CN109289881A - A kind of preparation and solar energy fixed nitrogen application of carbon nano-fiber support BiOX photocatalyst - Google Patents
A kind of preparation and solar energy fixed nitrogen application of carbon nano-fiber support BiOX photocatalyst Download PDFInfo
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- CN109289881A CN109289881A CN201811388166.XA CN201811388166A CN109289881A CN 109289881 A CN109289881 A CN 109289881A CN 201811388166 A CN201811388166 A CN 201811388166A CN 109289881 A CN109289881 A CN 109289881A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 60
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 51
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011941 photocatalyst Substances 0.000 title description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- -1 bismuth oxybromide bismuth oxyiodide Chemical compound 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000002497 iodine compounds Chemical class 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000002604 ultrasonography Methods 0.000 claims abstract description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 75
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 54
- 235000019441 ethanol Nutrition 0.000 claims description 42
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 39
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 230000001699 photocatalysis Effects 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 238000007146 photocatalysis Methods 0.000 claims description 11
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 6
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 238000005255 carburizing Methods 0.000 claims description 5
- 229940113088 dimethylacetamide Drugs 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229940107816 ammonium iodide Drugs 0.000 claims description 3
- 229910001451 bismuth ion Inorganic materials 0.000 claims description 3
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 3
- PNZDZRMOBIIQTC-UHFFFAOYSA-N ethanamine;hydron;bromide Chemical compound Br.CCN PNZDZRMOBIIQTC-UHFFFAOYSA-N 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims 2
- 229910021392 nanocarbon Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 76
- 239000011259 mixed solution Substances 0.000 abstract description 13
- 239000000835 fiber Substances 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000009987 spinning Methods 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 28
- 229910021529 ammonia Inorganic materials 0.000 description 14
- BDJYZEWQEALFKK-UHFFFAOYSA-N bismuth;hydrate Chemical compound O.[Bi] BDJYZEWQEALFKK-UHFFFAOYSA-N 0.000 description 12
- 238000011534 incubation Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000009620 Haber process Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UGVKQBKFTXCCNB-UHFFFAOYSA-N [Bi]=O.[Br] Chemical compound [Bi]=O.[Br] UGVKQBKFTXCCNB-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 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
- 238000005336 cracking Methods 0.000 description 1
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—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
- B01J35/58—Fabrics or filaments
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of photochemical catalysts, support bismuth oxybromide bismuth oxyiodide for carbon nano-fiber, molecular formula BiOI/BiOBr/CNFs is used for high-efficiency solar fixed nitrogen.The preparation method of catalyst, comprising steps of 1, take organic liquid be solvent；2, the organic matter of molecular weight > 5000 is dissolved in organic solvent, forms mixed solution；3, spinning is carried out using electrostatic spinning technique；4, carbon nano-fiber is obtained after fibers carbonization；5, take Organic Alcohol as solvent；6, organic alcohol solvent is added in bismuth salt compound, bromide compound and salt compounded of iodine compound, mixes and is sufficiently stirred；7, carbon nano-fiber, ultrasound is added；8, it is packed into reaction kettle, carries out isothermal reaction；9, it is cooled to room temperature and is centrifuged and is washed respectively with water and ethanol solution, collect powder after dry, obtain carbon nano-fiber support bismuth oxybromide bismuth oxyiodide.The catalyst that the method for the present invention obtains is environmentally friendly, it is cheap, can be produced in batches, and there is high-efficiency solar fixed nitrogen performance.
Description
Technical field
The present invention relates to a kind of catalysis material technical fields, support bromine more specifically to a kind of carbon nano-fiber
The preparation of bismuth oxide bismuth oxyiodide (BiOI/BiOBr/CNFs) photochemical catalyst and the application of solar energy fixed nitrogen.
Background technique
It is well known that the nitrogen in air containing 78% is difficult pair but since the N ≡ N in nitrogen molecule is highly stable
It is dissociated and is applied.Fixed nitrogen is industrially carried out using traditional haber process, but condition is more harsh, needs in high temperature
It is carried out under (300~600 DEG C) and high pressure (15~25MPa), then generates ammonia through catalyst, nitrogen and hydrogen effect.?
