CN107855130A - A kind of solar energy fixed nitrogen photochemical catalyst and application thereof and preparation method - Google Patents
A kind of solar energy fixed nitrogen photochemical catalyst and application thereof and preparation method Download PDFInfo
- Publication number
- CN107855130A CN107855130A CN201711177885.2A CN201711177885A CN107855130A CN 107855130 A CN107855130 A CN 107855130A CN 201711177885 A CN201711177885 A CN 201711177885A CN 107855130 A CN107855130 A CN 107855130A
- Authority
- CN
- China
- Prior art keywords
- solar energy
- solution
- fixed nitrogen
- energy fixed
- bismuth
- 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 106
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000001699 photocatalysis Effects 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 238000007146 photocatalysis Methods 0.000 claims abstract description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 235000011187 glycerol Nutrition 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 3
- 238000002156 mixing Methods 0.000 claims description 7
- 230000031709 bromination Effects 0.000 claims description 6
- 238000005893 bromination reaction Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- 229910001451 bismuth ion Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 230000007096 poisonous effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- -1 step:1st Substances 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000011534 incubation Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000004178 biological nitrogen fixation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical class [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J27/06—Halogens; Compounds thereof
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/45—Aggregated particles or particles with an intergrown morphology
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of solar energy fixed nitrogen photochemical catalyst, to hydrogenate bismuth oxybromide, molecular formula H BiOBr, for solar energy fixed nitrogen photocatalysis, for the solar energy fixed nitrogen light-catalyzed reaction using water as reducing agent.The preparation method of catalyst, including step：1st, ethylene glycol, isopropanol or glycerin solution are taken；2nd, bismuth-containing compound and bromine-containing compound are added into alcoholic solution, mixes and be sufficiently stirred；3rd, neutral solution is added after stirring to clarify solution, is fitted into after stirring in reactor, carries out isothermal reaction；4th, it is cooled to room temperature to be centrifuged and repeatedly washed with water and ethanol solution, after drying, is ground to powder；5th, calcine under an atmosphere of hydrogen, obtain hydrogenating bismuth oxybromide.The hydrogenation bismuth oxybromide photocatalyst that the inventive method obtains is green non-poisonous, cheap, raw material are simple, wide material sources, method is easy to operate and can have good solar energy fixed nitrogen photocatalysis performance largely to be prepared in the short time.
Description
Technical field
The present invention relates to a kind of catalysis material technical field, and bismuth oxybromide is hydrogenated more specifically to one kind is related to
(H-BiOBr) preparation and application of solar energy fixed nitrogen photochemical catalyst.
Background technology
It is well known that molybdenum base azotase can fix in air 60% nitrogen, it is a kind of more effective in biological field
Matrix nitrogen is reduced into ammonia.Relative to biological nitrogen fixation, the nitrogen in photocatalysis technology reducing atmosphere, which prepares ammonia, to be caused
People widely pay close attention to.Photocatalysis technology provides a kind of effective way for fixed nitrogen.Semiconductor light-catalyst can be by the sun
Chemical energy can be converted into, compared to the substantial amounts of combustion of fossil fuel of technical azotification endanger environment (traditional haber process in 25MPa,
Under the conditions of 723-773K), this course of reaction is more green, and reaction condition is gentleer, and reaction can be carried out in water.But
In the past few decades, photocatalysis technology fixed nitrogen be difficult make us it is satisfied, following reason may be attributed to：(1) nitrogen molecular is due to depositing
Altitude hold mode is formed in N ≡ N, nitrogen molecular is resolved into atom needs to absorb about 941.69kJ mol-1, driven in solar energy
Under dynamic, it is a greatly challenge to spend disconnection N ≡ N by the photo-generated carrier in semiconductor light-catalyst；(2) it is most of
Semiconductor possesses higher conduction band minimum, when result in the fixed nitrogen in water, acts on water by photochemical catalyst and preferentially decomposes generation
Hydrogen, this competition reaction reduces the effect of fixed nitrogen.
