CN106582762B - A kind of nitrogen-doped graphene/MnO2Composite material and preparation method - Google Patents
A kind of nitrogen-doped graphene/MnO2Composite material and preparation method Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title description 9
- 239000002131 composite material Substances 0.000 claims abstract description 53
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 45
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 18
- 239000011572 manganese Substances 0.000 claims abstract description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 27
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 16
- 229940071125 manganese acetate Drugs 0.000 claims description 15
- 239000002070 nanowire Substances 0.000 claims description 9
- 230000036571 hydration Effects 0.000 claims description 4
- 238000006703 hydration reaction Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 241000446313 Lamella Species 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- -1 graphite Alkene Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of nitrogen-doped graphene/MnO2Composite material and preparation method, method provided by the invention are added ammonium persulfate heating reaction, obtain nitrogen-doped graphene/MnO after mixing manganese source compound solution and graphene oxide solution2Composite material;This method can not only a step realize the reduction of graphene oxide, nitrogen atom doping and MnO2Load, and the MnO in obtained composite material2For threadiness, and then its specific surface area in the composite is increased, so that the catalytic activity of obtained composite material greatly enhances.
Description
Technical field
Technical field of nano material of the present invention more particularly to a kind of nitrogen-doped graphene/MnO2Composite material and its preparation
Method.
Background technique
The basic structural unit of graphene is the hexatomic ring of most rock-steady structure, and itself and fullerene and carbon nanotube phase
Than not only cheap, raw material is easy to get, and light weight, and ideal large specific surface area, thermal conductivity is good, is current ideal two wiener
Rice material, wide application prospect is shown in research fields such as microelectronics, functional material and chemical sensitisations.
It is one of numerous research fields of graphene that nitrogen-doped graphene, which loads compound, receives great pass in recent years
Note, and nitrogen-doped graphene is introduced into metal oxide, the catalytic performance of metal oxide can be improved, at present about metal
Oxide introducing nitrogen-doped graphene report is also relatively more, such as Applied Surface Science, 366 (2016), 552-
MnOx disclosed in 560 and nitrogen-doped graphene composite material, for another example ACS Appl.Mater.Interfaces 2016,8,
5251-5260 also discloses MnO2With nitrogen-doped graphene composite material;But presently disclosed nitrogen-doped graphene/MnO2It is multiple
Manganese dioxide is particle or sheet in condensation material, and catalytic performance is poor, has seriously affected its application, and disclosed preparation
The method and process of composite material is also comparatively laborious, it thus provides nitrogen-doped graphene/MnO that a kind of catalytic performance is good2It is compound
Material tool has very important significance.
Summary of the invention
In view of this, technical problem to be solved by the present invention lies in provide a kind of nitrogen-doped graphene/MnO2Composite wood
The composite material catalytic performance of material and preparation method thereof, the method preparation provided through the invention is good, and preparation method is simple.
The present invention also provides a kind of nitrogen-doped graphene/MnO2Composite material, it is described to be compounded in nitrogen-doped graphene piece
MnO on layer2For linear MnO2, the threadiness MnO210~20nm of diameter.
The present invention also provides a kind of nitrogen-doped graphene/MnO2The preparation method of composite material, comprising:
1) manganese source compound solution and graphene oxide solution are mixed, obtain the first mixed liquor,
The manganese source compound is hydration manganese acetate;
2) ammonium persulfate is added into the first mixed solution, 1~36h of hydro-thermal reaction under the conditions of 80~200 DEG C obtains nitrogen
Doped graphene/MnO2Composite material.
Preferably, the mass ratio of the graphene oxide and manganese source compound is 1: (5~30).
Preferably, the concentration of the graphene oxide solution is 2~3.5g/L.
Preferably, the concentration of the manganese source compound solution is 5~100g/L.
Preferably, the manganese acetate and the ammonium persulfate mass ratio 1: (2-10).
Preferably, the concentration of the ammonium persulfate solution is 10~100g/L.