Great amount of carbon dioxide is generated during technical azotification, aggravates greenhouse effects problem.Therefore, it is necessary to low-carbon environment-friendly, reaction condition temperature
The technology of sum replaces haber process to carry out fixed nitrogen.Solar energy photocatalytic nitrogen fixation technology, because its reaction condition is mild, high-efficiency environment friendly and it is standby
It is concerned.But since photochemical catalyst itself and process conditions limit, still there is some limiting factors: 1, can light induced electron will be high
Spend stable N ≡ N fracture；2, photochemical catalyst while carrying out fixed nitrogen reaction under water environment, also carries out water because of its non-selectivity
Cracking reaction, this competitive reaction reduce nitrogen-fixing efficiency；3, semiconductor catalyst quantum efficiency is low, and recycling rate of waterused is limited and is difficult to
The problems such as recycling is also the major issue that the needs in its practical fixed nitrogen application solve.
Now, more and more photochemical catalysts are used in solar energy fixed nitrogen.Such as: titanium dioxide, cadmium sulfide, graphite-phase
Carbonitride, bismuth molybdate etc..However, the layer structure of BiOX (BiOX) is conducive to the separation of photo-generate electron-hole, forbidden band
Narrower width, light abstraction width is wider, and has many advantages, such as simple production process, cheap, nontoxic.Nevertheless, traditional
BiOX still shows lower solar energy nitrogen fixing capacity.
Summary of the invention
It is an object of that present invention to provide a kind of preparation of photochemical catalyst and its high-efficiency solar fixed nitrogen methods.
To achieve the goals above, the technical solution of the present invention is as follows:
A kind of photochemical catalyst of the present invention, catalyst are that carbon nano-fiber supports bismuth oxybromide bismuth oxyiodide, molecular formula BiOI/
BiOBr/CNFs, structure are the 3D open architecture with bismuth oxybromide, bismuth oxyiodide and carbon nano-fiber.
Catalyst provided by the invention, be used for high-efficiency solar fixed nitrogen, be applied particularly to using water as reducing agent efficiently too
Positive energy fixed nitrogen light-catalyzed reaction.
The present invention provides a kind of preparation methods of photochemical catalyst, include the following steps:
S1, at room temperature using N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetone, ethyl alcohol, water as solvent；
S2, above-mentioned solvent is added greater than 5000 larger molecular organics in molecular weight, mixes and is sufficiently stirred；The molecule
Larger molecular organics of the amount greater than 5000 are polyacrylonitrile, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyvinylpyrrolidone；
S3, syringe, progress electrostatic spinning is added than the solution for 8%~25% in solute and solvent quality；Positive electricity used
Pressure is 10~18kV, and negative voltage used is -2~-5kV；Syringe needle to roller bearing distance be 8~20cm, flow rate of liquid be 0.5~
1.2mL/h；
It is pre-oxidized in S4, air, 150~240 DEG C of Pre oxidation, heating rate is 0.05~0.5 DEG C/min, is protected
After 18~30h of temperature, it is cooled to room temperature；
It is carbonized in S5, nitrogen, nitrogen flow is 80~150mL/h, and carburizing temperature is 500~800 DEG C, heating rate
It is cooled to room temperature after keeping the temperature 4~10h for 0.1~0.8 DEG C/min；
S6, at room temperature using ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine as solvent；
S7, the alcoholic solvent is added in bismuth salt compound, bromide compound and salt compounded of iodine compound, mixes and is sufficiently stirred；
The bismuth salt compound is five nitric hydrate bismuths, bismuth sulfate or bismuth ion complex compound；The bromide compound is sodium bromide, bromination
Potassium, CTAB or 2- ethylamine hydrobromide；The salt compounded of iodine compound is sodium iodide, potassium iodide or ammonium iodide；
S8, neutral solution is added after stirring to clarify solution, after stirring 20~80min, 10~50mg CNFs is added, and
It is fitted into after 3~10min of ultrasound in the autoclave that pressure is 1~2MPa, carries out 120~180 DEG C of isothermal reactions；
S9, it is cooled to room temperature and is centrifuged and is washed respectively with water and ethanol solution, after 50~80 DEG C dry, receive
Collection powder obtains carbon nano-fiber support bismuth oxybromide bismuth oxyiodide.
Wherein, in step s 8, the neutral solution is methanol, ethyl alcohol, isopropanol, the tert-butyl alcohol, octanol.
