magnetic graphite phase carbon nitride material of embodiment 5, comprising the following steps:
(1) by 12.5g dicyandiamide and 0.5g Ba (NO3)2After mixing, it is dissolved in 3 times of ultrapure water of mixture quality, room temperature
Lower stirring dissolves it sufficiently, obtains the triazine structure compound solution containing barium ions.
(2) the triazine structure compound solution containing barium ions is placed in a vacuum drying oven dry to anhydrous in 70 DEG C, obtained
To white solid.
(3) white solid is transferred in crucible, is placed in Muffle furnace, heating rate is 4 DEG C/min, temperature is 560 DEG C
Under conditions of high-temperature calcination 3.5h, prepared by way of thermal polycondensation barium ions doping graphite phase carbon nitride material；Reaction knot
It is cooled to room temperature after beam, obtains flaxen solid powder.
(4) the phosphoric acid solution of 2.0 mol/L, warp are added in flaxen solid powder by the mass volume ratio of 1g:10mL
4000 rpm are centrifuged 20min after 4000W ultrasound 18min elution, discard supernatant liquid, and this process was repeated three times, and removal barium ions is mixed
Doped ions (Ba in miscellaneous graphite phase carbon nitride material2+), obtain solid powder.
Solid powder through milli-Q water three times, removal is dry to perseverance in 75 DEG C after the acid solution of solid powder surfaces
The graphite phase carbon nitride material that weight adulterates to get barium ions.
(6) the graphite phase carbon nitride material of barium ions doping is dissolved in alcohol-water mixing by the mass volume ratio of 1g:80mL
In solution, and ultrasound 6h at room temperature, obtain suspension.
Wherein alcohol-water mixed solution is the same as embodiment 1.
(7) by 0.3g FeCl3∙6H2O and 0.9g FeCl2∙4H2O is put into suspension, simultaneously mechanical stirring is heated, in 65
DEG C it is gradually added into sodium hydroxide, makes the pH value of mixed solution to 10；Then in 75 DEG C of 1.5 h of back flow reaction, product is obtained.
(8) product is put into vacuum oven and dries extremely in 60 DEG C respectively after dehydrated alcohol and ultrapure water successively wash three times
The graphite phase carbon nitride material that constant weight is adulterated to get magnetic barium ions.
The graphite phase carbon nitride material of magnetism barium ions doping is applied to radioactivity in food as adsorbent210Pb's
Fast enriching and trace detection.The specific method is as follows:
1. testing sample solution will be obtained through the pretreated food samples such as dry and ashing, preparation.
The graphite phase carbon nitride material that 1.0 mg magnetism barium ions adulterate is placed in 5 mL solution to be measured, ultrasound 20
Min makes material uniformly in being dispersed in solution to be measured, mixed solution is put into oscillator vibrates 120 min therewith, to reach
Extraction equilibrium；Magnetic Isolation is carried out by magnet, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase210Pb concentration is measured；
3. the adsorbent material after separation is transferred in centrifuge tube, 0.5 mol/L nitric acid solution, 200 μ L, 4000W ultrasound is added
15min makes target species210Pb is desorbed from adsorbent；It repeats above operation 3 times, is evaporated after merging stripping liquid in 70 DEG C molten
Liquid, then dissolved with 0.5 mol/L nitric acid solution, 80 μ L, emit light using inductively coupled plasma according to GB5009.268-2016
Spectrometer (ICP-OES) measures its concentration, finally calculates target species in solution to be measured210The content of Pb.
Claims (10)
1. a kind of magnetic graphite phase carbon nitride material, it is characterised in that: the material, which refers to, to be constructed using barium ions as Doped ions
It is coplanar three s-triazine of 2 ~ 50nm cavity structure with stratiform, aperture is the multi-cluster compound of basic structural unit.
