CN110426431A - A kind of preparation and its application in the opto-electronic device of semiconductor composite nano particle - Google Patents
A kind of preparation and its application in the opto-electronic device of semiconductor composite nano particle Download PDFInfo
- Publication number
- CN110426431A CN110426431A CN201910711090.8A CN201910711090A CN110426431A CN 110426431 A CN110426431 A CN 110426431A CN 201910711090 A CN201910711090 A CN 201910711090A CN 110426431 A CN110426431 A CN 110426431A
- Authority
- CN
- China
- Prior art keywords
- mwnts
- mos
- composite nano
- preparation
- nano particle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000004065 semiconductor Substances 0.000 title claims abstract description 26
- 230000005693 optoelectronics Effects 0.000 title abstract description 5
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 100
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 imidazoles bromide Chemical class 0.000 claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 230000005611 electricity Effects 0.000 claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004146 energy storage Methods 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- 238000007146 photocatalysis Methods 0.000 claims abstract description 4
- 230000001699 photocatalysis Effects 0.000 claims abstract description 4
- 239000011232 storage material Substances 0.000 claims abstract description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 64
- 229910052961 molybdenite Inorganic materials 0.000 claims description 36
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 32
- 239000011684 sodium molybdate Substances 0.000 claims description 18
- 235000015393 sodium molybdate Nutrition 0.000 claims description 18
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 229910017435 S2 In Inorganic materials 0.000 claims 4
- 239000010931 gold Substances 0.000 abstract description 46
- 239000002086 nanomaterial Substances 0.000 abstract description 40
- 238000000034 method Methods 0.000 abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 239000005864 Sulphur Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052737 gold Inorganic materials 0.000 abstract description 4
- 239000003381 stabilizer Substances 0.000 abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002114 nanocomposite Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 239000011532 electronic conductor Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002060 nanoflake Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910003090 WSe2 Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- SDJHDRMYZQFJJO-UHFFFAOYSA-N ethanethioic s-acid;potassium Chemical compound [K].CC(S)=O SDJHDRMYZQFJJO-UHFFFAOYSA-N 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/305—Electrodes, e.g. test electrodes; Half-cells optically transparent or photoresponsive electrodes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
Application the invention discloses a kind of preparation of semiconductor composite nano particle and its in the opto-electronic device prepares the MoS with three-dimensional petal-like structures by hydro-thermal method with (3- mercaptopropyi) the imidazoles bromide of 1,3- bis- as sulphur source and stabilizer2/ GO/o-MWNTs composite nano materials, then gold nanoparticle is carried on the petal-like structures of above-mentioned composite nano materials using in-situ chemical reducing process, by the synergistic effect of nanogold, graphene oxide and oxidation multi-wall carbon nano-tube tube, make Au/MoS obtained2The specific surface area of/GO/o-MWNTs composite nano materials, electric conductivity, catalytic performance increase substantially；And 1,3- bis- (3- mercaptopropyi) imidazoles bromide has good conductive property, to make the photoelectric catalytically active of composite material further increase, therefore, there is very extensive application potential in photocatalysis, solar battery, supercapacitor and lithium electricity energy storage material.
Description
Technical field
The present invention relates to the preparation of technical field of blast furnace ironmaking more particularly to a kind of semiconductor composite nano particle and its
Application in photoelectric device.
Background technique
Molybdenum disulfide (MoS2) it is a kind of transition metal dichalcogenide haveing excellent performance, have similar with graphene two
Layer structure is tieed up, Mo and S atom constitute covalent bond in layer, and structure is sufficiently stable.It is higher due to biggish specific surface area
Catalytic activity and good optical property, MoS2It has been successfully applied to the fields such as energy conversion, storage, catalysis, sensing.However,
MoS2As a kind of typical semiconductor, conductive capability is not ideal enough, and its water solubility is poor, is difficult to be dissolved in water, therefore
MoS2Modification and functionalization for MoS2Using particularly significant.To improve ultra-thin MoS2The photoelectric properties of nanoparticle, grind
The person of studying carefully proposes MoS2Combine to form composite material with other conductive materials (such as metal nanoparticle, carbon nanomaterial)
Its electric conductivity can be enhanced, improve its stability.
Currently, the vertical structure hetero-junctions based on two-dimentional Transition-metal dichalcogenide has had study group to be prepared into now
The report of function, such as: Graphene/MoS2、MoS2/WS2、SnS2/MoS2、WSe2/MoS2Etc., these hetero-junctions are logical mostly
It crosses vapor phase method (CVD) and epitaxial growth method (VDEW) obtains, this method is that successively superposition is grown on clean substrate,
Interface quality is higher, but this method is complex and time-consuming, and experimental facilities is expensive, to limit its development and application.
