CN109289883A - A kind of preparation method of photocatalyst preparation - Google Patents
A kind of preparation method of photocatalyst preparation Download PDFInfo
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- CN109289883A CN109289883A CN201811057613.3A CN201811057613A CN109289883A CN 109289883 A CN109289883 A CN 109289883A CN 201811057613 A CN201811057613 A CN 201811057613A CN 109289883 A CN109289883 A CN 109289883A
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- photocatalyst
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910017582 La2Ti2O7 Inorganic materials 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 108010029541 Laccase Proteins 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 16
- 238000006731 degradation reaction Methods 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 16
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000004065 semiconductor Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 10
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 10
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 5
- APIDIPGVBRXKEJ-UHFFFAOYSA-N acetic acid titanium Chemical compound [Ti].CC(O)=O.CC(O)=O APIDIPGVBRXKEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/0004—Oxidoreductases (1.)
- C12N9/0055—Oxidoreductases (1.) acting on diphenols and related substances as donors (1.10)
- C12N9/0057—Oxidoreductases (1.) acting on diphenols and related substances as donors (1.10) with oxygen as acceptor (1.10.3)
- C12N9/0061—Laccase (1.10.3.2)
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12Y—ENZYMES
- C12Y110/00—Oxidoreductases acting on diphenols and related substances as donors (1.10)
- C12Y110/03—Oxidoreductases acting on diphenols and related substances as donors (1.10) with an oxygen as acceptor (1.10.3)
- C12Y110/03002—Laccase (1.10.3.2)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
-
- 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
- Y02P20/59—Biological synthesis; Biological purification
Abstract
The present invention relates to a kind of preparation methods of photocatalyst preparation, by perovskite type metal oxide La2Ti2O7With sulfide In2S3Assemble the P-N heterojunction structure La constructed2Ti2O7/In2S3, then Platinum Nanoparticles, laccase are loaded, the photocatalyst preparation that solar hydrogen making and solar energy degradation of formaldehyde may be implemented is prepared.Compared with prior art, perovskite type metal oxide La of the invention2Ti2O7With sulfide In2S3With ultra-thin two-dimension structure, visible absorption is continuously adjustable at 550 nanometers to 600 nanometers.The photocatalyst preparation can be realized full hydrogen production by water decomposition and indoor highly effective removal formaldehyde under sunlight.
Description
Technical field
The invention belongs to catalysis material technical fields, more particularly, to photolysis water hydrogen gas and remove indoor and other envelopes
Close the preparation method of the photocatalyst preparation of Pollutant Formaldehyde in space.
Background technique
Human society rapid development, but increasingly difficulty or ease meet the energy need that the mankind increase rapidly to existing energy reserves
It asks；In addition, the exploitation of fossil fuel, using and discharging and induce serious environmental problem, such as climate warming, Ocean acidification, sky
Gas pollution etc., the serious sustainable development for hindering society.Therefore, develop or find a kind of new sustainable using energy source
Mode is the key that solve the above problems；At the same time, with the development of science and technology the living standard of the mankind steps up, the mankind
Health perception, environmental consciousness gradually enhance, during house ornamentation or in automobile use process, wound of the formaldehyde pollutants to the mankind
Evil is huge, and conventional method is difficult to effectively remove the pollutant, therefore, the formaldehyde of (such as new house or new car) in enclosure space
The clearance technique of toxic gas urgently improves.
