CN110102315A - A kind of preparation and solar energy fixed nitrogen application of the indium sulfide photocatalyst with sulphur vacancy - Google Patents
A kind of preparation and solar energy fixed nitrogen application of the indium sulfide photocatalyst with sulphur vacancy Download PDFInfo
- Publication number
- CN110102315A CN110102315A CN201910349126.2A CN201910349126A CN110102315A CN 110102315 A CN110102315 A CN 110102315A CN 201910349126 A CN201910349126 A CN 201910349126A CN 110102315 A CN110102315 A CN 110102315A
- Authority
- CN
- China
- Prior art keywords
- indium
- acid
- room temperature
- solvent
- organic
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 48
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000005864 Sulphur Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011941 photocatalyst Substances 0.000 title abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000013216 MIL-68 Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- -1 indium salts compound Chemical class 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 150000002898 organic sulfur compounds Chemical class 0.000 claims abstract description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 62
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 60
- 235000019441 ethanol Nutrition 0.000 claims description 27
- 230000001699 photocatalysis Effects 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- 238000007146 photocatalysis Methods 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052738 indium Inorganic materials 0.000 claims description 12
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 9
- 230000001476 alcoholic effect Effects 0.000 claims description 9
- 229940113088 dimethylacetamide Drugs 0.000 claims description 9
- UVLYPUPIDJLUCM-UHFFFAOYSA-N indium;hydrate Chemical compound O.[In] UVLYPUPIDJLUCM-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- WPZSAUFQHYFIPG-UHFFFAOYSA-N propanethioamide Chemical compound CCC(N)=S WPZSAUFQHYFIPG-UHFFFAOYSA-N 0.000 claims description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 6
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 5
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- KYCHGXYBBUEKJK-UHFFFAOYSA-K indium(3+);trichloride;hydrate Chemical compound O.Cl[In](Cl)Cl KYCHGXYBBUEKJK-UHFFFAOYSA-K 0.000 claims description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 21
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000011534 incubation Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- SIXIBASSFIFHDK-UHFFFAOYSA-N indium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[In+3].[In+3] SIXIBASSFIFHDK-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 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
- 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
Landscapes
- 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 indium sulfide photocatalyst with sulphur vacancy, molecular formula In2S3, it is used for high-efficiency solar fixed nitrogen.The preparation method of catalyst, comprising steps of 1, take organic liquid be solvent；2, organic solvent is added in organic matter and indium salts compound；3, it is packed into reaction kettle, carries out isothermal reaction；4, it is cooled to room temperature and is centrifuged and is washed respectively with organic solvent and ethanol solution, collect powder after dry, obtain MIL-68 (In)；5, organic alcohol solvent is added in organic sulfur compound, mixes and be sufficiently stirred；6, MIL-68 (In) is added, mixes and is sufficiently stirred；7, it is packed into reaction kettle, carries out isothermal reaction；8, it is cooled to room temperature and is centrifuged and is washed respectively with water and ethanol solution, collect powder after dry, obtain indium sulfide；9, indium sulfide is annealed under nitrogen atmosphere, generates sulphur vacancy.The catalyst that the method for the present invention obtains is environmentally friendly, can be produced in batches, and has high-efficiency solar fixed nitrogen performance.
Description
Technical field
The present invention relates to a kind of catalysis material technical fields, more specifically to a kind of indium sulfide in sulfur-bearing vacancy
The preparation of photochemical catalyst and the application of solar energy fixed nitrogen.
Background technique
Ammonia (NH3) a kind of extremely important chemicals as synthesis of chemicals and chemical fertilizer, it is obtained in industry and agricultural
It is widely applied.All the time, traditional NH3Manufacturing method is Haber ammonia process, and the technique is usually using ferrum-based catalyst
By single component maximum in earth atmosphere under the reaction condition of high temperature and pressure --- nitrogen and hydrogen (H2) made together
With generation ammonia.However this method needs to consume mass energy, therefore, using a kind of low energy consumption and cleaning, safety method with
Energy consumption is reduced to be necessary.
Solar energy photocatalytic nitrogen fixation technology, because its reaction condition is mild, high-efficiency environment friendly and be concerned.In this reaction
In, semiconductor captures solar energy and generates electron hole pair, high energy electron is provided for activation N ≡ N, to promote its dissociation.But at present
Photocatalysis nitrogen fixation technology there are still some drawbacks that such as: photochemical catalyst is low to visible light utilization efficiency, and photo-generate electron-hole is compound
Fastly, catalyst does not have enough active sites to N2Carry out chemisorption etc..