2. a kind of preparation method of magnetic graphite phase carbon nitride material as described in claim 1, comprising the following steps:
(1), using triazine structure compound as presoma, after it is mixed with barium ions compound, the 1 ~ 3 of mixture quality is dissolved in
In ultrapure water again, stirring dissolves it sufficiently at room temperature, obtains the triazine structure compound solution containing barium ions；Before described
The mass ratio for driving body and the barium ions compound is 5:1 ~ 30:1；
(2) the triazine structure compound solution by described containing barium ions is dry to anhydrous in 60 ~ 80 DEG C, obtains white solid；
(3) the white solid is transferred in crucible, is placed in the calcining of Muffle furnace high temperature；It is cooled to room temperature, obtains after reaction
Flaxen solid powder；
(4) acid solution is added by the mass volume ratio of 1:5 ~ 20 in the flaxen solid powder, through 4000 W ultrasounds 10 ~ 20
4000 rpm are centrifuged 20min after min elution, obtain solid powder；
The solid powder through milli-Q water three times after in 60 ~ 80 DEG C of dry graphite adulterated to constant weights to get barium ions
Phase carbon nitride material；
(6) the graphite phase carbon nitride material of the barium ions doping is dissolved in alcohol-water mixing by the mass volume ratio of 1:60 ~ 120
In solution, and ultrasound 6h at room temperature, obtain suspension；
(7) by FeCl3∙6H2O and FeCl2∙4H2O is put into the suspension with the mass ratio of 1:1 ~ 1:3, heats and machinery stirs
It mixes, is gradually added into alkaline precipitating agent in 65 DEG C, makes the pH value of mixed solution to 10；Then in 70 ~ 90 DEG C of 30 min of back flow reaction ~
2 h, obtain product；
(8) the product is dried to constant weight in 45 ~ 80 DEG C to get magnetic respectively after dehydrated alcohol and ultrapure water successively wash three times
Property barium ions doping graphite phase carbon nitride material.
3. a kind of preparation method of magnetic graphite phase carbon nitride material as claimed in claim 2, it is characterised in that: the step
(1) the presoma in refers to urea, melamine, cyanamide, thiocarbamide, any one in dicyandiamide.
4. a kind of preparation method of magnetic graphite phase carbon nitride material as claimed in claim 2, it is characterised in that: the step
(1) the barium ions compound in refers to barium chloride, barium nitrate, any one in barium acetate.
5. a kind of preparation method of magnetic graphite phase carbon nitride material as claimed in claim 2, it is characterised in that: the step
(3) the high-temperature calcination condition in refers to that heating rate is 4 DEG C/min, and temperature is 500 ~ 580 DEG C, and the time is 3 ~ 5h.
6. a kind of preparation method of magnetic graphite phase carbon nitride material as claimed in claim 2, it is characterised in that: the step
(4) the acid solution in refers to concentration for any one in the nitric acid of the mol/L of 0.1 mol/L ~ 2.0, hydrochloric acid, phosphoric acid, acetic acid.
7. a kind of preparation method of magnetic graphite phase carbon nitride material as claimed in claim 2, it is characterised in that: the step
(6) middle alcohol-water mixed solution refers to the solution that dehydrated alcohol and water are mixed by the volume ratio of 1:2.
8. a kind of preparation method of magnetic graphite phase carbon nitride material as claimed in claim 2, it is characterised in that: the step
(7) neutral and alkali precipitating reagent refers to ammonium hydroxide, sodium hydroxide, any one in potassium hydroxide.
9. a kind of application of magnetic graphite phase carbon nitride material as described in claim 1, it is characterised in that: the magnetism barium ions
The graphite phase carbon nitride material of doping is applied to radioactivity in food as adsorbent210The fast enriching and trace detection of Pb.