Compared with fossil energy, solar energy has many advantages.Firstly, sun energy storage capacity is huge, it is estimated that one hour supports
Solar energy up to earth surface can satisfy 1 year energy requirement of the mankind；In addition, solar radiation is widely distributed and easy acquisition,
Other than south poles will appear polar night phenomenon, there is considerable solar radiation in the place of human living.Secondly, the exploitation of solar energy
Continued damage not will cause to environment with utilizing.Existing Solar use mode mainly includes solar energy-electric energy conversion, the sun
It can chemical energy conversion and solar energy conversion.Wherein solar energy chemical conversion is ideal energy development approach.For example, will
It is intermittent, not the solar radiation of easily collecting and storage be converted into the chemical energy (e.g., Hydrogen Energy etc.) of easily collecting and storage both can be with
Existing fossil energy is effectively matched using framework, is unlikely to overturn fossil energy economy completely, and can effectively avoid fossil energy
Source develops and uses brought environmental problem；In addition light degradation pollutant is also ideal effective environmental-friendly pollution treatment side
Formula, the Pollutant Formaldehyde light degradation in enclosure space can hold sequence effectively by contaminant degradation be free of contamination carbon dioxide and
Hydrone.
The conversion of solar energy chemical energy specifically include that 1. using solar energy photocatalyst surface by water decomposition be hydrogen and oxygen
Gas (i.e. solar hydrogen making) 2. utilizes solar energy and photocatalyst decomposing organic pollutant such as formaldehyde (solar energy purification environment).This two
Kind Solar use mode all relies on efficient photocatalyst.Photocatalyst is that one kind can be absorbed, conversion solar energy and is catalyzed
The catalyst of chemical reaction.Traditional photocatalyst such as TiO2(Energy&Environmental Science,5(2012)6506-
6512), CdS (The Journal of Physical Chemistry C, 115 (2011) 11466-11473) etc. faces the sun
The problems such as absorptivity is low, stability is poor causes solar hydrogen making efficiency and degradable organic pollutant (such as formaldehyde) inefficient.
Summary of the invention
It is high, steady that it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of catalytic activity
The preparation method of qualitative good photocatalyst.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of photocatalyst preparation, perovskite type metal oxide La2Ti2O7With sulfide In2S3By quiet
The P-N heterojunction structure La that electricity assembling is constructed2Ti2O7/In2S3, then Platinum Nanoparticles, laccase are loaded, it is prepared and solar energy may be implemented
The photocatalyst preparation of hydrogen manufacturing and solar energy degradation of formaldehyde, wherein the perovskite type metal oxide La2Ti2O7With sulfide
In2S3Mass ratio be 2.5:1.0-12.5:1.0, the content for loading Platinum Nanoparticles is 1-3wt%, the content of laccase is 0-1wt%.
The visible absorption for the photocatalyst preparation being prepared is continuously adjustable at 500 nanometers to 600 nanometers.
Above-mentioned preparation method specifically uses following steps:
(1) temperature 263K-283K is controlled, acetic acid titanium and lanthanum nitrate are mixed and are dissolved in deionized water, clear solution is obtained；
(2) temperature 273K-283K is controlled, sodium hydroxide and deionized water are mixed, clear solution is made, wherein hydroxide
The concentration of sodium is 2mol/L；
(3) temperature 273K-283K is controlled, above-mentioned solution is mixed dropwise and continuing vigorous stirs, it is mixed to obtain white " milky "
Close solution；
(4) temperature 603K is controlled, above-mentioned mixed solution is closed in reaction kettle and is kept for 24 hours, white solid is obtained,
Wash drying；
(5) white solid is placed in DMF, is kept for 48 hours under ultrasound condition, obtains ultra-thin N-type semiconductor
La2Ti2O7White " milky " liquid；
(6) control temperature 263K-283K, weigh indium nitrate, cetyl trimethylammonium bromide, thioacetamide mixing it is molten
In deionized water, clear solution is persistently stirred to get；
(7) clear solution is flowed back 90 minutes under the conditions of 368K and obtains yellow mercury oxide；
(8) yellow mercury oxide S2 dehydrated alcohol and deionized water are washed dry and does same treatment in (5), obtained ultra-thin
P-type semiconductor In2S3Yellow emulsion；；
(9) according to the ratio by the ultra-thin N-type semiconductor La of different quality ratio2Ti2O7With ultra-thin P-type semiconductor In2S3It mixes dropwise
Merge ultrasonic treatment, in the process, the two by ultrasound removing finds that surface both carries by measuring its Zeta electric potential
Variety classes charge, wherein La2Ti2O7Carry positive charge, In2S3In 453K item after the powder washing that carrying negative electrical charge obtains is dry
Two hours are handled under part；
(10) treated, and powder is mixed with the platinum acid chloride solution that concentration is 2wt%, is being configured with 400 nm filters
It is irradiated 1 hour under the conditions of 300 watts of xenon lamps, obtains water decomposition hydrogen manufacturing type photocatalyst.
