CN109112568A - It is a kind of based on boron, the catalyst of nitrogen co-doped mesoporous carbon and its preparation method and application - Google Patents
It is a kind of based on boron, the catalyst of nitrogen co-doped mesoporous carbon and its preparation method and application Download PDFInfo
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- CN109112568A CN109112568A CN201810935315.3A CN201810935315A CN109112568A CN 109112568 A CN109112568 A CN 109112568A CN 201810935315 A CN201810935315 A CN 201810935315A CN 109112568 A CN109112568 A CN 109112568A
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- boron
- catalyst
- nitrogen
- mesoporous carbon
- doped mesoporous
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 59
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 26
- -1 nitrogenous compound Chemical class 0.000 claims abstract description 17
- 229920001400 block copolymer Polymers 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000002608 ionic liquid Substances 0.000 claims abstract description 5
- 238000007711 solidification Methods 0.000 claims abstract description 3
- 230000008023 solidification Effects 0.000 claims abstract description 3
- 229920000557 Nafion® Polymers 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 230000036647 reaction Effects 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000005518 polymer electrolyte Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 229910052810 boron oxide Inorganic materials 0.000 claims description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229910052580 B4C Inorganic materials 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 3
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006471 dimerization reaction Methods 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- UYVXZUTYZGILQG-UHFFFAOYSA-N methoxyboronic acid Chemical compound COB(O)O UYVXZUTYZGILQG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229960002668 sodium chloride Drugs 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 3
- MNYOKDIIUJDYBM-UHFFFAOYSA-N 1-benzyl-3-methyl-2h-imidazole Chemical compound C1=CN(C)CN1CC1=CC=CC=C1 MNYOKDIIUJDYBM-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005273 aeration Methods 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 210000003850 cellular structure Anatomy 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 14
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229940015043 glyoxal Drugs 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910006654 β-PbO2 Inorganic materials 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/13—Ozone
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of based on boron, the catalyst of nitrogen co-doped mesoporous carbon and its preparation method and application.It is the following steps are included: 1) by 2.0 ~ 8.0g block copolymer, 0.2 ~ 4.0g boron-containing compound and 0.2 ~ 4.0g nitrogenous compound are dissolved in 20 ~ 80g organic solvent, 10 ~ 60g resin is added, 10 ~ 30g boracic ionic liquid is added, stir 30 ~ 60min, at room temperature after volatile organic solvent 5-20h, it is placed in 12 ~ 36h of solidification in 50 ~ 150 DEG C of normal pressure baking oven, it is placed in 100 ~ 200 DEG C of normal pressure baking oven again and solidifies 12-36h, obtain cured product, cured product carries out ball milling, obtain powdery product, it is roasted again, boron is based on up to described, the catalyst of nitrogen co-doped mesoporous carbon.The catalyst that the present invention obtains is meso-hole structure, has biggish specific surface area, relatively large aperture and regular cellular structure, prepares ozone for electrolysis water, cost is relatively low, and electrolytic process green non-pollution is easy to control, is conducive to O3The diffusion of molecule, due to O3It is extremely easy in decomposition, accelerates O3Diffusion increases O3Yield.
Description
Technical field
The present invention relates to a kind of based on boron, the catalyst of nitrogen co-doped mesoporous carbon and its preparation method and application.
Background technique
O3A kind of important strong oxidizer, be widely used in water process, chemical industry, petroleum, weaving, food, fragrance and
The fields such as the industrial departments such as pharmacy and air sterillization, sterilizing are a kind of good " environmentally protective disinfectants ".In recent years, with
The improvement of people's living standards, environmental consciousness constantly enhance, O3It has been to be concerned by more and more people and payes attention to.
Currently, synthesis O3Method be mainly high-frequency and high-voltage corona discharge method, need to use through overcompression, drying etc. pre-process
Oxygen or air, investment cost is high, and the ozone concentration of generation is low, and also generation has human body and environment while generating ozone
Harmful nitrogen oxides (NOx).In addition, high-frequency and high-voltage can also generate radio noise when discharging, thus in practical applications by very
Big limitation.There is document report to synthesize O using UV radiation3Method.UV radiation is the energy with ultraviolet light
The oxygen molecule in ground state is set to be decomposed into 2 oxygen atoms, then the reaction of the same oxygen molecule generates O3Method.For production
A large amount of O3For be not a kind of effective method.