10. a kind of application of magnetic graphite phase carbon nitride material as claimed in claim 9, comprising the following steps:
1. the graphite phase carbon nitride material that the mg magnetism barium ions of 1.0 mg ~ 10.0 adulterates is placed in 5 mL solution to be measured, ultrasound
20 min make material uniformly in being dispersed in solution to be measured, and mixed solution is put into 10 ~ 180 min of oscillation in oscillator therewith,
To reach extraction equilibrium；Magnetic Isolation is carried out using magnet, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase210Pb concentration is measured；
3. the adsorbent material after the separation is transferred in centrifuge tube, it is super that 0.5 mol/L nitric acid solution 200 μ L, 4000W is added
5 ~ 20min of sound, makes target species210Pb is desorbed from adsorbent；It repeats above operation 3 times, in 40 ~ 70 DEG C after merging stripping liquid
It is evaporated solution, then is dissolved with 0.5 mol/L nitric acid solution, 30 ~ 90 μ L, utilizes inductive coupling etc. according to GB5009.268-2016
Ion emission spectroscopy instrument measures its concentration, finally calculates target species in solution to be measured210The content of Pb.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112436143A (en) * | 2020-11-06 | 2021-03-02 | 风帆有限责任公司 | Preparation method of negative electrode lead paste and negative electrode plate of lead-acid storage battery |
| CN113358800A (en) * | 2021-05-26 | 2021-09-07 | 吉林化工学院 | Magnetic nitrogen-doped carbon material and method for extracting and analyzing phthalic acid ester in plastic bottled water by using same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301867A (en) * | 2013-06-25 | 2013-09-18 | 重庆工商大学 | Inorganic ion doped carbon nitride photocatalyst and preparation method thereof |
| CN105214709A (en) * | 2015-10-19 | 2016-01-06 | 天津大学 | Interlayer bimetallic ion doping carbonitride catalysis material and Synthesis and applications thereof |
| US20180190996A1 (en) * | 2017-01-05 | 2018-07-05 | City University Of Hong Kong | Method for preparing hierarchically porous doped carbon material and its use |
| US20180305231A1 (en) * | 2017-04-19 | 2018-10-25 | King Abdulaziz University | Composite, a method of making thereof, and a method for degrading a pollutant |
| CN109107523A (en) * | 2018-08-01 | 2019-01-01 | 中南林业科技大学 | Ultra-thin graphite-phase C3N4/ calcite nanosheet composite material and its preparation method and application |
-
2019
- 2019-07-08 CN CN201910610421.9A patent/CN110327873B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301867A (en) * | 2013-06-25 | 2013-09-18 | 重庆工商大学 | Inorganic ion doped carbon nitride photocatalyst and preparation method thereof |
| CN105214709A (en) * | 2015-10-19 | 2016-01-06 | 天津大学 | Interlayer bimetallic ion doping carbonitride catalysis material and Synthesis and applications thereof |
| US20180190996A1 (en) * | 2017-01-05 | 2018-07-05 | City University Of Hong Kong | Method for preparing hierarchically porous doped carbon material and its use |
| US20180305231A1 (en) * | 2017-04-19 | 2018-10-25 | King Abdulaziz University | Composite, a method of making thereof, and a method for degrading a pollutant |
| CN109107523A (en) * | 2018-08-01 | 2019-01-01 | 中南林业科技大学 | Ultra-thin graphite-phase C3N4/ calcite nanosheet composite material and its preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| JING YANG ET AL.: "Synthesis of a graphitic carbon nitride nanocomposite with magnetite as a sorbent for solid phase extraction of phenolic acids", 《MICROCHIMICA ACTA》 * |
| JUN-YINGTANG ET AL.: "Enhancement of photocatalytic performance in CO2 reduction over Mg/g-C3N4 catalysts under visible light irradiation", 《CATALYSIS COMMUNICATIONS》 * |
| MANWANG ET AL.: "Synthesis of g-C3N4/Fe3O4 nanocomposites and application as a new sorbent for solid phase extraction of polycyclic aromatic hydrocarbons in water samples", 《TALANTA》 * |
| RUI HU ET AL.: "Application of graphitic carbon nitride for the removal of Pb(II) and aniline from aqueous solutions", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 艾兵 等: "碱土金属掺杂类石墨相氮化碳的可见光催化性能研究（录用定稿）", 《化学试剂》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112436143A (en) * | 2020-11-06 | 2021-03-02 | 风帆有限责任公司 | Preparation method of negative electrode lead paste and negative electrode plate of lead-acid storage battery |
| CN113358800A (en) * | 2021-05-26 | 2021-09-07 | 吉林化工学院 | Magnetic nitrogen-doped carbon material and method for extracting and analyzing phthalic acid ester in plastic bottled water by using same |
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