CN106984354A - A kind of preparation method and applications of palladium doped graphite phase carbon nitride nano material - Google Patents
A kind of preparation method and applications of palladium doped graphite phase carbon nitride nano material Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000010439 graphite Substances 0.000 title claims abstract description 21
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 21
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 14
- 239000008103 glucose Substances 0.000 claims abstract description 14
- 210000002966 serum Anatomy 0.000 claims abstract description 12
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 6
- 239000001509 sodium citrate Substances 0.000 claims abstract description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 6
- 230000000007 visual effect Effects 0.000 claims abstract description 6
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000002845 discoloration Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000001514 detection method Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 102000004190 Enzymes Human genes 0.000 abstract description 5
- 108090000790 Enzymes Proteins 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 238000012800 visualization Methods 0.000 abstract description 3
- 206010012601 diabetes mellitus Diseases 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- 229940088598 enzyme Drugs 0.000 description 4
- 235000019420 glucose oxidase Nutrition 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical class CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 description 2
- 108010015776 Glucose oxidase Proteins 0.000 description 2
- 239000004366 Glucose oxidase Substances 0.000 description 2
- 102000003992 Peroxidases Human genes 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229940116332 glucose oxidase Drugs 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 108040007629 peroxidase activity proteins Proteins 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100285000 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) his-3 gene Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000126 substance 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
-
- B01J35/393—
-
- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
Abstract
The invention discloses a kind of preparation method and applications of palladium doped graphite phase carbon nitride nano material.The present invention prepares graphite phase carbon nitride nanometer sheet first with melamine, then adds H2PdCl4Solution, sodium borohydride solution and sodium citrate solution, are made Pd doping g C3N4 nano materials.Palladium doped graphite phase carbon nitride nano material produced by the present invention has similar biology enzyme（HRPO）Catalytic activity energy, establish a kind of visual rapid detection method of highly sensitive glucose in serum, method has sensitivity high（Up to 0.0735mM）, high specificity, strong, simple and quick and inexpensive anti-Matrix effects the advantages of, available in human serum sample trace glucose molecule live quick visualization detection, provide a kind of fast method for the clinical detection of diabetes.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, and in particular to a kind of palladium doped graphite phase carbon nitride nano material
Preparation method and applications.
Background technology
It is used as a kind of non-metal semiconductor materials, graphite phase carbon nitride（g-C3N4）With nontoxic, chemical stability height, system
Standby technique is simple, cheap and the advantages of excited by visible light.Hexagonal crystal system g-C3N4It is former by N between each unit in molecule
Son linking, the N atoms of joining place are with sp3Its in the form of hydridization and the C atoms formation covalent bond in adjacent 3 units, unit
His 3 N atoms are with sp2Hydridization form and adjacent side C atoms formation covalent bond.g-C3N4In material, N atoms are common for C-N-C hexatomic rings
Yoke system provides primary condition, while additionally providing a pair of lone pair electrons.So g-C3N4With certain ratio surface basic site
Put and possess stronger electron rich performance, this causes the material to show huge potentiality in the application aspect of electrochemistry.
g-C3N4As a kind of lamellar compound, its specific surface area is larger, not only the property with semiconductor, also with compared with
Strong photoluminescent property, the fluorescent optical sensor high available for sensitivity is built.Meanwhile, studies have reported that g-C3N4One kind can be used as
Photochemical catalyst is used for hydrogen production by water decomposition.Recently, some researchs also show graphite phase carbon nitride（g-C3N4）Also have some similar
Biology enzyme（HRPO）Catalytic activity, available for the structure of visualization bio-sensing new detecting technique, but merely
G-C3N4Similar HRPO activity it is relatively low, it is relatively low for building sensitivity during visual biosensor, it is impossible to full
Foot needs.Many researchs show simultaneously, by controlling g-C3N4Shape, introduces hetero atom such as Au, Ag and Fe etc. are to g-C3N4
Modification is doped, g-C can be improved3N4Catalytic activity.In the present invention, we use transition metal palladium（Pd）Come the g- that adulterates
C3N4Material, is prepared for Pd doping g-C3N4 nano materials（g-C3N4-PdNPs）, prepared Pd doping g-C3N4Nano material
（g-C3N4-PdNPs）With superpower similar biology enzyme（HRPO）Catalytic activity, available for build it is highly sensitive can
Depending on changing biology sensor.
