CN107201225A - Zn-Ag-In-S quantum dots, the catalyst based on the quantum dot and optoelectronic pole and its preparation - Google Patents
Zn-Ag-In-S quantum dots, the catalyst based on the quantum dot and optoelectronic pole and its preparation Download PDFInfo
- Publication number
- CN107201225A CN107201225A CN201610153039.6A CN201610153039A CN107201225A CN 107201225 A CN107201225 A CN 107201225A CN 201610153039 A CN201610153039 A CN 201610153039A CN 107201225 A CN107201225 A CN 107201225A
- Authority
- CN
- China
- Prior art keywords
- quantum dots
- source compound
- preparation
- quantum
- optoelectronic pole
- 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
- 239000002096 quantum dot Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 230000005693 optoelectronics Effects 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005864 Sulphur Substances 0.000 claims abstract description 9
- 108010024636 Glutathione Proteins 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229960003180 glutathione Drugs 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 229910052738 indium Inorganic materials 0.000 claims abstract description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 7
- 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 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 239000011943 nanocatalyst Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- LGHOYKSQIQISBI-UHFFFAOYSA-N acetic acid;indium Chemical compound [In].CC(O)=O LGHOYKSQIQISBI-UHFFFAOYSA-N 0.000 claims 1
- 230000005622 photoelectricity Effects 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 26
- 239000001257 hydrogen Substances 0.000 abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 24
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 238000007146 photocatalysis Methods 0.000 abstract description 15
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 239000003426 co-catalyst Substances 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 238000006303 photolysis reaction Methods 0.000 abstract description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 229910052961 molybdenite Inorganic materials 0.000 description 7
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 241000165940 Houjia Species 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- YZASAXHKAQYPEH-UHFFFAOYSA-N indium silver Chemical compound [Ag].[In] YZASAXHKAQYPEH-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960002663 thioctic acid Drugs 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
- C09K11/621—Chalcogenides
- C09K11/623—Chalcogenides with zinc or cadmium
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
-
- 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
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electrochemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of Zn Ag In S quantum dots, the catalyst based on the quantum dot and optoelectronic pole and its preparation.The preparation method of described Zn Ag In S quantum dots, it is characterised in that including：Zinc source compound, silver-colored source compound, indium source compound and glutathione are mixed, pH is adjusted, the aqueous solution containing sulphur source compound is added, heats up and is cooled down after stirring at this temperature, add ethanol, centrifuge, gained solid is Zn Ag In S quantum dots.The Zn Ag In S quantum dots of the present invention are nontoxic, with the efficient ability for realizing photolysis water hydrogen under conditions of without co-catalyst, with good visible absorption property, visible light wave range photocatalysis hydrogen production quantum efficiency up to more than 20%.
Description
Technical field
The present invention relates to Zn-Ag-In-S quantum dots, the catalyst based on the quantum dot and optoelectronic pole and its preparation,
Belong to nano material to prepare and the photocatalysis field based on nano material.
Background technology
With the fast development and the continuous growth of population of global economy, the consumption of fossil fuel also significantly increases
Plus, the thing followed is also brought sternly except the consumption of the fuel that supply falls short of demand to the environment that we depend on for existence
The threat of weight.Therefore, the new green energy resource of Devoting Major Efforts To Developing turns into survival and development of mankind more urgent task, its
Middle H2Extensive research has been obtained as a kind of environment-friendly type new energy of nontoxic pollution-free.
TiO was found since 19722Can be since photoelectrocatalysis hydrogen manufacturing, researcher develops substantial amounts of green wood
Material, in the hope of the high photo-quantum efficiency of acquisition, the photocatalysis hydrogen production effect of high stability, wherein, quantum dot is used as one
The nano material with quantum size effect is planted also to be applied in photoelectrocatalysis hydrogen manufacturing.At present, it is substantial amounts of to be based on
The material of quantum dot optoelectronic catalyzing manufacturing of hydrogen all employ cadmium source, and cadmium is a kind of highly toxic carcinogen, and this just gives
The practical application of this class quantum dot brings great difficulty；And these systems need co-catalyst just mostly
The purpose of photocatalysis hydrogen production can be realized.Therefore, the quantum dot for preparing novel non-toxic is applied to photoelectrocatalysis hydrogen manufacturing just
A major challenge as this field.