Ultra-thin N-type semiconductor La in step (9)2Ti2O7With ultra-thin P-type semiconductor In2S3Mass ratio be preferably 7.5:
1.0。
The water decomposition hydrogen manufacturing type photocatalyst is also mixed and is dried with laccase, deionized water, and degradation of formaldehyde type is prepared
Photocatalyst.
Compared with prior art, the invention has the following advantages that
(1) pass through control La2Ti2O7With In2S3Ratio, the hetero-junctions of the plane-plane contact of best assembling ratio can be made
Structure, the ultra-thin heterojunction structure have biggish specific surface, are conducive to the progress of catalysis reaction and the transmission of substance.
(2) La is ultrasonically treated by DMF solution2Ti2O7With In2S3, obtain the ultra-thin La that surface has opposite charges2Ti2O7
With In2S3, be conducive to the spontaneous homogeneous distribution of two components in assembling process.
(3) pass through regulation La2Ti2O7With In2S3Mass ratio, can be with Effective Regulation photocatalyst to the absorption energy of sunlight
Power, absorbing sunlight photon range can continuously regulate and control in 500 nanometers -600 nanometers.
(4) by the method for photo-reduction, in photocatalyst surface specificity in-situ impregnation noble metal nano platinum, and then enhance different
Matter structure shifts the ability of the capture electronics of electronics；In addition features above is more obvious to the killing effect of bacterium.
(5) by supporting laccase, the binding ability of photocatalyst and wood materials can be significantly increased, photocatalyst is conducive to
Fixation on wooden utensil.
Detailed description of the invention
Fig. 1 is the heterojunction structure La that perovskite type metal oxide and sulfide are constructed2Ti2O7/In2S3Scanning electron microscope shine
Photo in tablet self assembling process.
Fig. 2 is different quality than the hetero-junctions La that perovskite type metal oxide and sulfide are constructed2Ti2O7/In2S3Extinction
The relationship of rate and ratio.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Metal oxynitride supports laccase method:
Composite material P5 (7.5:1.0), laccase, deionized water mixing, drying, obtain degradation of formaldehyde type photocatalyst；
The application method of photolysis water hydrogen type photocatalyst:
(1) choose 1 piece of clean FTO electro-conductive glass (10 10 centimetres of cm x), by water decomposition hydrogen manufacturing type photocatalyst,
Ethylene glycol is mixed according to weight ratio 20:1, grinding, is scratched to FTO electro-conductive glass；
(2) the FTO electro-conductive glass that supports water decomposition hydrogen manufacturing type photocatalyst, platinized platinum (1 1 centimetre of cm x) are respectively as work
Electrode and to electrode, aqueous sodium persulfate solution (0.1 mol/L concentration) is used as electrolyte, constitutes photoelectrolytic cell；
(3) working electrode is as anode, and to electrode as cathode, both ends apply 0.2 volt of voltage, irradiates work in sunlight
Make to decompose water under electrode conditions, cathode collects hydrogen.
The application method of light degradation formaldehyde type photocatalyst:
(1) degradation of formaldehyde type photocatalyst, deionized water are mixed according to 1:20 weight ratio, ultrasonic disperse；
(2) object will be sprayed-on to clean out, the object of spraying will be avoided to be covered with film；
(3) select the preferable spray gun of atomizing effect, spray gun and by between spray object keep 5-15 cm distance；
(4) it to be spontaneously dried by spray object, is not wiped before dry.
