CN109999836A - A kind of preparation of indium oxide/indium sulfide heterojunction semiconductor material and photochemical catalyst purposes and solar energy fixed nitrogen application - Google Patents
A kind of preparation of indium oxide/indium sulfide heterojunction semiconductor material and photochemical catalyst purposes and solar energy fixed nitrogen application Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 45
- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 24
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 22
- 239000004065 semiconductor Substances 0.000 title claims abstract description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 15
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- -1 indium salts compound Chemical class 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005864 Sulphur Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 44
- 239000000843 powder Substances 0.000 claims description 40
- 235000019441 ethanol Nutrition 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- 230000001699 photocatalysis Effects 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000007146 photocatalysis Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical group CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- JKXCZYCVHPKTPK-UHFFFAOYSA-N hydrate;trihydrochloride Chemical compound O.Cl.Cl.Cl JKXCZYCVHPKTPK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001449 indium ion Inorganic materials 0.000 claims description 5
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 5
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical compound O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 claims description 4
- 125000005456 glyceride group Chemical group 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 239000004201 L-cysteine Substances 0.000 claims description 2
- 235000013878 L-cysteine Nutrition 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- IVULQSOWZDLIPB-UHFFFAOYSA-N O.[In].[N+](=O)(O)[O-] Chemical compound O.[In].[N+](=O)(O)[O-] IVULQSOWZDLIPB-UHFFFAOYSA-N 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract description 9
- 238000005406 washing Methods 0.000 abstract 2
- 239000003960 organic solvent Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 19
- 238000011534 incubation Methods 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
-
- 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
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of photochemical catalysts, are indium oxide/indium sulfide heterojunction semiconductor material, molecular formula In2O3/In2S3, it is used for solar energy fixed nitrogen.The preparation method of catalyst, comprising steps of 1, using water or organic solvent as solvent；2, indium salts compound, surfactant and alkalescent substance are dissolved in solvent；3, it is packed into reaction kettle, carries out hydro-thermal reaction；4, it is cooled to room temperature, is centrifugated and alternative water use and ethanol solution washing, dry indium hydroxide；5, indium hydroxide is put into Muffle furnace calcining, obtains indium oxide；6, indium oxide is added in 1 solvent, is stirred and ultrasonic；7, sulphur source, stirring is added；8, it is packed into reaction kettle, carries out secondary hydro-thermal reaction；9, it is cooled to room temperature and is centrifuged and alternative water use and ethanol solution washing, dry indium oxide/indium sulfide heterojunction semiconductor material.The catalyst economy that the present invention obtains is environmentally friendly, recyclable, can be produced in batches, and has solar energy fixed nitrogen performance.
Description
Technical field
The present invention relates to a kind of catalysis material technical fields, heterogeneous more specifically to a kind of indium oxide/indium sulfide
Pn junction p n material (In2O3/In2S3) preparation of photochemical catalyst and the application of solar energy fixed nitrogen.
Background technique
In atmosphere, the content highest of nitrogen, volume accounts for about the 78% of atmosphere total volume, and nitrogen so abundant is provided
Source, how stable nitrogen is converted ammonification becomes focus concerned by people to preferably utilize.Currently, utilizing
Nitrogen is converted ammonia by Haber-Bosch method, greatly advances the process of industrialization fixed nitrogen, but Haber-Bosch method needs
It just can be carried out under the reaction condition of the harshness such as high temperature (300~550 DEG C) high pressure (15~25MPa), this reaction not only needs
The a large amount of energy is consumed, greenhouse effects can be also generated.Therefore, how to realize that artificial fixed nitrogen is one and has in a mild condition
Problem in science to be solved.
In recent years, using some photochemical catalysts to nitrogen carry out reduction have begun working on and achieve it is a series of into
Exhibition.Semiconductor light-catalyst can generate photo-generate electron-hole pairs by capturing solar energy, and then by N2It is converted into NH3.But
Be photocatalyst applications in fixed nitrogen field there is also many problems, such as make nitrogen-fixing efficiency there are water-splitting competitive reaction
Reduction, can light induced electron be broken highly stable N ≡ N and semiconductor catalyst quantum efficiency is low, recycling rate of waterused compared with
It is low.