The content of the invention
It is an object of the invention to provide a kind of Zn-Ag-In-S quantum dots, the catalyst based on the quantum dot and
Optoelectronic pole and its preparation.
In order to achieve the above object, the invention provides a kind of preparation method of Zn-Ag-In-S quantum dots, its
It is characterised by, including：
Step 1：Zinc source compound, silver-colored source compound, indium source compound and glutathione are added to the water, obtained
To mixed liquor A；
Step 2：The pH value of mixed liquor A in regulating step 1 is 7-10, and addition contains sulphur source compound
The aqueous solution, obtains mixed liquid B；
Step 3：The mixed liquid B that step 2 is obtained is warming up to 70-100 DEG C and stirs 3-5h at this temperature
After cool down, add ethanol, centrifuge, gained solid is Zn-Ag-In-S quantum dots.
Preferably, described zinc source compound is zinc acetate, and described silver-colored source compound is silver nitrate, described
Indium source compound is indium acetate, and described sulphur source compound is vulcanized sodium.
Preferably, in described mixed liquid B, zinc source compound, silver-colored source compound, indium source compound, paddy
The mol ratio of the sweet peptide of Guang and sulphur source compound is 2-6: 1: 5-10: 50-100: 10-20.
Preferably, in described mixed liquor A, the ratio of zinc source compound and water is 1mol: 100-200L.
Preferably, the concentration of the aqueous solution containing sulphur source compound is 0.03-0.06mol/L.
Preferably, in described step 3, the volume ratio of mixed liquid B and ethanol is 1: 1-3.
Preferably, it is described to be cooled to be cooled to room temperature.
Preferably, described step 3 also includes purifying the Zn-Ag-In-S quantum dots of gained, and described carries
It is pure including：Washed, dried with ethanol.
Present invention also offers the Zn-Ag-In-S prepared by the preparation method of above-mentioned Zn-Ag-In-S quantum dots
Quantum dot.
Present invention also offers the catalyst based on Zn-Ag-In-S quantum dots, it is characterised in that including nanometer
Catalyst and above-mentioned Zn-Ag-In-S quantum dots.
Preferably, described nanocatalyst is MoS2Catalyst, C3N4Catalyst or graphen catalyst.
Preferably, the mass ratio of described Zn-Ag-In-S quantum dots and nanocatalyst is 1: 0.0015-0.012.
Present invention also offers the preparation method of the above-mentioned catalyst based on Zn-Ag-In-S quantum dots, it is special
Levy and be, including：Above-mentioned Zn-Ag-In-S quantum dots are placed in the aqueous solution of nanocatalyst, ultrasound
Processing, obtains the catalyst based on Zn-Ag-In-S quantum dots.
Present invention also offers the optoelectronic pole based on Zn-Ag-In-S quantum dots, including：Optoelectronic pole matrix, institute
The surface for the optoelectronic pole matrix stated is provided with above-mentioned Zn-Ag-In-S quantum dots.
Preferably, described optoelectronic pole matrix is NiO electrodes, NiS electrodes, TiO2Electrode or SnO electrodes.
Present invention also offers the preparation method of the above-mentioned optoelectronic pole based on Zn-Ag-In-S quantum dots, it is special
Levy and be, including：Optoelectronic pole matrix is dipped into the aqueous solution containing above-mentioned Zn-Ag-In-S quantum dots
2-24h, takes out drying, obtains the optoelectronic pole based on Zn-Ag-In-S quantum dots.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, Zn-Ag-In-S quantum dots of the invention are nontoxic, with efficient real under conditions of without co-catalyst
The ability of existing photolysis water hydrogen, with good visible absorption property, in the photocatalysis hydrogen production of visible light wave range
Quantum efficiency is up to more than 20%.
2nd, the preparation technology of Zn-Ag-In-S quantum dots of the invention is simple, easy to operate, without high temperature with it is lazy
Property gas protection, with large-scale production the characteristics of.
3rd, quantum dot prepared by the present invention and two dimension MoS2、C3N4The catalyst prepared is combined etc. nano material
Photocatalysis efficiency be up to 40%；The photocathode of preparation also shows the performance of excellent photoelectrocatalysis hydrogen manufacturing.
