CN110327872A - A kind of functionalization graphite phase carbon nitride material and its preparation method and application - Google Patents

A kind of functionalization graphite phase carbon nitride material and its preparation method and application Download PDF

Info

Publication number
CN110327872A
CN110327872A CN201910610420.4A CN201910610420A CN110327872A CN 110327872 A CN110327872 A CN 110327872A CN 201910610420 A CN201910610420 A CN 201910610420A CN 110327872 A CN110327872 A CN 110327872A
Authority
CN
China
Prior art keywords
carbon nitride
phase carbon
graphite phase
nitride material
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910610420.4A
Other languages
Chinese (zh)
Other versions
CN110327872B (en
Inventor
师彦平
康晶燕
哈伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanzhou Institute of Chemical Physics LICP of CAS
Original Assignee
Lanzhou Institute of Chemical Physics LICP of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanzhou Institute of Chemical Physics LICP of CAS filed Critical Lanzhou Institute of Chemical Physics LICP of CAS
Priority to CN201910610420.4A priority Critical patent/CN110327872B/en
Publication of CN110327872A publication Critical patent/CN110327872A/en
Application granted granted Critical
Publication of CN110327872B publication Critical patent/CN110327872B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0259—Compounds of N, P, As, Sb, Bi
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4055—Concentrating samples by solubility techniques
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4055—Concentrating samples by solubility techniques
    • G01N2001/4061—Solvent extraction

Abstract

The present invention relates to a kind of functionalization graphite phase carbon nitride material, the material refer to using sodium ion be Doped ions construct with stratiform, coplanar three s-triazine that aperture is 2 ~ 30nm cavity structure as the multi-cluster compound of basic structural unit.The invention also discloses the preparation method and application of the material.The present invention has to radioactive element90The good feature of Sr strong adsorption, selectivity.