Electrolysis water generates ozone, and using water as raw material, reaction condition is mild, and equipment investment is small, the O of generation3Concentration is high, is one
The very promising O of kind3The new method of generation.Currently, the research that electrolysis water generates ozone technology focuses mostly in β-PbO2Anode electricity
On extremely.Studies have shown that after long-time is electrolysed, β-PbO2The partial size of particle sharply declines, and in high condition
Under recrystallization process cause the former particle surface to form many nanoscale little particles, cause electrolysis water to generate ozone performance
Decline.And electrochemical stability and higher oxygen evolution potential that boron-doped diamond electrode is high, in electrochemistry formated ozone
It attracts attention in research.Result of study shows either to generate O3Efficiency or electrode stability, boron-doped diamond electricity
Pole is better than traditional β-PbO2Electrode.However, limiting answering for boron-doped diamond electrode due to diamond fancy price
With.
Summary of the invention
For above-mentioned technical problem of the existing technology, the purpose of the present invention is to provide one kind to be co-doped with based on boron, nitrogen
The catalyst and its preparation method and application of miscellaneous mesoporous carbon, catalyst prepared by the present invention is low in cost, prepares for electrolysis water
The ozone concentration of ozone, generation is high.
A kind of preparation method based on boron, the catalyst of nitrogen co-doped mesoporous carbon, it is characterised in that including following
Step:
1) 2.0 ~ 8.0g block copolymer, 0.2 ~ 4.0g boron-containing compound and 0.2 ~ 4.0g nitrogenous compound are dissolved in 20 ~ 80g
In organic solvent, 10 ~ 60g resin is added, 10 ~ 30g boracic ionic liquid is added, stirs 30 ~ 60min, volatilization has at room temperature
After solvent 5-20h, it is placed in 12 ~ 36h of solidification in 50 ~ 150 DEG C of normal pressure baking oven, then be placed in 100 ~ 200 DEG C of normal pressure baking oven
Solidify 12-36h, obtains cured product；
2) ball milling is carried out to cured product obtained by step 1), obtains powdery product, then roasted to get it is described based on boron,
The catalyst of nitrogen co-doped mesoporous carbon.
A kind of preparation method based on boron, the catalyst of nitrogen co-doped mesoporous carbon, it is characterised in that block copolymerization
The quality of object is 4 ~ 7g, and the block copolymer is P123, P103, P85, F38, F68 or F127, preferably P123 or F127；
Boron-containing compound quality be 0.5 ~ 2.0g, the boron-containing compound be boron oxide, boron nitride, boric acid, boron carbide, borine or
Methyl-boric acid, preferably boric acid or boron oxide.
A kind of preparation method based on boron, the catalyst of nitrogen co-doped mesoporous carbon, it is characterised in that nitrogenous chemical combination
Amount of substance is 0.5 ~ 2.0g, and the nitrogenous compound is melamine, cyanamid dimerization, urea, pyridine, formamide or three ethyl alcohol
Amine, preferably melamine or urea；
Organic solvent quality be 30 ~ 60g, the organic solvent be methanol, ethyl alcohol, isopropanol, ether, dichloroethanes or toluene,
Preferably ethyl alcohol or toluene.
A kind of preparation method based on boron, the catalyst of nitrogen co-doped mesoporous carbon, it is characterised in that resin quality
For 20 ~ 40g, the resin is phenolic resin, polyester resin, polyamide, epoxy resin, urea formaldehyde resin or polyimides
Resin, preferably phenolic resin；
The boracic ionic liquid be N- butyl-pyridinium tetrafluoroborate, 1- amyl -3- methyl imidazolium tetrafluoroborate, 1- oneself
Base -3- methyl imidazolium tetrafluoroborate, 1- amine propyl -3- methyl imidazolium tetrafluoroborate, 1- benzyl -3- methylimidazole tetrafluoro boron
Hydrochlorate or N- methoxy ethyl-N- methyl diethyl ammonium tetrafluoroborate, preferably N- butyl-pyridinium tetrafluoroborate or 1- amine
Propyl -3- methyl imidazolium tetrafluoroborate.
A kind of preparation method based on boron, the catalyst of nitrogen co-doped mesoporous carbon, it is characterised in that in step 2,
The step of ball milling are as follows: cured product obtained by step 1) is put into ball grinder, 6 ~ 30 beads are added, is 50 in rotation revolving speed
~ 400r/min, revolution revolving speed are to grind 0.5 ~ 6h under 100 ~ 800r/min, obtain powdery product；
The step of roasting are as follows: under aeration condition, the powdery product is placed in tube furnace, tube furnace is with 1 ~ 10
DEG C/heating rate of min is warming up to 200 ~ 400 DEG C, keep the temperature 1 ~ 5h, then 500 are warming up to the heating rate of 1 ~ 10 DEG C/min ~
It 1300 DEG C, after keeping the temperature 1 ~ 5h, after obtained product is cooled to room temperature, is rinsed, is filtered with hydrothermal solution, filter residue is again at 50 ~ 100 DEG C
It is lower vacuum drying 12 ~ for 24 hours.