Now, increasing photochemical catalyst, which is utilized, fixes nitrogen.Such as：Titanium dioxide, graphite phase carbon nitride, two
Molybdenum sulfide, wolframic acid etc..However, bismuth oxybromide (BiOBr) is by [Bi2O2]2+Layer and two Br sheaths composition and have
The semiconductor crystal of unique layer structure.In addition, it also has the advantages that simple production process, cheap, nontoxic.BiOBr attracts
People notice that most importantly it possesses suitable band gap, lower conduction band minimum, wider light abstraction width and one extensively
The surface texture of cause.Nevertheless, traditional BiOBr still shows the binding ability weaker with nitrogen.
The content of the invention
Present invention aims at provide a kind of high efficiency photocatalysis fixed nitrogen catalyst and its synthetic method, purposes and application.
To achieve these goals, the technical scheme is that：
A kind of solar energy fixed nitrogen photochemical catalyst of the present invention, catalyst are to hydrogenate bismuth oxybromide, molecular formula H-BiOBr.In tool
There is the flower ball-shaped Hollow Microspheres structure of Lacking oxygen.
Catalyst provided by the invention, for solar energy fixed nitrogen photocatalysis.Concrete application, reducing agent is used as applied to using water
Solar energy fixed nitrogen light-catalyzed reaction.
Present invention also offers a kind of preparation method of solar energy fixed nitrogen photochemical catalyst, comprise the following steps：
S1, the ethylene glycol, isopropanol or glycerin solution for taking 60~120 DEG C；
S2, bismuth-containing compound and bromine-containing compound added into the alcoholic solution, mix and be sufficiently stirred；
S3, neutral solution is added after stirring to clarify solution, the autoclave that pressure is 1~2Mpa is loaded after stirring
In, carry out 100~180 DEG C of isothermal reactions；
S4, it is cooled to room temperature and is centrifuged and is repeatedly washed with water and ethanol solution, after 50~80 DEG C are dried, grinds
It is milled to powder；
S5,2~6h is calcined under 100~300 DEG C, 300~380ml/min atmosphere of hydrogen, obtain hydrogenating bismuth oxybromide.
Wherein, in step S2, the bismuth-containing compound is five nitric hydrate bismuths, bismuth chloride or bismuth ion complex compound；It is described
Bromine-containing compound be bromination receive, KBr or CTAB.In step S3, the neutral solution is water, ethanol or isopropanol.
A kind of preparation method of solar energy fixed nitrogen photochemical catalyst of the present invention, specifically includes following steps：
S1,20ml~40ml ethylene glycol, isopropanol or glycerin solution are heated to 120 DEG C~200 DEG C, are cooled to 60 DEG C
~120 DEG C；
S2, the alcoholic solution that 0.2g~2.0g bismuth-containing compounds and 0.05g~0.5g bromine-containing compounds are added to heat, mixing is simultaneously
It is sufficiently stirred；
S3,60ml~120ml neutral solutions are added after stirring to clarify solution, load reaction under high pressure after resulting solution stirring
Kettle, carry out 100 DEG C~180 DEG C more than isothermal reaction 8h；
S4, it is cooled to room temperature and is centrifuged and is washed 3~5 times with water and ethanol solution, after 50~80 DEG C are dried, grinds
It is milled to powder；
S5,2~6h is calcined under 100~300 DEG C, 300~380ml/min atmosphere of hydrogen, obtain hydrogenating bismuth oxybromide.
Under preferred embodiment, step S2 to mixing time described in S3 is 10~35min.In addition, constant temperature described in step S3 is anti-
At once, fill solution volume account for autoclave liner volume ratio be 50%~90%, the reaction time is 8~24h.
The invention has the advantages that：
The photochemical catalyst of the present invention is H-BiOBr, and photochemical catalyst of the invention not only has remarkable photocatalysis fixed nitrogen
Can, and possess high quantum efficiency.Using water as reactant under sunshine, catalyst can produce 180 per hour per gram
~400 μm of ol ammonias, it is 2.6 times of traditional BiOBr yield.Accordingly under 380nm monochromatic light quantum efficiency reach 3.5~
4.5%.Effective fixed nitrogen performance is not only presented under field conditions (factors), and also has remarkable result in terms of dyestuff degraded.