Have many photocatalyst materials at present to be applied among solid nitrogen studies, for example, titanate, graphite phase carbon nitride,
Bismuth molybdate and BiOX etc. obtain preferable achievement in the research of photocatalysis fixed nitrogen.And with relatively narrow forbidden bandwidth
Indium oxide/indium sulfide heterojunction semiconductor material (In2O3/In2S3) it is conducive to the separation of photo-generate electron-hole, widen material light
Absorption region, improves the utilization rate of luminous energy and it has many advantages, such as simple production process, environmental-friendly, economic controllable.
Summary of the invention
It is an object of that present invention to provide a kind of preparation of photochemical catalyst and its solar energy fixed nitrogen methods.
To achieve the goals above, the technical solution of the present invention is as follows:
A kind of photochemical catalyst is invented, is indium oxide/indium sulfide heterojunction semiconductor material, molecular formula In2O3/In2S3, knot
Structure is the bouquet structure with indium oxide and indium sulfide.
Catalyst provided by the invention is used for solar energy fixed nitrogen, is applied particularly to the solar energy fixed nitrogen using water as reducing agent
Light-catalyzed reaction.
The present invention provides a kind of preparation methods of photochemical catalyst, include the following steps:
S1, at room temperature using water, ethyl alcohol, ethylene glycol, N,N-dimethylformamide or isopropanol as solvent；
S2, indium salts compound, surfactant and alkalescent substance are dissolved in above-mentioned solvent, are sufficiently stirred and are formed mixed
Close solution；The indium salts compound includes four trichloride hydrate indiums, indium nitrate hydrate, indium sulfate or indium ion complex compound；Institute
Stating surfactant includes lauryl sodium sulfate, stearic acid, quaternary ammonium compound, fatty glyceride, CTAB or polyvinyl pyrrole
Alkanone；The alkalescent substance includes urea, aniline, ammonium hydroxide；
S3, mixed solution obtained by the S2 is transferred in the autoclave that pressure is 1~2MPa, it is anti-carries out hydro-thermal
It answers；Wherein hydrothermal temperature is 90~150 DEG C, and the hydro-thermal time is 10~20h；
S4, it after being cooled to room temperature, is centrifuged, alternately washs 4~8 with 50~200mL water and ethyl alcohol respectively
It is secondary, the indium hydroxide powder of white is collected after dry at 50~80 DEG C；
S5, extracting waste indium hydroxide powder, which are put into the Muffle furnace that temperature is 350~550 DEG C, calcines 1~4h, heating rate
For 3~10 DEG C/min, flaxen indium oxide powder is collected；
S6, faint yellow indium oxide powder is added described in S1 in solvent, stir carry out after 10~30min ultrasonic disperse 10~
50min；
S7, sulphur source is add to the above mixed solution, stirs 20~60min；
S8, mixed solution obtained by the S7 is transferred in the autoclave that pressure is 1~2MPa, carries out secondary hydro-thermal
Reaction；Wherein hydrothermal temperature is 90~180 DEG C, and the hydro-thermal time is 3~10h；
S9, it is cooled to room temperature and is centrifuged and is washed 4~8 times with 50~200mL water and ethanol solution respectively,
At 50~80 DEG C after drying, collects powder and obtain indium oxide/indium sulfide heterojunction semiconductor material.
Wherein, the preparation method of photochemical catalyst according to claim 5, which is characterized in that in step S7, the sulphur source
For thioacetamide, thiocarbamide, sodium thiosulfate or L-cysteine.