A kind of preparation method based on boron, the catalyst of nitrogen co-doped mesoporous carbon, it is characterised in that the gas being passed through
Body is ammonia, nitrogen, argon gas, helium or air, preferably nitrogen or argon gas；
The temperature of hydrothermal solution is 60 ~ 100 DEG C, and the hydrothermal solution is the hydrochloric acid of the aqueous sulfuric acid of 0.1 ~ 1 mol/L, 0.1 ~ 1 mol/L
Aqueous solution, the sodium-chloride water solution of 0.1 ~ 1 mol/L, saturated aqueous sodium sulfate, saturation potassium sulfate solution or deionized water.
The catalyst based on boron, nitrogen co-doped mesoporous carbon of the method preparation.
The catalyst based on boron, nitrogen co-doped mesoporous carbon prepares the application in ozone in electrolysis water.
The application, it is characterised in that using solid polymer electrolyte ozone generator as reactor, tank house
Volume is 0.5-3L, and deionized water is added；The platinum carbon of the boron doping gold/mesoporous carbon catalyst and the platinum content containing 10-20% is catalyzed
Agent is respectively coated on the anode surface and cathode plane of proton exchange membrane, and the electric current of cell reaction is 5-20 A, and tank voltage is 3-6 V,
Cell reaction is carried out at 10-80 DEG C, obtains ozone product；Wherein the cell reaction time be 1 ~ for 24 hours.
The application, it is characterised in that the proton exchange membrane is Nafion N117, Nafion N115, Nafion
D520, Nafion NRE211, Nafion NRE212 or Nafion HP, preferably Nafion N117 or Nafion N115.
Compared with prior art, what the present invention obtained has the beneficial effect that:
(1) catalyst of the present invention prepare raw material be it is nonmetallic, raw material is easy to get, at low cost；
(2) catalyst stability of the present invention is good, in Electrolytic Water Experiment, after repetitive cycling uses 10-20 times, is still able to maintain
Preferable catalytic activity；
(3) catalyst activity of the present invention is higher, when carrying out Electrolytic Water Experiment, detects to obtain O through ozone detector3Volume mass
Concentration may be up to 156.72g/m3；
(4) catalyst of the present invention is meso-hole structure, has biggish specific surface area, relatively large aperture and regular hole
Road structure, is conducive to O3The diffusion of molecule, due to O3It is extremely easy in decomposition, accelerates O3Diffusion can increase O3Yield, and its stability
It is good, 20 hours are used more than, good catalytic effect is still able to maintain；
(5) catalyst synthesis processes process of the present invention is simple, and easy to operate, environmental pollution is small, and feed stock conversion is higher, can
Continuous production is advantageous to industrialized production；
(6) electro-catalysis process of the present invention uses deionized water as electrolyte, and cost is relatively low, and electrolytic process green is without dirt
Dye, is easy to control.
Detailed description of the invention
Fig. 1 is the TEM figure that embodiment 1 prepares catalyst；
Fig. 2 is the SEM figure that embodiment 1 prepares catalyst；
Fig. 3 is the TEM figure that embodiment 2 prepares catalyst；
Fig. 4 is the SEM figure that embodiment 2 prepares catalyst；
Fig. 5 is catalyst and PbO made from embodiment 1-62LSV curve comparison figure；
Fig. 6 is that the catalyst prepared in embodiment 1-6 generates O for electrolysis water3Stability contrast figure.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment 1:
Prepare the catalyst based on boron, nitrogen co-doped mesoporous carbon:
(1) 2.0g block copolymer P123,0.2g boron oxide and 0.2g melamine are dissolved in 20g methanol, 10g phenol is added
15g N- butyl-pyridinium tetrafluoroborate is added in urea formaldehyde, stirs 30min, after the methanol 5h that volatilizees at room temperature, by the compound
It is placed in 50 DEG C of normal pressure baking ovens and solidifies 12h, then solidify 12h in 100 DEG C of normal pressure baking ovens, obtain cured product；
(2) cured product obtained by step (1) carries out ball milling, the method are as follows: cured product is put into ball grinder, is added 6 small
Ball (2 diameters 1.2cm, 2 diameters 0.7cm, 2 diameter 0.5cm), rotation revolving speed be 50r/min, revolution revolving speed be 100r
Under/min, 0.5h is ground, powdery product is obtained；
(3) powdery product of step (2) is roasted, the method are as follows: under ammonia atmosphere, by the powdery product
It is placed in tube furnace, tube furnace is warming up to 200 DEG C with the heating rate of 1 DEG C/min, keeps the temperature 1h, then with the heating speed of 1 DEG C/min
Rate is warming up to 500 DEG C, keeps the temperature 1h, after obtained product is cooled to room temperature, is rinsed with 60 DEG C of 0.1mol/L aqueous sulfuric acids, into
Row filters, and filter residue is dried in vacuo 12h at 50 DEG C again to get the catalyst based on boron, nitrogen co-doped mesoporous carbon.Its TEM
Figure and SEM figure are as depicted in figs. 1 and 2 respectively, and simultaneously pore structure is not present in catalyst surface prepared by embodiment 1.