Now, more and more photochemical catalysts are used in solar energy fixed nitrogen.Such as: titanium dioxide, oxyhalide, graphite
Alkene, molybdenum sulfide etc..Indium sulfide (In2S3) as a kind of applicable photochemical catalyst, there is medium band structure, it can
Visible light is directly absorbed, while there is excellent photoelectric sensitivity and hypotoxicity.In addition, a variety of by defect project, doping etc.
Method is modified to its, usually there is more carrier transports in reaction, shows better photocatalysis effect.
Summary of the invention
It is an object of that present invention to provide a kind of preparation of photochemical catalyst and its high-efficiency solar fixed nitrogen methods.
To achieve the goals above, the technical solution of the present invention is as follows:
A kind of photochemical catalyst of the present invention, catalyst are a kind of photochemical catalyst, which is characterized in that catalyst is with sulphur vacancy
Indium sulfide, molecular formula In2S3, structure is hollow 1D structure.
Catalyst provided by the invention, be used for high-efficiency solar fixed nitrogen, be applied particularly to using water as reducing agent efficiently too
Positive energy fixed nitrogen light-catalyzed reaction.
The present invention provides a kind of preparation methods of photochemical catalyst, include the following steps:
S1, at room temperature using N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, methylene chloride or dimethyl sulfoxide as
Solvent；
S2, above-mentioned solvent is added in organic acid and indium salts compound, mixes and is sufficiently stirred；The organic acid is to benzene two
Formic acid, adipic acid, azelaic acid, M-phthalic acid or dimethyl terephthalate (DMT)；The indium salts compound is nitric hydrate indium, water
Close inidum chloride, protochloride indium or trifluoromethayl sulfonic acid indium；
S3, after above-mentioned S2 acquired solution is stirred 10~30min, it is packed into the autoclave that pressure is 1~2MPa, into
100~120 DEG C of isothermal reactions of row；
S4, it is cooled to room temperature and is centrifuged and is washed respectively with organic solvent and ethanol solution, collect powder after dry
End obtains MIL-68 (In)；The organic solvent be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, methylene chloride or
Dimethyl sulfoxide；
S5, at room temperature using ethyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine as solvent；
S6, MIL-68 (In) and organosulfur compound are added in above-mentioned alcoholic solvent, mix and is sufficiently stirred；It is described organic
Sulfide is thiocarbamide, thiopropionamide, thioacetic acid, sodium thiosulfate or thioacetamide；
S7, it after above-mentioned S6 solution is stirred 10~30min, is fitted into the autoclave that pressure is 1~2MPa, carries out
150~180 DEG C of isothermal reactions；
S8, it is cooled to room temperature and is centrifuged and is washed respectively with water and ethanol solution, collect powder after dry and obtain
Indium sulfide；
S9, by indium sulfide under nitrogen atmosphere with 100~300 DEG C of 1~3h of calcining, heating rate is 3~10 DEG C/h, is obtained
Indium sulfide with sulphur vacancy.
Wherein, in step S6, the organic sulfur compound is thiocarbamide, thiopropionamide, thioacetic acid, sodium thiosulfate or sulphur
For acetamide.
The present invention provides a kind of preparation methods of photochemical catalyst, specifically includes the following steps:
S1, at room temperature by 6~12mL N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, methylene chloride or dimethyl
Sulfoxide is as solvent；
S2, above-mentioned solvent is added in 0.2~0.4g organic acid and 0.4~0.8g indium salts compound, mixes and is sufficiently stirred；
The organic acid is terephthalic acid (TPA), adipic acid, azelaic acid, M-phthalic acid or dimethyl terephthalate (DMT)；The indium salts
Conjunction object is nitric hydrate indium, chloride hydrate indium, protochloride indium or trifluoromethayl sulfonic acid indium；
S3, it after above-mentioned S2 acquired solution is stirred 10~30min, is fitted into the autoclave that pressure is 1~2MPa,
Carry out 100~120 DEG C of isothermal reactions；
S4, it is cooled to room temperature and is centrifuged and is washed 6 times with organic solvent and ethanol solution respectively, 60~80
Powder is collected after drying at DEG C, obtains MIL-68 (In)；The organic solvent is N,N-dimethylformamide, N, N- dimethyl second
Amide, methylene chloride or dimethyl sulfoxide；
S5, at room temperature using 40~80mL ethyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine as molten
Agent；
S6, above-mentioned alcoholic solvent is added in 0.01~0.03g MIL-68 (In) and 0.6~1.2g organic sulfur compound, mixing is simultaneously
It is sufficiently stirred；The organic sulfur compound is thiocarbamide, thiopropionamide, thioacetic acid, sodium thiosulfate or thioacetamide；
S7, it after above-mentioned S6 acquired solution is stirred 10~30min, is fitted into the autoclave that pressure is 1~2MPa,
Carry out 150~180 DEG C of isothermal reactions；
S8, it is cooled to room temperature and is centrifuged and is washed 6 times with water and ethanol solution respectively, it is dry at 60~80 DEG C
Afterwards, it collects powder and obtains indium sulfide；
S9, by indium sulfide under nitrogen atmosphere with 100~300 DEG C calcine, heating rate be 3~10 DEG C/h, heat preservation 1~
It is cooled to room temperature after 2h, obtains the indium sulfide with sulphur vacancy.