Brief description of the drawings
Fig. 1 is the uv-visible absorption spectra (a) of Zn-Ag-In-S quantum dots, fluorescence spectra (b) and X-ray diffraction
Collection of illustrative plates (c).
Fig. 2 is the photocatalysis hydrogen production result figure of Zn-Ag-In-S quantum dots at different conditions.
Fig. 3 is Zn-Ag-In-S quantum dots and other nano materials (MoS2、C3N4) light of composite that is formed urges
Change hydrogen manufacturing result figure.
Fig. 4 is the photoelectrocatalysis hydrogen manufacturing result figure of Zn-Ag-In-S quantum dots.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate
The present invention rather than limitation the scope of the present invention.In addition, it is to be understood that read the content of the invention lectured it
Afterwards, those skilled in the art can make various changes or modifications to the present invention, and these equivalent form of values equally fall within this
Apply for appended claims limited range.
Embodiment 1
Zn-Ag-In-S quantum dots (nAg∶nIn=1: preparation method 20), concretely comprise the following steps：
Weigh zinc acetate 0.37g (2.0mmol), silver nitrate 67.90g (0.2mmol), indium acetate 1.16g (4.0
Mmol) add with glutathione 11.94g (40.0mmol) and fill three mouthfuls of 500mL of 250mL deionized waters
In flask, mixed liquor A is obtained, pH to 8.5 is adjusted with 0.2M sodium hydrate aqueous solution, adds afterwards molten
In the vulcanized sodium (0.62g, 8.0mmol) of 10mL water, mixed liquid B is obtained；Mixed liquid B is warming up to 100
DEG C and be cooled to room temperature after being stirred vigorously 4.5 hours at this temperature with 1500rpm rotating speed；Into mixed liquor
250mL ethanol is added, orange solids have been arrived in centrifugation, after being washed twice with ethanol, in 40 DEG C
Orange/yellow solid is dried to obtain in vacuum drying oven.If Fig. 1 is the ultraviolet-visible of the Zn-Ag-In-S quantum dots prepared
Absorption, fluorescence spectra and X ray diffracting spectrum.
Embodiment 2
Zn-Ag-In-S quantum dots (nAg∶nIn=1: preparation method 10), concretely comprise the following steps：
Weigh zinc acetate 0.37g (2.0mmol), silver nitrate 67.90g (0.4mmol), indium acetate 1.16g (4.0
Mmol) add with glutathione 11.94g (40.0mmol) and fill three mouthfuls of 500mL of 250mL deionized waters
Mixed in flask, obtain mixed liquor A, pH to 8.5, Zhi Houjia is adjusted with 0.2M sodium hydrate aqueous solution
Enter to be dissolved in the vulcanized sodium (0.62g, 8.0mmol) of 10mL water, obtain mixed liquid B；Mixed liquid B is heated up
Room temperature is cooled to 100 DEG C and after being stirred vigorously 4.5 hours at this temperature with 1500rpm rotating speed；To mixed
The ethanol that 250mL is added in liquid is closed, orange solids have been arrived in centrifugation, after being washed twice with ethanol, in
Orange/yellow solid is dried to obtain in 40 DEG C of vacuum drying oven.If Fig. 1 is the purple of the Zn-Ag-In-S quantum dots prepared
Outside-visible absorbance and fluorescence spectra and X ray diffracting spectrum.
Embodiment 3
Zn-Ag-In-S quantum dots (nAg∶nIn=1: preparation method 5), concretely comprise the following steps：
Weigh zinc acetate 0.37g (2.0mmol), silver nitrate 67.90g (0.8mmol), indium acetate 1.16g (4.0
Mmol) add with glutathione 11.94g (40.0mmol) and fill three mouthfuls of 500mL of 250mL deionized waters
Mixed in flask, obtain mixed liquor A, pH to 8.5, Zhi Houjia is adjusted with 0.2M sodium hydrate aqueous solution
Enter to be dissolved in the vulcanized sodium (0.62g, 8.0mmol) of 10mL water, obtain mixed liquid B；Mixed liquid B is heated up
Room temperature is cooled to 100 DEG C and after being stirred vigorously 4.5 hours at this temperature with 1500rpm rotating speed；To mixed
The ethanol that 250mL is added in liquid is closed, orange solids have been arrived in centrifugation, after being washed twice with ethanol, in
Brown solid is dried to obtain in 40 DEG C of vacuum drying oven.As Fig. 1 for prepare Zn-Ag-In-S quantum dots it is ultraviolet-
Visible absorbance and fluorescence spectra and X ray diffracting spectrum.