Electrolysis water prepares O3Experiment:
The above-mentioned catalyst based on boron, nitrogen co-doped mesoporous carbon being prepared is used for electrolysis water synthesis O3, the method are as follows:
Using solid polymer electrolyte (SPE) ozone generator, tank house volume is 0.5L, is co-doped with what is prepared based on boron, nitrogen
The catalyst of miscellaneous mesoporous carbon is coated in Nafion N117 proton exchange membrane anode surface, and the platinum carbon catalyst containing 10% platinum content is applied
Nafion N117 proton exchange membrane cathode plane is overlayed on, deionized water is added in tank house, the electric current of cell reaction is 5 A, slot electricity
Pressure is 3V.Electrolytic experiment is carried out at 10 DEG C.Electrosynthesis glyoxal O3In the process, anode gas outlet is connect with ozone detector, to detect O3
Concentration, the reaction of continuous electrolysis water, the ozone concentration of generation change with time, as shown in Figure 6；After cell reaction time 18h, warp
Ozone detector detects to obtain O3Volume mass concentration is 114.68g/m3。
Embodiment 2:
Prepare the catalyst based on boron, nitrogen co-doped mesoporous carbon:
(1) 3.0g block copolymer P103,0.5g boron nitride and 0.5g are dissolved in 30g ethyl alcohol containing cyanamid dimerization, 20g is added
10g 1- amyl -3- methyl imidazolium tetrafluoroborate is added in polyester resin, stirs 40min, after the ethyl alcohol 7h that volatilizees at room temperature,
The compound is placed in 70 DEG C of normal pressure baking ovens and solidifies 14h, then solidifies 14h in 120 DEG C of normal pressure baking ovens, obtains cured product；
(2) cured product of step (1) is subjected to ball milling, the method are as follows: cured product is put into ball grinder, is added 12 small
Ball (4 diameters 1.2cm, 4 diameters 0.7cm, 4 diameter 0.5cm), rotation revolving speed be 70r/min, revolution revolving speed be
1h is ground under 140r/min, obtains powdery product；
(4) (3) roast the powdery product of step (2), the method are as follows: in a nitrogen atmosphere, will be described powdered
Product is placed in tube furnace, and tube furnace is warming up to 250 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 2h, then with the liter of 2 DEG C/min
Warm rate is warming up to 600 DEG C, keeps the temperature 2h, after obtained product is cooled to room temperature, is rushed with 70 DEG C of 0.2 mol/L aqueous hydrochloric acid solution
It washes, is filtered, filter residue is dried in vacuo 14h at 60 DEG C again to get the catalyst based on boron, nitrogen co-doped mesoporous carbon.
Its TEM figure and SEM figure are as shown in Figure 3 and Figure 4 respectively, and there are pore structures for catalyst surface prepared by embodiment 2, and uniformly divide
Cloth, aperture are about 5nm.
