CN108380174A - Nitrogen-doped graphene material and its preparation method and application - Google Patents
Nitrogen-doped graphene material and its preparation method and application Download PDFInfo
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- CN108380174A CN108380174A CN201810123601.XA CN201810123601A CN108380174A CN 108380174 A CN108380174 A CN 108380174A CN 201810123601 A CN201810123601 A CN 201810123601A CN 108380174 A CN108380174 A CN 108380174A
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- nitrogen
- doped graphene
- quadracycline
- graphene material
- quartz ampoule
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 116
- 239000000463 material Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 claims abstract description 97
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000010453 quartz Substances 0.000 description 106
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 106
- 239000003708 ampul Substances 0.000 description 96
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 76
- 238000013019 agitation Methods 0.000 description 56
- 238000003760 magnetic stirring Methods 0.000 description 56
- 239000000243 solution Substances 0.000 description 54
- 238000012360 testing method Methods 0.000 description 30
- 238000002156 mixing Methods 0.000 description 29
- 239000012528 membrane Substances 0.000 description 28
- 238000002835 absorbance Methods 0.000 description 27
- 239000004098 Tetracycline Substances 0.000 description 23
- 229960002180 tetracycline Drugs 0.000 description 23
- 229930101283 tetracycline Natural products 0.000 description 23
- 235000019364 tetracycline Nutrition 0.000 description 23
- 150000003522 tetracyclines Chemical class 0.000 description 23
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 21
- 238000002474 experimental method Methods 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000004575 stone Substances 0.000 description 8
- 235000013339 cereals Nutrition 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 235000019394 potassium persulphate Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002328 demineralizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The present invention provides a kind of nitrogen-doped graphene material and its preparation method and application, which includes：Graphene oxide is heated under the argon-mixed protection of ammonia, nitrogen-doped graphene material is obtained through processing.The nitrogen-doped graphene material can be applied in going water removal in quadracycline.Nitrogen-doped graphene material prepared by the present invention can adsorb and the quadracycline in catalyzing oxidizing degrading water,, removal rate thorough with removal effect be fast and advantages of environment protection, therefore, it can be applied to the quickly and thoroughly degradation rich in quadracycline water body；In addition, the preparation method of the present invention has many advantages, such as that simple for process, the of low cost and period is short, it can be adapted for industrialization large-scale production nitrogen-doped graphene material.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of nitrogen-doped graphene material and preparation method thereof and
Using.
Background technology
In recent years, with the progress of medical level, what is all come therewith is then the increase of antibiotic concentration in sewage, and then right
Pressure is also growing day by day caused by environment.It, then can be to human health and warp if raw element cannot be effective against to be removed
Ji society generates serious harm, and therefore, it is necessary to having in water removal is reduced or even gone using technologies such as physics, chemistry, biologies
Malicious harmful substance.
The shortcomings that there are poor resistances when due to Biochemical method antibiotic, Physical, chemical method and physico
Method associated with is also widely used in antibiotic waste water processing, in Physical and chemical method, Adsorption and catalysis
Oxidation removal is two kinds of main paths to pollutant removal in water body, however simple absorption is the transfer of pollutant, dirty
Dye object is not decomposed removal, and therefore, oxidation technology has become pollutant in oxidation removal water body, especially micropollutants
Focus technology.In conventional processes, metal ion is often used as oxidation reaction due to active outer electronic structure
Catalyst introduces metal ion, brings secondary pollution therewith simultaneously although it has obtained certain catalytic effect,
The pressure of bigger is caused to environment, therefore, a kind of nonmetallic oxidation reaction effective catalyst of selection is then the hot spot of research.
Invention content
The present invention is directed to deficiency in the prior art, and primary and foremost purpose is to provide a kind of preparation side of nitrogen-doped graphene material
Method.
Second object of the present invention is to provide a kind of nitrogen-doped graphene material obtained using above-mentioned preparation method.
Third object of the present invention is to provide a kind of purposes of nitrogen-doped graphene material.
In order to achieve the above objectives, solution of the invention is：
A kind of preparation method of nitrogen-doped graphene material comprising following steps：
Graphene oxide is heated under the argon-mixed protection of ammonia, nitrogen-doped graphene material is obtained through processing.
Preferably, the grain size of graphene oxide is 2-50nm, specific surface area 300-500m2/ g, adsorption capacity 10-
35mg/g。
Preferably, the volume content of the argon-mixed middle ammonia of ammonia is 10-15%.
Preferably, the temperature of heating is 700 ± 50 DEG C, and the rate of heating is 10 ± 2 DEG C/min, and the retention time of heating is
1±0.5h。
Preferably, the process of processing is cooling, washing and drying.
Wherein, the process of washing is to be washed 4-6 times with water and ethyl alcohol successively.
The temperature of drying is 60 ± 10 DEG C.
A kind of nitrogen-doped graphene material, is prepared by such as above-mentioned preparation method.