Environmental pollution and control direction has very big application potential, and strong theoretical foundation and wider is provided for the type catalyst
Wealthy development space.
Brief description of the drawings
Fig. 1 is the XRD diffraction patterns of the catalyst of embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the catalyst of embodiment 1.
Fig. 3 is the UV-vis abosrption spectrograms of the catalyst of embodiment 1.
Fig. 4 is the current versus time curve figure of the catalyst of embodiment 1.
Fig. 5 is the AC impedance figure of the catalyst of embodiment 1.
Fig. 6 is the photocatalysis nitrogen fixation effect figure of the catalyst of embodiment 1~4.
Embodiment
A kind of preparation method for hydrogenating bismuth oxybromide high-efficiency solar fixed nitrogen photochemical catalyst of the present invention, belongs to catalysis material
Technical field.This method comprises the following steps：Bromine source and bismuth source are dissolved in alcoholic solution；Carry out hydro-thermal reaction；With water and alcohol
Wash and centrifuge；Drying and grinding obtains solid powder；Hydrogen calcining is passed through in tube furnace；Room temperature is cooled to be produced
Product.The hydrogenation bismuth oxybromide photocatalyst that the inventive method obtains is green non-poisonous, cheap, raw material are simple, source is wide
It is general, method is easy to operate and can have good solar energy fixed nitrogen photocatalysis performance largely to be prepared in the short time.
Below with reference to the accompanying drawing in the embodiment of the present invention, come the technical scheme in the embodiment of the present invention is made it is clear,
Complete statement.Embodiments described below is only the part of the present invention, is not whole embodiments.This area
Technical staff makes some nonessential improvement according to the above of the present invention and belongs to protection scope of the present invention.
It is an object of the present invention to provide a kind of high-efficiency solar fixed nitrogen photochemical catalyst, while one kind is provided and prepares the light
The method of catalyst.
20ml~40ml alcoholic solutions are heated to 120 DEG C~200 DEG C in the present invention, are cooled to 60 DEG C~120 DEG C.The alcohol
Solution includes but is not limited to ethylene glycol or glycerine.
0.2g~2.0g bismuth-containing compounds and 0.05g~0.5g bromine-containing compounds are added to the alcoholic solution of heat, mixes and fills
Divide stirring, mixing time is 10~35min.Bismuth-containing compound includes but is not limited to five nitric hydrate bismuths, bismuth chloride or bismuth ion
Complex compound.Bromine-containing compound include but is not limited to bromination receive, KBr or CTAB.
60ml~120ml neutral solutions are added after above-mentioned solution is stirred to clarify into solution in the present invention, resulting solution is stirred
Load autoclave after mixing, carry out 100 DEG C~180 DEG C incubation water heating reaction more than 8h.The neutral solution includes but unlimited
Yu Shui, ethanol or isopropanol.Product cooling is centrifuged to room temperature and washed 3 times~5 times with water and ethanol solution, dries
Powder is ground to after 50 DEG C~80 DEG C.Wherein, during synthetic reaction, the volume for filling solution accounts for the ratio of autoclave liner volume and is
50%~90%；Reaction time is 8~24h.
2h~6h is calcined under 100 DEG C~300 DEG C, 300~380ml/min atmosphere of hydrogen, obtains final products H-
BiOBr。
Compared with existing photocatalysis technology, the present invention has following advantage：
(1) the H-BiOBr catalysis materials that the present invention obtains, not only there is remarkable photocatalysis fixed nitrogen performance, Er Qieyong
There is high quantum efficiency.Using water as reactant under sunshine, catalyst can produce 180~400 μm of ol per hour per gram
Ammonia, it is 2.6 times of traditional BiOBr yield.Quantum efficiency reaches 3.5~4.5% under 380nm monochromatic light accordingly.Certainly
Fabulous nitrogen fixation effect is shown under the conditions of so, there is application prospect.