Electrolysis water prepares O3Experiment:
The above-mentioned catalyst based on boron, nitrogen co-doped mesoporous carbon being prepared is used for electrolysis water synthesis O3, the method are as follows:
Using solid polymer electrolyte (SPE) ozone generator, tank house volume is 1L, and the boron doping mesoporous carbon prepared is catalyzed
Agent is coated in Nafion N115 proton exchange membrane anode surface, and the platinum carbon catalyst containing 15% platinum content is coated in Nafion
N115 proton exchange membrane cathode plane, deionized water is added in tank house, and the electric current of cell reaction is 10 A, tank voltage 3V.20
Electrolytic experiment is carried out at DEG C.Electrosynthesis glyoxal O3In the process, anode gas outlet is connect with ozone detector, to detect O3Concentration, continuously
Electrolysis water reaction, the ozone concentration of generation change with time, as shown in Figure 6；After cell reaction time 12h, detected through ozone
Device detects to obtain O3Volume mass concentration is 130.78g/m3。
Embodiment 3:
Prepare the catalyst based on boron, nitrogen co-doped mesoporous carbon:
(1) 4.0g block copolymer P85,0.7g boric acid and 0.7g urea are dissolved in 40g isopropanol, 30g polyamide is added
20g1- hexyl -3- methyl imidazolium tetrafluoroborate is added in resin, stirs 50min, after the isopropanol 9h that volatilizees at room temperature, by this
Compound, which is placed in 90 DEG C of normal pressure baking ovens, solidifies 16h, then solidifies 16h in 130 DEG C of normal pressure baking ovens, obtains cured product；
(2) cured product of step (1) is subjected to ball milling, the method are as follows: cured product is put into ball grinder, is added 18 small
Ball (6 diameters 1.2cm, 6 diameters 0.7cm, 6 diameter 0.5cm), rotation revolving speed be 100r/min, revolution revolving speed be
1.5h is ground under 200r/min, obtains powdery product；
(3) powdery product of step (2) is roasted, the method are as follows: under an argon atmosphere, by the powdery product
It is placed in tube furnace, tube furnace is warming up to 300 DEG C with the heating rate of 3 DEG C/min, keeps the temperature 3h, then with the heating speed of 3 DEG C/min
Rate is warming up to 700 DEG C, keeps the temperature 3h, after obtained product is cooled to room temperature, is rinsed with 80 DEG C of 0.3 mol/L sodium-chloride water solution,
It is filtered, then is dried in vacuo 16h at 70 DEG C to get the catalyst based on boron, nitrogen co-doped mesoporous carbon.
Electrolysis water prepares O3Experiment:
The above-mentioned catalyst based on boron, nitrogen co-doped mesoporous carbon being prepared is used for electrolysis water synthesis O3, the method are as follows:
Using solid polymer electrolyte (SPE) ozone generator, tank house volume is 1.5L, and the boron doping mesoporous carbon prepared is urged
Agent is coated in Nafion D520 proton exchange membrane anode surface, and the platinum carbon catalyst containing 20% platinum content is coated in Nafion
Deionized water is added in tank house for D520 proton exchange membrane cathode plane, and the electric current of cell reaction is 15 A, and tank voltage is 4 V.30
Electrolytic experiment is carried out at DEG C.Electrosynthesis glyoxal O3In the process, anode gas outlet is connect with ozone detector, to detect O3Concentration, continuously
Electrolysis water reaction, the ozone concentration of generation change with time, as shown in Figure 6；After cell reaction time 15h, detected through ozone
Device detects to obtain O3Volume mass concentration is 119.57g/m3。
Embodiment 4:
Prepare the catalyst based on boron, nitrogen co-doped mesoporous carbon:
(1) by 4.0g block copolymer F38,0.8g boron carbide and 0.8g pyridinium dissolution in 50g ether, 40g asphalt mixtures modified by epoxy resin is added
25g1- amine propyl -3- methyl imidazolium tetrafluoroborate is added in rouge, stirs 60min, after the ether 12h that volatilizees at room temperature, by this
Compound, which is placed in 110 DEG C of normal pressure baking ovens, solidifies 18h, then solidifies 18h in 140 DEG C of normal pressure baking ovens, obtains cured product；
(2) cured product of step (1) is subjected to ball milling, the method are as follows: cured product is put into ball grinder, is added 24 small
Ball (8 diameters 1.2cm, 8 diameters 0.7cm, 8 diameter 0.5cm), rotation revolving speed be 150r/min, revolution revolving speed be
2h is ground under 300r/min, obtains powdery product；
(3) powdery product of step (2) is roasted, the method are as follows: under helium atmosphere, by the powdery product
It is placed in tube furnace, tube furnace is warming up to 350 DEG C with the heating rate of 4 DEG C/min, keeps the temperature 4h, then with the heating speed of 4 DEG C/min
Rate is warming up to 800 DEG C, keeps the temperature 4h, after obtained product is cooled to room temperature, is rinsed with 70 DEG C of 0.4 mol/L aqueous sodium persulfate solution,
It is filtered, filter residue is dried in vacuo 18h at 80 DEG C again to get the catalyst based on boron, nitrogen co-doped mesoporous carbon.