The present invention provides a kind of preparation methods of photochemical catalyst, specifically includes the following steps:
S1, at room temperature using N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetone, ethyl alcohol, water as solvent；
S2, above-mentioned solvent is added greater than 5000 larger molecular organics in molecular weight, mixes and is sufficiently stirred；The molecule
Big larger molecular organics of the amount greater than 5000 are polyacrylonitrile, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyvinylpyrrolidone；
S3, syringe, progress electrostatic spinning is added than the solution for 8%~25% in solute and solvent quality；Positive electricity used
Pressure is 10~18kV, and negative voltage used is -2~-5kV；Syringe needle to roller bearing distance be 8~20cm, flow rate of liquid be 0.5~
1.2mL/h；
It is pre-oxidized in S4, air, 150~240 DEG C of Pre oxidation, heating rate is 0.05~0.5 DEG C/min, is protected
After 18~30h of temperature, it is cooled to room temperature；
It is carbonized in S5, nitrogen, nitrogen flow is 80~150mL/h, and carburizing temperature is 500~800 DEG C, heating rate
It is cooled to room temperature after keeping the temperature 4~10h for 0.1~0.8 DEG C/min；
S6, at room temperature using 5~30mL ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine as solvent；
S7,0.1~1.0g bismuth salt compound, 0.01~0.3g bromide compound and 0.01~0.3g salt compounded of iodine compound are added
Enter the alcoholic solvent, mix and 5~30min is sufficiently stirred；
S8,40~80mL neutral solution, 20~80min of stirring is added after stirring to clarify solution, adds 10~50mg
CNFs, and the autoclave that pressure is 1~2MPa is packed into after 3~10min of ultrasound, carry out 120~180 DEG C of isothermal reaction 10h
More than；
S9, it is cooled to room temperature and is centrifuged and is washed 4~8 times with water and ethanol solution respectively, in 50~80 DEG C of dryings
Afterwards, it collects powder and obtains carbon nano-fiber support bismuth oxybromide bismuth oxyiodide.
Wherein, when isothermal reaction described in step S8, it is 60% that the volume for filling solution, which accounts for the ratio of autoclave liner volume,
~90%, the reaction time be 10~for 24 hours.
The present invention provides a kind of methods using above-mentioned catalyst solar energy fixed nitrogen, comprising the following steps: to 50~
10~50mg photochemical catalyst is added in 150mL water, and maintains 5~20 DEG C, before carrying out photocatalysis, 30~60min of stirring, then
40~120min is stirred under illumination, filters out catalyst with 0.1~0.4 μm of filter later.
The present invention has the advantage that
Photochemical catalyst of the invention not only has good solar energy fixed nitrogen performance, but also possesses higher quantum efficiency.
Using water as reducing agent under sunlight, BiOI/BiOBr/CNFs photochemical catalyst generates 281.1 μm of ol ammonias per hour per gram,
Ammonia yield is 1.5 times of BiOI/BiOBr, is 3.2 times of traditional BiOBr, is 5.4 times of traditional BiOI.In the energy, ring
Border pollution has broad application prospects with fields such as improvement, and strong theoretical basis is provided for the type catalyst.
Detailed description of the invention
Fig. 1 is the XRD diffraction pattern of 1 catalyst of embodiment.
Fig. 2 is the scanning electron microscope (SEM) photograph of 1 catalyst of embodiment.
Fig. 3 is the UV-vis abosrption spectrogram of 1 catalyst of embodiment.
Fig. 4 is that the forbidden bandwidth of 1 catalyst of embodiment estimates spectrogram.
Fig. 5 is the current versus time curve figure of 1 catalyst of embodiment.
Fig. 6 is the AC impedance figure of 1 catalyst of embodiment.
Fig. 7 is the solar energy nitrogen fixation effect figure of Examples 1 to 6 catalyst.
Fig. 8 is the solar energy nitrogen fixation effect figure of 7~12 catalyst of embodiment.
Specific embodiment
A kind of preparation of carbon nano-fiber support bismuth oxybromide bismuth oxyiodide photochemical catalyst of the present invention and high-efficiency solar are solid
Nitrogen method belongs to catalysis material technical field.This method comprises the following steps: 1, taking organic liquid is solvent；2, by molecule
Organic matter of the amount greater than 5000 is dissolved in organic solvent, forms mixture；3, spinning is carried out using electrostatic spinning technique；4, right
Fiber obtains carbon nano-fiber after being carbonized；5, take Organic Alcohol as solvent；6, by bismuth salt compound, bromide compound and iodine
Organic alcohol solvent is added in salt compound, mixes and is sufficiently stirred；7, carbon nano-fiber, ultrasound is added；8, it is fitted into reaction kettle, into
Row isothermal reaction；9, it is cooled to room temperature and is centrifuged and is repeatedly washed with water and ethanol solution respectively, collect powder after dry
End obtains carbon nano-fiber support bismuth oxybromide bismuth oxyiodide.The carbon nano-fiber that the method for the present invention obtains supports bismuth oxybromide
Bismuth oxyiodide photochemical catalyst is environmentally friendly, material source is extensive, cheap, method is controllable and easy to operate, can carry out batch
Production has good solar energy photocatalytic fixed nitrogen performance.