Wherein, when isothermal reaction described in step S3, it is 60% that the volume for filling solution, which accounts for the ratio of autoclave liner volume,
~90%, the reaction time is 3~5h；When isothermal reaction described in step S8, the volume for filling solution accounts for autoclave liner volume
Ratio is 60%~90%, and the reaction time is 24~48h.
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
Photochemical catalyst of the invention not only can use solar energy and convert ammonia for nitrogen, but also possess higher quantum effect
Rate.Using water as reducing agent under sunlight, SV-In2S3Photochemical catalyst produces 52.49 μm of ol ammonias per hour per gram, and ammonia generates
Amount is In2S31.5 times.It has broad application prospects to the production ammonia energy, reduction environmental pollution etc., is urged to produce the type
Agent provides certain theoretical basis.
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 UV-vis abosrption spectrogram of 1 catalyst of embodiment.
Fig. 4 is that the forbidden bandwidth of 1 catalyst of embodiment estimates spectrogram.
Fig. 5 is the current versus time curve figure of 1 catalyst of embodiment.
Fig. 6 is the AC impedance figure of 1 catalyst of embodiment.
Fig. 7 is the solar energy nitrogen fixation effect figure of Examples 1 to 3 catalyst.
Specific embodiment
The present invention a kind of preparation and high-efficiency solar fixed nitrogen method of the indium sulfide photocatalyst containing sulphur vacancy, belong to light
Catalysis material technical field.This method comprises the following steps: 1, using organic liquid as solvent；2, by organic acid and indium salts compound
Above-mentioned solvent is added, mix and is sufficiently stirred；3, it is fitted into reaction kettle, carries out isothermal reaction；4, it is cooled to room temperature and is centrifuged
It separates and is repeatedly washed with organic solvent and ethanol solution respectively, collect powder after dry, obtain MIL-68 (In)；5, it takes organic
Alcohol is as solvent；6, the alcoholic solvent is added in MIL-68 (In) and organic sulfur compound, mixes and is sufficiently stirred；7, it is packed into reaction
In kettle, isothermal reaction is carried out；8, it is cooled to room temperature and is centrifuged and is washed respectively with water and ethanol solution, collected after dry
Powder obtains indium sulfide；9, indium sulfide is annealed under nitrogen atmosphere, generates sulphur vacancy, obtains the sulphur containing sulphur vacancy
Change indium.The indium sulfide photocatalyst containing sulphur vacancy that the method for the present invention obtains is environmentally friendly, material source is extensive, method is controllable
And it is easy to operate, can be produced in batches, have 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 the technical program.Below
Described embodiment is only a part of the invention, is not whole embodiments.Those skilled in the art is according to this
The content of invention is made some nonessential improvement and is all belonged 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.
In the present invention using N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, methylene chloride or dimethyl sulfoxide as
Solvent is reacted at room temperature；The solvent includes but is not limited to N, N- dimethylformamide, DMAC N,N' dimethyl acetamide, two
Chloromethanes or dimethyl sulfoxide are as solvent.
Above-mentioned solvent is added in organic acid and indium salts compound, mixes and is sufficiently stirred；The organic acid is terephthaldehyde
Acid, adipic acid, azelaic acid, M-phthalic acid or dimethyl terephthalate (DMT)；The indium salts compound is nitric hydrate indium, hydration
Inidum chloride, protochloride indium or trifluoromethayl sulfonic acid indium.After stirring 10~30min, it is 1~2MPa's that mixed solution, which is packed into pressure,
In autoclave, 100~120 DEG C of isothermal reactions are carried out, after keeping the temperature 24~48h, are cooled to room temperature, be centrifuged and are divided
It is not washed with organic solvent and ethanol solution, collects powder after dry, obtain MIL-68 (In).Wherein, when synthetic reaction, filling
The ratio that the volume of solution accounts for autoclave liner volume is 60%~90%.