Wherein, the grain size of nitrogen-doped graphene material is 3-45nm, specific surface area 400-700m2/ g, adsorption capacity are
45‐60mg/g。
A kind of application such as above-mentioned nitrogen-doped graphene material in going water removal in quadracycline.
Wherein, the mass concentration of quadracycline is 15-60mg/L.
By adopting the above scheme, the beneficial effects of the invention are as follows：
The first, nitrogen-doped graphene material prepared by the present invention reaches adsorption saturation in order to prevent, while adsorbing and being catalyzed
Quadracycline in oxidative degradation water, to reach, removal rate is fast and the thorough purpose of removal effect；Also have simultaneously
Therefore advantages of environment protection can be applied to the quickly and thoroughly degradation rich in quadracycline water body.
The second, preparation method of the invention has many advantages, such as that simple for process, the of low cost and period is short, can be adapted for work
Industryization mass produces nitrogen-doped graphene material.
Description of the drawings
Fig. 1 is the SEM pattern schematic diagrames of the nitrogen-doped graphene material of the present invention.
Fig. 2 is the timing VA characteristic curve figure of the nitrogen-doped graphene material of the present invention.
Specific implementation mode
The present invention provides a kind of nitrogen-doped graphene materials and its preparation method and application.
<The preparation method of nitrogen-doped graphene material>
(1), graphene oxide (as predecessor) is heated under the argon-mixed protection of ammonia and obtains mixture；
(2), mixture is cooled to 25 ± 5 DEG C, is then washed 4-6 times with water and ethyl alcohol successively, be placed on vacuum baking later
It is dried in case, obtains nitrogen-doped graphene material.
Wherein, in step (1), the grain size of graphene oxide can be 2-50nm, preferably 8nm；Specific surface area can be with
For 300-500m2/ g, preferably 400m2/g；Adsorption capacity can be 10-35mg/g, preferably 30mg/g.
In step (1), the volume content of the argon-mixed middle ammonia of ammonia can be 10-15%, preferably 10%.
In step (1), the temperature of heating can be 700 ± 50 DEG C, preferably 700 DEG C；The rate of heating can be 10
± 2 DEG C/min, preferably 10 DEG C/min；The retention time of heating can be 1 ± 0.5h, preferably 1h.
In step (2), the process of processing is cooling, washing and drying.
In fact, the process of washing is that can be washed 4-6 times with water and ethyl alcohol successively, preferably 4 times.
The temperature of drying can be 60 ± 10 DEG C, preferably 60 DEG C.
<Nitrogen-doped graphene material>
Nitrogen-doped graphene material (Journal of the American are prepared by above-mentioned preparation method
Chemical Society,2009,131(43):15939)。
Wherein, as shown in Figure 1, the grain size of nitrogen-doped graphene material is 3-45nm, specific surface area 400-700m2/ g,
Adsorption capacity is 45-60mg/g.
Due to nitrogen-doped graphene material have good grain size, such as micropore, meso-hole structure so that graphene with commonly receive
Rice material, which is compared, have been shown to the stronger adsorption capacity of pollutant in water body, after the nitrogen doped in carbon nanomaterial,
I.e. the presence of pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen then changes the chemical inertness of hexahedron carbon structure as original honeycomb, to
It is catalyzed persulfate, an electron acceptor-electronics is formed between potassium peroxydisulfate, nitrogen-doped graphene material and pollutant and carries
The system of body-electron donor has achieved the purpose that the structure for destroying pollutant and has reduced pollutant concentration, urged to pollutant
Huge potentiality are demonstrated out in terms of changing oxidation removal.In addition, nitrogen-doped graphene material possesses nano level size and larger
Specific surface area, according to Lang Gemiaoer Tellurium determinations it is found that specific surface area is bigger, adsorption capacity is bigger.
<The application of nitrogen-doped graphene material>
It is a kind of as above-mentioned nitrogen-doped graphene material can be applied in going water removal in quadracycline, i.e. N doping stone
Quadracycline in black alkene material absorption and catalyzing oxidizing degrading water, wherein the mass concentration of quadracycline is 15-
60mg/L.In adsorption process, physical absorption, chemisorption and ion exchange adsorption are existed simultaneously, wherein be with physical absorption
It is main；Adsorpting type belongs to mono layer adsorption, and adsorption capacity increases with the increase of equilibrium concentration first, then tends towards stability,
And follow Langmuir Adsorption laws.