(2) preparation method of H-BiOBr catalysis materials is green, nontoxic, convenient, cheap, without special installation, controllability
By force, there is practicality.
Embodiment 1
40ml ethylene glycol solutions are heated to 160 DEG C, are cooled to 120 DEG C.The nitric hydrate bismuths of 1.92g five and 0.416g brominations
Sodium adds above-mentioned solution, mixes and is sufficiently stirred 35min to 120ml aqueous isopropanols are added after settled solution, resulting solution is stirred
Load 1~2Mpa autoclaves after mixing 30min, carry out 160 DEG C of incubation water heating reaction 12h.Product cooling to room temperature carry out from
The heart is separated and washed 5 times with water and ethanol solution, and drying is ground to powder after 60 DEG C.In 200 DEG C, 360ml/min atmosphere of hydrogen
Lower calcining 4h, obtains final products H-BiOBr.
Fig. 1 is the H-BiOBr photochemical catalyst XRD diffracting spectrums that the present embodiment obtains, through being contrasted with PDF standard cards
Know, the BiOBr for tetragonal phase obtained.
Fig. 2 be the present embodiment obtain H-BiOBr photochemical catalyst scanning electron microscope (SEM) photographs, 2.5 μ being polymerized for piece obtained
The hollow bouquets of m.
Fig. 3 is the H-BiOBr photochemical catalyst UV-vis absorption spectrums that the present embodiment obtains, and is absorbed compared to pure phase BiOBr
Side red shift, it is obviously improved in visible-range internal absorbance, there is a stronger light abstraction width, while band gap also relative narrower, add
Fast electric transmission speed, so as to lift photocatalytic activity.
Fig. 4 is the H-BiOBr photochemical catalyst photocurrent-time curve figures that the present embodiment obtains, compared to pure phase BiOBr,
Stronger photoelectric current is presented, illustrates to have efficiently separated light induced electron and hole.
Fig. 5 is the H-BiOBr photochemical catalyst AC impedance figures that the present embodiment obtains, compared to pure phase BiOBr, present compared with
Small resistance, while explanation is low for the recombination rate of photo-generated carrier, preferably promotes electric charge conversion with efficiently separating.
Embodiment 2
20ml ethylene glycol solutions are heated to 200 DEG C, are cooled to 60 DEG C.The nitric hydrate bismuths of 0.24g five and 0.052g brominations
Sodium adds above-mentioned solution, mixes and is sufficiently stirred 30min to addition 60ml aqueous isopropanols after settled solution, resulting solution stirring
Load autoclave after 30min, carry out 160 DEG C of incubation water heating reaction 20h.Product cooling is centrifuged to room temperature and is used in combination
Water and ethanol solution are washed 5 times, and drying is ground to powder after 60 DEG C.4h is calcined under 150 DEG C, 360ml/min atmosphere of hydrogen, is obtained
To final products H-BiOBr.
Embodiment 3
20ml ethylene glycol solutions are heated to 200 DEG C, are cooled to 60 DEG C.The nitric hydrate bismuths of 0.24g five and 0.052g brominations
Sodium adds above-mentioned solution, mixes and is sufficiently stirred 30min to addition 60ml aqueous isopropanols after settled solution, resulting solution stirring
Load autoclave after 30min, carry out 160 DEG C of incubation water heating reaction 20h.Product cooling is centrifuged to room temperature and is used in combination
Water and ethanol solution are washed 5 times, and drying is ground to powder after 60 DEG C.2h is calcined under 150 DEG C, 360ml/min atmosphere of hydrogen, is obtained
To final products H-BiOBr.