Using 40~80mL ethyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine as solvent, at room temperature
It is reacted；The alcohol includes but is not limited to ethyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine.
The alcoholic solvent is added in 0.01~0.03g MIL-68 (In) and 0.6~1.2g organic sulfur compound, mixes and fills
Divide stirring, mixing time is 10~30min；The organic sulfur compound includes but is not limited to thiocarbamide, thiopropionamide, thio second
Acid, sodium thiosulfate or thioacetamide；
It is fitted into the autoclave that pressure is 1~2MPa after above-mentioned solution is stirred to clarify solution in the present invention, into
150~180 DEG C of isothermal reactions of row.Product, which is cooled to room temperature, to be centrifuged and is washed 4~8 times with water and ethanol solution respectively,
Powder is collected after 50~80 DEG C of dryings.Wherein, when synthetic reaction, the volume for filling solution accounts for the ratio of autoclave liner volume
It is 60%~90%, the reaction time is 3~5h.
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 temperature of reaction system at 5~20 DEG C, before carrying out photocatalysis, stirring
30~60min, then 40~120min is stirred under light illumination, catalyst is filtered out 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, SV-In2S3Photochemical catalyst generates 52.49 μm of ol ammonias per hour per gram, and ammonia produces
Raw amount is In2S31.5 times.It has broad application prospects to the production ammonia energy, reduction environmental pollution etc., to produce the type
Catalyst provides certain theoretical basis.
(2)SV-In2S3The preparation method of catalysis material is environmentally protective, easy to operate, cheap, wants to special installation
Ask low, controllability is strong, has certain practicability.
Embodiment 1
0.408g nitric hydrate indium, 0.2g terephthalic acid (TPA) are added to 12mL N,N-dimethylformamide (DMF) solution
In, it is packed into 1~2MPa autoclave after 30min to clear solution is sufficiently stirred, carries out 100 DEG C of incubation water heating reaction 48h.
Product, which is cooled to room temperature, to be centrifuged and is washed 6 times with n,N-Dimethylformamide (DMF) and ethanol solution respectively, in 60
DEG C vacuum drying after collect powder, obtain MIL-68 (In).0.01g MIL-68 (In), 0.6g thiocarbamide are added to 80mL second
In alcoholic solution, it is packed into 1~2MPa autoclave after 30min to clear solution is sufficiently stirred, carries out 180 DEG C of incubation water heating reactions
3h.Product, which is cooled to room temperature, to be centrifuged and is washed 6 times with water and ethanol solution respectively, collects powder after dry in 60 DEG C,
Obtain In2S3.The In that will be obtained2S3Powder is calcined in a nitrogen atmosphere, calcination temperature be 300 DEG C, heating rate be 5 DEG C/
H is cooled to room temperature after keeping the temperature 1~2h, obtains the indium sulfide that final product has sulphur vacancy, molecular formula In2S3, with SV-In2S3-
300 indicate.
Fig. 1 is the SV-In that the present embodiment obtains2S3- 300 photochemical catalyst XRD diffracting spectrums, through being compared with PDF standard card
It learns, the In obtained for β phase2S3。
Fig. 2 is the SV-In that the present embodiment obtains2S3- 300 photochemical catalyst scanning electron microscope (SEM) photographs, being obtained is with the hollow knot of 1D
The interior diameter of structure is about 1.0 μm, and overall diameter is about 2.0 μm, and length is about 4~5 μm of club-shaped material.
Fig. 3 is the SV-In that the present embodiment obtains2S3- 300 photochemical catalyst UV-vis absorption spectrums, compared to pure In2S3It inhales
Bian Hongyi is received, is obviously improved in visible-range internal absorbance, there is stronger light abstraction width.
Fig. 4 is the SV-In that the present embodiment obtains2S3The forbidden bandwidth of -300 photochemical catalysts estimates map, the band of resulting materials
Gap relative narrower accelerates electron-transport speed, to promote photocatalytic activity.
Fig. 5 is the SV-In that the present embodiment obtains2S3- 300 photochemical catalyst photocurrent-time curve figures, before calcining
Pure phase In2S3, have stronger photoelectric current, illustrate to have efficiently separated light induced electron and hole.
Fig. 6 is the SV-In that the present embodiment obtains2S3- 300 photochemical catalyst AC impedance figures, compared to pure phase In2S3, show
Lesser resistance, at the same illustrate it is for the recombination rate of photo-generated carrier low, it is preferable to promote charge conversion and efficiently separate.