Electrolysis water prepares O3Experiment:
The above-mentioned catalyst based on boron, nitrogen co-doped mesoporous carbon being prepared is used for electrolysis water synthesis O3, the method are as follows:
Using solid polymer electrolyte (SPE) ozone generator, tank house volume is 2L, and the boron doping mesoporous carbon prepared is catalyzed
Agent is coated in Nafion NRE211 proton exchange membrane anode surface, and the platinum carbon catalyst containing 10% platinum content is coated in Nafion
NRE211 proton exchange membrane cathode plane, deionized water is added in tank house, and the electric current of cell reaction is 20 A, tank voltage 5V.
Electrolytic experiment is carried out at 40 DEG C.Electrosynthesis glyoxal O3In the process, anode gas outlet is connect with ozone detector, to detect O3Concentration, even
Continuous electrolysis water reaction, the ozone concentration of generation change with time, as shown in Figure 6；
After cell reaction time 15h, O is detected to obtain through ozone detector3Volume mass concentration is 108.59g/m3。
Embodiment 5:
Prepare the catalyst based on boron, nitrogen co-doped mesoporous carbon:
(1) 7.0g block copolymer F68,3.0g borine and 3.0g formamide are dissolved in 70g dichloroethanes, 50g urea is added
30g1- benzyl -3- methyl imidazolium tetrafluoroborate is added in formaldehyde resin, stirs 50min, and volatilize dichloroethanes 15h at room temperature
Afterwards, which is placed in 120 DEG C of normal pressure baking ovens and solidifies 20h, then solidify 20h in 180 DEG C of normal pressure baking ovens, production must be solidified
Object；
(2) cured product of step (1) is subjected to ball milling, the method are as follows: cured product is put into ball grinder, is added 30 small
Ball (10 diameters 1.2cm, 10 diameters 0.7cm, 10 diameter 0.5cm), rotation revolving speed be 200r/min, revolution revolving speed be
4h is ground under 400r/min, obtains powdery product；
(3) powdery product of step (2) is roasted, the method are as follows: in air atmosphere, by the powdery product
It is placed in tube furnace, tube furnace is warming up to 350 DEG C with the heating rate of 8 DEG C/min, keeps the temperature 4h, then with the heating speed of 8 DEG C/min
Rate is warming up to 1000 DEG C, keeps the temperature 4h, after obtained product is cooled to room temperature, is rinsed, is carried out with 90 DEG C of saturation potassium sulfate solutions
It filters, filter residue is dried in vacuo 20h at 80 DEG C again to get the catalyst based on boron, nitrogen co-doped mesoporous carbon.
Electrolysis water prepares O3Experiment:
The above-mentioned catalyst based on boron, nitrogen co-doped mesoporous carbon being prepared is used for electrolysis water synthesis O3, the method are as follows:
Using solid polymer electrolyte (SPE) ozone generator, tank house volume is 2L, and the boron doping mesoporous carbon prepared is catalyzed
Agent is coated in Nafion NRE212 proton exchange membrane anode surface, and the platinum carbon catalyst containing 15% platinum content is coated in Nafion
Deionized water is added in tank house for NRE212 proton exchange membrane cathode plane, and the electric current of cell reaction is 20 A, and tank voltage is 6 V.
Electrolytic experiment is carried out at 60 DEG C.Electrosynthesis glyoxal O3In the process, anode gas outlet is connect with ozone detector, to detect O3Concentration,
The reaction of continuous electrolysis water, the ozone concentration of generation change with time, as shown in Figure 6；After cell reaction time 20h, through ozone
Detector detects to obtain O3Volume mass concentration is 146.21g/m3。
Embodiment 6:
Prepare the catalyst based on boron, nitrogen co-doped mesoporous carbon:
(1) 8.0g block copolymer F127,4.0g methyl-boric acid and 4.0g triethanolamine are dissolved in 80g toluene, 60g is added
20gN- methoxy ethyl-N- methyl diethyl ammonium tetrafluoroborate is added in polyimide resin, stirs 60min, at room temperature
It volatilizees after toluene 20h, which is placed in 150 DEG C of normal pressure baking ovens and solidifies 36h, then is solidified in 200 DEG C of normal pressure baking ovens
36h obtains cured product；
(2) cured product of step (1) is subjected to ball milling, the method are as follows: cured product is put into ball grinder, is added 30 small
Ball (10 diameters 1.2cm, 10 diameters 0.7cm, 10 diameter 0.5cm), rotation revolving speed be 400r/min, revolution revolving speed be
6h is ground under 800r/min, obtains powdery product；
(3) powdery product of step (2) is roasted, the method are as follows: in air atmosphere, by the powdery product
It is placed in tube furnace, tube furnace is warming up to 400 DEG C with the heating rate of 10 DEG C/min, keeps the temperature 1-5h, then with the liter of 10 DEG C/min
Warm rate is warming up to 1300 DEG C, keeps the temperature 5h, after obtained product is cooled to room temperature, with 80 DEG C of hot water injections, is filtered, filter residue
The catalyst for 24 hours to get described based on boron, nitrogen co-doped mesoporous carbon is dried in vacuo at 100 DEG C again.