Compared with prior art, the present invention provides a kind of nitrogen-doped graphene/MnO2Composite material and preparation method,
Method provided by the invention is capable of the reduction of step realization graphene oxide, nitrogen atom doping and MnO2Load;In MnO2It generates
Process, the oxygen-containing functional group on graphene oxide make MnO as nucleating point2It is nucleated and axially grows, and obtain compound
MnO in material2For MnO2Nano wire, so increase its in the composite specific surface area (specific surface area 100~
200m2/ g, graphene oxide is not used is less than 50m2/ g) so that the catalytic activity of obtained composite material greatly enhances.
Detailed description of the invention
Fig. 1 is nitrogen-doped graphene/MnO that the embodiment of the present invention 1 is prepared2Composite material amplifies 2K times of scanning
Electron microscope;
Fig. 2 is nitrogen-doped graphene/MnO that the embodiment of the present invention 1 is prepared2Composite material amplifies 3K times of scanning
Electron microscope;
Fig. 3 is nitrogen-doped graphene/MnO prepared by comparative example 12Composite material scanning electron microscope (SEM) photograph;
Fig. 4 is nitrogen-doped graphene/MnO prepared by the embodiment of the present invention 1~3 and comparative example 1,22The electricity of composite material
Chemical data;
Fig. 5 is nitrogen-doped graphene/MnO prepared by this comparative example 22The scanning electron microscope (SEM) photograph of composite material.
Specific embodiment
The present invention provides a kind of nitrogen-doped graphene/MnO2Composite material, which is characterized in that described to be compounded in N doping
MnO on graphene sheet layer2For linear MnO2, the threadiness MnO210~20nm of diameter;The threadiness MnO2Specific surface
100~200m of product2/g。
The present invention also provides a kind of nitrogen-doped graphene/MnO2The preparation method of composite material, comprising:
1) manganese source compound solution and graphene oxide solution are mixed, obtain the first mixed liquor,
The manganese source compound is hydration manganese acetate;
2) ammonium persulfate is added into the first mixed solution, 1~36h of hydro-thermal reaction under the conditions of 80~200 DEG C obtains nitrogen
Doped graphene/MnO2Composite material.
According to the present invention, the present invention mixes manganese source compound solution and graphene oxide solution, obtains the first mixed liquor;
Wherein, the manganese source compound is preferably four hydration manganese acetates;The manganese source compound solution is preferably the water of manganese source compound
Solution;The concentration of the manganese source compound solution is preferably 5~100g/L, more preferably 10~40g/L;The graphene oxide
Solution is preferably graphene oxide water solution;The concentration of the graphene oxide solution is preferably 2~3.5mg/mL, more preferably
2.5~3mg/mL;The mass ratio of the graphene oxide and manganese source compound is 1:(5~30).The present invention is to mixed mode
There is no particular/special requirement, is uniformly mixed raw material.
According to the present invention, ammonium persulfate is added into the first mixed solution in the present invention, and hydro-thermal is anti-under the conditions of 80~200 DEG C
1~36h is answered, nitrogen-doped graphene/MnO is obtained2Composite material;;Wherein, the concentration of the ammonium persulfate solution be preferably 10~
100g/L, more preferably 30~80g/L, most preferably 50~60g/L;The manganese acetate and the ammonium persulfate mass ratio are preferred
It is 1: (2-10);The temperature of the heating reaction is preferably 80~200 DEG C, and more preferably 120~160 DEG C, the heating reaction
Time be preferably 1~36h, more preferably 10~16 hours, more preferably 12~14 hours.
Nitrogen-doped graphene/MnO provided by the invention2The preparation method of composite material can not only step realization oxidation stone
The reduction of black alkene, nitrogen atom doping and MnO2Load, and the MnO in obtained composite material2For threadiness, and then increase it
The catalytic activity of specific surface area in the composite, the composite material made greatly enhances.