In catalytic oxidation process, non-free radical reaction mechanism is mainly followed.Using nitrogen-doped graphene material (as electronics
Carrier) it is coated on glass-carbon electrode, in the phosphate buffer solution that pH is 7, as shown in Fig. 2, making it when potassium peroxydisulfate is added
Ultimate density be 0.75mmol/L after, due to electronics from nitrogen-doped graphene material/glass-carbon electrode be transferred to potassium peroxydisulfate (as
Electron acceptor) on, therefore, electric current declines, and a low ebb occurs in transient current profile；Due to the quadracycline conduct in water
Electron donor is transferred an electron in system on nitrogen-doped graphene material/glass-carbon electrode, and therefore, electric current rises rapidly.Such as
This iterative cycles carries out so that the carbocyclic ring of quadracycline is gradually opened, and structure is destroyed, and is efficiently gone to be finally reached
The purpose of demineralizing acid tetracycline.
Wherein, in above-mentioned microcosmic reaction mechanism nitrogen-doped graphene material, potassium peroxydisulfate and quadracycline addition
Sequence is uncorrelated with the macroscopically addition sequence of nitrogen-doped graphene material, potassium peroxydisulfate and quadracycline.
The present invention will be further described with reference to the accompanying drawings.
Embodiment 1：
The preparation method of the nitrogen-doped graphene material of the present embodiment includes the following steps：
(1), by 1g graphene oxides (grain size 8nm, specific surface area 400m2/ g, adsorption capacity 30mg/g) transfer
To porcelain boat, it is subsequently placed into tube furnace and is passed through the argon-mixed rate with 10 DEG C/min of ammonia and be heated to 700 DEG C, the guarantor of heating
It is 1h to hold the time, obtains mixture；
(2), mixture is naturally cooled to 25 DEG C, is then washed 4 times, is put later to vacuum with water and ethyl alcohol successively
Drying, obtains nitrogen-doped graphene material in case (60 DEG C).
Wherein, in step (1), the grain size of graphene oxide within 2-50nm, specific surface area is in 300-500m2/ g it
Interior, adsorption capacity is all possible within 10-35mg/g.
In step (1), the volume content of the argon-mixed middle ammonia of ammonia is also possible within 10-15%.
In step (1), the temperature of heating within 700 ± 50 DEG C, the rate of heating within 10 ± 2 DEG C/min plus
The retention time of heat is possible within 1 ± 0.5h.
In step (2), the temperature of drying is also possible within 60 ± 10 DEG C.
<Experiment>
It is tested as follows with the product obtained in above-described embodiment.
<Experiment 1>
The purpose of this experiment is to study the test by nitrogen-doped graphene material absorption property, to probe into salt in water
The removal situation of sour tetracycline.
It takes several quartz ampoules to place on magnetic stirring apparatus, quadracycline solution (matter is added in every quartz ampoule rapidly
Measure a concentration of 15-60mg/L) and nitrogen-doped graphene material (mass concentration 10-100mg/L), adjust pH value (pH value 3-
10) it, opens magnetic stirring apparatus and is stirred at 10-40 DEG C, 1 quartz ampoule is taken out after stirring 0-180min, by the quartz ampoule
Spectrophotometric determination absorbance is used in combination through filter membrane in interior mixed liquor, obtains the concentration situation of change of quadracycline and counts
Calculate its removal rate.
<Test 1-1>
It takes 8 quartz ampoules to place on magnetic stirring apparatus, 10mL, 35mg/L hydrochloric acid Fourth Ring is added in every quartz ampoule rapidly
Plain solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C, respectively
Quartz ampoule is taken out when mixing time is 0min, 0.5min, 2min, 5min, 10min, 30min, 60min and 120min, it will be upper
The filter membrane that the mixed liquor in quartz ampoule is respectively 0.45 μm by aperture is stated, spectrophotometer (wavelength 358nm) is used in combination to measure
Absorbance, then upon agitation between when being 0min, the adsorption capacity of nitrogen-doped graphene material is 0mg/g, and quadracycline is gone
Except rate is 0%；When being 0.5min between upon agitation, the adsorption capacity of nitrogen-doped graphene material is 123.31mg/g, hydrochloric acid four
The removal rate of ring element is 35.23%；When being 2min between upon agitation, the adsorption capacity of nitrogen-doped graphene material is
The removal rate of 141.52mg/g, quadracycline are 40.44%；When being 5min between upon agitation, nitrogen-doped graphene material
Adsorption capacity is 144.71mg/g, and the removal rate of quadracycline is 41.35%；When being 10min between upon agitation, N doping stone
The adsorption capacity of black alkene material is 155.03mg/g, and the removal rate of quadracycline is 44.29%；It is 30min between upon agitation
When, the adsorption capacity of nitrogen-doped graphene material is 158.54mg/g, and the removal rate of quadracycline is 45.30%；Work as stirring
When time is 60min, the adsorption capacity of nitrogen-doped graphene material is 168.13mg/g, and the removal rate of quadracycline is
48.04%；When being 120min between upon agitation, the adsorption capacity of nitrogen-doped graphene material is 174.27mg/g, hydrochloric acid Fourth Ring
The removal rate of element is 49.79%.