Therefore, the application it is urgent to provide a kind of preparation of semiconductor composite nano particle and its in the opto-electronic device is to solve above-mentioned technology
Problem.
Summary of the invention
In response to the problems existing in the prior art, the purpose of the present invention is to provide a kind of preparations of semiconductor composite nano particle
And its application in the opto-electronic device, using graphene oxide as substrate, sodium molybdate is molybdenum source, 1,3- bis- (3- mercaptopropyi) imidazoles
Bromide is sulphur source, reducing agent and stability protective agent, and oxide/carbon nanometer tube is raw material, has synthesized three-dimensional petal-shaped using hydro-thermal method
MoS2/ GO/o-MWNTs nanocomposite, and nanogold particle is further deposited to by MoS by chemical in situ reduction method2/
In the lamellar structure of GO/o-MWNTs nanocomposite, pass through nanogold, graphene oxide and oxidation multi-wall carbon nano-tube tube
Synergistic effect, overcomes single MoS2The defect of nano material makes Au/MoS obtained2/ GO/o-MWNTs composite nano materials
Specific surface area, electric conductivity and catalytic performance increase substantially.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of preparation method of semiconductor composite nano particle, includes the following steps:
S1, MWNTs is subjected in strong acid ultrasonic oxidation, is then centrifuged for, washes, dries obtained o-MWNTs；
S2, graphene oxide, o-MWNTs are dissolved in the water, ultrasonic disperse is uniform, then into mixed liquor be added sodium molybdate,
1,3- bis- (3- mercaptopropyi) imidazoles bromide, carries out hydro-thermal reaction after being uniformly mixed, to be centrifuged, washed extremely after reaction
Neutral, dry obtained MoS2/ GO/o-MWNTs black powder is spare；
S3, by MoS obtained above2/ GO/o-MWNTs black powder is dispersed in water, and is rapidly joined after ultrasonic disperse is uniform
HAuCl4Solution stands 20~40min after shaking uniformly, is then centrifuged for, washs, drying obtained Au/MoS2/ GO/o-MWNTs is multiple
Close nanoparticle.
The present invention passes through strong acid first and carries out oxidation processes to multi-walled carbon nanotube, then using graphene oxide as substrate,
Using sodium molybdate as molybdenum source, 1,3- bis- (3- mercaptopropyi) imidazoles bromide is sulphur source, reducing agent and stability protective agent, using hydro-thermal method
Three-dimensional petal-shaped MoS is synthesized2/ GO/o-MWNTs nanocomposite, and further pass through chemical in situ reduction method for nanometer
Gold particle deposits to MoS2In the lamellar structure of/GO/o-MWNTs nanocomposite, wherein oxide/carbon nanometer tube, graphite oxide
Alkene improves the permeability and electric conductivity of composite nanoparticle, and nanogold particle improves the catalytic performance of composite nano materials,
The present invention promotes composite Nano at the same time as electronic conductor with (3- mercaptopropyi) the imidazoles bromide of 1,3- bis- for sulphur source simultaneously
The electric conductivity of material；The present invention overcomes list in the synergistic effect of nanogold, graphene oxide and oxidation multi-wall carbon nano-tube tube
One MoS2The defect of nano material makes Au/MoS obtained2The specific surface area of/GO/o-MWNTs composite nano materials, electric conductivity
And catalytic performance increases substantially.
Wherein, 1,3- bis- (3- mercaptopropyi) imidazoles bromide the preparation method is as follows:
S1, it weighs in the 30mL acetonitrile solution of 0.705g sodium hydride addition imidazoles containing 0.015mol, shape after ice bath reacts three hours
At the acetonitrile suspension of white imidazole natrium.It is added dropwise to containing 0.06mol1, in the 50mL acetonitrile solution of 3- dibromopropane, is increased
Temperature is stirred overnight to 55 DEG C, and contact plate detects reaction process, and rotary evaporation removes acetonitrile after completion of the reaction, and toluene washing is added,
It is spin-dried for obtaining thick pale yellow oily liquids 1,3- bis- (3- bromopropyl) imidazoles bromide；
S2,0.8g1 is weighed, 3- bis- (3- bromopropyl) imidazoles bromide is dissolved in 30mL acetonitrile, and 0.48g thioacetic acid potassium is added, and increases
Temperature is to 50 DEG C, and reaction is overnight.After stopping reaction, a large amount of insoluble white solids of drag are filtered to remove, solvent is spin-dried for and obtains
To product 1, product is dissolved in ethyl alcohol and 6.0mmolNaOH aqueous solution is added by 3- bis- (3- thioacetic acid n-propyl) imidazoles bromide,
After 40 DEG C are stirred to react 4h, pH is adjusted to neutrality with HBr.Centrifugal filtration removes bottom white solid, and revolving removes solvent
Obtain final product 1,3- bis- (3- mercaptopropyi) imidazoles bromide.