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
Selecting concentration for the graphene oxide water solution and concentration of 2.5g/L is 50g/L manganese acetate aqueous solution, according to oxidation
Graphene is uniformly mixed with manganese acetate mass ratio 1: 15, and 100g/L over cure is added according to manganese acetate and ammonium persulfate mass ratio 1: 3
Acid ammonium solution, then being reacted 12 hours at a temperature of mixture under hydrothermal conditions 120 DEG C, the product deionized water that will be obtained
Washing is for several times until the PH of clear liquid is neutral;Finally by the cold dry end product that obtains of the product washed to get to N doping graphite
Alkene/MnO2Composite material.
The pattern of obtained composite material is detected, the result is shown in Figure 1~Fig. 2, wherein Fig. 1 is the embodiment of the present invention 1
Nitrogen-doped graphene/the MnO being prepared2Composite material amplifies 2K times of scanning electron microscope (SEM) photograph;Fig. 2 is the system of the embodiment of the present invention 1
Standby obtained nitrogen-doped graphene/MnO2Composite material amplifies 3k times of scanning electron microscope (SEM) photograph.It can be seen from the figure that of the invention
MnO in the composite material being prepared2Nano wire mutually wind be staggered into it is porous be similar to bladed structure, nanowire diameter is
10~20nm.Fig. 4 is nitrogen-doped graphene/MnO prepared by the embodiment of the present invention 1~3 and comparative example 1,22Composite material
Electrochemical data, by disk electrode test it can be seen that the compound that embodiment 2 obtains has preferable hydrogen reduction catalytic performance:
Take-off potential is 0.01V, and half wave potential -0.128V electric current is 1.16mA.
Embodiment 2
Selecting concentration for the graphene oxide water solution and concentration of 2g/L is 80g/L manganese acetate aqueous solution, according to oxidation stone
Black alkene is uniformly mixed with manganese acetate mass ratio 1: 25, and 50g/L persulfuric acid is added according to manganese acetate and ammonium persulfate mass ratio 1: 8
Ammonium salt solution, then being reacted 36 hours at a temperature of mixture under hydrothermal conditions 140 DEG C, the product deionized water that will be obtained
Washing is for several times until the PH of clear liquid is neutral;Finally by the cold dry end product that obtains of the product washed to get to N doping graphite
Alkene/MnO2Composite material.
The pattern of obtained composite material is detected, MnO in composite material2Nano wire mutually wind be staggered into it is porous
Similar to bladed structure, nanowire diameter is 10~20nm.By disk electrode test it can be seen that the answering of obtaining of embodiment 1
Closing object has best hydrogen reduction catalytic performance: take-off potential 0.005V, and half wave potential -0.156V electric current is 1.1mA.
Embodiment 3
Selecting concentration for the graphene oxide water solution and concentration of 3g/L is 25g/L manganese acetate aqueous solution, according to oxidation stone
Black alkene is uniformly mixed with manganese acetate mass ratio 1: 7, and 30g/L ammonium persulfate is added according to manganese acetate and ammonium persulfate mass ratio 1: 5
Obtained product is washed with deionized water then reacting 24 hours at a temperature of mixture under hydrothermal conditions 160 DEG C for solution
It washs for several times until the PH of clear liquid is neutral;Finally by the product washed it is cold it is dry obtain end product to get to nitrogen-doped graphene/
MnO2 composite material.
The pattern of obtained composite material is detected, MnO in composite material2Nano wire mutually wind be staggered into it is porous
Similar to bladed structure, nanowire diameter is 10~20nm.By disk electrode test it can be seen that the answering of obtaining of embodiment 1
Closing object has preferable hydrogen reduction catalytic performance: take-off potential is -0.015V, and half wave potential -0.18V electric current is 1.08mA.
Comparative example 1
According to Applied Surface Science, 366 (2016), 552-560, the method for report is prepared nitrogen and mixes
Miscellaneous graphene/MnO2Composite material, preparation flow: 1, the uniform mixed liquor of hydrothermal oxidization graphene and ammonium hydroxide, obtains at 120 DEG C
To the graphene of N doping;2, the uniform NRGO of 50mg ultrasound is added to 0.25M MnSO4With 0.5M KBrO3Homogeneous solution,
Then carrying out power density is 480W cm-2It is 24KHz radioreaction with frequency.