Embodiment 4
Zn-Ag-In-S quantum dots (nAg∶nIn=1: preparation method 2), concretely comprise the following steps：
Weigh zinc acetate 0.37g (2.0mmol), silver nitrate 67.90g (2.0mmol), indium acetate 1.16g (4.0
Mmol) add with glutathione 11.94g (40.0mmol) and fill three mouthfuls of 500mL of 250mL deionized waters
Mixed in flask, obtain mixed liquor A, pH to 8.5, Zhi Houjia is adjusted with 0.2M sodium hydrate aqueous solution
Enter to be dissolved in the vulcanized sodium (0.62g, 8.0mmol) of 10mL water, obtain mixed liquid B；Mixed liquid B is heated up
Room temperature is cooled to 100 DEG C and after being stirred vigorously 4.5 hours at this temperature with 1500rpm rotating speed；To mixed
The ethanol that 250mL is added in liquid is closed, orange solids have been arrived in centrifugation, after being washed twice with ethanol, in
Black solid is dried to obtain in 40 DEG C of vacuum drying oven.As Fig. 1 prepare Zn-Ag-In-S quantum dots it is ultraviolet-can
See absorption and fluorescence spectra and X ray diffracting spectrum.
Embodiment 5
Zn-Ag-In-S quantum dots are used for photolysis water hydrogen
Weigh Zn-Ag-In-S quantum dots 10mg to be dissolved in 100mL deionized waters, add 3.5g Vitamin Cs
Acid is as sacrifice agent, and 5uM nickel-lipoic acid complex compound is (according to following articles " Supporting Information "
Method synthesis described in part：Zhiji Han, Fen Qiu, Richard Eisenberg, Patrick L.Holland,
Todd D.Krauss；Robust Photogeneration of H2 in Water Using Semiconductor
Nanacrystals and a Nickel Catalyst；Science, 338 (7), 2012,1321-1324.) it is used as catalysis altogether
Agent, with the 0.2MNaOH aqueous solution regulation pH be 5.0 after be transferred in 250mL reactor.Use 300W
Xe lamps be light source, use 400nm-780nm optical filter, it is real that simulated solar irradiation carries out photocatalysis hydrogen production
Test；Timing sampling, the amount of the hydrogen produced is analyzed by GC.
Control experiment is being not added with co-catalyst, is being not added with sacrifice agent, is not added with light source and is not added with the condition of quantum dot respectively
It is lower to carry out, shown in the experimental result such as Fig. 2 (a) for the Zn-Ag-In-S quantum dots that embodiment 2 is obtained；Embodiment
Shown in photocatalysis effect such as Fig. 2 (b) of the quantum dot for the silver-colored ratio of different indiums that 1-4 is obtained.
As shown in Figure 2, photocatalysis body is tied up to and lived in the absence of still showing higher catalysis under the conditions of syncatalytic
Property, and in the case of sacrifice agent or illumination or quantum dot is lacked, the catalytic activity of system is very low or without catalysis
Activity；And the ratio of indium silver material to photocatalysis effect also with significantly affecting.
Embodiment 6
Composite based on Zn-Ag-In-S quantum dots is used for photolysis water hydrogen
By Zn-Ag-In-S quantum dots and such as two dimension MoS2、C3N4, the nano material such as graphene prepares
Catalyst show photocatalysis hydrogen production efficiency better than Zn-Ag-In-S quantum dots, as follows with Zn-Ag-In-S
With MoS2Exemplified by catalyst with reference to preparation.
The Zn-Ag-In-S quantum dots 1mL prepared in the embodiment 2 for taking 10mg/mL is in filling different content
(0.16mL, 0.32mL, 0.64mL, 1.28mL 0.09mg/mL MoS2The aqueous solution in, normal
The lower ultrasound 2h of temperature, prepares Zn-Ag-In-S@MoS2Catalyst.By obtained aqueous solution constant volume to 100
ML, add 3.5g ascorbic acid, with the 0.2M NaOH aqueous solution regulation pH be 5.0 after be transferred to 250mL
Reactor in；It is light source with 300W Xe lamps, using 400nm-780nm optical filter, simulation is too
Sunlight carries out photocatalysis hydrogen production experiment；Timing sampling, the amount of the hydrogen produced, experimental result are analyzed by GC
As shown in Figure 3.