Embodiment 1-4 and comparative example 1-3
Water decomposition hydrogen manufacturing type photocatalyst specific embodiment 1-4
Raw material is prepared according to the proportion in table 1:
The raw material proportioning table of table 1 embodiment 1-4 and comparative example 1-3
| Reagent name | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| La2Ti2O7 | 42.86 | 50.00mg | 52.94mg | 54.55mg | 52.94mg | 52.94mg | 52.94mg |
| In2S3 | 17.14mg | 10.00mg | 7.06mg | 5.45mg | 7.06mg | 7.06mg | 7.06mg |
| La2Ti2O7/In2S3 | 60.00mg | 60.00mg | 60.00mg | 60.00mg | 60.00mg | 60.00mg | 60.00mg |
| Chloroplatinic acid | 1.20mg | 1.20mg | 1.20mg | 1.20mg | 0.60mg | 1.20mg | 1.80mg |
| Laccase | 0.15mg | 0.15mg | 0.15mg | 0.15mg | 0.15mg | 0.00mg | 0.15mg |
Table 2 is embodiment 1-4 and comparative example 1-3 photocatalytic water performance and according to GB/ under the conditions of 400 nanometers of edge filters
Formaldehyde performance is gone in T16129 detection.
Table 2
Fig. 1 is the heterojunction structure La that perovskite type metal oxide and sulfide are constructed2Ti2O7/In2S3Scanning electron microscope shine
Photo in tablet self assembling process.By controlling La2Ti2O7With In2S3Ratio, the face face of best assembling ratio can be made
The heterojunction structure of contact, the ultra-thin heterojunction structure have biggish specific surface, are conducive to the progress of catalysis reaction and the biography of substance
Defeated: figure a is In2S3The smooth presentation ultra-thin two-dimension structure in surface, figure b-f are followed successively by La2Ti2O7/In2S32.5:1.0 5.0:
1.0,7.5:1.0,10.0:1.0,12.5；1.0, we can see that with La2Ti2O7Amount gradually increase, hetero-junctions table
The smooth degree in face gradually increases, and specific surface area is first to reduce increasing, and the specific surface area that wherein ratio is 7.5:1.0 is minimum,
This shows that the hetero-junctions of electrostatic assembly under the conditions of the ratio is the most abundant；Figure g is original La2Ti2O7Scanning electron microscope diagram
Picture, as can be seen from the picture, original La2Ti2O7Surface is smooth, and ultra-thin two-dimension structure is presented；Scheming h is during synthesizing hetero-junctions
Original DM F sample dispersion liquid and different proportion two component mixed liquors, from image it can be seen that ultrasound removing it is original
La2Ti2O7And original I n2S3There is good dispersibility in DMF liquid, illustrate that its peeling effect is good, and mixed in the two
In dispersion liquid later, the two component can precipitate quickly, illustrate that electrostatic force obviously plays in an assembling process
The effect that can not be substituted.
Fig. 2 is different quality than the hetero-junctions La that perovskite type metal oxide and sulfide are constructed2Ti2O7/In2S3Extinction
The relationship of rate and ratio: from Fig. 2 this it appears that hetero-junctions compares more original La2Ti2O7There is apparent visible absorption, with
In2S3Amount be continuously increased, the visible light absorbing ability of hetero-junctions is increasingly closer to original I n2S3Sample.This illustrates In2S3
La can be successfully assembled into2Ti2O7Surface, and hetero-junctions can be effectively improved to visible light using absorption, and then improving should
The photocatalytic activity of product.
Embodiment 5
A kind of preparation method of photocatalyst preparation, perovskite type metal oxide La2Ti2O7With sulfide In2S3By quiet
The P-N heterojunction structure La that electricity assembling is constructed2Ti2O7/In2S3, then Platinum Nanoparticles, laccase are loaded, it is prepared and solar energy may be implemented
The photocatalyst preparation of hydrogen manufacturing and solar energy degradation of formaldehyde, wherein perovskite type metal oxide La2Ti2O7With sulfide In2S3's
Mass ratio is 2.5:1.0, and the content for loading Platinum Nanoparticles is 1wt%, and the visible absorption for the photocatalyst preparation being prepared is 500
Nanometer to 600 nanometers it is continuously adjustable.