Embodiment 2
0.408g nitric hydrate indium, 0.2g terephthalic acid (TPA) are added to 12mL N,N-dimethylformamide (DMF) solution
In, it is packed into 1~2MPa autoclave after 30min to clear solution is sufficiently stirred, carries out 100 DEG C of incubation water heating reaction 48h.
Product, which is cooled to room temperature, to be centrifuged and is washed 6 times with n,N-Dimethylformamide (DMF) and ethanol solution respectively, in 60
DEG C vacuum drying after collect powder, obtain MIL-68 (In).0.01g MIL-68 (In), 0.6g thiocarbamide are added to 80mL second
In alcoholic solution, it is packed into 1~2MPa autoclave after 30min to clear solution is sufficiently stirred, carries out 180 DEG C of incubation water heating reactions
3h.Product, which is cooled to room temperature, to be centrifuged and is washed 6 times with water and ethanol solution respectively, collects powder after dry in 60 DEG C,
Obtain In2S3.The In that will be obtained2S3Powder is calcined in a nitrogen atmosphere, calcination temperature be 200 DEG C, heating rate be 5 DEG C/
H is cooled to room temperature after keeping the temperature 1~2h, obtains the indium sulfide that final product has sulphur vacancy, molecular formula In2S3, with SV-In2S3-
200 indicate.
Embodiment 3
0.408g nitric hydrate indium, 0.2g terephthalic acid (TPA) are added to 12mL N,N-dimethylformamide (DMF) solution
In, it is packed into 1~2MPa autoclave after 30min to clear solution is sufficiently stirred, carries out 100 DEG C of incubation water heating reaction 48h.
Product, which is cooled to room temperature, to be centrifuged and is washed 6 times with n,N-Dimethylformamide (DMF) and ethanol solution respectively, in 60
DEG C vacuum drying after collect powder, obtain MIL-68 (In).0.01g MIL-68 (In), 0.6g thiocarbamide are added to 80mL second
In alcoholic solution, it is packed into 1~2MPa autoclave after 30min to clear solution is sufficiently stirred, carries out 180 DEG C of incubation water heating reactions
3h.Product, which is cooled to room temperature, to be centrifuged and is washed 6 times with water and ethanol solution respectively, collects powder after dry in 60 DEG C,
Obtain final product In2S3。
The test of solar energy photocatalytic fixed nitrogen is carried out for Examples 1 to 3 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: being added 0.02g catalyst and 100mL deionized water in quartzy photo catalysis reactor, and being passed through cooling circulating water will reaction
System temperature maintains 15 DEG C.Before carrying out photocatalysis, it is passed through the high pure nitrogen that flow velocity is 80mL/min, is stirred under no light
30min, then every 15min takes out 5mL solution under 300W Xenon light shining.It is further filtered with 0.22 μm of filter, and instills Na Shi
Reagent measures absorbance under ultraviolet specrophotometer 420nm wavelength.Photocatalysis fixed nitrogen is carried out for Examples 1 to 3 sample
Test.
Fig. 7 illustrates 1 hour solar energy photocatalytic nitrogen fixation effect of Examples 1 to 3 catalyst.It is obvious that embodiment 2 is urged
Agent shows optimal photocatalysis solar energy photocatalytic nitrogen fixation effect, and photochemical catalyst generates 52.49 μm of ol ammonia per hour per gram
Gas.It is 35.56 μm of ol/ (hg) that 1 catalyst of embodiment, which generates ammonia amount, and it is 47.41 μ that 3 catalyst of embodiment, which generates ammonia amount,
Mol/ (hg), to find out, photochemical catalyst SV-In of the invention2S3- 200 possess 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 In2S3Fixed nitrogen light-catalyzed reaction is carried out, present invention employs in a nitrogen atmosphere with certain temperature
The method calcined is spent, the 1D hollow rod-shape structure indium sulfide with sulphur vacancy has been successfully prepared.Catalyst presents good
Solar energy photocatalytic fixed nitrogen performance.Since there is indium sulfide hollow and surface lamellar structure can increase contact area, simultaneously
With relatively narrow forbidden bandwidth, enhance the absorption to visible light.After calcining in nitrogen, the sulphur vacancy of generation can increase material
Active site, promote its photocatalytic activity.Therefore, so that this material is under sunlight, there is good photocatalysis fixed nitrogen effect
Fruit.
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 the indium sulfide with sulphur vacancy, molecular formula In2S3。
2. photochemical catalyst according to claim 1, which is characterized in that in the 1D hollow structure of the indium sulfide with sulphur vacancy.