Embodiment 7
Optoelectronic pole based on Zn-Ag-In-S quantum dots is prepared and its applied to photoelectrocatalysis hydrogen manufacturing
The NiO electrodes of preparation (are made according to the method described in following articles：A.Nattestad, A.J.
Mozer, M.K.R.Fischer, Y.-B.Cheng, A.Mishra, P.Bauerle and U.Bach；Highly
efficient photocathodes for dye-sensitized tandem solar cells；Nature Materials, 9,
2010,31-35.) it is dipped into the 10mg/mL Zn-Ag-In-S quantum dot aqueous solution, 100 is taken out after 10 hours
DEG C drying.The electrode containing Zn-Ag-In-S quantum dots using preparation is photocathode, and platinum plate electrode is light anode,
Put it into and fill 100mL electrolyte solutions (0.5M Na2SO4Solution, pH 6.8) reactor in；
It is light source with 300W Xe lamps, using 400nm-780nm optical filter, simulated solar irradiation uses electrification
Learn the voltage progress photoelectrocatalysis hydrogen manufacturing experiment that work stand control applies；Timing sampling, is analyzed by GC and produced
Hydrogen amount, experimental result is as shown in Figure 4.
From above experimental result, individually or with other materials it is combined as with Zn-Ag-In-S quantum dots
Catalyst or it is prepared into after electrode, efficient photocatalysis system can be achieved in the case of without co-catalyst
Hydrogen, illustrates that using quantum dot prepared by the present invention be the excellent nano material for realizing photocatalysis hydrogen production.
Claims (10)
1. a kind of preparation method of Zn-Ag-In-S quantum dots, it is characterised in that including：
Step 1：Zinc source compound, silver-colored source compound, indium source compound and glutathione are added to the water, obtained
To mixed liquor A；
Step 2：The pH value of mixed liquor A in regulating step 1 is 7-10, and addition contains sulphur source compound
The aqueous solution, obtains mixed liquid B；
Step 3：The mixed liquid B that step 2 is obtained is warming up to 70-100 DEG C and stirs 3-5h at this temperature
After cool down, add ethanol, centrifuge, gained solid is Zn-Ag-In-S quantum dots.
2. the preparation method of Zn-Ag-In-S quantum dots as claimed in claim 1, it is characterised in that described
Zinc source compound be zinc acetate, described silver-colored source compound is silver nitrate, and described indium source compound is acetic acid
Indium, described sulphur source compound is vulcanized sodium.
3. the preparation method of Zn-Ag-In-S quantum dots as claimed in claim 1, it is characterised in that described
Mixed liquid B in, zinc source compound, silver-colored source compound, indium source compound, glutathione and sulphur source chemical combination
The mol ratio of thing is 2-6: 1: 5-10: 50-100: 10-20.
4. the preparation method of Zn-Ag-In-S quantum dots as claimed in claim 1, it is characterised in that described
The aqueous solution containing sulphur source compound concentration be 0.03-0.06mol/L.
5. the preparation method of Zn-Ag-In-S quantum dots as claimed in claim 1, it is characterised in that described
Step 3 also includes purifying the Zn-Ag-In-S quantum dots of gained, and described purification includes：Washed with ethanol,
Drying.
6. prepared by the preparation method of the Zn-Ag-In-S quantum dots any one of claim 1-5
Zn-Ag-In-S quantum dots.
7. a kind of catalyst based on Zn-Ag-In-S quantum dots, it is characterised in that including nanocatalyst and
Zn-Ag-In-S quantum dots described in claim 6.
8. the preparation method of the catalyst based on Zn-Ag-In-S quantum dots described in claim 7, its feature
It is, including：Zn-Ag-In-S quantum dots described in claim 6 are placed in the aqueous solution of nanocatalyst
In, it is ultrasonically treated, obtain the catalyst based on Zn-Ag-In-S quantum dots.
9. a kind of optoelectronic pole based on Zn-Ag-In-S quantum dots, including：Optoelectronic pole matrix, described photoelectricity
The surface of pole matrix is provided with the Zn-Ag-In-S quantum dots described in claim 6.