<Test 1-2>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 35mg/L quadracycline is added in the quartz ampoule rapidly
Solution and 1mg nitrogen-doped graphene materials adjust pH value to 4, open magnetic stirring apparatus later and are stirred at 25 DEG C, are being stirred
Time takes out quartz ampoule when being 120min, the filter membrane for being 0.45 μm by aperture by the mixed liquor in quartz ampoule, and light splitting light is used in combination
Degree meter (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 167.60mg/g, hydrochloric acid Fourth Ring
The removal rate of element is 47.89%.
<Test 1-3>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 35mg/L quadracycline is added in the quartz ampoule rapidly
Solution and 1mg nitrogen-doped graphene materials adjust pH value to 6, open magnetic stirring apparatus later and are stirred at 25 DEG C, are being stirred
Time takes out quartz ampoule when being 120min, the filter membrane for being 0.45 μm by aperture by the mixed liquor in quartz ampoule, and light splitting light is used in combination
Degree meter (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 169.76mg/g, hydrochloric acid Fourth Ring
The removal rate of element is 48.50%.
<Test 1-4>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 35mg/L quadracycline is added in the quartz ampoule rapidly
Solution and 1mg nitrogen-doped graphene materials adjust pH value to 8, open magnetic stirring apparatus later and are stirred at 25 DEG C, are being stirred
Time takes out quartz ampoule when being 120min, the filter membrane for being 0.45 μm by aperture by the mixed liquor in quartz ampoule, and light splitting light is used in combination
Degree meter (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 166.21mg/g, hydrochloric acid Fourth Ring
The removal rate of element is 47.49%.
<Test 1-5>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 35mg/L quadracycline is added in the quartz ampoule rapidly
Solution and 1mg nitrogen-doped graphene materials adjust pH value to 10, open magnetic stirring apparatus later and are stirred at 25 DEG C, are being stirred
The time is mixed to take out quartz ampoule when 120min, light splitting is used in combination in the filter membrane for being 0.45 μm by aperture by the mixed liquor in quartz ampoule
Photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 60.15mg/g, hydrochloric acid four
The removal rate of ring element is 17.18%.
<Test 1-6>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 15.75mg/L hydrochloric acid four is added in the quartz ampoule rapidly
Ring element solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C,
Mixing time takes out quartz ampoule when being 120min, by aperture is 0.45 μm of filter membrane by the mixed liquor in quartz ampoule, is used in combination point
Light photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 108.87mg/g, hydrochloric acid
The removal rate of tetracycline is 69.12%.
<Test 1-7>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 17.50mg/L hydrochloric acid four is added in the quartz ampoule rapidly
Ring element solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C,
Mixing time takes out quartz ampoule when being 120min, by aperture is 0.45 μm of filter membrane by the mixed liquor in quartz ampoule, is used in combination point
Light photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 118.47mg/g, hydrochloric acid
The removal rate of tetracycline is 67.70%.
<Test 1-8>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 19.25mg/L hydrochloric acid four is added in the quartz ampoule rapidly
Ring element solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C,
Mixing time takes out quartz ampoule when being 120min, by aperture is 0.45 μm of filter membrane by the mixed liquor in quartz ampoule, is used in combination point
Light photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 127.25mg/g, hydrochloric acid
The removal rate of tetracycline is 66.10%.
<Test 1-9>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 21.00mg/L hydrochloric acid four is added in the quartz ampoule rapidly
Ring element solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C,
Mixing time takes out quartz ampoule when being 120min, by aperture is 0.45 μm of filter membrane by the mixed liquor in quartz ampoule, is used in combination point
Light photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 132.00mg/g, hydrochloric acid
The removal rate of tetracycline is 62.86%.
<Test 1-10>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 22.75mg/L hydrochloric acid four is added in the quartz ampoule rapidly
Ring element solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C,
Mixing time takes out quartz ampoule when being 120min, by aperture is 0.45 μm of filter membrane by the mixed liquor in quartz ampoule, is used in combination point
Light photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 138.26mg/g, hydrochloric acid
The removal rate of tetracycline is 60.78%.
<Test 1-11>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 24.50mg/L hydrochloric acid four is added in the quartz ampoule rapidly
Ring element solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C,
Mixing time takes out quartz ampoule when being 120min, by aperture is 0.45 μm of filter membrane by the mixed liquor in quartz ampoule, is used in combination point
Light photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 150.62mg/g, hydrochloric acid
The removal rate of tetracycline is 61.48%.
<Test 1-12>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 26.25mg/L hydrochloric acid four is added in the quartz ampoule rapidly
Ring element solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C,
Mixing time takes out quartz ampoule when being 120min, by aperture is 0.45 μm of filter membrane by the mixed liquor in quartz ampoule, is used in combination point
Light photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 154.12mg/g, hydrochloric acid
The removal rate of tetracycline is 58.71%.