The present invention provides a kind of preparation methods of photochemical catalyst, specifically includes the following steps:
S1, at room temperature using 30~80mL water, ethyl alcohol, ethylene glycol, N,N-dimethylformamide or isopropanol as solvent；
S2,0.2~0.5g indium salts compound, 0.5~1g surfactant and 0.1~0.5g alkalescent substance are dissolved in 40
In solvent described in~100mLS1, it is sufficiently stirred and forms mixed solution；The indium salts compound include four trichloride hydrate indiums,
Indium nitrate hydrate, indium sulfate or indium ion complex compound；The surfactant includes lauryl sodium sulfate, stearic acid, season
Ammonium compound, fatty glyceride, CTAB or polyvinylpyrrolidone；The alkalescent substance includes urea, aniline, ammonium hydroxide；
S3, mixed solution obtained by the S2 is transferred in the autoclave that pressure is 1~2MPa, it is anti-carries out hydro-thermal
It answers；Wherein hydrothermal temperature is 90~150 DEG C, and the hydro-thermal time is 10~20h；
S4, it after being cooled to room temperature, is centrifuged, alternately washs 4~8 with 50~200mL water and ethyl alcohol respectively
Indium hydroxide white powder that is secondary, being collected after dry at 50~80 DEG C；
S5, extracting waste indium hydroxide powder, which are put into the Muffle furnace that temperature is 350~550 DEG C, calcines 1~4h, heating rate
For 3~10 DEG C/min, flaxen indium oxide powder is obtained；
S6, faint yellow indium oxide powder is added in solvent described in 30~80mL S1, is surpassed after stirring 10~30min
Sound disperses 10~50min, obtains mixed liquor；
S7,0.01~0.1g sulphur source is added in above-mentioned S6 mixed solution, stirs 20~60min；
S8, mixed solution obtained by the S7 is transferred in the autoclave that pressure is 1~2MPa, carries out secondary hydro-thermal
Reaction；Wherein hydrothermal temperature is 90~180 DEG C, and the hydro-thermal time is 3~10h；
S9, it is cooled to room temperature and is centrifuged and is washed 4~8 times with water and ethanol solution respectively, at 50~80 DEG C
After drying, collects powder and obtain indium oxide/indium sulfide heterojunction semiconductor material.
Wherein, when isothermal reaction described in step S8, it is 60% that the volume for filling solution, which accounts for the ratio of autoclave liner volume,
~90%.
The present invention provides a kind of methods using above-mentioned catalyst solar energy fixed nitrogen, comprising the following steps: to 50~
10~50mg photochemical catalyst is added in 150mL water, and maintains 5~20 DEG C, before carrying out photocatalysis, 30~60min of stirring, then
40~120min is stirred under illumination, filters out catalyst with 0.1~0.4 μm of filter later.
The present invention has the advantage that
The photochemical catalyst of invention not only has good solar energy fixed nitrogen performance, but also possesses higher quantum efficiency.?
Under sunlight, using water as reducing agent, In2O3/In2S3Photochemical catalyst generates 40.04 μm of ol ammonias per hour per gram, and ammonia produces
Raw amount is In2O34.7 times, be In2S36 times.It has broad application prospects in fields such as the energy, Environmental pollution and controls,
Strong theoretical basis is provided for the type catalyst.
Detailed description of the invention
Fig. 1 is the XRD diffraction pattern of 1 catalyst of embodiment.
Fig. 2 is the scanning electron microscope (SEM) photograph of 1 catalyst of embodiment.
Fig. 3 is the xps energy spectrum analysis chart of 1 catalyst of embodiment.
Fig. 4 is the UV-vis abosrption spectrogram of 1 catalyst of embodiment.
Fig. 5 is that the forbidden bandwidth of 1 catalyst of embodiment estimates spectrogram.
Fig. 6 is the current versus time curve figure of 1 catalyst of embodiment.
Fig. 7 is the solar energy nitrogen fixation effect figure of Examples 1 to 6 catalyst.
Specific embodiment
The present invention provides a kind of indium oxide/indium sulfide heterojunction semiconductor material light catalysis agent preparation and the efficient sun
Energy fixed nitrogen method, belongs to catalysis material technical field.This method comprises the following steps: 1, Yi Shui, ethyl alcohol, ethylene glycol, N, N-
Dimethylformamide or isopropanol are solvent；2, indium salts compound, alkalescent substance and surfactant are dissolved in above-mentioned solvent
In, form mixed solution；3, it is packed into reaction kettle, carries out hydro-thermal reaction；4, it is cooled to room temperature and is centrifuged and uses water respectively
It is washed with ethanol solution, is collected after dry and obtain white powder；5, extracting waste powder is put into Muffle furnace calcining, obtains yellowish toner
End；6, pale yellow powder is added in 1 solvent, simultaneously ultrasonic disperse is sufficiently stirred；7, sulphur source is added, is sufficiently stirred；8, it fills
Enter reaction kettle, carries out secondary hydro-thermal reaction；9, it is cooled to room temperature and is centrifuged and is washed respectively with water and ethanol solution, do
Powder is collected after dry, obtains indium oxide/indium sulfide heterojunction semiconductor material.Indium oxide/indium sulfide that the method for the present invention obtains
Heterojunction semiconductor material light catalysis agent is environmental-friendly, abundant raw materials, economical and efficient, production method is simple, can carry out volume production,
With good solar energy photocatalytic fixed nitrogen performance.