10. the preparation method of the optoelectronic pole based on Zn-Ag-In-S quantum dots described in claim 9, its
It is characterised by, including：Optoelectronic pole matrix is dipped into containing the Zn-Ag-In-S quantum described in claim 6
2-24h in the aqueous solution of point, takes out drying, obtains the optoelectronic pole based on Zn-Ag-In-S quantum dots.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610153039.6A CN107201225A (en) | 2016-03-17 | 2016-03-17 | Zn-Ag-In-S quantum dots, the catalyst based on the quantum dot and optoelectronic pole and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610153039.6A CN107201225A (en) | 2016-03-17 | 2016-03-17 | Zn-Ag-In-S quantum dots, the catalyst based on the quantum dot and optoelectronic pole and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107201225A true CN107201225A (en) | 2017-09-26 |
Family
ID=59903740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610153039.6A Pending CN107201225A (en) | 2016-03-17 | 2016-03-17 | Zn-Ag-In-S quantum dots, the catalyst based on the quantum dot and optoelectronic pole and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107201225A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084994A (en) * | 2017-12-13 | 2018-05-29 | 重庆大学 | A kind of method based on aqueous silver-colored indium zinc sulphur fluorescence quantum selective enumeration method cadmium ion |
| CN110368954A (en) * | 2019-05-13 | 2019-10-25 | 江苏大学 | Hydro-thermal doping method prepares Cu:Ag-In-Zn-S quantum dot light catalyst and its application |
| CN114011435A (en) * | 2021-12-07 | 2022-02-08 | 合肥工业大学 | Water-soluble silver-indium-sulfur quantum dot photocatalyst and room-temperature preparation method |
| CN116285948A (en) * | 2023-02-22 | 2023-06-23 | 徐州工程学院 | Preparation method of melamine resin coated zinc oxide quantum dot composite fluorescent powder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265948A (en) * | 2013-04-28 | 2013-08-28 | 温州大学 | Preparation method for doping type four-element multicolor fluorescent Ag-N-In-S quantum dot |
| CN104338547A (en) * | 2013-07-29 | 2015-02-11 | 中国科学院理化技术研究所 | Photocatalyst based on quantum dot/rod and molybdenum disulfide nanosheet, preparation method thereof, photocatalysis system and hydrogen production method by reforming biomass |
| CN104451765A (en) * | 2014-12-25 | 2015-03-25 | 江南大学 | Preparation method of cadmium telluride quantum dot sensitization nickel oxide photoelectrode |
-
2016
- 2016-03-17 CN CN201610153039.6A patent/CN107201225A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265948A (en) * | 2013-04-28 | 2013-08-28 | 温州大学 | Preparation method for doping type four-element multicolor fluorescent Ag-N-In-S quantum dot |
| CN104338547A (en) * | 2013-07-29 | 2015-02-11 | 中国科学院理化技术研究所 | Photocatalyst based on quantum dot/rod and molybdenum disulfide nanosheet, preparation method thereof, photocatalysis system and hydrogen production method by reforming biomass |
| CN104451765A (en) * | 2014-12-25 | 2015-03-25 | 江南大学 | Preparation method of cadmium telluride quantum dot sensitization nickel oxide photoelectrode |
Non-Patent Citations (1)
| Title |
|---|
| 罗志山: "AgInS2纳米晶和AuPt纳米合金电催化剂的合成及催化应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084994A (en) * | 2017-12-13 | 2018-05-29 | 重庆大学 | A kind of method based on aqueous silver-colored indium zinc sulphur fluorescence quantum selective enumeration method cadmium ion |
| CN108084994B (en) * | 2017-12-13 | 2019-08-06 | 重庆大学 | A method of based on aqueous silver-colored indium zinc sulphur fluorescence quantum selective enumeration method cadmium ion |
| CN110368954A (en) * | 2019-05-13 | 2019-10-25 | 江苏大学 | Hydro-thermal doping method prepares Cu:Ag-In-Zn-S quantum dot light catalyst and its application |
| CN110368954B (en) * | 2019-05-13 | 2022-02-15 | 江苏大学 | Cu-Ag-In-Zn-S quantum dot photocatalyst prepared by hydrothermal doping method and application thereof |
| CN114011435A (en) * | 2021-12-07 | 2022-02-08 | 合肥工业大学 | Water-soluble silver-indium-sulfur quantum dot photocatalyst and room-temperature preparation method |