<Test 1-13>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 28.00mg/L hydrochloric acid four is added in the quartz ampoule rapidly
Ring element solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C,
Mixing time takes out quartz ampoule when being 120min, by aperture is 0.45 μm of filter membrane by the mixed liquor in quartz ampoule, is used in combination point
Light photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 158.68mg/g, hydrochloric acid
The removal rate of tetracycline is 56.67%.
<Test 1-14>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 29.75mg/L hydrochloric acid four is added in the quartz ampoule rapidly
Ring element solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C,
Mixing time takes out quartz ampoule when being 120min, by aperture is 0.45 μm of filter membrane by the mixed liquor in quartz ampoule, is used in combination point
Light photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 166.16mg/g, hydrochloric acid
The removal rate of tetracycline is 55.85%.
<Test 1-15>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 31.50mg/L hydrochloric acid four is added in the quartz ampoule rapidly
Ring element solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C,
Mixing time takes out quartz ampoule when being 120min, by aperture is 0.45 μm of filter membrane by the mixed liquor in quartz ampoule, is used in combination point
Light photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 166.77mg/g, hydrochloric acid
The removal rate of tetracycline is 52.94%.
<Test 1-16>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 33.25mg/L hydrochloric acid four is added in the quartz ampoule rapidly
Ring element solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C,
Mixing time takes out quartz ampoule when being 120min, by aperture is 0.45 μm of filter membrane by the mixed liquor in quartz ampoule, is used in combination point
Light photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 168.74mg/g, hydrochloric acid
The removal rate of tetracycline is 50.75%.
<Test 1-17>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 35.00mg/L hydrochloric acid four is added in the quartz ampoule rapidly
Ring element solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C,
Mixing time takes out quartz ampoule when being 120min, by aperture is 0.45 μm of filter membrane by the mixed liquor in quartz ampoule, is used in combination point
Light photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 174.27mg/g, hydrochloric acid
The removal rate of tetracycline is 49.79%.
<Test 1-18>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 36.75mg/L hydrochloric acid four is added in the quartz ampoule rapidly
Ring element solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C,
Mixing time takes out quartz ampoule when being 120min, by aperture is 0.45 μm of filter membrane by the mixed liquor in quartz ampoule, is used in combination point
Light photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 181.06mg/g, hydrochloric acid
The removal rate of tetracycline is 49.27%.
<Test 1-19>
It takes 1 quartz ampoule to place on magnetic stirring apparatus, 10mL, 38.50mg/L hydrochloric acid four is added in the quartz ampoule rapidly
Ring element solution and 1mg nitrogen-doped graphene materials adjust pH value to 7, open magnetic stirring apparatus later and are stirred at 25 DEG C,
Mixing time takes out quartz ampoule when being 120min, by aperture is 0.45 μm of filter membrane by the mixed liquor in quartz ampoule, is used in combination point
Light photometer (wavelength 358nm) measures absorbance, then the adsorption capacity of nitrogen-doped graphene material is 182.83mg/g, hydrochloric acid
The removal rate of tetracycline is 47.49%.
<Experiment 2>
The purpose of this experiment is to study the test by the catalytic degradation performance to nitrogen-doped graphene material, to probe into
The removal situation of quadracycline in water.
It takes several quartz ampoules to place on magnetic stirring apparatus, quadracycline solution (matter is added in every quartz ampoule rapidly
Measure a concentration of 15-60mg/L), potassium persulfate solution (mass concentration 0.5-5mmol/L) and nitrogen-doped graphene material (quality
A concentration of 10-100mg/L), pH value (pH value 3-10) is adjusted, magnetic stirring apparatus is opened and is stirred at 10-40 DEG C, stirred
1 quartz ampoule is taken out after 0-180min, and spectrophotometric determination extinction is used in combination by the mixed liquor in the quartz ampoule through filter membrane
Degree, obtains the concentration situation of change of quadracycline and calculates removal rate.
Due to adding potassium persulfate solution, nitrogen-doped graphene material exists simultaneously absorption and catalysis in system
Oxidative degradation, experiment 1 has studied removal situation of the absorption property to quadracycline, and this experimental study is to inhale
Echo removal situation of the performance to quadracycline of catalysis oxidation double action.
<Test 2-1>
Take 8 quartz ampoules to place on magnetic stirring apparatus, be added in every quartz ampoule rapidly 9mL quadracyclines solution,
1mL potassium persulfate solutions and 1mg nitrogen-doped graphene materials so that a concentration of 35mg/ of final mass of quadracycline solution
The ultimate density of L, potassium persulfate solution are 0.75mmol/L, adjust pH value to 7, open magnetic stirring apparatus later and at 25 DEG C
Stirring takes out stone when mixing time is 0min, 0.5min, 2min, 5min, 10min, 30min, 60min and 120min respectively
Mixed liquor in above-mentioned quartz ampoule by aperture is respectively 0.45 μm of filter membrane by Ying Guan, and spectrophotometer is used in combination, and (wavelength is
358nm) measure absorbance, then upon agitation between when being 0min, the removal rate of quadracycline is 0%；It is between upon agitation
When 0.5min, the removal rate of quadracycline is 58.82%；When being 2min between upon agitation, the removal rate of quadracycline is
60.39%；When being 5min between upon agitation, the removal rate of quadracycline is 75.90%；When being 10min between upon agitation, salt
The removal rate of sour tetracycline is 80.41%；When being 30min between upon agitation, the removal rate of quadracycline is 95.08%；When
When mixing time is 60min, the removal rate of quadracycline is 97.43%；When being 120min between upon agitation, quadracycline
Removal rate be 100.00%.