3. a kind of purposes of catalyst as claimed in claim 1 or 2, which is characterized in that for responding 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 N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, methylene chloride or dimethyl sulfoxide as molten
Agent；
S2, above-mentioned solvent is added in organic acid and indium salts compound, mixes and is sufficiently stirred；The organic acid is terephthaldehyde
Acid, adipic acid, azelaic acid, M-phthalic acid or dimethyl terephthalate (DMT)；The indium salts compound is nitric hydrate indium, hydration
Inidum chloride, protochloride indium or trifluoromethayl sulfonic acid indium；
S3, the autoclave that pressure is 1~2MPa will be packed into after above-mentioned S2 acquired solution stirs 10~30min, 100~
120 DEG C are reacted；
S4, it is cooled to room temperature and is centrifuged and is washed respectively with organic solvent and ethanol solution, collect powder after dry, obtain
To MIL-68 (In)；The organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, methylene chloride or dimethyl
Sulfoxide；
S5, at room temperature using ethyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine as solvent；
S6, MIL-68 (In) and organosulfur compound are added in above-mentioned alcoholic solvent, mix and is sufficiently stirred；
S7, it after above-mentioned S6 solution is stirred 10~30min, is fitted into the autoclave that pressure is 1~2MPa, 150~180
It DEG C is reacted；
S8, it is cooled to room temperature and is centrifuged and is washed respectively with water and ethanol solution, collect powder after dry and vulcanized
Indium；
S9, by indium sulfide under nitrogen atmosphere with 100~300 DEG C of 1~3h of calcining, heating rate is 3~10 DEG C/h, is had
The indium sulfide in sulphur vacancy.
6. the preparation method of photochemical catalyst according to claim 5, which is characterized in that in step S6, the organic sulfur compound
For thiocarbamide, thiopropionamide, thioacetic acid, sodium thiosulfate or thioacetamide.
7. according to the preparation method of any photochemical catalyst of claim 5~6, which comprises the following steps:
S1, at room temperature by 6~12mL N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, methylene chloride or dimethyl sulfoxide
As solvent；
S2, above-mentioned solvent is added in 0.2~0.4g organic acid and 0.4~0.8g indium salts compound, mixes and is sufficiently stirred；It is described
Organic acid is terephthalic acid (TPA), adipic acid, azelaic acid, M-phthalic acid or dimethyl terephthalate (DMT)；The indium salts compound
For nitric hydrate indium, chloride hydrate indium, protochloride indium or trifluoromethayl sulfonic acid indium；
S3, it after above-mentioned S2 acquired solution is stirred 10~30min, is fitted into the autoclave that pressure is 1~2MPa, carries out
100~120 DEG C of isothermal reactions；
S4, it is cooled to room temperature and is centrifuged and is washed 6 times with organic solvent and ethanol solution respectively, in 60~80 DEG C of dryings
After collect powder, obtain MIL-68 (In)；The organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, two
Chloromethanes or dimethyl sulfoxide；
It is S5, molten as alcohol for 40~80mL ethyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine at room temperature
Agent；
S6, above-mentioned alcoholic solvent is added in 0.01~0.03g MIL-68 (In) and 0.6~1.2g organic sulfur compound, mixed and abundant
Stirring；The organic sulfur compound is thiocarbamide, thiopropionamide, thioacetic acid, sodium thiosulfate or thioacetamide；
S7, it after above-mentioned S6 acquired solution is stirred 10~30min, is fitted into the autoclave that pressure is 1~2MPa, 150
~180 DEG C are reacted；
S8, it is cooled to room temperature and is centrifuged and is washed repeatedly with water and ethanol solution respectively, after dry at 60~80 DEG C,
It collects powder and obtains indium sulfide；
S9, by indium sulfide under nitrogen atmosphere with 100~300 DEG C calcine, heating rate be 3~10 DEG C/h, keep the temperature 1~2h after it is cold
But to room temperature, the indium sulfide with sulphur vacancy is obtained.
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 S3
When reaction, it is 60%~90% that the volume for filling solution, which accounts for the ratio of autoclave liner volume, and the reaction time is 3~5h；Step
Described in S8 when isothermal reaction, it is 60%~90% that the volume for filling solution, which accounts for the ratio of autoclave liner volume, and the reaction time is
24~48h.