Description

A kind of functionalization graphite phase carbon nitride material and its preparation method and application
Technical field
The present invention relates to technical field of analysis and detection more particularly to a kind of functionalization graphite phase carbon nitride material and its preparations Methods and applications.
Background technique
In recent years, energy issue of world increasingly highlights, and nuclear energy is faced with new opportunity to develop.However, nuclear reactor uses Can generate in the process a large amount of " spentnuclear fuel ", spentnuclear fuel contain it is a large amount of it is unspent can fertile material238U and232Th, it is newly-generated Easy fissioner239Pu、235U and233The transuranic elements such as neptunium, americium, the curium generated in U and irradiation process, in addition there are height to put Thermonuclear element90Sr、137Cs and99Tc etc., these radioactive substances enter after environment the health that can seriously affect the mankind.In addition, core Leakage problem also has received widespread attention at present, about 630000- after Japanese Fukushima nuclear power station leaked in especially 2011 770000 TBq radionuclide (including90Sr、131I、134Cs and137Cs etc.) intrusion external environment, lead to ambient enviroment Soil, air and water it is heavily contaminated.
90The radioactive half-life of Sr is up to 29 years, and bio-toxicity is very strong, and the bone for being easily collected on organism is open-minded interior and difficult To excrete.90After Sr enters bone tissue, accumulates in the inanimate matter of ossis, radiate marrow, lead to leucocyte, red Cell and blood platelet all substantially reduce, and regeneration sexual dysfunction occurs, and will lead to the hair of leukaemia and osteosarcoma by strontium radiation for a long time It is raw.Therefore radionuclide in food and environmental water sample90Sr sample pre-treatments and trace detection are constantly subjected to the extensive pass of people Note, have very important significance to its sorption extraction and detection research (P.J. Reddy, V. Pulhani,J Radioanal Nucl. Chem.,2017 (314), 359–370) 。
Due to the radionuclide in environmental water sample or food90Sr has system complexity, radioactive concentration lower, nucleic The features such as existence form multiplicity and shortage standard reference materials, therefore, radionuclide90The detection of Sr will usually pass through sample Analysis measurement can be carried out after pre-treatment.Currently, about radionuclide in environmental water sample or food90Sr sample pre-treatments Main method has: chemical precipitation method, solvent extraction, membrane distillation method and chromatogram column technique etc..These methods, which have, to be easy by multiple Miscellaneous matrix interference, pretreatment process is more complex, and selectivity is poor, and acid solution used in elution process causes instrument and equipment Serious damage, the disadvantages of will cause secondary pollution.Therefore, develop and establish it is a kind of green preparation, selectivity it is good, collection extraction with Be detected on integrated sample pre-treatments materials and methods it is significant (M. Khayet,Desalination, 2013(321), 60-66; R. Kamaraj, S. Vasudevan , Chem. Eng. Res. Des., 2015(93), 522-530) 。
Graphite phase carbon nitride material because its is cheap and easy to get, energy conservation and environmental protection and have excellent physical property and stable chemistry Performance becomes the hot spot material studied now.In recent years, research shows that graphite phase carbon nitride material, especially metal-doped graphite Phase carbon nitride material has good photocatalytic activity, has wide application in the fields such as environmental pollution improvement and clean energy resource Prospect.Studies have shown that the doped metallic elements in graphite phase carbon nitride material, can be improved the specific surface area of material, enhancing Its thermal stability forms the composite material with special cavity structure.However, up to the present, not having will also be metal-doped Graphite phase carbon nitride material is applied to the relevant report of radioactive element extraction.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of pair of radioactive elements90Sr strong adsorption, selectivity are good Functionalization graphite phase carbon nitride material.
Another technical problem to be solved by this invention is to provide the preparation side of the functionalization graphite phase carbon nitride material Method.
Third technical problem to be solved by this invention is to provide the application of the functionalization graphite phase carbon nitride material.
To solve the above problems, a kind of functionalization graphite phase carbon nitride material of the present invention, it is characterised in that: the material Material refer to using sodium ion be Doped ions construct with stratiform, coplanar three s-triazine that aperture is 2 ~ 30nm cavity structure as base The multi-cluster compound of this structural unit.
A kind of preparation method of functionalization graphite phase carbon nitride material as described above, comprising the following steps:
(1), using triazine structure compound as presoma, after it is mixed with sodium ion 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 sodium ion；Before described The mass ratio for driving body and the sodium ion compound is 5:1 ~ 35:1；
(2) triazine structure compound solution by described containing sodium ion is dry to anhydrous, 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 20 min after min elution, obtain solid powder；
The solid powder through milli-Q water three times after dry to constant weight to get functionalization graphite phase carbon nitride composite wood Material.
The step (1) in presoma refer to urea, melamine, cyanamide, thiocarbamide, any one in dicyandiamide.
The step (1) in sodium ion compound refer to sodium chloride (NaCl), sodium nitrate (NaNO3), sodium sulphate (Na2SO4), any one in sodium acetate (NaCOOH).
The step (2) with the step (5) in drying condition each mean temperature be 60 ~ 80 DEG C.
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 ~ 1.0 nitric acid, hydrochloric acid, phosphoric acid, vinegar Any one in acid.
A kind of application of functionalization graphite phase carbon nitride material as described above, it is characterised in that: the functionalization graphite-phase Carbon nitride material is applied to radionuclide in food or environmental water sample as adsorbent90The Rapid Extraction and trace detection of Sr.
A kind of application of functionalization graphite phase carbon nitride material as described above, comprising the following steps:
1. the mg functionalization graphite phase carbon nitride material of 1.0 mg ~ 10.0 is placed in 5 mL solution to be measured, 20 min of ultrasound make Mixed solution uniformly in being dispersed in solution to be measured, is put into oscillator vibrates 60 min therewith by material, flat to reach extraction Weighing apparatus；4000rpm is centrifuged 20min again, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase90Sr 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 10 ~ 20min of sound, makes target species90Sr is desorbed from adsorbent；It repeats above operation 3 times, in 40 ~ 75 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 measured90The content of Sr.
Compared with the prior art, the present invention has the following advantages:
1, the present invention has good chemistry and physical stability, shows through transmissioning electric mirror test, the graphite phase carbon nitride of blank With apparent layer structure (referring to fig. 2 (a)), Na+The graphite phase carbon nitride material of doping is two-dimensional single-layer fold structure (referring to fig. 2 (b)) illustrates Na on the surface of the material without metal nanoparticle+Doping be by way of chemical complexing, and Simple physical mixed, the graphite phase carbon nitride material after acid solution elutes other than with two-dimensional single layer structure, The hole configurations (referring to fig. 2 (c)) of about 30 nm is presented in material surface；In addition, energy spectrum analysis map shows blank graphite-phase nitrogen Change carbon and there was only two kinds of elements of C, N (Cu element derives from copper mesh), Na+The graphite phase carbon nitride material of doping contains C, N and Na tri- Kind element, also illustrates Na+Successful doping, after acid solution elutes, in material Na element be not present explanation our success It is prepared for functionalization graphite phase carbon nitride material ((d) ~ Fig. 2 (f) referring to fig. 2).
2, by the investigation (referring to Fig. 3) to selectivity of the invention, common metal ion [Na (I), K (I), Cs are selected (I), Ca(II), Ce(II), Ba(II), Co(II), Mg(II), Sr(II), Mn(II), Ni(II), Zn(II) With Fe (III)] it is used as interfering ion, concentration is (30 μ g/mL), and 5.0 mg functionalization graphite phase carbon nitride materials are distinguished It is placed in the above-mentioned solution of 5 mL, mixed solution is put into oscillator vibrates 60 min therewith by 20 min of ultrasound, is then centrifuged (4000rpm, 20min), adsorbent material and water phase after respectively obtaining separation.According to GB5009.268-2016 in water phase Each concentration of metal ions is measured.The experimental results showed that being compared with blank graphite phase carbon nitride, functionalization graphite-phase of the present invention Carbon nitride material is to target species90Sr has good absorption property, is almost not affected by the interference of other metal ions.
3, the present invention will combine the advantages of graphite phase carbon nitride material with ion blotting method, not only increase the ratio of material Surface area and effective adsorption site, and improve the selectivity of material, and in conjunction with ICP-OES, establish high sensitivity, Analysis determining method applied widely realizes radioactive element in sample90The determination of trace of Sr.
4, the method for the present invention is simple, low in cost, raw material is green, pollution-free, resulting functionalization graphite phase carbon nitride material Material has filled up domestic radionuclide90The blank of Sr enrichment material changes the monopoly position of such external material, is radioactivity The sample pre-treatments and analysis detection of nucleic provide new material, new method and relevant theoretical foundation.
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 functionalization graphite phase carbon nitride material of the present invention.