Obtained composite material pattern is detected, as a result sees that Fig. 3, Fig. 3 are that N doping graphite is prepared in comparative example 1
Alkene/MnO2The scanning electron microscope (SEM) photograph of composite material.Fig. 4 is N doping stone prepared by the embodiment of the present invention 1~3 and comparative example 1,2
Black alkene/MnO2The electrochemical data of composite material, by disk electrode test it can be seen that the obtained compound of comparative example 1 have compared with
The hydrogen reduction catalytic performance (negative take-off potential, half wave potential and small electric current) of difference.
Comparative example 2
According to the preparation method of embodiment 1, only manganese source compound is changed into manganese nitrate or manganese sulfate, obtain N doping graphite
Alkene/MnO2Composite material;
Obtained composite material pattern is detected, Fig. 5 is that nitrogen-doped graphene/MnO2 is prepared is multiple for comparative example 2
The scanning electron microscope (SEM) photograph of condensation material the result shows that, MnO2No longer it is nano wire and is bar-like, compound is also no longer class blade knot
Structure.Fig. 4 is nitrogen-doped graphene/MnO prepared by the embodiment of the present invention 1~3 and comparative example 1,22The electrochemistry of composite material
Data, by disk electrode test, it can be seen that the compound that comparative example 1 obtains has poor hydrogen reduction catalytic performance, (negative is risen
Beginning current potential, half wave potential and the smallest electric current).
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (7)
1. a kind of nitrogen-doped graphene/MnO2Composite material, which is characterized in that described to be compounded on nitrogen-doped graphene lamella
MnO2For linear MnO2, the threadiness MnO2Diameter be 10~20nm;
MnO in the composite material2Nano wire mutually wind be staggered into it is porous be similar to bladed structure.
2. a kind of nitrogen-doped graphene/MnO2The preparation method of composite material, comprising:
1) manganese source compound solution and graphene oxide solution are mixed, obtain the first mixed liquor,
The manganese source compound is hydration manganese acetate;
2) ammonium persulfate is added into the first mixed solution, 1~36h of hydro-thermal reaction under the conditions of 80~200 DEG C obtains N doping
Graphene/MnO2Composite material.
3. preparation method according to claim 2, which is characterized in that the quality of the graphene oxide and manganese source compound
Than for 1:(5~30).
4. preparation method according to claim 2, which is characterized in that the concentration of the graphene oxide solution be 2~
3.5g/L。
5. preparation method according to claim 2, which is characterized in that the concentration of the manganese source compound solution be 5~
100g/L。
6. preparation method according to claim 2, which is characterized in that the manganese acetate is with the ammonium persulfate mass ratio
1:(2-10)。
7. preparation method according to claim 2, which is characterized in that the concentration of the ammonium persulfate solution be 10~
100g/L。
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CN109399619B (en) * | 2018-12-31 | 2021-06-04 | 太原理工大学 | Preparation method of nitrogen-doped graphene aerogel |
CN114544739B (en) * | 2022-01-19 | 2024-02-23 | 江苏大学 | MnO (MnO) 2 Preparation method of N-doped graphene electrochemical sensor and zinc ion detection application |
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CN103943371A (en) * | 2014-04-14 | 2014-07-23 | 上海交通大学 | Nitrogen-doped graphene wrapping hydroxyl manganese oxide nanowire composite material and manufacturing method thereof |
CN106076379A (en) * | 2016-06-12 | 2016-11-09 | 南昌航空大学 | A kind of controllable synthesis method of novel graphite alkene Mn oxide nano composite material |
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CN103943371A (en) * | 2014-04-14 | 2014-07-23 | 上海交通大学 | Nitrogen-doped graphene wrapping hydroxyl manganese oxide nanowire composite material and manufacturing method thereof |
CN106076379A (en) * | 2016-06-12 | 2016-11-09 | 南昌航空大学 | A kind of controllable synthesis method of novel graphite alkene Mn oxide nano composite material |
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Title |
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