Below with reference to the attached drawing in the embodiment of the present invention, to make clear, complete statement to this art scheme.Following institute
The embodiment of description is only the skill in a part of inventive embodiments of the invention, is not whole embodiments.This field
Technical staff's above content according to the present invention is made some nonessential improvement and is all belonged to the scope of protection of the present invention.
It is an object of the present invention to provide a kind of photochemical catalysts, provide a kind of preparation method of photochemical catalyst, mention simultaneously
For a kind of photocatalysis method of high-efficiency solar fixed nitrogen.
N,N-Dimethylformamide, n,N-dimethylacetamide, acetone, ethyl alcohol, water are as solvent in the present invention, at room temperature
It is reacted；The solvent includes but is not limited to N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetone, ethyl alcohol, water work
For solvent.
Above-mentioned solvent is added greater than 5000 larger molecular organics in molecular weight, mixes and is sufficiently stirred；The molecular weight
Larger molecular organics greater than 5000 are polyacrylonitrile, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyvinylpyrrolidone.By solute with it is molten
Syringe is added in the solution that agent mass ratio is 8%~25%, carries out electrostatic spinning；Positive voltage used is 10~18kV, negative electricity used
Pressure is -2~-5kV；Syringe needle is 8~20cm to roller bearing distance, and flow rate of liquid is 0.5~1.2mL/h；It is pre-oxidized in air,
150~240 DEG C of Pre oxidation, heating rate is that 0.05~0.5 DEG C/min is cooled to room temperature after keeping the temperature 18~30h；Nitrogen
In be carbonized, nitrogen flow be 80~150mL/h, carburizing temperature be 500~800 DEG C, heating rate be 0.1~0.8 DEG C/
Min is cooled to room temperature after keeping the temperature 4~10h.
Using 5~30mL ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine as solvent, carry out at room temperature anti-
It answers；The alcohol includes but is not limited to ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine.
0.1~1.0g bismuth salt compound, 0.01~0.3g bromide compound and 0.01~0.3g salt compounded of iodine compound are added
The alcoholic solution is mixed and is sufficiently stirred, and mixing time is 5~30min；The bismuth-containing compound includes but is not limited to five hydrations
Bismuth nitrate, bismuth sulfate or bismuth ion complex compound；The bromine-containing compound includes but is not limited to sodium bromide, potassium bromide, CTAB or 2-
Ethylamine hydrobromide；The salt compounded of iodine compound is sodium iodide, potassium iodide or ammonium iodide；
40~80mL neutral solution, and 3~10min of ultrasound is added after above-mentioned solution is stirred to clarify solution in the present invention
It is fitted into autoclave afterwards, 120~180 DEG C of isothermal reactions 10 of progress~for 24 hours；The neutral solution includes but is not limited to first
Alcohol, ethyl alcohol, isopropanol, the tert-butyl alcohol or octanol.Product, which is cooled to room temperature, to be centrifuged and washes 4 with water and ethanol solution respectively
~8 times, powder is collected after dry at 50~80 DEG C.Wherein, when synthetic reaction, the volume for filling solution accounts for autoclave liner volume
Ratio be 60%~90%；Reaction time be 10~for 24 hours.
The present invention provides a kind of methods using above-mentioned catalyst solar energy fixed nitrogen, comprising the following steps: to 50~
10~50mg photochemical catalyst is added in 150mL water, and maintains 5~20 DEG C, before carrying out photocatalysis, 30~60min of stirring, then
40~120min is stirred under illumination, filters out catalyst with 0.1~0.4 μm of filter later.
Compared with existing photocatalysis technology, the present invention is had the advantage that
(1) photochemical catalyst of the invention not only has good solar energy fixed nitrogen performance, but also possesses higher quantum effect
Rate.Using water as reducing agent under sunlight, BiOI/BiOBr/CNFs photochemical catalyst generates 281.1 μm of ol ammonias per hour per gram,
Its ammonia yield is 1.5 times of BiOI/BiOBr, is 3.2 times of traditional BiOBr, is 5.4 times of traditional BiOI.The energy,
The fields such as Environmental pollution and control have broad application prospects, and strong theoretical basis is provided for the type catalyst.
(2) preparation method of BiOI/BiOBr/CNFs catalysis material is environmentally protective, easy to operate, cheap, to spy
Different equipment requirement is low, and controllability is strong, has certain practicability.