Preferably, in step S1, the solid-to-liquid ratio of the MWNTs and strong acid is 1mg:(5~10) mL.
Preferably, it according to volume ratio is 1:0.5~5 that the strong acid, which is the concentrated sulfuric acid and concentrated nitric acid,.
Preferably, in step S1, the centrifugal condition is that 10000r/min is centrifuged 5min.
Preferably, in step S2, the graphene oxide, o-MWNTs, sodium molybdate amount ratio be 1:1~5:10~20.
Preferably, in step S2, the sodium molybdate and 1, the molar ratio of 3- bis- (3- mercaptopropyi) imidazoles bromide be 1:2~
5。
Preferably, in step S2, the hydrothermal temperature is 180~220 DEG C, and the time is 8~12h.
In step S3, the MoS2/ GO/o-MWNTs and HAuCl4Amount ratio be (1~5) mg:1 μm of ol.
Preferably, in step S2, the drying is to be freeze-dried 12h at -30 DEG C.
The present invention also provides the Au/MoS2/ GO/o-MWNTs composite nanoparticle is in photocatalysis, solar battery, super
Application in grade capacitor and lithium electricity energy storage material.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention is provided with (3- mercaptopropyi) the imidazoles bromide of 1,3- bis- as sulphur source and stabilizer by hydro-thermal method preparation
There is the MoS of three-dimensional petal-like structures2Then/GO/o-MWNTs composite nano materials use in-situ chemical reducing process by gold nano
Particle is carried on MoS2On the petal-like structures of/GO/o-MWNTs composite nano materials, pass through nanogold, graphene oxide and oxygen
The synergistic effect of multi-walled carbon nano-tube, to overcome single MoS2The defect of nano material makes Au/MoS obtained2/GO/
The specific surface area of o-MWNTs composite nano materials, electric conductivity, catalytic performance increase substantially.
(2) MoS of the present invention2(3- mercaptopropyi) the imidazoles bromide of 1,3- bis- of Surface-modification of Nanoparticles has good lead
Electrical property, therefore can further improve Au/MoS2The electric conductivity of/GO/o-MWNTs composite nano materials, to make composite wood
The photoelectric catalytically active of material further increases.
(2) present invention in the three-dimensional petal-like structures as made from hydro-thermal method MoS2With nanogold, graphene oxide and
Oxidation multi-wall carbon nano-tube tube forms a kind of novel heterojunction structure, is conducive to the transmission of light induced electron and hole in photoelectrochemical process
Separation, therefore, in photocatalysis, solar battery, supercapacitor and lithium electricity energy storage material have very extensive application
Potentiality.
(3) present invention passes through one step system of hydro-thermal method using (3- mercaptopropyi) the imidazoles bromide of 1,3- bis- as sulphur source and stabilizer
Obtain MoS2/ GO/o-MWNTs composite nano materials have the good characteristics such as controllable, the easy to operate, favorable repeatability of reaction condition.
Detailed description of the invention
(a), (b) are respectively MoS made from embodiment 1 in Fig. 12The transmitted electron of/GO/o-MWNTs nanocomposite
Microscope, scanning electron microscope characterization result.
(a), (b) are respectively Au/MoS made from embodiment 1 in Fig. 22The transmission electricity of/GO/o-MWNTs composite nano materials
Sub- microscope, scanning electron microscope characterization result.
(a), (b), (c), (d) are respectively naked ITO, ITO/MoS in Fig. 32Modified electrode, ITO/MoS2/ GO/o-MWNTs is repaired
Adorn electrode, ITO/Au/MoS2Cyclic voltammetric (CV) comparison diagram of/GO/o-MWNTs modified electrode.
(a), (b), (c) difference ITO/MoS in Fig. 42Modified electrode, ITO/MoS2/ GO/o-MWNTs modified electrode, ITO/
Au/MoS2The i-t curve graph of/GO/o-MWNTs modified electrode.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated；It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention；Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method
And equipment.
The present invention is described in further detail below through specific implementation examples and in conjunction with the accompanying drawings.