<Test 2-2>
Take 8 quartz ampoules to place on magnetic stirring apparatus, be added in every quartz ampoule rapidly 9mL quadracyclines solution,
1mL potassium persulfate solutions and 1mg nitrogen-doped graphene materials so that a concentration of 35mg/ of final mass of quadracycline solution
The ultimate density of L, potassium persulfate solution are 0.75mmol/L, adjust pH value to 7, open magnetic stirring apparatus later and at 15 DEG C
Stirring takes out stone when mixing time is 0min, 0.5min, 2min, 5min, 10min, 30min, 60min and 120min respectively
Mixed liquor in above-mentioned quartz ampoule by aperture is respectively 0.45 μm of filter membrane by Ying Guan, and spectrophotometer is used in combination, and (wavelength is
358nm) measure absorbance, then upon agitation between when being 0min, the removal rate of quadracycline is 0%；It is between upon agitation
When 0.5min, the removal rate of quadracycline is 56.30%；When being 2min between upon agitation, the removal rate of quadracycline is
59.50%；When being 5min between upon agitation, the removal rate of quadracycline is 68.50%；When being 10min between upon agitation, salt
The removal rate of sour tetracycline is 77.03%；When being 30min between upon agitation, the removal rate of quadracycline is 90.41%；When
When mixing time is 60min, the removal rate of quadracycline is 94.36%；When being 120min between upon agitation, quadracycline
Removal rate be 100.00%.
<Test 2-3>
Take 8 quartz ampoules to place on magnetic stirring apparatus, be added in every quartz ampoule rapidly 9mL quadracyclines solution,
1mL potassium persulfate solutions and 1mg nitrogen-doped graphene materials so that a concentration of 35mg/ of final mass of quadracycline solution
The ultimate density of L, potassium persulfate solution are 0.75mmol/L, adjust pH value to 7, open magnetic stirring apparatus later and at 35 DEG C
Stirring takes out stone when mixing time is 0min, 0.5min, 2min, 5min, 10min, 30min, 60min and 120min respectively
Mixed liquor in above-mentioned quartz ampoule by aperture is respectively 0.45 μm of filter membrane by Ying Guan, and spectrophotometer is used in combination, and (wavelength is
358nm) measure absorbance, then upon agitation between when being 0min, the removal rate of quadracycline is 0%；It is between upon agitation
When 0.5min, the removal rate of quadracycline is 62.29%；When being 2min between upon agitation, the removal rate of quadracycline is
80.35%；When being 5min between upon agitation, the removal rate of quadracycline is 90.62%；When being 10min between upon agitation, salt
The removal rate of sour tetracycline is 95.50%；When being 30min between upon agitation, the removal rate of quadracycline is 100.00%；When
When mixing time is 60min, the removal rate of quadracycline is 100.00%；When being 120min between upon agitation, hydrochloric acid Fourth Ring
The removal rate of element is 100.00%.
<Test 2-4>
Take 8 quartz ampoules to place on magnetic stirring apparatus, be added in every quartz ampoule rapidly 9mL quadracyclines solution,
1mL potassium persulfate solutions and 1mg nitrogen-doped graphene materials so that a concentration of 35mg/ of final mass of quadracycline solution
The ultimate density of L, potassium persulfate solution are 0.75mmol/L, adjust pH value to 4, open magnetic stirring apparatus later and at 25 DEG C
Stirring takes out stone when mixing time is 0min, 0.5min, 2min, 5min, 10min, 30min, 60min and 120min respectively
Mixed liquor in above-mentioned quartz ampoule by aperture is respectively 0.45 μm of filter membrane by Ying Guan, and spectrophotometer is used in combination, and (wavelength is
358nm) measure absorbance, then upon agitation between when being 0min, the removal rate of quadracycline is 0%；It is between upon agitation
When 0.5min, the removal rate of quadracycline is 53.92%；When being 2min between upon agitation, the removal rate of quadracycline is
59.25%；When being 5min between upon agitation, the removal rate of quadracycline is 65.48%；When being 10min between upon agitation, salt
The removal rate of sour tetracycline is 72.78%；When being 30min between upon agitation, the removal rate of quadracycline is 78.73%；When
When mixing time is 60min, the removal rate of quadracycline is 85.07%；When being 120min between upon agitation, quadracycline
Removal rate be 86.78%.