The content of the invention
It is an object of the invention in view of the shortcomings of the prior art, providing a kind of palladium doped graphite phase carbon nitride nano material
Preparation method and applications.Palladium doped graphite phase carbon nitride nano material produced by the present invention has some similar biology enzymes（It is peppery
Root peroxidase）Catalytic activity energy catalyzing hydrogen peroxide aoxidize 3,3', 5,5'- tetramethyl benzidines and produce discoloration, for can
Depending on changing the content of detection glucose in serum and the structure of highly sensitive visible sensor.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method of palladium doped graphite phase carbon nitride nano material, specifically includes following steps：
（1）g-C3N4The preparation of nanometer sheet：Take melamine in an alumina crucible with cover, be placed on Muffle furnace
In, 600 DEG C are warming up to, and 2h is incubated, obtain block g-C3N4；By block g-C3N4It is ground into powder, takes powdered g-C3N4
It is dissolved in deionized water, ultrasonic 10h；Obtained solution is centrifuged, the light yellow clear liquid in upper strata is taken, size is obtained for 70-
200nm g-C3N4Nanometer sheet dispersion liquid；
（2）Pd doping g-C3N4The preparation of nano material：Take step（1）The g-C3N4 nanometer sheet dispersion liquids of synthesis, by its ultrasound
After 0.5 h, 0.1M H are added under agitation2PdCl4Solution, then 0.5 h is stirred at room temperature obtains suspension；In suspension
The sodium borohydride solution of 0.04M brand-new is rapidly joined, 20min is continuously stirred, then, is added dropwise in gained suspension
After 0.01 M sodium citrate solutions, 0.5 h of stirring, ultrasonic 10min；Dispersion is centrifuged, thoroughly cleaned with secondary water, is obtained
To Pd doping g-C3N4Nano material（g-C3N4-PdNPs）.
Step（1）In heating rate be 2.3 DEG C/min.
Step（1）In obtained g-C3N4Nanometer sheet dispersion liquid concentration is 1g/L.
Step（2）In, g-C3N4Nanometer sheet dispersion liquid, H2PdCl4Solution, sodium borohydride solution and sodium citrate solution
Volume ratio is 500:1:15:20.
Obtained Pd doping g-C3N4In nano material, Pd nano particle size is 3-7nm.
The present invention is also protected using palladium doped graphite phase carbon nitride applications to nanostructures made from the above method, described
Palladium doped graphite phase carbon nitride nano material energy catalyzing hydrogen peroxide aoxidizes 3,3', 5,5'- tetramethyl benzidines and produces discoloration, uses
In the content and the structure of highly sensitive visible sensor of Visual retrieval glucose in serum.
The beneficial effects of the present invention are：Present invention transition metal palladium（Pd）Come the g-C that adulterates3N4Material, is prepared for Pd and mixes
Miscellaneous g-C3N4Nano material (g-C3N4- PdNPs), prepared Pd doping g-C3N4Nano material has superpower similar biology enzyme
（HRPO）Catalytic activity, and stability is good（Normal temperature can be placed 3 months and never degenerated）, solve simple g-C3N4
Similar HRPO activity it is low, and biological HRPO heat endurance is poor, price height, can not preserve for a long time
Shortcoming.Prepared Pd doping g-C3N4Nano material（g-C3N4-PdNPs）Alternative biological HRPO, its is similar peppery
The catalytic activity of root peroxidase is simple Technique of Nano Pd（PdNPs）8 times, can efficient catalytic hydrogen peroxide（H2O2）Aoxidize 3,3',
5,5'- tetramethyl benzidines（TMB）Discoloration is produced, for building in highly sensitive visible sensor and human serum sample
The live quick visualization detection of trace glucose molecule, a kind of fast method is provided for the clinical detection of diabetes.