9. a kind of method that can be carried out fixed nitrogen using the sun using above-mentioned catalyst, which is characterized in that add into 50~150mL water
Enter 10~50mg photochemical catalyst, and maintenance system temperature is 5~20 DEG C, before carrying out photocatalysis, 30~60min of stirring, then
40~120min is stirred under illumination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910349126.2A CN110102315A (en) | 2019-04-28 | 2019-04-28 | A kind of preparation and solar energy fixed nitrogen application of the indium sulfide photocatalyst with sulphur vacancy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910349126.2A CN110102315A (en) | 2019-04-28 | 2019-04-28 | A kind of preparation and solar energy fixed nitrogen application of the indium sulfide photocatalyst with sulphur vacancy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110102315A true CN110102315A (en) | 2019-08-09 |
Family
ID=67487247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910349126.2A Pending CN110102315A (en) | 2019-04-28 | 2019-04-28 | A kind of preparation and solar energy fixed nitrogen application of the indium sulfide photocatalyst with sulphur vacancy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110102315A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479315A (en) * | 2019-09-11 | 2019-11-22 | 湖北民族大学 | A kind of porous indium sulfide/spherical molybdenum disulfide composite material and preparation method and application |
| CN110548545A (en) * | 2019-09-20 | 2019-12-10 | 暨南大学 | Application of titanium-based metal organic framework material in photocatalytic nitrogen fixation |
| CN110639619A (en) * | 2019-10-28 | 2020-01-03 | 商丘师范学院 | Metal sulfide composite catalyst Uio-66/In based on metal organic framework In-situ growth2S3Preparation method of (1) |
| CN111790405A (en) * | 2020-07-09 | 2020-10-20 | 湖南大学 | Photocatalyst capable of degrading antibiotics and preparation method and application thereof |
| CN112371190A (en) * | 2020-11-23 | 2021-02-19 | 西安建筑科技大学 | In2S3MIL-53(Fe) high-efficiency photocatalytic composite material, preparation method and application |
| CN113461046A (en) * | 2021-07-28 | 2021-10-01 | 四川恒瑞天成科技有限公司 | Comb-shaped nitrogen-doped indium sulfide gas-sensitive material, preparation method and application |
| CN115959701A (en) * | 2023-02-20 | 2023-04-14 | 西南交通大学 | Preparation method and application of 3D self-assembly hydrangea-shaped indium sulfide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105478142A (en) * | 2015-11-19 | 2016-04-13 | 江苏大学 | Indium-sulfide mesoporous hollow microsphere photocatalyst, and preparation method and uses thereof |
| CN109261166A (en) * | 2018-08-16 | 2019-01-25 | 华南理工大学 | A kind of preparation of the flower-like nanometer material of tin dope indium sulfide and its application in photo catalytic reduction |
-
2019
- 2019-04-28 CN CN201910349126.2A patent/CN110102315A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105478142A (en) * | 2015-11-19 | 2016-04-13 | 江苏大学 | Indium-sulfide mesoporous hollow microsphere photocatalyst, and preparation method and uses thereof |
| CN109261166A (en) * | 2018-08-16 | 2019-01-25 | 华南理工大学 | A kind of preparation of the flower-like nanometer material of tin dope indium sulfide and its application in photo catalytic reduction |
Non-Patent Citations (3)
| Title |
|---|
| CARRASCO-JAIM ET AL.: "" Photocatalytic hydrogen production by biomimetic indium sulfide using Mimosa pudica leaves as template"", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| JINGJING ZHANG ET AL.: ""Tailored indium sulfide-based materials for solar-energy conversion and utilization"", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY C: PHOTOCHEMISTRY REVIEWS》 * |
| YUAN FANG ET AL.: ""MOF-derived In2S3 nanorods for photocatalytic removal of dye and Antibiotics"", 《JOURNAL OF SOLID STATE CHEMISTRY》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479315B (en) * | 2019-09-11 | 2022-04-15 | 湖北民族大学 | Porous indium sulfide/spherical molybdenum disulfide composite material and preparation method and application thereof |
| CN110479315A (en) * | 2019-09-11 | 2019-11-22 | 湖北民族大学 | A kind of porous indium sulfide/spherical molybdenum disulfide composite material and preparation method and application |
| CN110548545A (en) * | 2019-09-20 | 2019-12-10 | 暨南大学 | Application of titanium-based metal organic framework material in photocatalytic nitrogen fixation |
| CN110548545B (en) * | 2019-09-20 | 2022-09-20 | 暨南大学 | Application of titanium-based metal organic framework material in photocatalytic nitrogen fixation |
| CN110639619A (en) * | 2019-10-28 | 2020-01-03 | 商丘师范学院 | Metal sulfide composite catalyst Uio-66/In based on metal organic framework In-situ growth2S3Preparation method of (1) |