Electrolysis water prepares O3Experiment:
The above-mentioned catalyst based on boron, nitrogen co-doped mesoporous carbon being prepared is used for electrolysis water synthesis O3, the method are as follows:
Using solid polymer electrolyte (SPE) ozone generator, tank house volume is 3L, and the boron doping mesoporous carbon prepared is catalyzed
Agent is coated in Nafion HP proton exchange membrane anode surface, and the platinum carbon catalyst containing 20% platinum content is coated in Nafion HP matter
Deionized water is added in tank house for proton exchange cathode plane, and the electric current of cell reaction is 15 A, and tank voltage is 5 V.At 80 DEG C into
Row electrolytic experiment.Electrosynthesis glyoxal O3In the process, anode gas outlet is connect with ozone detector, to detect O3Concentration, continuous electrolysis water
Reaction, the ozone concentration of generation change with time, as shown in Figure 6；After cell reaction time 20h, detected through ozone detector
Obtain O3Volume mass concentration is 137.68g/m3。
Application Example 1:
Catalyst and β-PbO prepared by embodiment 1 ~ 62Carry out LSV performance test, test condition be at room temperature, to 0-3V into
Row test, as a result as shown in Figure 5；
What LSV curve was shown is the performance of OER, and OER is oxygen evolution reaction, is to synthesize the competitive reaction of ozone, therefore OER performance is got over
Difference is more conducive to synthesize ozone.(in addition, LVS slope is bigger, OER performance is better)；From fig. 5, it can be seen that with voltage strength
Increase, the LSV slope of a curve of catalyst prepared by embodiment 5 ~ 6 is smaller, that is, be conducive to synthesize ozone, this with embodiment 1 ~
6 obtained conclusions are consistent.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated, protection scope of the present invention is also only in those skilled in the art's root
According to present inventive concept it is conceivable that equivalent technologies mean.
Claims (10)
1. a kind of preparation method based on boron, the catalyst of nitrogen co-doped mesoporous carbon, it is characterised in that the following steps are included:
1) 2.0 ~ 8.0g block copolymer, 0.2 ~ 4.0g boron-containing compound and 0.2 ~ 4.0g nitrogenous compound are dissolved in 20 ~ 80g
In organic solvent, 10 ~ 60g resin is added, 10 ~ 30g boracic ionic liquid is added, stirs 30 ~ 60min, volatilization has at room temperature
After solvent 5-20h, it is placed in 12 ~ 36h of solidification in 50 ~ 150 DEG C of normal pressure baking oven, then be placed in 100 ~ 200 DEG C of normal pressure baking oven
Solidify 12-36h, obtains cured product；
2) ball milling is carried out to cured product obtained by step 1), obtains powdery product, then roasted to get it is described based on boron,
The catalyst of nitrogen co-doped mesoporous carbon.
2. a kind of preparation method based on boron, the catalyst of nitrogen co-doped mesoporous carbon according to claim 1, feature exist
In block copolymer quality be 4 ~ 7g, the block copolymer be P123, P103, P85, F38, F68 or F127, preferably
P123 or F127；
Boron-containing compound quality be 0.5 ~ 2.0g, the boron-containing compound be boron oxide, boron nitride, boric acid, boron carbide, borine or
Methyl-boric acid, preferably boric acid or boron oxide.
3. a kind of preparation method based on boron, the catalyst of nitrogen co-doped mesoporous carbon according to claim 1, feature exist
It is 0.5 ~ 2.0g in nitrogenous compound quality, the nitrogenous compound is melamine, cyanamid dimerization, urea, pyridine, formamide
Or triethanolamine, preferably melamine or urea；
Organic solvent quality be 30 ~ 60g, the organic solvent be methanol, ethyl alcohol, isopropanol, ether, dichloroethanes or toluene,
Preferably ethyl alcohol or toluene.