Embodiment 4
The nitric hydrate bismuths of 1.92g five and 0.416g sodium bromides are added into ethylene glycol solution at room temperature, mixes and fully stirs
Mix 35min and load autoclave after stirring 30min to addition 120ml aqueous isopropanols, resulting solution after settled solution, carry out
160 DEG C of incubation water heatings react 12h.Product cooling is centrifuged to room temperature and washed 5 times with water and ethanol solution, dries 60
Powder is ground to after DEG C.It is pure phase BiOBr to obtain final products.
Photocatalysis fixed nitrogen test is carried out for the sample of embodiment 1~4.
All photocatalysis experiments are performed with 300W xenon lamps simulated solar irradiation at room temperature.For photocatalysis fixed nitrogen process：
0.02g catalyst and 100ml deionized waters are added in glass fixed nitrogen reactor, and is passed through recirculated water to maintain room temperature.Mixing
Solution is passed through nitrogen 65ml/min and 30min is stirred under dark, extracts 5ml solution out per 30min under light illumination.Further with 0.22
The filtering of μm filter, and instill nessler reagent and determine absorbance under ultraviolet specrophotometer 420nm.
Fig. 6 illustrates 3 hours photocatalysis nitrogen fixation effects of the catalyst of embodiment 1~4.It is obvious that the catalyst of embodiment 1 shows
Show optimal photocatalysis nitrogen fixation effect, reach within 3 hours 216.5 μm of ol/L.The catalyst of embodiment 2 is 123 μm of ol/L, is implemented
The catalyst of example 3 is 105.75 μm of ol/L, and the catalyst of embodiment 4 of unhydrogenation processing is 85.75 μm of ol/L.So as to find out,
The H-BiOBr photochemical catalysts of the present invention possess the photocatalysis nitrogen fixation effect of brilliance.
In order to preferably using BiOBr carry out fixed nitrogen light-catalyzed reaction, present invention employs low temperature hydrogen calcining method,
It is successfully prepared the BiOBr Hollow Microspheres of the flower ball-shaped with a large amount of Lacking oxygens.Under using water as reducing agent, present fabulous
Photocatalysis fixed nitrogen performance.Due to the reducing property of hydrogen, hydrogenation process can make nano grain surface confusion remove oxygen atom.
This is that a kind of easy method is gone to manufacture Lacking oxygen and controls the amount of Lacking oxygen.Meanwhile Hollow Microspheres structure possess it is one high
Hydrogen storage capacity, profit present the absorbability of brilliance under sunshine irradiation in this way.In addition, in photocatalytic system
In, the effective energy coupling of exciton, photon, nitrogen molecular, present the fixation of photocatalysis Driven by Solar Energy nitrogen unexpected
Performance.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope of present disclosure, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (10)
1. a kind of solar energy fixed nitrogen photochemical catalyst, it is characterised in that catalyst is to hydrogenate bismuth oxybromide, molecular formula H-BiOBr.
2. solar energy fixed nitrogen photochemical catalyst according to claim 1, it is characterised in that in the flower ball-shaped cavity with Lacking oxygen
Micro-sphere structure.
3. a kind of purposes of catalyst, it is characterised in that for solar energy fixed nitrogen photocatalysis.
4. a kind of application of catalyst, it is characterised in that applied to the solar energy fixed nitrogen light-catalyzed reaction using water as reducing agent.
5. a kind of preparation method of solar energy fixed nitrogen photochemical catalyst, it is characterised in that comprise the following steps：
S1, the ethylene glycol, isopropanol or glycerin solution for taking 60~120 DEG C；
S2, bismuth-containing compound and bromine-containing compound added into the alcoholic solution, mix and be sufficiently stirred；
S3, neutral solution is added after stirring to clarify solution, be fitted into after stirring in the autoclave that pressure is 1~2Mpa, enter
100~180 DEG C of isothermal reactions of row；
S4, it is cooled to room temperature and is centrifuged and is repeatedly washed with water and ethanol solution, after 50~80 DEG C are dried, is ground to
Powder；
S5,2~6h is calcined under 100~300 DEG C, 300~380ml/min atmosphere of hydrogen, obtain hydrogenating bismuth oxybromide.