Above-mentioned preparation method specifically uses following steps:
(1) temperature 263K is controlled, acetic acid titanium and lanthanum nitrate are mixed and are dissolved in deionized water, clear solution is obtained；
(2) temperature 273K is controlled, sodium hydroxide and deionized water are mixed, clear solution is made, wherein sodium hydroxide
Concentration is 2mol/L；
(3) temperature 273K is controlled, above-mentioned solution is mixed dropwise and continuing vigorous stirs, it is molten to obtain white " milky " mixing
Liquid；
(4) temperature 603K is controlled, above-mentioned mixed solution is closed in reaction kettle and is kept for 24 hours, white solid is obtained,
Wash drying；
(5) white solid is placed in DMF, is kept for 48 hours under ultrasound condition, obtains ultra-thin N-type semiconductor
La2Ti2O7White " milky " liquid；
(6) control temperature 263K, weigh indium nitrate, cetyl trimethylammonium bromide, thioacetamide mixing be dissolved in
In ionized water, clear solution is persistently stirred to get；
(7) clear solution is flowed back 90 minutes under the conditions of 368K and obtains yellow mercury oxide；
(8) yellow mercury oxide S2 dehydrated alcohol and deionized water are washed dry and does same treatment in (5), obtained ultra-thin
P-type semiconductor In2S3Yellow emulsion；；
It (9) is in mass ratio 2.5:1.0 by ultra-thin N-type semiconductor La2Ti2O7With ultra-thin P-type semiconductor In2S3It mixes dropwise
And be ultrasonically treated, in the process, the two by ultrasound removing finds that surface both carries not by measuring its Zeta electric potential
With type charge, wherein La2Ti2O7Carry positive charge, In2S3In 453K condition after the powder washing that carrying negative electrical charge obtains is dry
Two hours of lower processing；
(10) treated, and powder is mixed with the platinum acid chloride solution that concentration is 2wt%, is being configured with 400 nm filters
It is irradiated 1 hour under the conditions of 300 watts of xenon lamps, obtains water decomposition hydrogen manufacturing type photocatalyst.
Embodiment 6
A kind of preparation method of photocatalyst preparation, perovskite type metal oxide La2Ti2O7With sulfide In2S3By quiet
The P-N heterojunction structure La that electricity assembling is constructed2Ti2O7/In2S3, then Platinum Nanoparticles, laccase are loaded, it is prepared and solar energy may be implemented
The photocatalyst preparation of hydrogen manufacturing and solar energy degradation of formaldehyde, wherein the perovskite type metal oxide La2Ti2O7With sulfide
In2S3Mass ratio be 7.5:1.0, the content for loading Platinum Nanoparticles is 2wt%, the content of laccase is 0.5wt%.It is prepared
The visible absorption of photocatalyst preparation is continuously adjustable at 500 nanometers to 600 nanometers.