Embodiment 1
Five nitric hydrate bismuth of 0.48g, 0.0612g sodium bromide and 0.0664g potassium iodide are added to 10mL ethylene glycol solution
In, 60mL ethanol solution is added after 20min to clear solution is sufficiently stirred, 0.03g is added after mixed solution stirring 30min
CNFs solution is packed into 1~2MPa autoclave after ultrasonic 5min, carries out 160 DEG C of incubation water heatings reaction 12h.Product is cooled to
Room temperature is centrifuged and is washed 6 times with water and ethanol solution respectively, collects powder after dry in 60 DEG C, obtains final products
BiOI/BiOBr/CNFs。
Fig. 1 be the present embodiment obtain BiOI/BiOBr/CNFs photochemical catalyst XRD diffracting spectrum, through with PDF standard card
Comparison learns that obtained is the BiOBr and BiOI of tetragonal phase.
Fig. 2 is the BiOI/BiOBr/CNFs photochemical catalyst scanning electron microscope (SEM) photograph that the present embodiment obtains, and being obtained is to open with 3D
The diameter for putting structure is about 1.0 μm of filamentary composites.
Fig. 3 is the BiOI/BiOBr/CNFs photochemical catalyst UV-vis absorption spectrum that the present embodiment obtains, compared to pure phase
BiOBr ABSORPTION EDGE red shift is obviously improved in visible-range internal absorbance, there is stronger light abstraction width.
Fig. 4 is the forbidden bandwidth estimation map for the BiOI/BiOBr/CNFs photochemical catalyst that the present embodiment obtains, resulting materials
Band gap relative narrower, electron-transport speed is accelerated, to promote photocatalytic activity.
Fig. 5 is the BiOI/BiOBr/CNFs photochemical catalyst photocurrent-time curve figure that the present embodiment obtains, compared to pure
Phase BiOBr and BiOI, there is stronger photoelectric current, illustrate to have efficiently separated light induced electron and hole.
Fig. 6 is the BiOI/BiOBr/CNFs photochemical catalyst AC impedance figure that the present embodiment obtains, compared to pure phase BiOBr
And BiOI, present lesser resistance, at the same illustrate it is low for the recombination rate of photo-generated carrier, it is preferable promote charge conversion with
It efficiently separates.
Embodiment 2
Five nitric hydrate bismuth of 0.48g, 0.0816g sodium bromide and 0.0332g potassium iodide are added to 10mL ethylene glycol solution
In, 60mL ethanol solution is added after 20min to clear solution is sufficiently stirred, 0.03g is added after mixed solution stirring 30min
CNFs solution is packed into 1~2MPa autoclave after ultrasonic 5min, carries out 160 DEG C of incubation water heatings reaction 12h.Product is cooled to
Room temperature is centrifuged and is washed 6 times with water and ethanol solution respectively, collects powder after dry in 60 DEG C, obtains final products
BiOI/BiOBr/CNFs。
Embodiment 3
Five nitric hydrate bismuth of 0.48g, 0.0408g sodium bromide and 0.0996g potassium iodide are added to 10mL ethylene glycol solution
In, 60mL ethanol solution is added after 20min to clear solution is sufficiently stirred, 0.03g is added after mixed solution stirring 30min
CNFs solution is packed into 1~2MPa autoclave after ultrasonic 5min, carries out 160 DEG C of incubation water heatings reaction 12h.Product is cooled to
Room temperature is centrifuged and is washed 6 times with water and ethanol solution respectively, collects powder after dry in 60 DEG C, obtains final products
BiOI/BiOBr/CNFs。
Embodiment 4
Five nitric hydrate bismuth of 0.48g, 0.0204g sodium bromide and 0.1328g potassium iodide are added to 10mL ethylene glycol solution
In, 60mL ethanol solution is added after 20min to clear solution is sufficiently stirred, 0.03g is added after mixed solution stirring 30min
CNFs solution is packed into 1~2MPa autoclave after ultrasonic 5min, carries out 160 DEG C of incubation water heatings reaction 12h.Product is cooled to
Room temperature is centrifuged and is washed 6 times with water and ethanol solution respectively, collects powder after dry in 60 DEG C, obtains final products
BiOI/BiOBr/CNFs。
Embodiment 5
Five nitric hydrate bismuth of 0.48g and 0.102g sodium bromide are added in 10mL ethylene glycol solution, 20min is sufficiently stirred
60mL ethanol solution is added after to clear solution, 0.03g CNFs solution is added after stirring 30min in mixed solution, after ultrasonic 5min
It is packed into 1~2MPa autoclave, carries out 160 DEG C of incubation water heating reaction 12h.Product, which is cooled to room temperature, to be centrifuged and divides
It is not washed 6 times with water and ethanol solution, collects powder after dry in 60 DEG C, obtain final products BiOBr/CNFs.