Embodiment 1
The present embodiment provides a kind of preparation methods of semiconductor composite nano particle, include the following steps:
S1,5mgMWNTs is subjected to ultrasonic oxidation 2h in 50mL strong acid, then 10000r/min takes solid to use after being centrifuged 5min
It is washed to neutral and dries obtained o-MWNTs at 60 DEG C；Wherein, the strong acid is the concentrated sulfuric acid and concentrated nitric acid according to volume ratio
For 1:3；
S2,5mg graphene oxide, 10mgo-MWNTs are dissolved into 20mL Yu Shuizhong, ultrasonic disperse is uniform, then into mixed liquor
75mg sodium molybdate, 1,3- bis- (3- mercaptopropyi) imidazoles bromide is added, in 200 DEG C of progress hydro-thermal reactions after being uniformly mixed
12h is washed repeatedly to be centrifuged removal supernatant, precipitating water and dehydrated alcohol after reaction until removing undesired impurities, lead to
It crosses and solid powder is collected by centrifugation, and solid powder is placed in -30 DEG C of freeze drying box dry 12h, MoS is made2/GO/o-
MWNTs black powder is spare；The molar ratio of the sodium molybdate and 1,3- bis- (3- mercaptopropyi) imidazoles bromide is 1:3；
S3, by 5mgMoS obtained above2/ GO/o-MWNTs black powder is scattered in 5mL water, and ultrasonic disperse is uniformly rear quick
The HAuCl of 1mL1mmol/L is added4Solution stands 30min after shaking uniformly, is then centrifuged for, washs, drying obtained Au/MoS2/
GO/o-MWNTs composite nanoparticle.
(a), (b) are respectively MoS made from step S2 in Fig. 12The transmitted electron of/GO/o-MWNTs nanocomposite is aobvious
Micro mirror, scanning electron microscope characterization result, by result in figure it is found that MoS2/ GO/o-MWNTs nanocomposite is petal
The three-dimensional spherical structure of shape, by many irregular MoS2Nano flake assembling generates, and wherein graphene oxide is as MoS2Growth
The substrate of layer, o-MWNTs and MoS2It is evenly distributed in the nanometer sheet of graphene oxide and forms three-dimensional petal-like structures, thus
Increase the specific surface area of nanocomposite, and provides more active sites for the deposition of nano Au particle.
(a), (b) are respectively and carry out gold chloride by in-situ chemical reducing process to deposit receiving for nano Au particle modification in Fig. 2
Nano composite material Au/MoS2Transmission electron microscope, the scanning electron microscope characterization knot of/GO/o-MWNTs composite nano materials
Fruit, by result in figure it is found that gold nanoparticle is evenly distributed on MoS2On nano flake, show that nanogold particle is successfully modified
To MoS2/ GO/o-MWNTs composite nanoparticle surface, and MoS2The three-dimensional petal-shaped structure of/GO/o-MWNTs composite nanoparticle
Type is constant, and the successful load of nanogold particle considerably increases can be with the specific surface area of nanocomposite, electric conductivity and light
Electrocatalysis characteristic.
Embodiment 2
The present embodiment provides a kind of preparation methods of semiconductor composite nano particle, include the following steps:
75mg sodium molybdate is dissolved into 20mL Yu Shuizhong, ultrasonic disperse is uniform, then according to sodium molybdate and 1, (the 3- sulfydryl third of 3- bis-
Base) imidazoles bromide molar ratio be 1:3 1,3- bis- (3- mercaptopropyi) imidazoles bromide is added into solution, after being uniformly mixed
In 200 DEG C of progress hydro-thermal reaction 12h, washed repeatedly to be centrifuged removal supernatant, precipitating water and dehydrated alcohol after reaction
Until removing undesired impurities, drying in -30 DEG C of freeze drying box is placed in by the way that solid powder is collected by centrifugation, and by solid powder
MoS is made in 12h2Nano material is spare.
Respectively by MoS made from the present embodiment2MoS made from nano material, embodiment 12/ GO/o-MWNTs composite Nano
Material, Au/MoS2/ GO/o-MWNTs composite nano materials are configured to the dispersion liquid of 5mg/mL, will be each after being protected from light ultrasonic 30min
Uniform be spun on clean ITO electro-conductive glass of dispersion liquid forms ITO/MoS2Modified electrode, ITO/MoS2/ GO/o-MWNTs is repaired
Adorn electrode, ITO/Au/MoS2/ GO/o-MWNTs modified electrode, and dry spare.
(a), (b), (c), (d) are respectively naked ITO, ITO/MoS in Fig. 32Modified electrode, ITO/MoS2/ GO/o-MWNTs is repaired
Adorn electrode, ITO/Au/MoS2Cyclic voltammetric (CV) comparison diagram of/GO/o-MWNTs modified electrode, by result in figure it is found that oxidation
Reduction peak current ITO/Au/MoS2/ GO/o-MWNTs modified electrode > ITO/MoS2/ GO/o-MWNTs modified electrode > ITO/MoS2
Thus modified electrode > naked ITO illustrates that the present invention is made by the collaboration of nanogold, graphene oxide and oxidation multi-wall carbon nano-tube tube
With to overcome single MoS2The defect of nano material makes Au/MoS obtained2The ratio of/GO/o-MWNTs composite nano materials
Surface area, electric conductivity, catalytic performance increase substantially.