6. the preparation method of solar energy fixed nitrogen photochemical catalyst according to claim 5, it is characterised in that described in step S2
Bismuth-containing compound is five nitric hydrate bismuths, bismuth chloride or bismuth ion complex compound；The bromine-containing compound be bromination receive, KBr or
CTAB。
7. the preparation method of solar energy fixed nitrogen photochemical catalyst according to claim 5, it is characterised in that described in step S3
Neutral solution is water, ethanol or isopropanol.
8. according to the preparation method of any solar energy fixed nitrogen photochemical catalyst of claim 5~7, it is characterised in that including with
Lower step：
S1,20ml~40ml ethylene glycol, isopropanol or glycerin solution are heated to 120 DEG C~200 DEG C, be cooled to 60 DEG C~
120℃；
S2, the alcoholic solution that 0.2g~2.0g bismuth-containing compounds and 0.05g~0.5g bromine-containing compounds are added to heat, are mixed simultaneously abundant
Stirring；
S3,60ml~120ml neutral solutions are added after stirring to clarify solution, load autoclave after resulting solution stirring,
Carry out 100 DEG C~180 DEG C more than isothermal reaction 8h；
S4, it is cooled to room temperature and is centrifuged and is washed 3~5 times with water and ethanol solution, after 50~80 DEG C are dried, is ground to
Powder；
S5,2~6h is calcined under 100~300 DEG C, 300~380ml/min atmosphere of hydrogen, obtain hydrogenating bismuth oxybromide.
9. the preparation method of solar energy fixed nitrogen photochemical catalyst according to claim 8, it is characterised in that
Step S2 to mixing time described in S3 be 10~35min.
10. the preparation method of solar energy fixed nitrogen photochemical catalyst according to claim 8, it is characterised in that permanent described in step S3
Temperature reaction when, fill solution volume account for autoclave liner volume ratio be 50%~90%, the reaction time is 8~24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711177885.2A CN107855130A (en) | 2017-11-23 | 2017-11-23 | A kind of solar energy fixed nitrogen photochemical catalyst and application thereof and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711177885.2A CN107855130A (en) | 2017-11-23 | 2017-11-23 | A kind of solar energy fixed nitrogen photochemical catalyst and application thereof and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107855130A true CN107855130A (en) | 2018-03-30 |
Family
ID=61702360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711177885.2A Pending CN107855130A (en) | 2017-11-23 | 2017-11-23 | A kind of solar energy fixed nitrogen photochemical catalyst and application thereof and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107855130A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108906085A (en) * | 2018-07-17 | 2018-11-30 | 河南师范大学 | A kind of Bi2S3The preparation method and applications of/BiOBr composite photocatalyst material |
| CN108993548A (en) * | 2018-07-19 | 2018-12-14 | 大连工业大学 | A kind of visible light responsive photocatalyst and application thereof, preparation method and application method |
| CN108993550A (en) * | 2018-08-06 | 2018-12-14 | 宁夏大学 | A kind of bromine oxygen bismuth photochemical catalyst and preparation method thereof that surface Lacking oxygen is modified |
| CN109248695A (en) * | 2018-09-07 | 2019-01-22 | 同济大学 | A kind of Bi base shape fixed nitrogen photochemical catalyst and preparation method thereof that Lacking oxygen mediates |
| CN109261173A (en) * | 2018-11-21 | 2019-01-25 | 大连工业大学 | A kind of the solar energy fixed nitrogen method and application of hydrotreated bismuth deposit bismuth oxybromide |
| CN113649040A (en) * | 2021-06-16 | 2021-11-16 | 华东理工大学 | Preparation method and application of carbon nitride-titanium dioxide heterojunction material for efficiently synthesizing ammonia by visible light |