Embodiment 6
Five nitric hydrate bismuth of 0.48g and 0.166g potassium iodide are added in 10mL ethylene glycol solution, 20min is sufficiently stirred
60mL ethanol solution is added after to clear solution, 0.03g CNFs solution is added after stirring 30min in mixed solution, after ultrasonic 5min
It is packed into 1~2MPa autoclave, carries out 160 DEG C of incubation water heating reaction 12h.Product, which is cooled to room temperature, to be centrifuged and divides
It is not washed 6 times with water and ethanol solution, collects powder after dry in 60 DEG C, obtain final products BiOI/CNFs.
Embodiment 7
Five nitric hydrate bismuth of 0.48g, 0.0612g sodium bromide and 0.0664g potassium iodide are added to 10mL ethylene glycol solution
In, 60mL ethanol solution is added after 20min to clear solution is sufficiently stirred, mixed solution is packed into 1~2MPa high after stirring 30min
Reaction kettle is pressed, 160 DEG C of incubation water heating reaction 12h are carried out.Product, which is cooled to room temperature, to be centrifuged and respectively with water and ethyl alcohol
Solution is washed 6 times, is collected powder after dry in 60 DEG C, is obtained final products BiOI/BiOBr.
Embodiment 8
Five nitric hydrate bismuth of 0.48g, 0.0816g sodium bromide and 0.0332g potassium iodide are added to 10mL ethylene glycol solution
In, 60mL ethanol solution is added after 20min to clear solution is sufficiently stirred, mixed solution is packed into 1~2MPa high after stirring 30min
Reaction kettle is pressed, 160 DEG C of incubation water heating reaction 12h are carried out.Product, which is cooled to room temperature, to be centrifuged and respectively with water and ethyl alcohol
Solution is washed 6 times, is collected powder after dry in 60 DEG C, is obtained final products BiOI/BiOBr.
Embodiment 9
Five nitric hydrate bismuth of 0.48g, 0.0408g sodium bromide and 0.0996g potassium iodide are added to 10mL ethylene glycol solution
In, 60mL ethanol solution is added after 20min to clear solution is sufficiently stirred, mixed solution is packed into 1~2MPa high after stirring 30min
Reaction kettle is pressed, 160 DEG C of incubation water heating reaction 12h are carried out.Product, which is cooled to room temperature, to be centrifuged and with water and ethyl alcohol respectively
Solution is washed 6 times, is collected powder after dry in 60 DEG C, is obtained final products BiOI/BiOBr.
Embodiment 10
Five nitric hydrate bismuth of 0.48g, 0.0204g sodium bromide and 0.1328g potassium iodide are added to 10mL ethylene glycol solution
In, 60mL ethanol solution is added after 20min to clear solution is sufficiently stirred, mixed solution is packed into 1~2MPa high after stirring 30min
Reaction kettle is pressed, 160 DEG C of incubation water heating reaction 12h are carried out.Product, which is cooled to room temperature, to be centrifuged and with water and ethyl alcohol respectively
Solution is washed 6 times, is collected powder after dry in 60 DEG C, is obtained final products BiOI/BiOBr.
Embodiment 11
Five nitric hydrate bismuth of 0.48g and 0.102g sodium bromide are added in 10mL ethylene glycol solution, 20min is sufficiently stirred
60mL ethanol solution is added after to clear solution, mixed solution is packed into 1~2MPa autoclave after stirring 30min, carries out 160
DEG C incubation water heating reacts 12h.Product, which is cooled to room temperature, to be centrifuged and is washed 6 times with water and ethanol solution respectively, in 60 DEG C
Powder is collected after drying, obtains final products BiOBr.
Embodiment 12
Five nitric hydrate bismuth of 0.48g and 0.166g potassium iodide are added in 10mL ethylene glycol solution, 20min is sufficiently stirred
60mL ethanol solution is added after to clear solution, mixed solution is packed into 1~2MPa autoclave after stirring 30min, carries out 160
DEG C incubation water heating reacts 12h.Product, which is cooled to room temperature, to be centrifuged and is washed 6 times with water and ethanol solution respectively, in 60 DEG C
Powder is collected after drying, obtains final products BiOI.
The test of solar energy photocatalytic fixed nitrogen is carried out for 1~12 sample of embodiment.