| CN110639619B (en) * | 2019-10-28 | 2022-05-27 | 商丘师范学院 | Metal sulfide composite catalyst Uio-66/In based on metal organic framework In-situ growth2S3Preparation method of (1) |
| CN111790405A (en) * | 2020-07-09 | 2020-10-20 | 湖南大学 | Photocatalyst capable of degrading antibiotics and preparation method and application thereof |
| CN111790405B (en) * | 2020-07-09 | 2022-04-12 | 湖南大学 | Photocatalyst capable of degrading antibiotics and preparation method and application thereof |
| CN112371190A (en) * | 2020-11-23 | 2021-02-19 | 西安建筑科技大学 | In2S3MIL-53(Fe) high-efficiency photocatalytic composite material, preparation method and application |
| CN112371190B (en) * | 2020-11-23 | 2023-04-18 | 西安建筑科技大学 | In 2 S 3 MIL-53 (Fe) high-efficiency photocatalytic composite material, preparation method and application |
| CN113461046A (en) * | 2021-07-28 | 2021-10-01 | 四川恒瑞天成科技有限公司 | Comb-shaped nitrogen-doped indium sulfide gas-sensitive material, preparation method and application |
| CN115959701A (en) * | 2023-02-20 | 2023-04-14 | 西南交通大学 | Preparation method and application of 3D self-assembly hydrangea-shaped indium sulfide |
| CN115959701B (en) * | 2023-02-20 | 2024-04-26 | 西南交通大学 | Preparation method and application of 3D self-assembled hydrangea-shaped indium sulfide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110102315A (en) | A kind of preparation and solar energy fixed nitrogen application of the indium sulfide photocatalyst with sulphur vacancy | |
| CN109999836A (en) | A kind of preparation of indium oxide/indium sulfide heterojunction semiconductor material and photochemical catalyst purposes and solar energy fixed nitrogen application | |
| CN102500388B (en) | Copper and bismuth co-doped nano titanium dioxide photocatalyst and preparation and application thereof | |
| CN112023938B (en) | Bimetallic ion doped nano composite photocatalyst and preparation method thereof | |
| CN103480395B (en) | Preparation and application of core-shell-structure bismuth sulfide@bismuth oxide composite microspheres | |
| CN105771948A (en) | Double-shell titanium dioxide catalyst with high photocatalytic hydrogen generation performance and preparation method thereof | |
| CN103447052B (en) | Preparation and application of hollow tree-like bismuth oxide-bismuth sulfide complex | |
| CN104338529A (en) | Preparation method of MnOx-CeO2 composite semiconductor catalyst | |
| CN109261173A (en) | A kind of the solar energy fixed nitrogen method and application of hydrotreated bismuth deposit bismuth oxybromide | |
| CN105126821B (en) | A kind of flower-shaped Bi2MoO6Preparation and its in photo catalytic reduction CO2In application | |
| CN106492872A (en) | A kind of preparation method for improving graphite phase carbon nitride yield | |
| CN112316970A (en) | Preparation method and application of multi-defect graphite-phase carbon nitride photocatalyst | |
| CN111841530A (en) | Catalyst for promoting water photolysis to produce hydrogen and preparation method thereof | |
| CN103521244B (en) | Photocatalytic water-splitting hydrogen production material CdS/Sr1.6Zn0.4Nb2O7 and preparation method thereof | |
| CN109589985B (en) | Preparation method of doped nano zinc germanate and catalytic reduction of carbon dioxide by using doped nano zinc germanate | |
| CN103785425B (en) | A kind of flower-shaped Bi 2o (OH) 2sO 4the preparation method of photochemical catalyst and application | |
| CN107349951B (en) | CuO/g-C3N4Preparation method of capillary-like nano-composite | |
| CN114289036A (en) | Sulfide photocatalyst containing rare earth elements and preparation method and application thereof | |
| CN106732587B (en) | A kind of preparation method of the ZnO polycrystal nanobelt package assembly of high H2-producing capacity atomic state Ag modification | |
| CN114849789A (en) | Preparation method and application of MIL-125 loaded 1T-phase molybdenum sulfide composite photocatalyst | |
| CN109569569A (en) | A kind of photochemical catalyst and its preparation method and application with ternary heterojunction structure | |
| CN109894142A (en) | A kind of molecular sieve carried CdS-Pt composite photo-catalyst of nanoscale twins MFI and preparation method thereof | |
| CN109289880A (en) | A kind of BiOI (100)/BiOI (001) is the same as phase homojunction and preparation method | |
| CN103433064A (en) | Preparation method of nitrogen-doped zinc sulfide with visible-light catalytic activity and high stability and application thereof | |
| CN107081150A (en) | One kind carries platinum sodium titanate mixed crystal nano wire assembly 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190809 |