Below with reference to the attached drawing in the embodiment of the present invention, to make clear, complete statement to this programme.It is following to be retouched
The embodiment stated is only a part of the invention, is not whole embodiments.Those skilled in the art is according to the present invention
Above content make it is some it is nonessential improvement all belong to the scope of protection of the present invention.
It is an object of the present invention to provide a kind of photochemical catalysts, provide a kind of preparation method of photochemical catalyst, mention simultaneously
For a kind of photocatalysis method of high-efficiency solar fixed nitrogen.
Using 30~80mL water, ethyl alcohol, ethylene glycol, n,N-Dimethylformamide or isopropanol as solvent, carry out at room temperature
Reaction；The solvent includes but is not limited to water, ethyl alcohol, ethylene glycol, N,N-dimethylformamide or isopropanol.
Institute is added in 0.2~0.5g indium salts compound, 0.5~1.0g surfactant and 0.1~0.5g alkalescent substance
It states in solvent, mix and is sufficiently stirred, mixing time is 5~30min；The indium salts compound include four trichloride hydrate indiums,
Surfactant described in indium nitrate hydrate, indium sulfate or indium ion complex compound includes lauryl sodium sulfate, stearic acid, quaternary ammonium
Compound, fatty glyceride, CTAB or polyvinylpyrrolidone；The alkalescent substance includes urea, aniline, ammonium hydroxide；
It is fitted into autoclave after stirring to clarify acquired solution in the present invention, carries out 100~180 DEG C of isothermal reactions
10~for 24 hours；Product, which is cooled to room temperature, to be centrifuged and is washed 4~8 times with water and ethanol solution respectively, in 50~80 DEG C of dryings
After collect powder.It is that 1~4h is calcined in 350~550 DEG C of Muffle furnace that the powder, which is put to temperature, heating rate is 3~10 DEG C/
Min obtains pale yellow powder.The pale yellow powder is added to 30~80 mL water, ethyl alcohol, ethylene glycol, N, N- dimethyl formyl
In amine or isopropanol solvent, acquired solution is again loaded into autoclave by 10~50min of ultrasound, carries out 90~180 DEG C of perseverances
3~10h of temperature reaction.Product, which is cooled to room temperature, to be centrifuged and is washed 4~8 times with water and ethanol solution respectively, 50~80
Powder is collected after DEG C dry.Wherein, when synthetic reaction, fill solution volume account for autoclave liner volume ratio be 60%~
90%.
The present invention provides a kind of methods using above-mentioned catalyst solar energy fixed nitrogen, comprising the following steps: to 50~
10~50mg photochemical catalyst is added in 150mL water, and maintains 5~20 DEG C, before carrying out photocatalysis, 30~60min of stirring, then
40~120min is stirred under illumination, filters out catalyst with 0.1~0.4 μm of filter later.
Compared with existing photocatalysis technology, the present invention is had the advantage that
(1) photochemical catalyst of the invention not only has good solar energy fixed nitrogen performance, but also possesses higher quantum effect
Rate.Using water as reducing agent under sunlight, In2O3/In2S3Photochemical catalyst generates 40.04 μm of ol ammonias, ammonia per hour per gram
Gas yield is In2O34.7 times, be In2S36 times.There is wide application in fields such as the energy, Environmental pollution and controls
Prospect provides strong theoretical basis for the type catalyst.
(2)In2O3/In2S3Catalysis material has very high controllability, and requires lower, economic ring to consersion unit
It protects, is Ke Xunhuanliyong, can be produced in batches, there is certain practicability.