Brief description of the drawings
Fig. 1 is prepared g-C3N4The transmission electron microscope phenogram of-PdNPs nano materials；
Fig. 2 is prepared g-C3N4- PdNPs, simple g-C3N4With simple PdNPs catalytic performance comparison diagram（It is catalyzed peroxide
Change hydroxide TMB and produce discoloration）；
G-C prepared by Fig. 33N4Solution colours and UV absorption of-the PdNPs in trace glucose in detecting blood serum sample
Spectrogram；
G-C prepared by Fig. 43N4The color of-PdNPs solution when detecting different glucose standard liquid, and concentration-
A650 standard working curves.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment
Pd doping g-C with superpower similar HRPO catalytic activity3N4Nano material（g-C3N4-PdNPs）'s
Specific preparation process is as follows：
（1）Graphite phase carbon nitride is prepared using melamine（g-C3N4）Nanometer sheet：5g melamines are taken in an oxygen with cover
Change in aluminium crucible, be placed in Muffle furnace, 600 DEG C are risen to from 25 DEG C with the 2.3 DEG C/min rate of heat addition, and at 600 DEG C
2h is heated, obtain block g-C3N4.By block g-C3N4It is ground into powder, takes the powdered g-C of 100mg3N4100mL is dissolved in go
In ionized water, ultrasonic 10h.Obtained solution is centrifuged, the light yellow clear liquid in upper strata is taken, the g- that size is 70-200nm is obtained
C3N4Nanometer sheet dispersion liquid.
（2）Pd doping g-C3N4Nano material（g-C3N4-PdNPs）Preparation：The size for taking the above-mentioned synthesis of 5ml is 70-
200nm g-C3N4Nanometer sheet dispersion liquid, after its ultrasonic 0.5 h, adds 10 μ L 0.1M H under agitation2PdCl4Solution.Again
0.5 h is stirred at room temperature.The sodium borohydride solution for the brand-new that 150 μ L concentration are 0.04M is rapidly joined in suspension, even
Continuous stirring 20min, then, is added dropwise 200 μ L concentration for 0.01 M sodium citrate solutions, stirring 0.5 in above-mentioned suspension
After h, ultrasonic 10min.Dispersion is centrifuged, thoroughly cleaned with secondary water, Pd doping g-C is obtained3N4Nano material（g-
C3N4-PdNPs）（g-C3N4Nanometer chip size is 70-200nm；Pd nano particle size is 3-7nm）.Finally, by obtained g-
C3N4- PdNPs is dispersed in 5ml secondary water again, and 5 DEG C of preservations are used.
The prepared Pd doping g-C with superpower similar HRPO catalytic activity3N4Nano material（g-C3N4-
PdNPs）In the specifically used process and mode of Visual retrieval glucose in serum content：
（1）The glucose standards solution of 7 100 μ L various concentrations is taken in the range of the mM of concentration 0 to 1mM, it is dense with 100 μ L respectively
Spend the GOx for 10mg/ml（Glucose oxidase）Solution is mixed, and 0.5h is incubated in 37 DEG C of constant-temperature metal bath.To after reaction
Solution in sequentially add 100 μ L concentration for 50mM, the PB buffer solutions of pH=5.5,50 μ L concentration are 4mM TMB solution, 50 μ L
G-C obtained by the present invention3N4- PdNPs solution, places 0.5h by observing color by bore hole after 20 min of shaking after shaking
Change determines absorbance of the wavelength in 650nm by ultraviolet specrophotometer（A650）, by abscissa of concentration, A650 be vertical
Coordinate makes standard working curve, with the standard of comparing.