(a), (b), (c) difference ITO/MoS in Fig. 42Modified electrode, ITO/MoS2/ GO/o-MWNTs modified electrode, ITO/
Au/MoS2The i-t curve graph of/GO/o-MWNTs modified electrode.Electrolyte used is 5mmol/L potassium ferricyanide solution, used
Bias be -0.3V, the time interval of photoswitch is 10 seconds, and using three-electrode system, working electrode used is filamentary silver, Ag/
AgCl electrode (the KCl solution containing saturation) is used as reference electrode, and platinum (Pt) silk is used as to electrode.
Result can be seen that photoelectric current ITO/Au/MoS from Fig. 42/ GO/o-MWNTs modified electrode > ITO/MoS2/GO/
O-MWNTs modified electrode > ITO/MoS2Modified electrode, the probability that photoelectric current is bigger to illustrate that electron-hole is compound after illumination is fewer,
Illustrate the MoS of three-dimensional petal-like structures in the present invention2With nanogold, graphene oxide and oxidation multi-wall carbon nano-tube tube in energy level knot
Be on structure it is matched, a kind of novel heterojunction structure can be formed, thus be conducive in photoelectrochemical process the transmission of light induced electron and
The separation in hole, therefore can be good at reducing electron-hole recombinations probability, to improve Au/MoS2The light of/GO/o-MWNTs
Electroresponse.
Embodiment 3-6
Embodiment 3-6 provides a kind of preparation method of semiconductor composite nano particle, compared with Example 1, the difference is that,
It changes the step in S2, the sodium molybdate and 1, the molar ratio of 3- bis- (3- mercaptopropyi) imidazoles bromide, in addition to above-mentioned difference, other
Operate all the same, details are not described herein；The photoelectric current result of specific experiment conditional parameter and the modified electrode measured such as following table institute
Show.
| Embodiment | Molar ratio | Photoelectric current (mAcm-2) |
| 3 | 1:1 | 1.68 |
| 4 | 1:2 | 2.15 |
| 5 | 1:5 | 2.38 |
| 6 | 1:6 | 1.57 |
Comparative example 1 and 3~6 result of embodiment are it is found that change the step sodium molybdate described in S2 and 1, (the 3- sulfydryl of 3- bis-
Propyl) molar ratio of imidazoles bromide can be to Au/MoS obtained2The photoelectric conversion efficiency of/GO/o-MWNTs composite nano materials produces
Raw significant impact, when control sodium molybdate and 1, when the molar ratio of 3- bis- (3- mercaptopropyi) imidazoles bromide is in the range of 1:2~5
Au/MoS obtained2The ITO electrode of/GO/o-MWNTs composite nano materials modification all has higher photoelectric current, and works as molybdic acid
The molar ratio of sodium and 1,3- bis- (3- mercaptopropyi) imidazoles bromide Au/MoS obtained when being 1:32/ GO/o-MWNTs composite Nano
The photoelectric current of material reaches maximum.
Embodiment 7-12
Embodiment 7-12 provides a kind of preparation method of semiconductor composite nano particle, and compared with Example 1, difference exists
In, change the step in S2, the graphene oxide, o-MWNTs, sodium molybdate amount ratio, in addition to above-mentioned difference, other operations are equal
Identical, details are not described herein；The photoelectric current result of specific experiment conditional parameter and the modified electrode measured is as shown in the table.
| Embodiment | Amount ratio | Photoelectric current (mAcm-2) |
| 7 | 1:0:15 | 0.95 |
| 8 | 0:1:15 | 0.82 |
| 9 | 1:1:15 | 2.04 |
| 10 | 1:5:15 | 2.31 |
| 11 | 1:2:10 | 2.12 |
| 12 | 1:2:20 | 1.92 |
Comparative example 1 and embodiment 7,8 result of embodiment it is found that the present invention by using graphene oxide as substrate, In
Growth in situ o-MWNTs and MoS in the nanometer sheet of graphene oxide2Three-dimensional petal-like structures are formed, graphene oxide, oxygen are passed through
The synergistic effect of multi-walled carbon nano-tube, to overcome single MoS2The defect of nano material makes Au/MoS obtained2/GO/
The specific surface area of o-MWNTs composite nano materials, electric conductivity, catalytic performance increase substantially.Comparative example 1 and embodiment
9~12 results it is found that change the graphene oxide, o-MWNTs, sodium molybdate amount ratio can be to Au/MoS obtained2/GO/
The photoelectric current of o-MWNTs nanocomposite generates significant impact, when the control graphene oxide, o-MWNTs, sodium molybdate
Amount ratio be 1:1~5:10~20 when, Au/MoS obtained2/ GO/o-MWNTs nanocomposite all has higher light
Electric current illustrates Au/MoS at this time2/ GO/o-MWNTs nanocomposite can significantly reduce photoproduction in photic electrochemical process
The compound probability of electronics and hole, to improve Au/MoS2The photoelectric respone of/GO/o-MWNTs.