| CN116285948A (en) * | 2023-02-22 | 2023-06-23 | 徐州工程学院 | Preparation method of melamine resin coated zinc oxide quantum dot composite fluorescent powder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Fe-B alloy coupled with Fe clusters as an efficient cocatalyst for photocatalytic hydrogen evolution | |
| Jin et al. | Ni, Co-based selenide anchored g-C3N4 for boosting photocatalytic hydrogen evolution | |
| Shen et al. | In-situ construction of metallic Ni3C@ Ni core–shell cocatalysts over g-C3N4 nanosheets for shell-thickness-dependent photocatalytic H2 production | |
| Ma et al. | Knack behind the high performance CdS/ZnS-NiS nanocomposites: Optimizing synergistic effect between cocatalyst and heterostructure for boosting hydrogen evolution | |
| Gong et al. | Dodecahedron ZIF-67 anchoring ZnCdS particles for photocatalytic hydrogen evolution | |
| Guo et al. | Formation of unique hollow ZnSnO3@ ZnIn2S4 core-shell heterojunction to boost visible-light-driven photocatalytic water splitting for hydrogen production | |
| Kumar et al. | Noble metal-free metal-organic framework-derived onion slice-type hollow cobalt sulfide nanostructures: Enhanced activity of CdS for improving photocatalytic hydrogen production | |
| Hu et al. | Noble-metal-free Ni2P as cocatalyst decorated rapid microwave solvothermal synthesis of inorganic-organic CdS-DETA hybrids for enhanced photocatalytic hydrogen evolution | |
| Mu et al. | Metal-organic framework-derived rodlike AgCl/Ag/In2O3: A plasmonic Z-scheme visible light photocatalyst | |
| CN104762634B (en) | Optical electro-chemistry decomposes aquatic products hydrogen, the optoelectronic pole for producing oxygen and its preparation and application | |
| Liu et al. | Construction of Au/g-C3N4/ZnIn2S4 plasma photocatalyst heterojunction composite with 3D hierarchical microarchitecture for visible-light-driven hydrogen production | |
| CN107201226A (en) | CuInS2Quantum dot, CuInS2/ ZnS quantum dot and its preparation and application | |
| CN110560105B (en) | Preparation of nickel phosphide-loaded sulfur indium zinc nano microsphere composite material and application of composite material in photocatalytic hydrogen production | |
| Qiu et al. | Integrated pn/Schottky junctions for efficient photocatalytic hydrogen evolution upon Cu@ TiO2-Cu2O ternary hybrids with steering charge transfer | |
| CN106622322B (en) | It is a kind of using bimetal nano particles as two-dimensional nano piece composite photo-catalyst of hetero-junctions and preparation method thereof | |
| Sun et al. | A novel hollow flower-like 0D/3D Zn0. 5Cd0. 5S/NiCoZn-LDH photocatalyst with nn heterojunction for high hydrogen production | |
| Ali et al. | Role of the radiations in water splitting for hydrogen generation | |
| CN105239091B (en) | It is a kind of based on metal oxide, quantum dot and produce hydrogen catalyst photocathode and its preparation and application | |
| CN107201225A (en) | Zn-Ag-In-S quantum dots, the catalyst based on the quantum dot and optoelectronic pole and its preparation | |
| Ma et al. | Hydrothermal synthesis of WO 3/CoS 2 n–n heterojunction for Z-scheme photocatalytic H 2 evolution | |
| Su et al. | Metal organic framework-derived Co3O4/NiCo2O4 hollow double-shell polyhedrons for effective photocatalytic hydrogen generation | |
| CN110508291B (en) | Au-ZnIn2S4Preparation method of nano array electrode photocatalytic nitrogen fixation material | |
| CN106807349A (en) | A kind of nano metal simple substance modification transition metal hydroxide array catalyst and its preparation method and application | |
| CN110124694A (en) | A kind of preparation and the reduction application of electro-catalysis nitrogen of ultrathin nanometer sheet vanadium doping nanometer nickel sulfide powder | |
| CN106179410A (en) | A kind of photocatalyst of photocatalytic hydrogen production by water decomposition and preparation method thereof |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170926 |