Fig. 2 is the pattern and structural characterization figure of functionalization graphite phase carbon nitride material of the present invention.Wherein: (a) being blank stone The transmission electron microscope phenogram of black phase carbon nitride material；It (b) is Na+The transmission electron microscope phenogram of doped graphite phase carbon nitride material； It (c) is the Na after acid solution elution+The transmission electron microscope phenogram of doped graphite phase carbon nitride material；(d) blank graphite-phase nitrogenizes The energy spectrum analysis map of carbon material；It (e) is Na+The energy spectrum analysis map of doped graphite phase carbon nitride material；(f) it is washed for acid solution Na after de-+The energy spectrum analysis map of doped graphite phase carbon nitride material.
Fig. 3 is measurement and itself and the blank nitrogen of the selective absorption performance of functionalization carbonitride graphite phase material of the present invention Change the comparison of carbon graphite phase material absorption property.
Specific embodiment
A kind of functionalization graphite phase carbon nitride material, which, which refers to using sodium ion as what Doped ions were constructed, has layer Shape, aperture are that coplanar three s-triazine of 2 ~ 30nm 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 functionalization graphite phase carbon nitride material, comprising the following steps:
(1) after 15g urea being mixed with 1g NaCl, it is dissolved in 32 mL ultrapure waters, stirring dissolves it sufficiently at room temperature, obtains To the triazine structure compound solution containing sodium ion.
(2) the triazine structure compound solution containing sodium ion is placed in a vacuum drying oven, it is dry to anhydrous in 60 DEG C, Obtain white solid.
(3) white solid is transferred in crucible, is placed in Muffle furnace, is 4 DEG C/min, temperature 540 in heating rate High-temperature calcination 4h under conditions of DEG C prepares the graphite phase carbon nitride material of sodium ion doping by way of thermal polycondensation；Reaction knot It is cooled to room temperature after beam, obtains flaxen solid powder.
(4) the nitric acid solution 20mL that concentration is 0.5 mol/L is added in the flaxen solid powder of 1.0g, through 4000W ultrasound 4000 rpm are centrifuged 20 min after 20 min elution, discard supernatant liquid, and this process was repeated three times, remove graphite phase carbon nitride material In Doped ions (Na+) obtain solid powder.
Solid powder through milli-Q water three times, removal be put into vacuum oven after the acid solution of solid powder surfaces In in 80 DEG C it is dry to constant weight to get functionalization graphite phase carbon nitride composite material.
The functionalization graphite phase carbon nitride material is applied to radionuclide in food or environmental water sample as adsorbent90Sr Rapid Extraction and trace detection.The specific method is as follows:
1. preparation obtains testing sample solution by environmental water sample or through pretreated food samples such as dry and ashing.
1.0 mg functionalization graphite phase carbon nitride materials are placed in 5 mL solution to be measured, 20 min of ultrasound keep material equal It is even in being dispersed in solution to be measured mixed solution to be put into oscillator vibrate 60 min therewith, to reach extraction equilibrium；Again 4000rpm is centrifuged 20min, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase90Sr 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 species90Sr 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, 30 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 measured90The content of Sr.
A kind of preparation method of the functionalization graphite phase carbon nitride material of embodiment 2, comprising the following steps:
(1) after 5g melamine being mixed with 1g sodium acetate, it is dissolved in 18 mL ultrapure waters, stirring keeps it sufficiently molten at room temperature Solution, obtains the triazine structure compound solution containing sodium ion.
(2) the triazine structure compound solution containing sodium ion is placed in a vacuum drying oven, it is dry to anhydrous in 80 DEG C, Obtain white solid.
(3) white solid is transferred in crucible, is placed in Muffle furnace, is 4 DEG C/min, temperature 500 in heating rate High-temperature calcination 3h under conditions of DEG C prepares the graphite phase carbon nitride material of sodium ion doping by way of thermal polycondensation；Reaction knot It is cooled to room temperature after beam, obtains flaxen solid powder.
(4) the nitric acid solution 5mL that concentration is 0.1 mol/L is added in the flaxen solid powder of 1.0g, through 4000W ultrasound 4000 rpm are centrifuged 20 min after 10 min elution, discard supernatant liquid, and this process was repeated three times, remove graphite phase carbon nitride material In Doped ions (Na+) obtain solid powder.
Solid powder through milli-Q water three times, removal be put into vacuum oven after the acid solution of solid powder surfaces In in 60 DEG C it is dry to constant weight to get functionalization graphite phase carbon nitride composite material.
The functionalization graphite phase carbon nitride material is applied to radionuclide in food or environmental water sample as adsorbent90Sr Rapid Extraction and trace detection.The specific method is as follows:
1. preparation obtains testing sample solution by environmental water sample or through pretreated food samples such as dry and ashing.
10.0 mg functionalization graphite phase carbon nitride materials are placed in 5 mL solution to be measured, 20 min of ultrasound keep material equal It is even in being dispersed in solution to be measured mixed solution to be put into oscillator vibrate 60 min therewith, to reach extraction equilibrium；Again 4000rpm is centrifuged 20min, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase90Sr 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 20min makes target species90Sr 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, 90 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 measured90The content of Sr.
A kind of preparation method of the functionalization graphite phase carbon nitride material of embodiment 3, comprising the following steps:
(1) after 35g cyanamide being mixed with 1g sodium nitrate, it is dissolved in 36mL ultrapure water, stirring dissolves it sufficiently at room temperature, obtains To the triazine structure compound solution containing sodium ion.
(2) the triazine structure compound solution containing sodium ion is placed in a vacuum drying oven, it is dry to anhydrous in 70 DEG C, Obtain white solid.
(3) white solid is transferred in crucible, is placed in Muffle furnace, is 4 DEG C/min, temperature 520 in heating rate High-temperature calcination 5h under conditions of DEG C prepares the graphite phase carbon nitride material of sodium ion doping by way of thermal polycondensation；Reaction knot It is cooled to room temperature after beam, obtains flaxen solid powder.
(4) the nitric acid solution 10mL that concentration is 1.0mol/L is added in the flaxen solid powder of 1.0g, through 4000W ultrasound 4000 rpm are centrifuged 20min after 15 min elution, discard supernatant liquid, and this process was repeated three times, remove graphite phase carbon nitride material In Doped ions (Na+) obtain solid powder.
Solid powder through milli-Q water three times, removal be put into vacuum oven after the acid solution of solid powder surfaces In in 70 DEG C it is dry to constant weight to get functionalization graphite phase carbon nitride composite material.
The functionalization graphite phase carbon nitride material is applied to radionuclide in food or environmental water sample as adsorbent90Sr Rapid Extraction and trace detection.The specific method is as follows:
1. preparation obtains testing sample solution by environmental water sample or through pretreated food samples such as dry and ashing.
5.0 mg functionalization graphite phase carbon nitride materials are placed in 5 mL solution to be measured, 20 min of ultrasound keep material equal It is even in being dispersed in solution to be measured mixed solution to be put into oscillator vibrate 60 min therewith, to reach extraction equilibrium；Again 4000rpm is centrifuged 20min, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase90Sr 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 species90Sr is desorbed from adsorbent；It repeats above operation 3 times, is evaporated solution in 50 DEG C after merging stripping liquid, It is dissolved again with 0.5 mol/L nitric acid solution, 60 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 measured90The content of Sr.
A kind of preparation method of the functionalization graphite phase carbon nitride material of embodiment 4, comprising the following steps:
(1) after 25g thiocarbamide being mixed with 1g sodium sulphate, it is dissolved in 39 mL ultrapure waters, stirring dissolves it sufficiently at room temperature, obtains To the triazine structure compound solution containing sodium ion.
(2) the triazine structure compound solution containing sodium ion is placed in a vacuum drying oven, it is dry to anhydrous in 65 DEG C, Obtain white solid.
(3) white solid is transferred in crucible, is placed in Muffle furnace, is 4 DEG C/min, temperature 580 in heating rate High-temperature calcination 3.5h under conditions of DEG C prepares the graphite phase carbon nitride material of sodium ion doping by way of thermal polycondensation；Reaction After be cooled to room temperature, obtain flaxen solid powder.
(4) the hydrochloric acid solution 15mL that concentration is 1.0 mol/L is added in the flaxen solid powder of 1.0g, through 4000W ultrasound 4000 rpm are centrifuged 20 min after 10 min elution, discard supernatant liquid, and this process was repeated three times, remove graphite phase carbon nitride material In Doped ions (Na+) obtain solid powder.
Solid powder through milli-Q water three times, removal be put into vacuum oven after the acid solution of solid powder surfaces In in 75 DEG C it is dry to constant weight to get functionalization graphite phase carbon nitride composite material.
The functionalization graphite phase carbon nitride material is applied to radionuclide in food or environmental water sample as adsorbent90Sr Rapid Extraction and trace detection.The specific method is as follows:
1. preparation obtains testing sample solution by environmental water sample or through pretreated food samples such as dry and ashing.