4. a kind of preparation method based on boron, the catalyst of nitrogen co-doped mesoporous carbon according to claim 1, feature exist
It is 20 ~ 40g in resin quality, the resin is phenolic resin, polyester resin, polyamide, epoxy resin, urea formaldehyde resin
Or polyimide resin, preferably phenolic resin；
The boracic ionic liquid be N- butyl-pyridinium tetrafluoroborate, 1- amyl -3- methyl imidazolium tetrafluoroborate, 1- oneself
Base -3- methyl imidazolium tetrafluoroborate, 1- amine propyl -3- methyl imidazolium tetrafluoroborate, 1- benzyl -3- methylimidazole tetrafluoro boron
Hydrochlorate or N- methoxy ethyl-N- methyl diethyl ammonium tetrafluoroborate, preferably N- butyl-pyridinium tetrafluoroborate or 1- amine
Propyl -3- methyl imidazolium tetrafluoroborate.
5. a kind of preparation method based on boron, the catalyst of nitrogen co-doped mesoporous carbon according to claim 1, feature exist
In step 2, the step of the ball milling are as follows: cured product obtained by step 1) is put into ball grinder, 6 ~ 30 beads are added,
Rotation revolving speed is 50 ~ 400r/min, revolution revolving speed is to grind 0.5 ~ 6h under 100 ~ 800r/min, obtain powdery product；
The step of roasting are as follows: under aeration condition, the powdery product is placed in tube furnace, tube furnace is with 1 ~ 10
DEG C/heating rate of min is warming up to 200 ~ 400 DEG C, keep the temperature 1 ~ 5h, then 500 are warming up to the heating rate of 1 ~ 10 DEG C/min ~
It 1300 DEG C, after keeping the temperature 1 ~ 5h, after obtained product is cooled to room temperature, is rinsed, is filtered with hydrothermal solution, filter residue is again at 50 ~ 100 DEG C
It is lower vacuum drying 12 ~ for 24 hours.
6. a kind of preparation method based on boron, the catalyst of nitrogen co-doped mesoporous carbon according to claim 5, feature exist
In the gas being passed through be ammonia, nitrogen, argon gas, helium or air, preferably nitrogen or argon gas；
The temperature of hydrothermal solution is 60 ~ 100 DEG C, and the hydrothermal solution is the hydrochloric acid of the aqueous sulfuric acid of 0.1 ~ 1 mol/L, 0.1 ~ 1 mol/L
Aqueous solution, the sodium-chloride water solution of 0.1 ~ 1 mol/L, saturated aqueous sodium sulfate, saturation potassium sulfate solution or deionized water.
7. the catalyst based on boron, nitrogen co-doped mesoporous carbon of any method preparation according to claim 1 ~ 6.
8. the catalyst according to claim 7 based on boron, nitrogen co-doped mesoporous carbon prepares answering in ozone in electrolysis water
With.
9. application according to claim 8, it is characterised in that using solid polymer electrolyte ozone generator as anti-
Device is answered, tank house volume is 0.5-3L, and deionized water is added；By the boron doping gold/mesoporous carbon catalyst and platinum content containing 10-20%
Platinum carbon catalyst be respectively coated on the anode surface and cathode plane of proton exchange membrane, the electric current of cell reaction is 5-20 A, slot electricity
Pressure is 3-6 V, and cell reaction is carried out at 10-80 DEG C, obtains ozone product；Wherein the cell reaction time be 1 ~ for 24 hours.
10. application according to claim 9, it is characterised in that the proton exchange membrane is Nafion N117, Nafion
N115, Nafion D520, Nafion NRE211, Nafion NRE212 or Nafion HP, preferably Nafion N117 or
Nafion N115。
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| CN114808003A (en) * | 2022-05-09 | 2022-07-29 | 浙江工业大学 | Boron-nitrogen co-doped carbon aerogel catalyst and synthesis method and application thereof |
| CN114808003B (en) * | 2022-05-09 | 2024-01-30 | 浙江工业大学 | Boron-nitrogen co-doped carbon aerogel catalyst and synthetic method and application thereof |
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Application publication date: 20190101 Assignee: Wuzhou Tongxin Energy Materials Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980054078 Denomination of invention: A catalyst based on boron and nitrogen co doped mesoporous carbon and its preparation method and application Granted publication date: 20201016 License type: Common License Record date: 20231226 |