Embodiment 1
Tetra- chloride hydrate indium of 0.2736g, 0.7627g lauryl sodium sulfate and 0.2803g urea are added to 80mL water
In solution, 60min is sufficiently stirred to clear solution, then above-mentioned acquired solution is transferred in 1~2 MPa autoclave,
Incubation water heating is carried out at 120 DEG C and reacts 12h, and product, which is cooled to room temperature, to be centrifuged and washed respectively with water and ethanol solution
6 times, powder is collected after dry in 60 DEG C, products therefrom is put into Muffle furnace, 500 DEG C of calcining 2h.It is produced after taking 0.1g to calcine again
32mL water is added in object, and 0.05g thioacetamide is added after mixed solution ultrasound 30min, is packed into 1~2MPa high after stirring 30min
Reaction kettle is pressed, incubation water heating is carried out at 150 DEG C and reacts 5h.Product, which is cooled to room temperature, to be centrifuged and respectively with water and second
Alcoholic solution is washed 6 times, is collected powder after dry in 60 DEG C, is obtained final products In2O3/In2S3。
Fig. 1 is the In that the present embodiment obtains2O3/In2S3Photochemical catalyst XRD diffracting spectrum, through being compared with PDF standard card
It learns, obtained is body-centred cubic In2O3With the In of cube structure2S3。
Fig. 2 is the In that the present embodiment obtains2O3/In2S3Photochemical catalyst scanning electron microscope (SEM) photograph, obtained diameter are about 5.0 μm of flowers
Ball.
Fig. 3 is the In that the present embodiment obtains2O3/In2S3Photochemical catalyst xps energy spectrum analysis chart, illustrates In2O3/In2S3Light
In, O and S element contained in catalyst.
Fig. 4 is the In that the present embodiment obtains2O3/In2S3Photochemical catalyst UV-vis absorption spectrum, compared to pure phase In2O3It inhales
The red shift of take-up side is obviously improved in visible-range internal absorbance, there is stronger light abstraction width.
Fig. 5 is the In that the present embodiment obtains2O3/In2S3The forbidden bandwidth of photochemical catalyst estimates map, the band of resulting materials
Gap relative narrower accelerates electron-transport speed, to promote photocatalytic activity.
Fig. 6 is the In that the present embodiment obtains2O3/In2S3Photochemical catalyst photocurrent-time curve figure, compared to pure phase In2O3
And In2S3, have stronger photoelectric current, illustrate to have efficiently separated light induced electron and hole.
Embodiment 2
Tetra- chloride hydrate indium of 0.2736g, 0.7627g lauryl sodium sulfate and 0.2803g urea are added to 80mL water
In solution, 60min is sufficiently stirred to clear solution, then above-mentioned acquired solution is transferred in 1~2 MPa autoclave,
Incubation water heating is carried out at 120 DEG C and reacts 12h, and product, which is cooled to room temperature, to be centrifuged and washed respectively with water and ethanol solution
6 times, powder is collected after dry in 60 DEG C, products therefrom is put into Muffle furnace, 500 DEG C of calcining 2h are carried out.0.1g is taken to calcine again
32mL water is added in product afterwards, and 0.03g thioacetamide is added after mixed solution ultrasound 30min, stir and be packed into 1 after 30min~
2MPa autoclave carries out incubation water heating at 150 DEG C and reacts 5h.Product, which is cooled to room temperature, to be centrifuged and uses respectively
Water and ethanol solution are washed 6 times, are collected powder after dry in 60 DEG C, are obtained final products In2O3/In2S3。
Embodiment 3
Tetra- chloride hydrate indium of 0.2736g, 0.7627g lauryl sodium sulfate and 0.2803g urea are added to 80mL water
In solution, 60min is sufficiently stirred to clear solution, then above-mentioned acquired solution is transferred in 1~2 MPa autoclave,
Incubation water heating is carried out in 120 DEG C and reacts 12h, and product, which is cooled to room temperature, to be centrifuged and washed respectively with water and ethanol solution
6 times, powder is collected after dry in 60 DEG C, products therefrom is put into Muffle furnace, 500 DEG C of calcining 2h are carried out.0.1g is taken to calcine again
32mL water is added in product afterwards, and 0.04g thioacetamide is added after mixed solution ultrasound 30min, stir and be packed into 1 after 30min~
2MPa autoclave carries out incubation water heating at 150 DEG C and reacts 5h.Product, which is cooled to room temperature, to be centrifuged and uses respectively