Embodiment 13-18
Embodiment 13-18 provides a kind of preparation method of semiconductor composite nano particle, and compared with Example 1, difference exists
In changing the step in S2, the hydrothermal temperature and time, in addition to above-mentioned difference, other operations are all the same, no longer superfluous herein
It states；The photoelectric current result of specific experiment conditional parameter and the modified electrode measured is as shown in the table.
Comparative example 1 and 13~16 result of embodiment it is found that change the step hydrothermal temperature described in S2 can be to system
The Au/MoS obtained2The PhotoelectrocatalytiPerformance Performance of/GO/o-MWNTs composite nano materials generates significant impact, and in step S2
The raising of hydrothermal temperature, Au/MoS obtained2The photoelectric current first increases and then decreases of/GO/o-MWNTs composite nano materials, works as water
Hot temperature Au/MoS obtained when being 200 DEG C2The photoelectric current of/GO/o-MWNTs composite nano materials reaches maximum.
Comparative example 1 and 17~18 result of embodiment it is found that change the step the extension of the hydro-thermal reaction time described in S2,
Au/MoS obtained2The photoelectric current first increases and then decreases of/GO/o-MWNTs composite nano materials, when the hydro-thermal time reaching 10h
Au/MoS obtained2The photoelectric current of/GO/o-MWNTs composite nano materials reaches maximum, continues to extend the hydro-thermal reaction time Au/
MoS2The photoelectric current of/GO/o-MWNTs composite nano materials reduces.
Embodiment 19-21
Embodiment 19-21 provides a kind of preparation method of semiconductor composite nano particle, and compared with Example 1, difference exists
In changing the step in S3, the MoS2/ GO/o-MWNTs and HAuCl4Amount ratio, in addition to above-mentioned difference, other operations are homogeneous
Together, details are not described herein；The photoelectric current result of specific experiment conditional parameter and the modified electrode measured is as shown in the table.
| Embodiment | Amount ratio (mg: μm ol) | Photoelectric current (mAcm-2) |
| 19 | 1:1 | 1.98 |
| 20 | 3:1 | 2.31 |
| 21 | 6:1 | 1.75 |
Comparative example 1 and 19~21 result of embodiment are it is found that with MoS described in step S32/ GO/o-MWNTs with
HAuCl4Amount ratio increase, Au/MoS obtained2The photoelectric current of/GO/o-MWNTs composite nano materials is gradually increased, when it
When amount ratio reaches 5:1, Au/MoS obtained2The PhotoelectrocatalytiPerformance Performance of/GO/o-MWNTs composite nano materials reaches maximum, after
It is continuous to increase MoS2The photoelectric current of the dosage of/GO/o-MWNTs, composite nanoparticle obtained reduces.
Comparative example 1
This comparative example provides a kind of preparation method of semiconductor composite nano particle, compared with Example 1, the difference is that,
In step S2, the drying is to be dried in vacuo 12h at 60 DEG C, and in addition to above-mentioned difference, other operations are all the same, no longer superfluous herein
It states.
By Au/MoS made from this comparative example2/ GO/o-MWNTs composite nano materials are configured to the dispersion liquid of 5mg/mL, keep away
After light ultrasound 30min, uniform be spun on clean ITO electro-conductive glass of dispersion liquid is formed into ITO/Au/MoS2/GO/o-MWNTs
Modified electrode, this its photoelectric current of measurement are 1.58mAcm-2.With 1 Comparative result of embodiment, illustrate the present invention using freeze-drying
The photoelectric catalytically active for being conducive to keep composite nano materials, to reduce the recombination probability of its photo-generate electron-hole.
Comparative example 2
This comparative example provides a kind of preparation method of semiconductor composite nano particle, compared with Example 1, the difference is that,
In step S2, using thiocarbamide as sulphur source and reducing agent, in addition to above-mentioned difference, other operations are all the same, and details are not described herein.
By Au/MoS made from this comparative example2/ GO/o-MWNTs composite nano materials are configured to the dispersion liquid of 5mg/mL, keep away
After light ultrasound 30min, uniform be spun on clean ITO electro-conductive glass of dispersion liquid is formed into ITO/Au/MoS2/GO/o-MWNTs
Modified electrode, this its photoelectric current of measurement are 1.34mAcm-2.With 1 Comparative result of embodiment, illustrate the present invention with 1,3-, bis- (3-
Mercaptopropyi) imidazoles bromide is sulphur source, and the electric conductivity of composite nano materials is promoted at the same time as electronic conductor, therefore it can
The photoelectric catalytically active of composite nano materials is further increased, to reduce the recombination probability of its photo-generate electron-hole.