<Test 2-5>
Take 8 quartz ampoules to place on magnetic stirring apparatus, be added in every quartz ampoule rapidly 9mL quadracyclines solution,
1mL potassium persulfate solutions and 1mg nitrogen-doped graphene materials so that a concentration of 35mg/ of final mass of quadracycline solution
The ultimate density of L, potassium persulfate solution are 0.75mmol/L, adjust pH value to 6, open magnetic stirring apparatus later and at 25 DEG C
Stirring takes out stone when mixing time is 0min, 0.5min, 2min, 5min, 10min, 30min, 60min and 120min respectively
Mixed liquor in above-mentioned quartz ampoule by aperture is respectively 0.45 μm of filter membrane by Ying Guan, and spectrophotometer is used in combination, and (wavelength is
358nm) measure absorbance, then upon agitation between when being 0min, the removal rate of quadracycline is 0%；It is between upon agitation
When 0.5min, the removal rate of quadracycline is 58.58%；When being 2min between upon agitation, the removal rate of quadracycline is
63.50%；When being 5min between upon agitation, the removal rate of quadracycline is 73.86%；When being 10min between upon agitation, salt
The removal rate of sour tetracycline is 81.70%；When being 30min between upon agitation, the removal rate of quadracycline is 89.76%；When
When mixing time is 60min, the removal rate of quadracycline is 93.87%；When being 120min between upon agitation, quadracycline
Removal rate be 95.04%.
<Test 2-6>
Take 8 quartz ampoules to place on magnetic stirring apparatus, be added in every quartz ampoule rapidly 9mL quadracyclines solution,
1mL potassium persulfate solutions and 1mg nitrogen-doped graphene materials so that a concentration of 35mg/ of final mass of quadracycline solution
The ultimate density of L, potassium persulfate solution are 0.75mmol/L, adjust pH value to 8, open magnetic stirring apparatus later and at 25 DEG C
Stirring takes out stone when mixing time is 0min, 0.5min, 2min, 5min, 10min, 30min, 60min and 120min respectively
Mixed liquor in above-mentioned quartz ampoule by aperture is respectively 0.45 μm of filter membrane by Ying Guan, and spectrophotometer is used in combination, and (wavelength is
358nm) measure absorbance, then upon agitation between when being 0min, the removal rate of quadracycline is 0%；It is between upon agitation
When 0.5min, the removal rate of quadracycline is 58.79%；When being 2min between upon agitation, the removal rate of quadracycline is
61.88%；When being 5min between upon agitation, the removal rate of quadracycline is 71.08%；When being 10min between upon agitation, salt
The removal rate of sour tetracycline is 79.17%；When being 30min between upon agitation, the removal rate of quadracycline is 88.98%；When
When mixing time is 60min, the removal rate of quadracycline is 91.40%；When being 120min between upon agitation, quadracycline
Removal rate be 92.24%.
<Test 2-7>
Take 8 quartz ampoules to place on magnetic stirring apparatus, be added in every quartz ampoule rapidly 9mL quadracyclines solution,
1mL potassium persulfate solutions and 1mg nitrogen-doped graphene materials so that a concentration of 35mg/ of final mass of quadracycline solution
The ultimate density of L, potassium persulfate solution are 0.75mmol/L, adjust pH value to 10, open magnetic stirring apparatus later and at 25 DEG C
Lower stirring is taken out when mixing time is 0min, 0.5min, 2min, 5min, 10min, 30min, 60min and 120min respectively
Mixed liquor in above-mentioned quartz ampoule by aperture is respectively 0.45 μm of filter membrane by quartz ampoule, and spectrophotometer is used in combination, and (wavelength is
358nm) measure absorbance, then upon agitation between when being 0min, the removal rate of quadracycline is 0%；It is between upon agitation
When 0.5min, the removal rate of quadracycline is 30.95%；When being 2min between upon agitation, the removal rate of quadracycline is
39.43%；When being 5min between upon agitation, the removal rate of quadracycline is 43.09%；When being 10min between upon agitation, salt
The removal rate of sour tetracycline is 45.41%；When being 30min between upon agitation, the removal rate of quadracycline is 47.12%；When
When mixing time is 60min, the removal rate of quadracycline is 48.82%；When being 120min between upon agitation, quadracycline
Removal rate be 51.28%.