Water and ethanol solution are washed 6 times, are collected powder after dry in 60 DEG C, are obtained final products In2O3/In2S3。
Embodiment 4
Tetra- chloride hydrate indium of 0.2736g, 0.7627g lauryl sodium sulfate and 0.2803g urea are added to 80mL water
In solution, 60min is sufficiently stirred to clear solution, then above-mentioned acquired solution is transferred in 1~2 MPa autoclave,
Incubation water heating is carried out at 120 DEG C and reacts 12h, and product, which is cooled to room temperature, to be centrifuged and washed respectively with water and ethanol solution
6 times, powder is collected after dry in 60 DEG C, products therefrom is put into Muffle furnace, 500 DEG C of calcining 2h are carried out.0.1g is taken to calcine again
32mL water is added in product afterwards, and 0.06g thioacetamide is added after mixed solution ultrasound 30min, stir and be packed into 1 after 30min~
2MPa autoclave carries out incubation water heating at 150 DEG C and reacts 5h.Product, which is cooled to room temperature, to be centrifuged and uses respectively
Water and ethanol solution are washed 6 times, are collected powder after dry in 60 DEG C, are obtained final products In2O3/In2S3。
Embodiment 5
Tetra- chloride hydrate indium of 0.2736g, 0.7627g 12 are obtained into sodium alkyl sulfate and 0.2803g urea is added to
In 80mL aqueous solution, 60min is sufficiently stirred to clear solution, above-mentioned acquired solution is then transferred to 1~2MPa reaction under high pressure
In kettle, incubation water heating is carried out at 120 DEG C and reacts 12h, product, which is cooled to room temperature, to be centrifuged and respectively with water and ethyl alcohol
Solution is washed 6 times, collects powder after dry in 60 DEG C, products therefrom is put into Muffle furnace, 500 DEG C of calcining 2h are carried out.It takes again
32mL water is added in product after 0.1g calcining, and 0.1g thioacetamide is added after mixed solution ultrasound 30min, fills after stirring 30min
Enter 1~2MPa autoclave, incubation water heating is carried out at 150 DEG C and reacts 5h.Product, which is cooled to room temperature, to be centrifuged simultaneously
It is washed 6 times with water and ethanol solution respectively, collects powder after dry in 60 DEG C, obtain final products In2S3。
Embodiment 6
Tetra- chloride hydrate indium of 0.2736g, 0.7627g lauryl sodium sulfate and 0.2803g urea are added to 80mL water
In solution, 60min is sufficiently stirred to clear solution, then above-mentioned acquired solution is transferred in 1~2 MPa autoclave,
Incubation water heating is carried out at 120 DEG C and reacts 12h, and product, which is cooled to room temperature, to be centrifuged and washed respectively with water and ethanol solution
6 times, powder is collected after dry in 60 DEG C, products therefrom is put into Muffle furnace, 500 DEG C of calcining 2h is carried out, obtains final products
In2O3。
The test of solar energy photocatalytic fixed nitrogen is carried out for Examples 1 to 6 sample.
All photocatalysis, which are tested, to be executed at 10~25 DEG C with 300W xenon lamp simulated solar irradiation.For photocatalysis fixed nitrogen mistake
Journey: 0.02g catalyst and 100mL water are added in glass photocatalytic reactor, and is passed through recirculated water to maintain 15 DEG C.Carry out
Before photocatalysis, it is passed through the nitrogen that flow velocity is 80mL/min, no light stirs 30min, then every 30min extraction under Xenon light shining
5mL solution.It is further filtered with 0.22 μm of filter, and instills nessler reagent, measured under ultraviolet specrophotometer 420nm wavelength
Absorbance.The test of photocatalysis fixed nitrogen is carried out for Examples 1 to 6 sample.
Fig. 7 illustrates 2 hours solar energy photocatalytic nitrogen fixation effects of Examples 1 to 6 catalyst.It is obvious that embodiment 1 is urged
Agent shows optimal photocatalysis solar energy photocatalytic nitrogen fixation effect, and photochemical catalyst generates 40.04 μm of ol ammonia per hour per gram
Gas.It is 13.35 μm of ol/ (hg) that 2 catalyst of embodiment, which generates ammonia amount, and it is 20.02 μ that 3 catalyst of embodiment, which generates ammonia amount,
Mol/ (hg), it is 29.20 μm of ol/ (hg) that embodiment 4, which generates ammonia amount, and it is 6.67 that 5 catalyst of embodiment, which generates ammonia amount,
μm ol/ (hg), it is 8.47 μm of ol/ (hg) that 6 catalyst of embodiment, which generates ammonia amount,.To find out, photocatalysis of the invention
Agent In2O3/In2S3Possess brilliant photocatalysis nitrogen fixation effect.