| CN114749115A (en) * | 2022-03-24 | 2022-07-15 | 福州大学 | Gas-phase photocatalytic nitrogen fixation reaction method |
| CN114956118A (en) * | 2022-04-08 | 2022-08-30 | 大连理工大学 | Method for reducing nitrogen into ammonia by visible light photocatalysis |
| CN115779936A (en) * | 2022-10-26 | 2023-03-14 | 江苏科技大学 | Spherical BiOBr/BiOCl composite material and preparation method and application thereof |
| CN116586083A (en) * | 2023-07-03 | 2023-08-15 | 辽宁大学 | Mo-doped BiOBr photocatalyst rich in oxygen vacancies and preparation method and application thereof |
| WO2023246306A1 (en) * | 2023-02-15 | 2023-12-28 | 安徽科技学院 | Preparation method for cd0.5zn0.5s and experimental method for nitrogen fixation under photocatalysis thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241415A (en) * | 2011-05-12 | 2011-11-16 | 上海师范大学 | Bismuth oxybromide particles with three-dimensional flower-like microstructure and preparation method and use thereof |
| CN106362729A (en) * | 2016-08-31 | 2017-02-01 | 中国科学院新疆理化技术研究所 | In-situ preparation method of photocatalyst strontium bismuth niobium oxide containing oxygen vacancy defect |
| CN106890653A (en) * | 2017-01-18 | 2017-06-27 | 常州大学 | A kind of Lacking oxygen auto-dope BiOI visible light catalysts and its preparation method and application |
-
2017
- 2017-11-23 CN CN201711177885.2A patent/CN107855130A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241415A (en) * | 2011-05-12 | 2011-11-16 | 上海师范大学 | Bismuth oxybromide particles with three-dimensional flower-like microstructure and preparation method and use thereof |
| CN106362729A (en) * | 2016-08-31 | 2017-02-01 | 中国科学院新疆理化技术研究所 | In-situ preparation method of photocatalyst strontium bismuth niobium oxide containing oxygen vacancy defect |
| CN106890653A (en) * | 2017-01-18 | 2017-06-27 | 常州大学 | A kind of Lacking oxygen auto-dope BiOI visible light catalysts and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| HAO LI ET AL: "Efficient Visible Light Nitrogen Fixation with BiOBr Nanosheets of Oxygen Vacancies on the Exposed {001} Facets", 《J. AM. CHEM. SOC.》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108906085A (en) * | 2018-07-17 | 2018-11-30 | 河南师范大学 | A kind of Bi2S3The preparation method and applications of/BiOBr composite photocatalyst material |
| CN108993548A (en) * | 2018-07-19 | 2018-12-14 | 大连工业大学 | A kind of visible light responsive photocatalyst and application thereof, preparation method and application method |
| CN108993550B (en) * | 2018-08-06 | 2021-01-29 | 宁夏大学 | Surface oxygen vacancy modified bismuth oxybromide photocatalyst and preparation method thereof |
| CN108993550A (en) * | 2018-08-06 | 2018-12-14 | 宁夏大学 | A kind of bromine oxygen bismuth photochemical catalyst and preparation method thereof that surface Lacking oxygen is modified |
| CN109248695B (en) * | 2018-09-07 | 2021-09-03 | 同济大学 | Oxygen vacancy mediated Bi-based layered nitrogen fixation photocatalyst and preparation method thereof |
| CN109248695A (en) * | 2018-09-07 | 2019-01-22 | 同济大学 | A kind of Bi base shape fixed nitrogen photochemical catalyst and preparation method thereof that Lacking oxygen mediates |
| CN109261173A (en) * | 2018-11-21 | 2019-01-25 | 大连工业大学 | A kind of the solar energy fixed nitrogen method and application of hydrotreated bismuth deposit bismuth oxybromide |
| CN113649040A (en) * | 2021-06-16 | 2021-11-16 | 华东理工大学 | Preparation method and application of carbon nitride-titanium dioxide heterojunction material for efficiently synthesizing ammonia by visible light |
| CN114749115A (en) * | 2022-03-24 | 2022-07-15 | 福州大学 | Gas-phase photocatalytic nitrogen fixation reaction method |
| CN114956118A (en) * | 2022-04-08 | 2022-08-30 | 大连理工大学 | Method for reducing nitrogen into ammonia by visible light photocatalysis |