2.0 mg functionalization graphite phase carbon nitride materials are placed in 5 mL solution to be measured, 20 min of ultrasound keep material equal It is even in being dispersed in solution to be measured mixed solution to be put into oscillator vibrate 60 min therewith, to reach extraction equilibrium；Again 4000rpm is centrifuged 20min, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase90Sr 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 species90Sr is desorbed from adsorbent；It repeats above operation 3 times, is evaporated solution in 45 DEG C after merging stripping liquid, It is dissolved again with 0.5 mol/L nitric acid solution, 50 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 measured90The content of Sr.
A kind of preparation method of the functionalization graphite phase carbon nitride material of embodiment 5, comprising the following steps:
(1) after 15g dicyandiamide being mixed with 1g NaCl, it is dissolved in 40 mL ultrapure waters, stirring dissolves it sufficiently at room temperature, Obtain the triazine structure compound solution containing sodium ion.
(2) the triazine structure compound solution containing sodium ion is placed in a vacuum drying oven, it is dry to anhydrous in 75 DEG C, Obtain white solid.
(3) white solid is transferred in crucible, is placed in Muffle furnace, is 4 DEG C/min, temperature 540 in heating rate High-temperature calcination 4.5h under conditions of DEG C prepares the graphite phase carbon nitride material of sodium ion doping by way of thermal polycondensation；Reaction After be cooled to room temperature, obtain flaxen solid powder.
(4) the phosphoric acid solution 10mL that concentration is 0.5 mol/L is added in the flaxen solid powder of 1.0g, through 4000W ultrasound 4000 rpm are centrifuged 20 min after 15 min elution, discard supernatant liquid, and this process was repeated three times, remove graphite phase carbon nitride material In Doped ions (Na+) obtain solid powder.
Solid powder through milli-Q water three times, removal be put into vacuum oven after the acid solution of solid powder surfaces In in 65 DEG C it is dry to constant weight to get functionalization graphite phase carbon nitride composite material.
The functionalization graphite phase carbon nitride material is applied to radionuclide in food or environmental water sample as adsorbent90Sr Rapid Extraction and trace detection.The specific method is as follows:
1. preparation obtains testing sample solution by environmental water sample or through pretreated food samples such as dry and ashing.
8.0 mg functionalization graphite phase carbon nitride materials are placed in 5 mL solution to be measured, 20 min of ultrasound keep material equal It is even in being dispersed in solution to be measured mixed solution to be put into oscillator vibrate 60 min therewith, to reach extraction equilibrium；Again 4000rpm is centrifuged 20min, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase90Sr 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 20min makes target species90Sr is desorbed from adsorbent；It repeats above operation 3 times, is evaporated solution in 75 DEG C after merging stripping liquid, It is dissolved again with 0.5 mol/L nitric acid solution, 70 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 measured90The content of Sr.
A kind of preparation method of the functionalization graphite phase carbon nitride material of embodiment 6, comprising the following steps:
(1) after 15g urea being mixed with 1g NaCl, it is dissolved in 32 mL ultrapure waters, stirring dissolves it sufficiently at room temperature, obtains To the triazine structure compound solution containing sodium ion.
(2) the triazine structure compound solution containing sodium ion is placed in a vacuum drying oven, it is dry to anhydrous in 60 DEG C, Obtain white solid.
(3) white solid is transferred in crucible, is placed in Muffle furnace, is 4 DEG C/min, temperature 560 in heating rate High-temperature calcination 4h under conditions of DEG C prepares the graphite phase carbon nitride material of sodium ion doping by way of thermal polycondensation；Reaction knot It is cooled to room temperature after beam, obtains flaxen solid powder.
(4) the acetum 20mL that concentration is 0.8 mol/L is added in the flaxen solid powder of 1.0g, through 4000W ultrasound 4000 rpm are centrifuged 20 min after 20 min elution, discard supernatant liquid, and this process was repeated three times, remove graphite phase carbon nitride material In Doped ions (Na+) obtain solid powder.
Solid powder through milli-Q water three times, removal be put into vacuum oven after the acid solution of solid powder surfaces In in 80 DEG C it is dry to constant weight to get functionalization graphite phase carbon nitride composite material.
The functionalization graphite phase carbon nitride material is applied to radionuclide in food or environmental water sample as adsorbent90Sr Rapid Extraction and trace detection.The specific method is as follows:
1. preparation obtains testing sample solution by environmental water sample or through pretreated food samples such as dry and ashing.
1.0 mg functionalization graphite phase carbon nitride materials are placed in 5 mL solution to be measured, 20 min of ultrasound keep material equal It is even in being dispersed in solution to be measured mixed solution to be put into oscillator vibrate 60 min therewith, to reach extraction equilibrium；Again 4000rpm is centrifuged 20min, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase90Sr 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 Sound 15min, makes target species90Sr 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 measured90The content of Sr.