Above-mentioned preparation method specifically uses following steps:
(1) temperature 273K is controlled, acetic acid titanium and lanthanum nitrate are mixed and are dissolved in deionized water, clear solution is obtained；
(2) temperature 280K is controlled, sodium hydroxide and deionized water are mixed, clear solution is made, wherein sodium hydroxide
Concentration is 2mol/L；
(3) temperature 280K is controlled, above-mentioned solution is mixed dropwise and continuing vigorous stirs, it is molten to obtain white " milky " mixing
Liquid；
(4) temperature 603K is controlled, above-mentioned mixed solution is closed in reaction kettle and is kept for 24 hours, white solid is obtained,
Wash drying；
(5) white solid is placed in DMF, is kept for 48 hours under ultrasound condition, obtains ultra-thin N-type semiconductor
La2Ti2O7White " milky " liquid；
(6) control temperature 273K, weigh indium nitrate, cetyl trimethylammonium bromide, thioacetamide mixing be dissolved in
In ionized water, clear solution is persistently stirred to get；
(7) clear solution is flowed back 90 minutes under the conditions of 368K and obtains yellow mercury oxide；
(8) yellow mercury oxide S2 dehydrated alcohol and deionized water are washed dry and does same treatment in (5), obtained ultra-thin
P-type semiconductor In2S3Yellow emulsion；；
It (9) is in mass ratio 7.5:1.0 by ultra-thin N-type semiconductor La2Ti2O7With ultra-thin P-type semiconductor In2S3It mixes dropwise
And be ultrasonically treated, in the process, the two by ultrasound removing finds that surface both carries not by measuring its Zeta electric potential
With type charge, wherein La2Ti2O7Carry positive charge, In2S3In 453K condition after the powder washing that carrying negative electrical charge obtains is dry
Two hours of lower processing；
(10) treated, and powder is mixed with the platinum acid chloride solution that concentration is 2wt%, is being configured with 400 nm filters
It is irradiated 1 hour under the conditions of 300 watts of xenon lamps, obtains water decomposition hydrogen manufacturing type photocatalyst.
(11) water decomposition hydrogen manufacturing type photocatalyst is also mixed and is dried with laccase, deionized water, and degradation of formaldehyde type is prepared
Photocatalyst.
Embodiment 7
A kind of preparation method of photocatalyst preparation, perovskite type metal oxide La2Ti2O7With sulfide In2S3By quiet
The P-N heterojunction structure La that electricity assembling is constructed2Ti2O7/In2S3, then Platinum Nanoparticles, laccase are loaded, it is prepared and solar energy may be implemented
The photocatalyst preparation of hydrogen manufacturing and solar energy degradation of formaldehyde, wherein the perovskite type metal oxide La2Ti2O7With sulfide
In2S3Mass ratio be 12.5:1.0, the content for loading Platinum Nanoparticles is 3wt%, the content of laccase is 1wt%.The light being prepared
The visible absorption of catalyst preparation is continuously adjustable at 500 nanometers to 600 nanometers.
Above-mentioned preparation method specifically uses following steps:
(1) temperature 283K is controlled, acetic acid titanium and lanthanum nitrate are mixed and are dissolved in deionized water, clear solution is obtained；
(2) temperature 283K is controlled, sodium hydroxide and deionized water are mixed, clear solution is made, wherein sodium hydroxide
Concentration is 2mol/L；
(3) temperature 283K is controlled, above-mentioned solution is mixed dropwise and continuing vigorous stirs, it is molten to obtain white " milky " mixing
Liquid；
(4) temperature 603K is controlled, above-mentioned mixed solution is closed in reaction kettle and is kept for 24 hours, white solid is obtained,
Wash drying；
(5) white solid is placed in DMF, is kept for 48 hours under ultrasound condition, obtains ultra-thin N-type semiconductor
La2Ti2O7White " milky " liquid；
(6) control temperature 283K, weigh indium nitrate, cetyl trimethylammonium bromide, thioacetamide mixing be dissolved in
In ionized water, clear solution is persistently stirred to get；
(7) clear solution is flowed back 90 minutes under the conditions of 368K and obtains yellow mercury oxide；
(8) yellow mercury oxide S2 dehydrated alcohol and deionized water are washed dry and does same treatment in (5), obtained ultra-thin
P-type semiconductor In2S3Yellow emulsion；；
It (9) is in mass ratio 12.5:1.0 by ultra-thin N-type semiconductor La2Ti2O7With ultra-thin P-type semiconductor In2S3It mixes dropwise
Merge ultrasonic treatment, in the process, the two by ultrasound removing finds that surface both carries by measuring its Zeta electric potential
Variety classes charge, wherein La2Ti2O7Carry positive charge, In2S3In 453K item after the powder washing that carrying negative electrical charge obtains is dry
Two hours are handled under part；
(10) treated, and powder is mixed with the platinum acid chloride solution that concentration is 2wt%, is being configured with 400 nm filters
It is irradiated 1 hour under the conditions of 300 watts of xenon lamps, obtains water decomposition hydrogen manufacturing type photocatalyst.