Table 1 tests 1-1 to the performance value of the nitrogen-doped graphene material and quadracycline of experiment 2-7
As shown in Table 1, from experiment 1-1 to experiment 1-5 in, due to mixed liquor pH value influence nitrogen-doped graphene material with
Therefore the combination situation of quadracycline solution increases afterwards as the pH value of mixed liquor first reduces, nitrogen-doped graphene material
First increases and then decreases trend is presented in adsorption capacity, and the removal rate of quadracycline is also that first increases and then decreases trend is presented.From reality
It tests in 1-6 to experiment 1-19, with the continuous raising of quadracycline solution concentration, the adsorption capacity of nitrogen-doped graphene material
Continuous increase tendency is presented, to meet absorption principle；Since the adsorption capacity of nitrogen-doped graphene material is with quadracycline
The increase of concentration and the rate that increases is limited, therefore, the removal rate of quadracycline, which is presented, constantly reduces trend.From experiment 2-1
Into experiment 2-3, since the rate of adsorption is increased with the raising of temperature, reaction rate constant increases with the raising of temperature
Greatly, therefore, the removal rate of increased trend after first reducing with whipping temp, quadracycline is in apparent ascendant trend, and
Whipping temp is higher, and the removal rate of quadracycline is more thorough.In from experiment 2-4 to experiment 2-7, since adsorption effect is by pH
After the influence of value, catalytic oxidation effect is also affected therewith, and therefore, with the continuous increase of pH value, quadracycline is gone
Except rate is in first increases and then decreases trend.
Therefore, the nitrogen-doped graphene material that prepared by the present invention can adsorb and the hydrochloric acid Fourth Ring in catalyzing oxidizing degrading water
Element, with removal effect, therefore thorough, removal rate can be applied to be rich in hydrochloric acid Fourth Ring with advantages of environment protection soon
The quickly and thoroughly degradation of plain water body.
The above-mentioned description to embodiment is that this hair can be understood and used for the ease of those skilled in the art
It is bright.Those skilled in the art obviously readily can make various modifications to these embodiments, and described herein one
As principle be applied in other embodiment, without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments.
Those skilled in the art's principle according to the present invention, not departing from improvement that scope of the invention is made and modification all should be at this
Within the protection domain of invention.
Claims (10)
1. a kind of preparation method of nitrogen-doped graphene material, it is characterised in that：It includes the following steps：
Graphene oxide is heated under the argon-mixed protection of ammonia, the nitrogen-doped graphene material is obtained through processing.
2. preparation method according to claim 1, it is characterised in that：The grain size of the graphene oxide is 2-50nm, than
Surface area is 300-500m2/ g, adsorption capacity 10-35mg/g.
3. preparation method according to claim 1, it is characterised in that：The volume content of the argon-mixed middle ammonia of ammonia is
10-15%.
4. preparation method according to claim 1, it is characterised in that：The temperature of the heating is 700 ± 50 DEG C, described to add
The rate of heat is 10 ± 2 DEG C/min, and the retention time of the heating is 1 ± 0.5h.
5. preparation method according to claim 1, it is characterised in that：The process of the processing is cooling, washing and drying.
6. preparation method according to claim 5, it is characterised in that：The process of the washing is to be washed successively with water and ethyl alcohol
Wash 4-6；And/or
The temperature of the drying is 60 ± 10 DEG C.
7. a kind of nitrogen-doped graphene material, it is characterised in that：It is by preparation method system as claimed in any one of claims 1 to 6
It is standby to obtain.
8. nitrogen-doped graphene material according to claim 7, it is characterised in that：The grain of the nitrogen-doped graphene material
Diameter is 3-45nm, specific surface area 400-700m2/ g, adsorption capacity 45-60mg/g.
9. a kind of application of nitrogen-doped graphene material as claimed in claim 7 in going water removal in quadracycline.
10. application according to claim 9, it is characterised in that：The mass concentration of the quadracycline is 15-60mg/
L。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112897631A (en) * | 2021-01-18 | 2021-06-04 | 南开大学 | Method for degrading dye and pesticide by using microwave-induced reinforced iron-modified nitrogen-doped carbon-based material |
| CN113045721A (en) * | 2021-02-18 | 2021-06-29 | 北京理工大学 | 15N and14n-interspersed uniform nitrogen-doped graphene, and preparation method and application thereof |
| CN115739151A (en) * | 2022-11-04 | 2023-03-07 | 山西大学 | Preparation and application of nitrogen-doped graphene-supported magnetic nanoparticle material |
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| CN113045721B (en) * | 2021-02-18 | 2022-02-18 | 北京理工大学 | 15N and14n-interspersed uniform nitrogen-doped graphene, and preparation method and application thereof |
| CN115739151A (en) * | 2022-11-04 | 2023-03-07 | 山西大学 | Preparation and application of nitrogen-doped graphene-supported magnetic nanoparticle material |
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Inventor after: Feng Leiyu Inventor after: Chen Xutao Inventor after: Huang Yujun Inventor after: Li Xuyao Inventor after: Peng Kangshou Inventor after: Chen Yinguang Inventor before: Feng Leiyu Inventor before: Chen Xutao Inventor before: Huang Yujun Inventor before: Li Xuyao Inventor before: Peng Kangshou Inventor before: Chen Yinguang |
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Application publication date: 20180810 |