The above, only of the invention illustrates embodiment, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, under the premise of not departing from the method for the present invention, that makes several changes
It also should be regarded as protection scope of the present invention into supplement；All those skilled in the art, do not depart from spirit of that invention and
In the case where range, using the equivalent variations of a little change, modification and differentiation that disclosed above technology contents are made, it is
Equivalent embodiment of the invention；Meanwhile any equivalent variations that all substantial technologicals according to the present invention do above-described embodiment
Change, modification and differentiation, still fall within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of semiconductor composite nano particle, which comprises the steps of:
S1, MWNTs is subjected in strong acid ultrasonic oxidation, is then centrifuged for, is washed to neutral, the obtained o-MWNTs of drying；
S2, graphene oxide, o-MWNTs are dissolved in the water, ultrasonic disperse is uniform, then into mixed liquor be added sodium molybdate,
1,3- bis- (3- mercaptopropyi) imidazoles bromide, carries out hydro-thermal reaction after being uniformly mixed, to be centrifuged, wash after reaction,
Dry obtained MoS2/ GO/o-MWNTs black powder is spare；
S3, by MoS obtained above2/ GO/o-MWNTs black powder is dispersed in water, and is rapidly joined after ultrasonic disperse is uniform
HAuCl4Solution stands 20 ~ 40min after shaking uniformly, is then centrifuged for, washs, drying obtained Au/MoS2/ GO/o-MWNTs is compound
Nanoparticle.
2. a kind of preparation method of semiconductor composite nano particle according to claim 1, which is characterized in that step S1
In, the solid-to-liquid ratio of the MWNTs and strong acid is 1mg:(5 ~ 10) mL.
3. a kind of preparation method of semiconductor composite nano particle according to claim 1 or 2, which is characterized in that described
It according to volume ratio is 1:0.5 ~ 5 that strong acid, which is the concentrated sulfuric acid and concentrated nitric acid,.
4. a kind of preparation method of semiconductor composite nano particle according to claim 1, which is characterized in that step S1
In, the centrifugal condition is that 10000r/min is centrifuged 5min.
5. a kind of preparation method of semiconductor composite nano particle according to claim 1, which is characterized in that step S2
In, the graphene oxide, o-MWNTs, sodium molybdate amount ratio be 1:1 ~ 5:10 ~ 20.
6. a kind of preparation method of semiconductor composite nano particle according to claim 1, which is characterized in that step S2
In, the sodium molybdate and 1, the molar ratio of 3- bis- (3- mercaptopropyi) imidazoles bromide is 1:2 ~ 5.
7. a kind of preparation method of semiconductor composite nano particle according to claim 1, which is characterized in that step S2
In, the hydrothermal temperature is 180 ~ 220 DEG C, and the time is 8 ~ 12h.
8. a kind of preparation method of semiconductor composite nano particle according to claim 1, which is characterized in that step S3
In, the MoS2/ GO/o-MWNTs and HAuCl4Amount ratio be (1 ~ 5) mg:1 μm of ol.
9. a kind of preparation method of semiconductor composite nano particle according to claim 1, which is characterized in that step S2
In, the drying is to be freeze-dried 12h at -30 DEG C.