(11) water decomposition hydrogen manufacturing type photocatalyst is also mixed and is dried with laccase, deionized water, and degradation of formaldehyde type is prepared
Photocatalyst.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (8)
1. a kind of preparation method of photocatalyst preparation, which is characterized in that by perovskite type metal oxide La2Ti2O7With sulfide
In2S3Assemble the P-N heterojunction structure La constructed2Ti2O7/In2S3, then Platinum Nanoparticles, laccase are loaded, it is prepared and the sun may be implemented
The photocatalyst preparation of energy hydrogen manufacturing and solar energy degradation of formaldehyde.
2. a kind of preparation method of photocatalyst preparation according to claim 1, which is characterized in that the perovskite type metal
Oxide La2Ti2O7With sulfide In2S3Mass ratio be 2.5:1.0-12.5:1.0.
3. a kind of preparation method of photocatalyst preparation according to claim 1, which is characterized in that load the content of Platinum Nanoparticles
Content for 1-3wt%, laccase is 0-1wt%.
4. a kind of preparation method of photocatalyst preparation according to claim 1, which is characterized in that this method specifically use with
Lower step:
(1) temperature 263K-283K is controlled, acetic acid titanium and lanthanum nitrate are mixed and are dissolved in deionized water, clear solution is obtained；
(2) temperature 273K-283K is controlled, sodium hydroxide and deionized water are mixed, clear solution is made；
(3) temperature 273K-283K is controlled, above-mentioned solution is mixed dropwise and continuing vigorous stirs, it is molten to obtain white " milky " mixing
Liquid；
(4) temperature 603K is controlled, above-mentioned mixed solution is closed in reaction kettle and is kept for 24 hours, white solid is obtained, is washed
It is dry；
(5) white solid is placed in DMF, is kept for 48 hours under ultrasound condition, obtains ultra-thin N-type semiconductor La2Ti2O7
White " milky " liquid；
(6) control temperature 263K-283K, weigh indium nitrate, cetyl trimethylammonium bromide, thioacetamide mixing be dissolved in
In ionized water, clear solution is persistently stirred to get；
(7) clear solution is flowed back 90 minutes under the conditions of 368K and obtains yellow mercury oxide；
(8) yellow mercury oxide S2 dehydrated alcohol and deionized water are washed dry and does same treatment in (5), obtain ultra-thin p-type
Semiconductor In2S3Yellow emulsion；
(9) according to the ratio by the ultra-thin N-type semiconductor La of different quality ratio2Ti2O7With ultra-thin P-type semiconductor In2S3It mixes dropwise simultaneously
Ultrasonic treatment handles two hours after obtained powder washing is dry under the conditions of 453K；
(10) treated, and powder is mixed with platinum acid chloride solution, is shone under the conditions of being configured with 300 watts of xenon lamps of 400 nm filters
It penetrates 1 hour, obtains water decomposition hydrogen manufacturing type photocatalyst.
5. a kind of preparation method of photocatalyst preparation according to claim 4, which is characterized in that the hydrogen-oxygen in step (2)
The concentration for changing sodium is 2mol/L.
6. a kind of preparation method of photocatalyst preparation according to claim 4, which is characterized in that ultra-thin N-type in step (9)
Semiconductor La2Ti2O7With ultra-thin P-type semiconductor In2S3Mass ratio be preferably 7.5:1.0.
7. a kind of preparation method of photocatalyst preparation according to claim 4, which is characterized in that chlorine described in step (10)
The concentration of platinic acid solution is 2wt%.
8. a kind of preparation method of photocatalyst preparation according to claim 4, which is characterized in that the water decomposition hydrogen manufacturing type
Photocatalyst is also mixed and is dried with laccase, deionized water, and degradation of formaldehyde type photocatalyst is prepared.
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