Catalyst provided by the invention is used for solar energy photocatalytic fixed nitrogen.Since length is limited, total Test can not be enumerated
Data, the present invention only provide part test data and support beneficial effects of the present invention.
In order to preferably utilize In2O3Fixed nitrogen light-catalyzed reaction is carried out, present invention employs indium sulfides to be compounded on indium oxide
Heterojunction structure is formed, the bouquet structure with indium sulfide and indium oxide is successfully prepared.Good solar energy is presented in catalyst
It is catalyzed fixed nitrogen performance.Since the bouquet structure of 3D indium oxide is provided compared with multiple reaction site, be conducive to electron-transport, will have compared with
The indium sulfide of narrow forbidden bandwidth is combined on indium oxide, enhances material to visible absorption, and it is compound after, lead valence
It is more advantageous to the separation of light induced electron with the structure constituted, greatly reduces the recombination rate of photo-generate electron-hole.It increases simultaneously
The specific surface area of material provides more active sites for photocatalysis fixed nitrogen.Therefore, so that this material has under sunlight
Good photocatalysis nitrogen fixation effect.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of photochemical catalyst, which is characterized in that catalyst is indium oxide/indium sulfide heterojunction semiconductor material, molecular formula
In2O3/In2S3。
2. photochemical catalyst according to claim 1, which is characterized in that in the flower ball-shaped structure with indium oxide and indium sulfide.
3. a kind of purposes of catalyst as claimed in claim 1 or 2, which is characterized in that be used for solar energy photocatalytic fixed nitrogen.
4. the purposes of catalyst according to claim 3, which is characterized in that be applied to by nitrogen source, water of nitrogen be reducing agent
Solar energy fixed nitrogen light-catalyzed reaction.
5. a kind of preparation method of photochemical catalyst, which comprises the steps of:
S1, at room temperature using water, ethyl alcohol, ethylene glycol, N,N-dimethylformamide (DMF) or isopropanol as solvent；
S2, indium salts compound, surfactant and alkalescent substance are dissolved in above-mentioned solvent, are sufficiently stirred and form mixing and is molten
Liquid；The indium salts compound includes four trichloride hydrate indiums, indium nitrate hydrate, indium sulfate or indium ion complex compound；The table
Face activating agent includes lauryl sodium sulfate, stearic acid, quaternary ammonium compound, fatty glyceride, CTAB or polyvinylpyrrolidone；
The alkalescent substance includes urea, aniline, ammonium hydroxide；
S3, mixed solution obtained by the S2 is transferred in the autoclave that pressure is 1~2MPa, carries out hydro-thermal reaction；Its
Middle hydrothermal temperature is 90~150 DEG C, and the hydro-thermal time is 10~20h；
S4, it after being cooled to room temperature, is centrifuged, alternately washs 4-8 times with 50~200mL water and ethyl alcohol respectively, 50
The indium hydroxide powder of white is collected after~80 DEG C of dryings；
S5, extracting waste indium hydroxide powder, which are put into the Muffle furnace that temperature is 350~550 DEG C, calcines 1~4h, heating rate 3
~10 DEG C/min, collect flaxen indium oxide powder；
S6, faint yellow indium oxide powder is added described in S1 in solvent, stir carry out after 10~30min ultrasonic disperse 10~
50min；
S7, sulphur source is added in above-mentioned S6 mixed solution, stirs 20~60min；
S8, the S7 mixed solution is transferred in the autoclave that pressure is 1~2MPa, carries out secondary hydro-thermal reaction；Its
Middle hydrothermal temperature is 90~180 DEG C, and the hydro-thermal time is 3~10h；
S9, it is cooled to room temperature and is centrifuged and is washed 4~8 times with 50~200mL water and ethanol solution respectively, 50~80
At DEG C after drying, collects powder and obtain indium oxide/indium sulfide heterojunction semiconductor material.
6. the preparation method of photochemical catalyst according to claim 5, which is characterized in that in step S7, the sulphur source is thio
Acetamide, thiocarbamide, sodium thiosulfate or L-cysteine.