10. a kind of preparation method of semiconductor composite nano particle according to claim 1, which is characterized in that the Au/
MoS2/ GO/o-MWNTs composite nanoparticle answering in photocatalysis, solar battery, supercapacitor and lithium electricity energy storage material
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910711090.8A CN110426431A (en) | 2019-08-02 | 2019-08-02 | A kind of preparation and its application in the opto-electronic device of semiconductor composite nano particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910711090.8A CN110426431A (en) | 2019-08-02 | 2019-08-02 | A kind of preparation and its application in the opto-electronic device of semiconductor composite nano particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110426431A true CN110426431A (en) | 2019-11-08 |
Family
ID=68413850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910711090.8A Pending CN110426431A (en) | 2019-08-02 | 2019-08-02 | A kind of preparation and its application in the opto-electronic device of semiconductor composite nano particle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110426431A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115078496A (en) * | 2022-05-07 | 2022-09-20 | 广东省科学院生物与医学工程研究所 | Nano composite material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6432320B1 (en) * | 1998-11-02 | 2002-08-13 | Patrick Bonsignore | Refrigerant and heat transfer fluid additive |
| CN109569665A (en) * | 2018-11-28 | 2019-04-05 | 东莞理工学院 | A kind of preparation method and application of copper sulfide/vulcanization molybdenum composite material |
-
2019
- 2019-08-02 CN CN201910711090.8A patent/CN110426431A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6432320B1 (en) * | 1998-11-02 | 2002-08-13 | Patrick Bonsignore | Refrigerant and heat transfer fluid additive |
| CN109569665A (en) * | 2018-11-28 | 2019-04-05 | 东莞理工学院 | A kind of preparation method and application of copper sulfide/vulcanization molybdenum composite material |
Non-Patent Citations (2)
| Title |
|---|
| 吴晓惠 等: "金纳米粒子修饰的三维花状二硫化钼复合材料的制备及其用于检测过氧化氢的研究", 《分析测试学报》 * |
| 王星: "离子液体增强的肿瘤标志物分子印迹纳米传感器", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑（月刊）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115078496A (en) * | 2022-05-07 | 2022-09-20 | 广东省科学院生物与医学工程研究所 | Nano composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ren et al. | Facile synthesis of PtAu nanoparticles supported on polydopamine reduced and modified graphene oxide as a highly active catalyst for methanol oxidation | |
| Xu et al. | A graphene oxide–molecular Cu porphyrin-integrated BiVO 4 photoanode for improved photoelectrochemical water oxidation performance | |
| Badhulika et al. | Graphene hybrids: synthesis strategies and applications in sensors and sensitized solar cells | |
| Zheng et al. | Flowerlike molybdenum sulfide/multi-walled carbon nanotube hybrid as Pt-free counter electrode used in dye-sensitized solar cells | |
| Zhang et al. | Facile synthesis of heterostructured nickel/nickel oxide wrapped carbon fiber: flexible bifunctional gas-evolving electrode for highly efficient overall water splitting | |
| Zhang et al. | A novel Z-scheme ZnIn2S4/WO3 photocatalyst based photoelectrochemical immunosensor for the sensitive detection of prostate specific antigen | |
| Wang et al. | MnO2 and carbon nanotube co-modified C3N4 composite catalyst for enhanced water splitting activity under visible light irradiation | |
| CN107393725A (en) | A kind of carbon material supported NiCo of porous, electrically conductive2O4Composite and its preparation method and application | |
| CN102504533B (en) | Biomolecular functionalized graphene/gold nano-particle composite film and preparation method thereof | |
| CN104538642B (en) | Sulfur-doped carbon nanotube Pt-loaded catalyst for direct methanol fuel cell and preparation method of catalyst | |
| Chen et al. | Efficient charge separation between ZnIn 2 S 4 nanoparticles and polyaniline nanorods for nitrogen photofixation | |
| Zhang et al. | Improved photoelectrocatalytic hydrogen generation through BiVO4 quantum-dots loaded on nano-structured SnO2 and modified with carbon quantum-dots | |
| CN105070924B (en) | A kind of DMFC molybdenum sulfide functionalized carbon nano-tube carries Pt catalyst and preparation method thereof | |
| CN108760851B (en) | Application of CuS/GO/MWCNTs composite nanoparticle modified electrode in electrochemical detection of hydrogen peroxide | |
| Zhang et al. | MXene-based mixed-dimensional Schottky heterojunction towards self-powered flexible high-performance photodetector | |
| CN108232213A (en) | A kind of nitrogen-doped graphene-carbon nanotube-cobaltosic oxide hybrid material and preparation method thereof | |
| Elrouby | Electrochemical applications of carbon nanotube | |
| Zha et al. | Coconut shell carbon nanosheets facilitating electron transfer for highly efficient visible-light-driven photocatalytic hydrogen production from water | |
| Behara et al. | Synchronization of charge carrier separation by tailoring the interface of Si–Au–TiO2 heterostructures via click chemistry for PEC water splitting | |
| CN109244484A (en) | A kind of preparation method of porous graphene/carbon nano tube flexible self-supported membrane material | |
| Rashed et al. | Surface modification of CuO nanoparticles with conducting polythiophene as a non-enzymatic amperometric sensor for sensitive and selective determination of hydrogen peroxide | |
| Chen et al. | One-step synthesis of Pt nanoparticles/reduced graphene oxide composite with enhanced electrochemical catalytic activity | |
| Chen et al. | N-Doped nanodots/np+-Si photocathodes for efficient photoelectrochemical hydrogen generation | |
| Xu et al. | The one-step hydrothermal synthesis of CdS nanorods modified with carbonized leaves from Japanese raisin trees for photocatalytic hydrogen evolution | |
| Yousefi et al. | Decoration of g-C3N4 by inorganic cluster of polyoxometalate through organic linker strategy for enhancing photoelectrocatalytic performance under visible light |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191108 |
|
| RJ01 | Rejection of invention patent application after publication |