All photocatalysis, which are tested, to be executed at 10~25 DEG C with 300W xenon lamp simulated solar irradiation.For photocatalysis fixed nitrogen mistake
Journey: 0.02g catalyst and 100mL water are added in glass photocatalytic reactor, and is passed through recirculated water to maintain 15 DEG C.Carry out
Before photocatalysis, it is passed through the nitrogen that flow velocity is 60mL/min, no light stirs 30min, then every 15min extraction under Xenon light shining
5mL solution.It is further filtered with 0.22 μm of filter, and instills nessler reagent, measured under ultraviolet specrophotometer 420nm wavelength
Absorbance.The test of photocatalysis fixed nitrogen is carried out for 1~12 sample of embodiment.
Fig. 7 illustrates 1 hour solar energy photocatalytic nitrogen fixation effect of Examples 1 to 6 catalyst.It is obvious that embodiment 1 is urged
Agent shows optimal photocatalysis solar energy photocatalytic nitrogen fixation effect, and photochemical catalyst generates 281.1 μm of ol ammonia per hour per gram
Gas.It is 186.4 μm of ol/ (hg) that 2 catalyst of embodiment, which generates ammonia amount, and it is 144.2 μ that 3 catalyst of embodiment, which generates ammonia amount,
Mol/ (hg), it is 104.2 μm of ol/ (hg) that embodiment 4, which generates ammonia amount, and it is 122.4 that 5 catalyst of embodiment, which generates ammonia amount,
μm ol/ (hg), it is 78.1 μm of ol/ (hg) that 6 catalyst of embodiment, which generates ammonia amount,.Fig. 8 illustrates the catalysis of embodiment 7~12
1 hour solar energy photocatalytic nitrogen fixation effect of agent.It is obvious that 7 catalyst of embodiment shows optimal solar energy photocatalytic fixed nitrogen
Effect, photochemical catalyst generates 187.5 μm of ol ammonias per hour per gram.It is 135.4 μm of ol/ that 8 catalyst of embodiment, which generates ammonia amount,
(hg), it is 109.3 μm of ol/ (hg) that 9 catalyst of embodiment, which generates ammonia amount, and 10 catalyst of embodiment generates ammonia amount and is
67.7 μm of ol/ (hg), it is 88.5 μm of ol/ (hg) that 11 catalyst of embodiment, which generates ammonia amount, and 12 catalyst of embodiment generates
Ammonia amount is 52.1 μm of ol/ (hg).To find out, photochemical catalyst BiOI/BiOBr/CNFs of the invention possesses brilliant light
It is catalyzed nitrogen fixation effect.
Catalyst provided by the invention is used for solar energy photocatalytic fixed nitrogen.Since length is limited, total Test can not be enumerated
Data, the present invention only provide part test data and support beneficial effects of the present invention.
In order to preferably carry out fixed nitrogen light-catalyzed reaction using BiOX, present invention employs compound and attached in BiOX race
In on carbon nano-fiber, being successfully prepared the 3D open architecture with bismuth oxybromide, bismuth oxyiodide and carbon nano-fiber.Catalysis
Good solar energy photocatalytic fixed nitrogen performance is presented in agent.Since the laminated structure of BiOX is conducive to electron-transport, while bromine
Bismuth oxide and bismuth oxyiodide all have relatively narrow forbidden bandwidth, enhance to visible absorption, after compound, lead the straight of valence band composition
Connect the separation that Z-type structure is more advantageous to light induced electron.Carbon fiber not only provides bigger specific surface area as supporter simultaneously,
Brilliant adsorption capacity is presented, and carbon fiber has good electric conductivity, is conducive to the transmitting of extensively raw exciton.Therefore, make
This material is obtained under sunlight, there is good photocatalysis nitrogen fixation effect.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of photochemical catalyst, which is characterized in that catalyst is that carbon nano-fiber (CNFs) supports bismuth oxybromide bismuth oxyiodide, point
Minor BiOI/BiOBr/CNFs.
2. photochemical catalyst according to claim 1, which is characterized in that in bismuth oxybromide, bismuth oxyiodide and Nano carbon fibers
The 3D open architecture of dimension.
3. a kind of purposes of catalyst, which is characterized in that be used for visible light-responded solar energy photocatalytic fixed nitrogen.
4. the purposes of catalyst according to claim 3, which is characterized in that be applied to by nitrogen source, water of nitrogen be reducing agent
Solar energy fixed nitrogen light-catalyzed reaction.