7. according to the preparation method of any photochemical catalyst of claim 5~6, which comprises the following steps:
S1, at room temperature using 30~80mL water, ethyl alcohol, ethylene glycol, N,N-dimethylformamide or isopropanol as solvent；
S2,0.2~0.5g indium salts compound, 0.5~1g surfactant and 0.1~0.5g alkalescent substance be dissolved in 40~
In the above-mentioned solvent of 100mL, it is sufficiently stirred and forms mixed solution；The indium salts compound includes four trichloride hydrate indiums, nitric acid
Indium hydrate, indium sulfate or indium ion complex compound, surfactant include lauryl sodium sulfate, stearic acid, quaternary ammonium compound, rouge
Fatty acid glyceride, CTAB or polyvinylpyrrolidone；Alkalescent substance includes urea, aniline, ammonium hydroxide；
S3, above-mentioned S2 mixed solution is transferred in the autoclave that pressure is 1~2MPa, carries out hydro-thermal reaction；Wherein water
Hot temperature is 90~150 DEG C, and the hydro-thermal time is 10~20h；
S4, it after being cooled to room temperature, is centrifuged, is alternately washed 4~8 times with 50~200mL water and ethyl alcohol respectively,
It is collected after 50~80 DEG C of dryings and obtains indium hydroxide white powder；
S5, extracting waste indium hydroxide powder, which are put into the Muffle furnace that temperature is 350~550 DEG C, calcines 1~4h, heating rate 3
~10 DEG C/min, obtain flaxen indium oxide powder；
S6, faint yellow indium oxide powder is added in solvent described in 30~80mL S1, carries out ultrasound point after stirring 10~30min
Dissipate 10~50min；
S7,0.01~0.1g sulphur source is add to the above mixed solution, stirs 20~60min；
S8, above-mentioned mixed solution is transferred in the autoclave that pressure is 1~2MPa, carries out secondary hydro-thermal reaction；Wherein
Hydrothermal temperature is 90~180 DEG C, and the hydro-thermal time is 3~10h；
S9, it is cooled to room temperature and is centrifuged and is washed 4~8 times with 50~200mL water and ethanol solution respectively, 50~80
At DEG C after drying, collects powder and obtain indium oxide/indium sulfide heterojunction semiconductor material.
8. the preparation method of solar energy fixed nitrogen photochemical catalyst according to claim 7, which is characterized in that constant temperature described in step S8
When reaction, it is 60%~90% that the volume for filling solution, which accounts for the ratio of autoclave liner volume,.
9. a kind of method using above-mentioned catalyst high-efficiency solar fixed nitrogen, which is characterized in that be added 10 into 50~150mL water
~50mg photochemical catalyst, and maintaining temperature is 5~20 DEG C, before carrying out photocatalysis, stirs 30~60min, then stir under light illumination
Mix 40~120min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100850010B1 (en) * | 2007-03-19 | 2008-08-04 | 희성금속 주식회사 | Method for manufacturing indium oxide powder by ultrasonic chemistry reaction and method for manufacturing ito target |
| CN105664973A (en) * | 2016-02-26 | 2016-06-15 | 大连理工大学 | Three-dimensional flower-like In2S3/In2O3 composite microsphere photocatalytic material and preparation method thereof |
| CN109225194A (en) * | 2018-09-11 | 2019-01-18 | 同济大学 | Photocatalysis fixed nitrogen Zn doped indium oxide photocatalyst material and its preparation method and application |
| CN109289881A (en) * | 2018-11-21 | 2019-02-01 | 大连工业大学 | A kind of preparation and solar energy fixed nitrogen application of carbon nano-fiber support BiOX photocatalyst |
-
2019
- 2019-04-28 CN CN201910349372.8A patent/CN109999836A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100850010B1 (en) * | 2007-03-19 | 2008-08-04 | 희성금속 주식회사 | Method for manufacturing indium oxide powder by ultrasonic chemistry reaction and method for manufacturing ito target |
| CN105664973A (en) * | 2016-02-26 | 2016-06-15 | 大连理工大学 | Three-dimensional flower-like In2S3/In2O3 composite microsphere photocatalytic material and preparation method thereof |
| CN109225194A (en) * | 2018-09-11 | 2019-01-18 | 同济大学 | Photocatalysis fixed nitrogen Zn doped indium oxide photocatalyst material and its preparation method and application |
| CN109289881A (en) * | 2018-11-21 | 2019-02-01 | 大连工业大学 | A kind of preparation and solar energy fixed nitrogen application of carbon nano-fiber support BiOX photocatalyst |
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Application publication date: 20190712 |