Claims (9)

1. a kind of functionalization graphite phase carbon nitride material, it is characterised in that: the material refers to be constructed by Doped ions of sodium ion Have stratiform, aperture be that coplanar three s-triazine of 2 ~ 30nm cavity structure is the multi-cluster compound of basic structural unit.
2. a kind of preparation method of functionalization 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 sodium ion 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 sodium ion；Before described The mass ratio for driving body and the sodium ion compound is 5:1 ~ 35:1；
(2) triazine structure compound solution by described containing sodium ion is dry to anhydrous, 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 20 min after min elution, obtain solid powder；
The solid powder through milli-Q water three times after dry to constant weight to get functionalization graphite phase carbon nitride composite wood Material.
3. a kind of preparation method of functionalization graphite phase carbon nitride material as claimed in claim 2, it is characterised in that: the step Suddenly (1) in presoma refer to urea, melamine, cyanamide, thiocarbamide, any one in dicyandiamide.
4. a kind of preparation method of functionalization graphite phase carbon nitride material as claimed in claim 2, it is characterised in that: the step Suddenly (1) in sodium ion compound refer to sodium chloride, sodium nitrate, sodium sulphate, any one in sodium acetate.
5. a kind of preparation method of functionalization graphite phase carbon nitride material as claimed in claim 2, it is characterised in that: the step Suddenly (2) with the step (5) in drying condition each mean temperature be 60 ~ 80 DEG C.
6. a kind of preparation method of functionalization graphite phase carbon nitride material as claimed in claim 2, it is characterised in that: the step Suddenly (3) in high-temperature calcination condition refer to heating rate be 4 DEG C/min, temperature be 500 ~ 580 DEG C, the time be 3 ~ 5h.
7. a kind of preparation method of functionalization graphite phase carbon nitride material as claimed in claim 2, it is characterised in that: the step Suddenly (4) in acid solution refer to that concentration is the nitric acid of the mol/L of 0.1 mol/L ~ 1.0, hydrochloric acid, phosphoric acid, any one in acetic acid.
8. a kind of application of functionalization graphite phase carbon nitride material as described in claim 1, it is characterised in that: the function fossil Black phase carbon nitride material is applied to radionuclide in food or environmental water sample as adsorbent90The Rapid Extraction and trace of Sr is examined It surveys.
9. a kind of application of functionalization graphite phase carbon nitride material as claimed in claim 8, comprising the following steps:
1. the mg functionalization graphite phase carbon nitride material of 1.0 mg ~ 10.0 is placed in 5 mL solution to be measured, 20 min of ultrasound make Mixed solution uniformly in being dispersed in solution to be measured, is put into oscillator vibrates 60 min therewith by material, flat to reach extraction Weighing apparatus；4000rpm is centrifuged 20min again, adsorbent material and water phase after respectively obtaining separation；
2. according to GB5009.268-2016 to the target species in water phase90Sr 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 10 ~ 20min of sound, makes target species90Sr is desorbed from adsorbent；It repeats above operation 3 times, in 40 ~ 75 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 measured90The content of Sr.
CN201910610420.4A 2019-07-08 2019-07-08 Functional graphite-phase carbon nitride material and preparation method and application thereof Active CN110327872B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910610420.4A CN110327872B (en) 2019-07-08 2019-07-08 Functional graphite-phase carbon nitride material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910610420.4A CN110327872B (en) 2019-07-08 2019-07-08 Functional graphite-phase carbon nitride material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110327872A true CN110327872A (en) 2019-10-15
CN110327872B CN110327872B (en) 2022-02-18