5. a kind of preparation method of photochemical catalyst, which comprises the steps of:
S1, at room temperature using N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetone, ethyl alcohol, water as solvent；
S2, above-mentioned solvent is added greater than 5000 larger molecular organics in molecular weight, mixes and is sufficiently stirred；The molecular weight is big
In 5000 larger molecular organics be polyacrylonitrile, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyvinylpyrrolidone；
S3, syringe, progress electrostatic spinning is added than the solution for 8%~25% in solute and solvent quality；Positive voltage used is
10~18kV, negative voltage used are -2~-5kV；Syringe needle is 8~20cm to roller bearing distance, and flow rate of liquid is 0.5~1.2mL/h；
It is pre-oxidized in S4, air, 150~240 DEG C of Pre oxidation, heating rate is 0.05~0.5 DEG C/min, heat preservation 18
After~30h, it is cooled to room temperature；
It is carbonized in S5, nitrogen, nitrogen flow is 80~150mL/h, and carburizing temperature is 500~800 DEG C, and heating rate is
It 0.1~0.8 DEG C/min, after keeping the temperature 4~10h, is cooled to room temperature；
S6, at room temperature using ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine as solvent；
S7, the alcoholic solvent is added in bismuth salt compound, bromide compound and salt compounded of iodine compound, mixes and is sufficiently stirred；It is described
Bismuth salt compound is five nitric hydrate bismuths, bismuth sulfate or bismuth ion complex compound；The bromide compound be sodium bromide, potassium bromide,
CTAB or 2- ethylamine hydrobromide；The salt compounded of iodine compound is sodium iodide, potassium iodide or ammonium iodide；
S8, neutral solution is added after stirring to clarify solution, after stirring 10~30min, 10~50mgCNFs, and ultrasound 3 is added
It is fitted into after~10min in the autoclave that pressure is 1~2MPa, carries out 120~180 DEG C of isothermal reactions；
S9, it is cooled to room temperature and is centrifuged and is washed respectively with water and ethanol solution, after dry at 50~80 DEG C, collect
Powder obtains carbon nano-fiber support bismuth oxybromide bismuth oxyiodide.
6. the preparation method of photochemical catalyst according to claim 5, which is characterized in that in step S8, the neutral solution is
Methanol, ethyl alcohol, isopropanol, the tert-butyl alcohol or octanol.
7. according to the preparation method of any photochemical catalyst of claim 5~6, which comprises the following steps:
S1, at room temperature using N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetone, ethyl alcohol, water as solvent；
Above-mentioned solvent is added in S2, the larger molecular organics by molecular weight greater than 5000, mix and it is sufficiently stirred 10~for 24 hours；It is described
Larger molecular organics of the molecular weight greater than 5000 are polyacrylonitrile, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyvinylpyrrolidone；
S3, syringe, progress electrostatic spinning is added than the solution for 8%~25% in solute and solvent quality；Positive voltage used is
10~18kV, negative voltage used are -2~-5kV；Syringe needle is 8~20cm to roller bearing distance, and flow rate of liquid is 0.5~1.2mL/h；
It is pre-oxidized in S4, air, 150~240 DEG C of Pre oxidation, heating rate is 0.05~0.5 DEG C/min, heat preservation 18
After~30h, it is cooled to room temperature；
It is carbonized in S5, nitrogen, nitrogen flow is 80~150mL/h, and carburizing temperature is 500~800 DEG C, and heating rate is
It 0.1~0.8 DEG C/min, after keeping the temperature 4~10h, is cooled to room temperature；
S6, at room temperature using 5~30mL ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine as solvent；
S7, institute is added in 0.1~1.0g bismuth salt compound, 0.01~0.3g bromide compound and 0.01~0.3g salt compounded of iodine compound
Alcoholic solvent is stated, mix and 5~30min is sufficiently stirred；
S8,40~80mL neutral solution, 20~80min of stirring is added after stirring to clarify solution, adds 10~50mg CNFs,
And be fitted into after 3~10min of ultrasound pressure be 1~2MPa autoclave in, carry out 120~180 DEG C of isothermal reaction 10h with
On；
S9, it is cooled to room temperature and is centrifuged and is washed 4~8 times with water and ethanol solution respectively, after 50~80 DEG C dry, receive
Collection powder obtains carbon nano-fiber support bismuth oxybromide bismuth oxyiodide.
8. the preparation method of solar energy fixed nitrogen photochemical catalyst according to claim 7, which is characterized in that constant temperature described in step S8
When reaction, fill solution volume account for autoclave liner volume ratio be 60%~90%, the reaction time be 10~for 24 hours.
9. a kind of method using above-mentioned catalyst high-efficiency solar fixed nitrogen, which is characterized in that be added 10 into 50~150mL water
~50mg photochemical catalyst, and maintaining temperature is 5~20 DEG C, before carrying out photocatalysis, stirs 30~60min, then stir under light illumination
40~120min is mixed, filters out catalyst with the filter that aperture is 0.1~0.4 μm later.
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