（2）The detection of glucose content in blood serum sample.100 μ L blood serum samples are taken, are respectively 10mg/ with 100 μ L concentration
Ml GOx（Glucose oxidase）Solution is mixed, and 0.5h is incubated in 37 DEG C of constant-temperature metal bath.Into reacted solution according to
100 μ L concentration of secondary addition are 50mM, and the PB buffer solutions of pH=5.5,50 μ L concentration are 4mM TMB solution, and the 50 μ L present invention are made
The g-C obtained3N40.5h is placed after-PdNPs solution, shaking.Then, color change is observed by bore hole, compares various concentrations above
Glucose standards solution color, the content of glucose in visual detection blood serum sample；Or surveyed by ultraviolet specrophotometer
Standing wave length is in 650nm absorbances（A650）, with reference to above-mentioned standard working curve, obtain the content of glucose in blood serum sample.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (6)
1. a kind of preparation method of palladium doped graphite phase carbon nitride nano material, it is characterised in that：Specifically include following steps：
（1）g-C3N4The preparation of nanometer sheet：Take melamine in an alumina crucible with cover, be placed in Muffle furnace,
600 DEG C are warming up to, and is incubated 2h, block g-C is obtained3N4；By block g-C3N4It is ground into powder, takes powdered g-C3N4It is dissolved in
In deionized water, ultrasonic 10h；Obtained solution is centrifuged, the light yellow clear liquid in upper strata is taken, it is 70-200nm's to obtain size
g-C3N4Nanometer sheet dispersion liquid；
（2）Pd doping g-C3N4The preparation of nano material：Take step（1）The g-C3N4 nanometer sheet dispersion liquids of synthesis, by its ultrasound
After 0.5 h, 0.1M H are added under agitation2PdCl4Solution, then 0.5 h is stirred at room temperature obtains suspension；In suspension
The sodium borohydride solution of 0.04M brand-new is rapidly joined, 20min is continuously stirred, then, is added dropwise in gained suspension
After 0.01 M sodium citrate solutions, 0.5 h of stirring, ultrasonic 10min；Dispersion is centrifuged, thoroughly cleaned with secondary water, is obtained
To Pd doping g-C3N4Nano material.
2. the preparation method of palladium doped graphite phase carbon nitride nano material according to claim 1, it is characterised in that：Step
（1）In heating rate be 2.3 DEG C/min.
3. the preparation method of palladium doped graphite phase carbon nitride nano material according to claim 1, it is characterised in that：Step
（1）In obtained g-C3N4Nanometer sheet dispersion liquid concentration is 1g/L.
4. the preparation method of palladium doped graphite phase carbon nitride nano material according to claim 1, it is characterised in that：Step
（2）In, g-C3N4Nanometer sheet dispersion liquid, H2PdCl4The volume ratio of solution, sodium borohydride solution and sodium citrate solution is 500:
1:15:20。
5. the preparation method of palladium doped graphite phase carbon nitride nano material according to claim 1, it is characterised in that：It is made
Pd doping g-C3N4In nano material, Pd nano particle size is 3-7nm.
6. palladium doped graphite phase carbon nitride applications to nanostructures made from a kind of preparation method as claimed in claim 1, its
It is characterised by：The palladium doped graphite phase carbon nitride nano material energy catalyzing hydrogen peroxide aoxidizes 3,3', 5,5'- tetramethyl biphenyls
Amine produces discoloration, content and the structure of highly sensitive visible sensor for Visual retrieval glucose in serum.
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Cited By (8)
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| CN108273541A (en) * | 2018-03-19 | 2018-07-13 | 福州大学 | A kind of green high-efficient prepares the methods and applications of graphite phase carbon nitride nanometer sheet |
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| CN109187677A (en) * | 2018-07-09 | 2019-01-11 | 福建师范大学 | A kind of Pt/g-C3N4Composite material, electrochemical sensor and preparation method thereof, purposes |
| CN109351364A (en) * | 2018-10-18 | 2019-02-19 | 南昌航空大学 | A kind of preparation method and applications of graphene/class graphite phase carbon nitride/Pd nano particle multi-level nano-structure composite material |
| CN109709182A (en) * | 2019-03-04 | 2019-05-03 | 济南大学 | A kind of g-C3N4-MnO2The photic electrochemical process super sensitivity detection glutathione of nanocomposite |
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