| CN115779936A (en) * | 2022-10-26 | 2023-03-14 | 江苏科技大学 | Spherical BiOBr/BiOCl composite material and preparation method and application thereof |
| WO2023246306A1 (en) * | 2023-02-15 | 2023-12-28 | 安徽科技学院 | Preparation method for cd0.5zn0.5s and experimental method for nitrogen fixation under photocatalysis thereof |
| CN116586083A (en) * | 2023-07-03 | 2023-08-15 | 辽宁大学 | Mo-doped BiOBr photocatalyst rich in oxygen vacancies and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107855130A (en) | A kind of solar energy fixed nitrogen photochemical catalyst and application thereof and preparation method | |
| Luo et al. | The embedded CuInS2 into hollow-concave carbon nitride for photocatalytic H2O splitting into H2 with S-scheme principle | |
| CN105384193B (en) | Preparation method of niobium (V) pentoxide urchin-like nano sphere and application of nano sphere as photocatalyst | |
| CN105289689A (en) | Synthesis and application of nitrogen-doped graphene quantum dot/similar-graphene phase carbon nitride composite material | |
| CN106865506B (en) | It is a kind of to form controllable nickel cobalt compound nano line and the preparation method and application thereof | |
| CN109999836A (en) | A kind of preparation of indium oxide/indium sulfide heterojunction semiconductor material and photochemical catalyst purposes and solar energy fixed nitrogen application | |
| CN110560105B (en) | Preparation of nickel phosphide-loaded sulfur indium zinc nano microsphere composite material and application of composite material in photocatalytic hydrogen production | |
| CN105771948B (en) | The preparation method of bivalve titanium deoxide catalyst with high photocatalysis hydrogen production performance | |
| CN109289881A (en) | A kind of preparation and solar energy fixed nitrogen application of carbon nano-fiber support BiOX photocatalyst | |
| CN106944074B (en) | A kind of visible-light response type composite photo-catalyst and its preparation method and application | |
| CN112076738B (en) | Boron-doped defective zinc oxide and preparation method and application thereof | |
| CN104324740A (en) | Flower-shaped MoS2 loaded Ag3PO4 nanosphere composite visible light catalyst and preparation method thereof | |
| CN106807411B (en) | A kind of preparation method of ferrous acid La doped silver bromide compound photocatalyst | |
| CN110605126A (en) | Cavity BiOCl @ CeO2Preparation method and application of nano composite material | |
| CN114618537B (en) | Red phosphorus/strontium titanate heterojunction photocatalyst, and preparation method and application thereof | |
| CN109261173A (en) | A kind of the solar energy fixed nitrogen method and application of hydrotreated bismuth deposit bismuth oxybromide | |
| CN112076774A (en) | Catalyst of titanium carbide quantum dot-loaded carbon defect inverse opal carbon nitride and preparation method thereof | |
| CN115069262A (en) | Oxygen vacancy modified MoO 3-x /Fe-W 18 O 49 Photocatalyst, preparation thereof and application thereof in nitrogen fixation | |
| CN106362742A (en) | Ag/ZnO nano-composite, preparation method thereof and application of composite | |
| CN112604690A (en) | Method for preparing rare earth perovskite/biochar composite material by using agricultural and forestry wastes and application thereof | |
| CN111939958A (en) | g-C3N4/Bi2WO6/CuS ternary composite photocatalyst and preparation method thereof | |
| CN107986334A (en) | A kind of preparation method of Ti-Mo codopes tungsten trioxide photoelectrode | |
| CN109772394A (en) | Phosphorus doping carbon/cuprous oxide composite catalyst and its preparation method and application | |
| CN113952963A (en) | CuInS based on Co modification2Preparation method and application of photocatalyst | |
| CN107008337B (en) | Non-stoichiometric copper bismuthate nano material and preparation method and application 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: 20180330 |