Family

ID=68144360

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910610420.4A Active CN110327872B (en) 2019-07-08 2019-07-08 Functional graphite-phase carbon nitride material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110327872B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106582765A (en) * 2016-12-23 2017-04-26 中南大学 Sodium doped graphite phase carbon nitride prepared by one-step synthesis and application thereof
CN106955727A (en) * 2017-04-14 2017-07-18 中国石油大学(华东) The g C that a kind of surface is modified3N4Preparation
CN108855182A (en) * 2018-06-05 2018-11-23 中国地质大学（武汉） A kind of porous g-C of element doping3N4The preparation method of nanometer sheet

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106582765A (en) * 2016-12-23 2017-04-26 中南大学 Sodium doped graphite phase carbon nitride prepared by one-step synthesis and application thereof
CN106955727A (en) * 2017-04-14 2017-07-18 中国石油大学(华东) The g C that a kind of surface is modified3N4Preparation
CN108855182A (en) * 2018-06-05 2018-11-23 中国地质大学（武汉） A kind of porous g-C of element doping3N4The preparation method of nanometer sheet

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JIAN ZHANG ET AL.: "A convenient method to prepare a novel alkali metal sodium doped carbon nitride photocatalyst with a tunable band structure", 《RSC ADV.》 *
ZULEI ZHANG ET AL.: "Synthesis and characterization of whisker surface imprinted polymer and selective solid-phase extraction of trace Sr(II) from environment aqueous solution", 《DESALINATION AND WATER TREATMENT》 *

Also Published As

Publication number Publication date
CN110327872B (en) 2022-02-18

Similar Documents

Publication Publication Date Title
Aggarwal et al. A review on the determination of isotope ratios of boron with mass spectrometry
CN106145100B (en) The preparation method of sulfonated graphene and its method for detecting heavy metal ion
CN101601805B (en) Method for detecting peimine and peiminine in Chinese medicament fritillaria extract
CN107976430A (en) The assay method of arsenic in a kind of coal
CN110975807A (en) Preparation method and application of magnetic biomass charcoal material
CN109439317A (en) Based on target europium-organic framework materials fluorescence probe, synthetic method and application
CN103421030B (en) As the binary aromatic acid cerium complexes and preparation method thereof of cadmium ion fluorescent probe
CN113896901B (en) Lead halide-based metal organic framework material, preparation and application thereof, ammonia gas sensor and intelligent sensing device
CN110327873B (en) Magnetic graphite phase carbon nitride material and preparation method and application thereof
CN108593913B (en) Immunoreaction double-pulse detection method based on mass spectrometry technology
Zhang et al. A novel method of three-dimensional hetero-spectral correlation analysis for the fingerprint identification of humic acid functional groups for hexavalent chromium retention
CN106053562A (en) Modified electrode for detecting sodium nitrite, preparation method and applications thereof
CN110327872A (en) A kind of functionalization graphite phase carbon nitride material and its preparation method and application
CN110003251B (en) Preparation and application of dual-fluorescence response europium-based molecular crystalline material
CN109164162B (en) Uranium isotope abundance measurement method using graphene oxide as ionization enhancer
Chen et al. Preconcentration and Separation of Trace As (III) and Sb (III) by Carbon Nanofibers Loaded With Ammonium Pyrroinedithiocarbamate Prior to ICP-MS Determination
CN109705029A (en) The compound-modified carbon quantum dot of hydroxylpyridinones and its preparation and application
CN110988095A (en) Preparation method of nano material modified electrode and method for detecting heavy metal ions and phenolic compounds
Lan et al. Synthesis, properties and applications of silica-immobilized 8-quinolinol: Part 2. On-line column preconcentration of copper, nickel and cadmium from sea water and determination by inductively-coupled plasma atomic emission spectrometry
McHugh et al. Designing porous ion emitters for thermal ionization mass spectrometry: Evaluating metal–organic frameworks
CN102350297B (en) Adsorbent, preparation method and application thereof
CN108845120A (en) The immune response pulse detection method of one metal ion species label
CN108828212A (en) A kind of immune response pulse detection method based on analytical technique of mass spectrum
CN113687405A (en) Method for measuring and analyzing lead-210 in soil or organism
CN113340862A (en) Fluorescent molecular sensor, preparation method thereof and detection method of trace uranyl ions in water

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant