CN108654670A - A kind of method of carbon-nitrogen doped zinc titanium bimetal nano particles processing arylamine class pharmacy waste water - Google Patents
A kind of method of carbon-nitrogen doped zinc titanium bimetal nano particles processing arylamine class pharmacy waste water Download PDFInfo
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- CN108654670A CN108654670A CN201810398529.1A CN201810398529A CN108654670A CN 108654670 A CN108654670 A CN 108654670A CN 201810398529 A CN201810398529 A CN 201810398529A CN 108654670 A CN108654670 A CN 108654670A
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- Prior art keywords
- carbon
- waste water
- aniline
- bis
- trifluoromethyl
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 42
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000002351 wastewater Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 18
- 238000012545 processing Methods 0.000 title abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000011787 zinc oxide Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 19
- 239000010439 graphite Substances 0.000 claims abstract description 19
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 9
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 30
- JBGNFLUETJDDBA-UHFFFAOYSA-N n,n-bis(trifluoromethyl)aniline Chemical group FC(F)(F)N(C(F)(F)F)C1=CC=CC=C1 JBGNFLUETJDDBA-UHFFFAOYSA-N 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000006303 photolysis reaction Methods 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 5
- 235000015110 jellies Nutrition 0.000 claims description 5
- 239000008274 jelly Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005273 aeration Methods 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 235000004694 Eucalyptus leucoxylon Nutrition 0.000 claims description 3
- 244000166102 Eucalyptus leucoxylon Species 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012982 microporous membrane Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052571 earthenware Inorganic materials 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 35
- 238000006731 degradation reaction Methods 0.000 abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- SLFVYFOEHHLHDW-UHFFFAOYSA-N n-(trifluoromethyl)aniline Chemical compound FC(F)(F)NC1=CC=CC=C1 SLFVYFOEHHLHDW-UHFFFAOYSA-N 0.000 abstract description 3
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003911 water pollution Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 16
- -1 Aromatic amine compounds Chemical class 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 7
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- JWJOTENAMICLJG-QWBYCMEYSA-N dutasteride Chemical compound O=C([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)N[C@@H]4CC3)C)CC[C@@]21C)NC1=CC(C(F)(F)F)=CC=C1C(F)(F)F JWJOTENAMICLJG-QWBYCMEYSA-N 0.000 description 6
- 229960004199 dutasteride Drugs 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000003851 biochemical process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- XWMVIJUAZAEWIE-UHFFFAOYSA-N 2,5-bis(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=CC=C1C(F)(F)F XWMVIJUAZAEWIE-UHFFFAOYSA-N 0.000 description 1
- 229940113178 5 Alpha reductase inhibitor Drugs 0.000 description 1
- 239000002677 5-alpha reductase inhibitor Substances 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- QTERRLQSXYDXAH-UHFFFAOYSA-N [C].N1=C(N)N=C(N)N=C1N Chemical compound [C].N1=C(N)N=C(N)N=C1N QTERRLQSXYDXAH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- CYGKLLHTPPFPHH-UHFFFAOYSA-N aniline;hydrate Chemical compound O.NC1=CC=CC=C1 CYGKLLHTPPFPHH-UHFFFAOYSA-N 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940054749 avodart Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction 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
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention belongs to water pollution control technology fields, and in particular to a kind of method of carbon-nitrogen doped zinc titanium bimetal nano particles processing arylamine class pharmacy waste water.The present invention forms graphite phase carbon nitride by carbon source and nitrogen source of melamine by high-temperature calcination, and then supported nano zinc oxide forms the graphite phase carbon nitride nano particle that zinc oxide loads in graphite phase carbon nitride（ZnO@g‑C3N4）, the carbon-nitrogen doped zinc titanium bimetal nano particles with optics catalytic performance are prepared finally by sol-gal process.The carbon-nitrogen doped zinc titanium bimetal nano particles that the present invention prepares can (trifluoromethyl) aniline bis- to 2,5 under mild acid conditions realize good degradation rate, and can be used for the degradation of other arylamine waste water, having can industrial applications foreground.
Description
Technical field
The invention belongs to water pollution control technology fields, and in particular to a kind of carbon-nitrogen doped zinc titanium bimetal nano particles
The method for handling arylamine class pharmacy waste water.
Background technology
Dutasteride, entitled (5 α, 17 β)-N- [2,5- bis- (trifluoromethyl) phenyl] -3- oxo -4- azepines of chemistry are male
Steroid -1- alkene -17- formamides, be Glaxo Smith Kline companies of Britain develop dual 5α-reductase inhibitor, 2003
June is ratified to list through U.S. FDA, trade name Avodart, for preventing and treating benign prostatic hyperplasis.03 month 2014 06
Day, CFDA annotated sale of the drug in Chinese market.
Amino benzenes derivates 2 are used in the production of dutasteride, bis- (trifluoromethyl) aniline of 5- as key intermediate,
In reaction the mol ratio usage amount of the intermediate be much higher than another structure fragment usage amount (Chinese Journal of Pharmaceuticals,
2013,44(10)：966-968, the synthesis of dutasteride), lead to remaining a large amount of bis- (trifluoromethyl) aniline of 2,5- in reaction solution.
Aromatic amine compounds have very high toxicity, have teratogenesis or carcinogenesis to human body.Many countries have all formulated stringent arylamine
(such as aniline, paranitroanilinum, diphenylamines) discharge standard, according to the integrated wastewater discharge standard in China, aromatic amine compounds
Secondary discharge standard mass concentration≤2mg/L of waste water.Therefore the processing of aromatic amine compounds industrial wastewater is ten score values
The problem of must paying attention to.
The common method of processing arylamine waste water has Physical, biochemical process and a chemical method, and activated carbon is useless at present in Physical
The adsorbent generally used in water process, can be used for the processing of all kinds of waste water, but its regeneration cycle use it is complex.
When handling waste water, using easily causing secondary pollution in solvent extraction solvent recovery process.Poison of the biochemical process due to arylamine waste water
Property is strong, biodegradability is poor, and effect is poor when concentration for the treatment of big waste water.
For chemical method using Fenton and fenton-type reagent method as a kind of important method in high-level oxidation technology, Fenton is anti-
Should utilize Fe2+It is catalyzed H2O2It decomposes and generates OH free radicals, to cause the oxidative degradation of organic matter.Fenton methods because
It is mild with reaction condition, easy to operate, expense is relatively low and advantages of environment protection, is widely used in various organic
In the advanced oxidation treatment research of waste water, but catalyst cannot recycle and the secondary pollution because of caused by the loss of catalyst
It is its major defect.
In various semiconductor light-catalysts, due to Ti02, price high with photocatalytic activity be relatively low and stability
It is strong to wait unique advantage, by the extensive concern of domestic and foreign scholars.But Ti02The lower quantum effect of photocatalysis and light are urged
Change activity, and focuses mostly on the utilization of light in UV light region；And powdered form catalyst is not easily recycled utilization in application, easily
Secondary pollution etc. is caused, these are all the main bugbears for restricting its development.
There is not the processing method of bis- (trifluoromethyl) aniline of 2,5- in document report dutasteride's waste water, so finding can
The cleaning treatment technique of bis- (trifluoromethyl) aniline of 2,5- has the meaning of reality effectively in degradation dutasteride's waste water.
Invention content
The purpose of the present invention is overcoming deficiency in the prior art, a kind of carbon-nitrogen doped zinc titanium bimetal nano grain is provided
The method of subprocessing arylamine class pharmacy waste water, the present invention form graphite-phase by carbon source and nitrogen source of melamine by high-temperature calcination
Carbonitride, then supported nano zinc oxide forms the graphite phase carbon nitride nano particle that zinc oxide loads in graphite phase carbon nitride
(ZnO@g-C3N4), it prepares the carbon-nitrogen doped zinc titanium bimetallic with optics catalytic performance finally by sol-gel method and receives
Rice corpuscles.The carbon-nitrogen doped zinc titanium bimetal nano particles that the present invention prepares can be under mild acid conditions to the bis- (trifluoros of 2,5-
Methyl) aniline realizes good degradation rate, and can be used for the degradation of other arylamine waste water, having can industrial applications foreground.
According to an aspect of the present invention, the present invention provides a kind of preparation of carbon-nitrogen doped zinc titanium bimetal nano particles
Method includes the following steps：
1)ZnO@g-C3N4Preparation：6.5g zinc powders are placed in the sodium hydrate aqueous solution of 1mol/L, 30ml is then added dropwise
The hydrogen peroxide solution of 30%wt reacts 18-20h, so in the stainless steel hydrothermal reaction kettle of tetrafluoroethene liner at 60-70 DEG C
The methanol solution 200ml that the melamine of a concentration of 2mol/L is added afterwards reacts 6-8h at 100-120 DEG C, is finally placed in close
It calcines 4-6h in the crucible closed at 550-600 DEG C under nitrogen atmosphere, room temperature, absolute ethyl alcohol washing is cooled to after calcining
The graphite phase carbon nitride nano particle of dry zinc oxide load (is abbreviated as ZnO@g-C afterwards3N4)；The present invention is with melamine
Carbon source and nitrogen source form graphite phase carbon nitride (g-C by high-temperature calcination3N4), zinc powder is obtained into zinc oxide using hydrogen peroxide oxidation,
To make zinc oxide load on graphite phase carbon nitride material；In addition, the addition of hydrogen peroxide can not only make zinc powder in the present invention
It is changed into zinc oxide, and the hydrogen bond that amino and hydrogen peroxide in melamine can be made to pass through generation forms MHP (cyanamides-dioxygen
Water), supramolecular aggregation then is obtained using 550-600 DEG C of high-temperature calcination while successive logical nitrogen, makes to prepare
Graphite phase carbon nitride achieve the purpose that oxygen doping, to change material obtain catalytic performance；
2) titania oxide supported process：The tetraisopropyl titanate of 10mmol is dissolved in isopropanol, and the stone of zinc oxide load is added
Black phase carbon nitride nano particle is dispersed with stirring uniformly, the aqueous solution of nitric acid 20ml of 0.5mol/L is then added dropwise, after completion of dropwise addition
8-10h is stirred at 60-70 DEG C, is removed solvent, is obtained yellow gum object；Jelly is calcined under argon atmosphere under high temperature,
Room temperature is cooled to after calcining, filtration drying obtains carbon-nitrogen doped zinc titanium pair after ultrasound 10-12h at 60-70 DEG C through toluene
Metal nanoparticle；The present invention prepares TiO using tetraisopropyl titanate as presoma by sol-gel method2, loaded with zinc oxide
Graphite phase carbon nitride nano particle be carrier, by the TiO of formation2Original position loads in graphite phase carbon nitride, forms carbon nitrogen and mixes
Miscellaneous zinc titanium bimetal nano particles.
Preferably, the addition for the graphite phase carbon nitride nano particle that zinc oxide loads in step 2) is 15-25g；
Preferably, the temperature that the step 2) jelly is calcined under argon atmosphere under high temperature is 600-700 DEG C；
Last calcining is that calcination temperature, which determines, ultimately forms carbon-nitrogen doped zinc titanium bimetallic in order to eliminate the stomata in gel
The exterior appearance of nano-particle, to influence the catalytic activity of nano-particle.
According to another aspect of the present invention, the present invention provides a kind of carbon-nitrogen doped zinc titanium bimetal nano particles
Purposes, for arylamine class waste water of degrading under the irradiation of ultraviolet light and/or visible light.
Preferably, the arylamine is bis- (trifluoromethyl) aniline of 2,5-；Carbon-nitrogen doped zinc titanium bimetal nano particles exist
It is as follows for bis- (trifluoromethyl) the aniline concrete schemes of 2,5- of degrading under the irradiation of ultraviolet light and/or visible light：In 2,5- bis- (three
Methyl fluoride) aniline waste water in, carbon-nitrogen doped zinc titanium bimetal nano particles are added and are dispersed with stirring, under conditions of aeration,
Using ultraviolet light and/or visible light pair 2, the waste water of bis- (trifluoromethyl) aniline of 5- carries out photodissociation, and HPLC detects 2,5- bis- (three
Methyl fluoride) when no longer changing, carbon-nitrogen doped zinc titanium bimetal nano grain is recycled by filtering with microporous membrane the degradation rate of aniline
Son.
Preferably, the pH of the waste water of bis- (trifluoromethyl) aniline of 2, the 5- is 6.0 ± 0.5；It is reacted in light-catalyzed reaction
The acid-base value of liquid influences carbon-nitrogen doped zinc titanium bimetal nano particles surface potential, to influence the generation of hydroxyl radical free radical；
General organic amine substance is easy degradation under weak basic condition, it may be possible to since in acid condition, amine substance can be with acid
At salt, influence to degrade；But in the present invention, optimal degradation effect is achieved near pH=6.0.
Preferably, using ultraviolet light and/or visible light pair 2, the waste water of bis- (trifluoromethyl) aniline of 5- carries out photodissociation, light
It is 40-45 DEG C to solve temperature；Degradation rate is slow under cryogenic conditions, and higher than 50 DEG C, its degradation rate is no longer significantly increased, in order to save
About energy consumption, this patent photodissociation temperature are set to 40-45 DEG C.
Preferably, pH is for the initial concentration of the waste water of 6.0 ± 0.5 bis- (trifluoromethyl) aniline of 2,5- in the present invention
Carbon-nitrogen doped zinc titanium is added in the waste water for 6.0 ± 0.5 bis- (trifluoromethyl) aniline of 2,5- in 80-100mg/L, every liter of pH
The weight of bimetal nano particles is 0.04-0.2g；
Carbon-nitrogen doped zinc titanium bimetal nano particles prepared by the present invention can also degrade other schemes under visible light
Class compound, such as aniline, paranitroanilinum and diphenylamines.
Compared with prior art, the invention has the advantages that：
1) present invention forms graphite phase carbon nitride by carbon source and nitrogen source of melamine by high-temperature calcination, then in graphite
Supported nano zinc oxide forms graphite phase carbon nitride nano particle (the ZnO@g-C of zinc oxide load on phase carbon nitride3N4), finally
The carbon-nitrogen doped zinc titanium bimetal nano particles with optics catalytic performance are prepared by sol-gel method；Overcome biography
The nano-titanium dioxide of system can not be the shortcomings that visible region uses, and improves the catalytic efficiency in ultraviolet region；
2) carbon-nitrogen doped zinc titanium bimetal nano particles prepared by the present invention have excellent photocatalysis performance, Neng Gou
Bis- (trifluoromethyl) aniline of 2, the 5- that degrades under ultraviolet and/or visible light, degradation rate are up to 99% or more；
3) carbon-nitrogen doped zinc titanium bimetal nano particles prepared by the present invention can also be used for photocatalytic degradation aniline, to nitre
The scope of application of base aniline and diphenylamines, catalyst is wider；
4) the carbon-nitrogen doped zinc titanium bimetal nano particles that prepare of the present invention can realize recovery, using urging afterwards three times
Change degradation arylamine performance and declines unobvious；Using the method that can be combined by acid dip and calcining after five times, to its catalytic
It can be activated.
Specific implementation mode
In order to make the objectives, technical solutions and advantages of the present invention clearer, With reference to embodiment, to this
Invention is further described.It should be understood that these descriptions are merely illustrative, and it is not intended to limit the scope of the present invention.
Embodiment 1
It is prepared as follows carbon-nitrogen doped zinc titanium bimetal nano particles：
1)ZnO@g-C3N4Preparation：6.5g zinc powders are placed in the sodium hydrate aqueous solution of 50ml 1mol/L, are then dripped
The hydrogen peroxide solution for adding 30ml 30%wt reacts in the stainless steel hydrothermal reaction kettle of tetrafluoroethene liner at 60-70 DEG C
18-20h, the methanol solution 200ml that the melamine of a concentration of 2mol/L is then added react 6-8h at 100-120 DEG C, most
It is placed in closed crucible and calcines 4-6h at 550-600 DEG C under nitrogen atmosphere, room temperature is cooled to after calcining, it is anhydrous
The graphite phase carbon nitride nano particle of dry zinc oxide load (is abbreviated as ZnO@g-C at 60 DEG C after ethyl alcohol washing3N4)；
2) titania oxide supported process：The tetraisopropyl titanate of 10mmol is dissolved in 100ml isopropanols, and 20g zinc oxide is added
The graphite phase carbon nitride nano particle of load (is abbreviated as ZnO@g-C3N4) be dispersed with stirring uniformly, the nitre of 0.5mol/L is then added dropwise
Aqueous acid 20ml stirs 8-10h at 60-70 DEG C after completion of dropwise addition, remove solvent, obtain yellow gum object；Jelly is in argon gas
Calcining 6h is carried out under atmosphere under high temperature, room temperature is cooled to after calcining, through toluene at 60-70 DEG C mistake after ultrasound 10-12h
It is filtered dry dry zinc titanium bimetal nano particles that must be carbon-nitrogen doped.
The carbon-nitrogen doped zinc titanium bimetal nano particles that different calcination temperatures are prepared in step 2) are abbreviated as Cat/X, X
Represent different calcination temperatures.
Embodiment 2
The Cat-X that different calcination temperatures obtain using in embodiment 1 is as photochemical catalyst, (trifluoromethyl) benzene bis- to 2,5-
Amine carries out light degradation, and technique is as follows：
500ml 2 is added according to reactor IFA300 (Beijing Bo Feilai Science and Technology Ltd.s) is middle in multipurpose flange form,
(self-control is configured to using bis- (trifluoromethyl) the aniline standard items of 2,5- with water a concentration of bis- (trifluoromethyl) aniline-water solutions of 5-
The aqueous solution of 10mg/L adjusts pH to 7.0 to obtain the final product), it is separately added into what different calcination temperatures prepared by embodiment 1 were prepared
Cat/X, nano-TiO2(Fei Laike is moored with the Microsolar300 xenon lamps of each 20mg of nano ZnO particles, the 300W of use in Beijing
Skill Co., Ltd) light source analogy visible light is irradiated at 30 DEG C, and irradiation while, is constantly aerated, and HPLC takes every 1h
The concentration of sample pair 2, bis- (trifluoromethyl) aniline of 5- is detected, and when the front and back concentration of sampling twice no longer changes, is stopped
Irradiation, the photocatalytic activity for counting bis- (trifluoromethyl) aniline of 2,5- in each catalyst system and catalyzing are shown in Table 1：
The photodegradation rate of 1 different catalysts of table (trifluoromethyl) aniline bis- to 2,5-
| Catalyst | NA | TiO2 | ZnO | Cat/250 | Cat/450 | Cat/550 | Cat/650 | Cat/750 | Cat/850 |
| Degradation rate/% | 23.2 | 30.3 | 44.6 | 65.2 | 69.8 | 76.4 | 89.2 | 83.4 | 65.2 |
Note：NA representatives are not added with any catalyst, only carry out illumination and aeration.
The above result shows that in the case of not adding catalyst, degradation 2 can also only be played by illumination and aeration, 5- is bis-
The effect of (trifluoromethyl) aniline, but degradation rate is relatively low, only 23.2%；TiO is added2Fail to effectively improve degradation rate, it is main
It wants the reason is that TiO2Visible light can not be efficiently used；ZnO nano particle is with respect to TiO2The degradation of bis- (trifluoromethyl) aniline of 2,5-
Rate gets a promotion, and is 44.6%, but do not have industrial applications foreground, degradation rate still has to be hoisted；What different calcination temperatures obtained
Cat/X light degradation properties are different, the most excellent with the degradation property that calcination temperature at 650 DEG C obtains.
Embodiment 3
Using Cat/650 as Photodegradation catalyst, different pH environment, Cat/650 dosages and 2,5- bis- (trifluoromethyls) are investigated
Degradation rate under aniline-water solution initial concentration, testing program are as follows：
500ml 2 is added according to reactor IFA300 (Beijing Bo Feilai Science and Technology Ltd.s) is middle in multipurpose flange form,
(self-control is configured to using bis- (trifluoromethyl) the aniline standard items of 2,5- from water different dense bis- (trifluoromethyl) aniline-water solutions of 5-
The aqueous solution of degree adjusts pH to different pH using hydrochloric acid or sodium hydroxide), it is separately added into the preparation of embodiment 1 of different weight
Microsolar300 xenon lamps (Beijing Bo Feilai Science and Technology Ltd.s) light source analogy visible light of Cat/650, the 300W of use exist
It is irradiated at 40-45 DEG C, irradiation while is constantly aerated, and HPLC samples (trifluoromethyl) benzene bis- to 2,5- every 1h
The concentration of amine is detected, and when the front and back concentration of sampling twice no longer changes, is stopped irradiation, is counted 2 in each catalyst system and catalyzing,
The photocatalytic activity of bis- (trifluoromethyl) aniline of 5- is shown in Table 2：
Influence of 2 different affecting factors of table to degradation rate
Embodiment 4
Cat/650 is filtered to isolate using nanofiltration membrane after photocatalytic degradation, then in 50 DEG C after acetone elution
Under be dried under reduced pressure to constant weight, carry out recovery experiment, access times and 2, the degradation rate relationship of bis- (trifluoromethyl) aniline of 5-
As shown in table 3, light degradation technological operation is carried out according to the process conditions in 2 sequence 17 of table：
The relationship of table 3 Cat/650 access times and degradation rate
| Access times | R-1 | R-2 | R-3 | R-4 | R-5 |
| Degradation rate | 99.9 | 99.2 | 98.9 | 92.3 | 86.6 |
Note：R-1 represents first time recovery service condition.
The above result shows that Cat/650 photocatalysis performances in preceding recovery three times decline unobvious, use the 4th time
After be decreased obviously, fall to 86.6% using the degradation rate of bis- (trifluoromethyl) aniline of 2,5- after the 5th time, can not be returned again
Receipts are applied mechanically.
In order to solve the problems, such as that Cat/650 Photocatalytic Degradation Properties decline, the present invention is to using four later Cat/650
Recycling, has carried out following activation method：
One, calcining and activating
Heterogeneous catalyst often can be such that its catalytic performance is activated by the method for calcining, by the Cat/ after recycling
650 calcine 6h in 650 DEG C under nitrogen atmosphere, are then cooled to room temperature, using the process conditions pair 2 in 2 sequence 17 of table, 5- is bis-
(trifluoromethyl) aniline is tested, and 2,5- bis- (trifluoromethyl) degradation rate of aniline are 79.2%, and activity is not carried
There is downward trend instead in height.
Two, acid dip and calcining combine
Cat/650 after recycling is placed in the aqueous hydrochloric acid solution of 0.5mol/L ultrasonic immersing 2-3h at room temperature, then mistake
It is dried after filter, washing, finally calcines 6h in 650 DEG C under nitrogen atmosphere, be then cooled to Cat/650 after room temperature must activate, adopt
With the process conditions pair 2 in 2 sequence 17 of table, bis- (trifluoromethyl) aniline of 5- are tested, 2,5- bis- (trifluoromethyl) aniline drops
Solution rate is 99.2%, plays the role of activation.
Embodiment 5
It uses freshly prepared Cat/650 for Photodegradation catalyst, takes aniline, paranitroanilinum and diphenylamines standard items point
The aqueous solution of a concentration of 50mg/L is not formulated as with water, is investigated to its photocatalysis effect, process conditions are as follows
It is dense according to 500ml is added in reactor IFA300 (Beijing Bo Feilai Science and Technology Ltd.s) in multipurpose flange form
(it is new that 20mg is added using hydrochloric acid or sodium hydroxide adjusting pH to 6.5 or 8.0) in self-control to the arylamine class aqueous solution that degree is 50mg/L
Microsolar300 xenon lamps (Beijing Bo Feilai Science and Technology Ltd.s) light source analogy of the Cat/650 of fresh preparation, the 300W of use
Visible light is irradiated at 40-45 DEG C, and irradiation while is constantly aerated, and HPLC samples the concentration to arylamine every 1h
It is detected, when the front and back concentration of sampling twice no longer changes, stops irradiation, count the light of each arylamine in each catalyst system and catalyzing
Catalysis degradation modulus is shown in Table shown in 4：
The degradation effect of different aromatic amino-derivatives under the different pH value of table 4
For aniline solution, degradation effect is optimal under mildly acidic conditions, with bis- (trifluoromethyl) the aniline results of 2,5-
Unanimously；And paranitroanilinum degradation rate under alkalescent (pH=8.0) is optimal, but it is also only 83.2%, the later stage needs into one
Step optimization；Diphenylamine solution either can realize good degradation rate under the conditions of weak acid or weak base, make making for catalyst
More wide in range with range, the later stage is adapted to the degradation under different quality.
Although embodiments of the present invention are described in detail, it should be understood that, without departing from the present invention's
In the case of spirit and scope, can embodiments of the present invention be made with various changes, replacement and change.
Claims (9)
1. a kind of preparation method of carbon-nitrogen doped zinc titanium bimetal nano particles, includes the following steps：
1）ZnO@g-C3N4Preparation：6.5g zinc powders are placed in the sodium hydrate aqueous solution of 1mol/L, 30ml 30% is then added dropwise
The hydrogen peroxide solution of wt reacts 18-20h in the stainless steel hydrothermal reaction kettle of tetrafluoroethene liner at 60-70 DEG C, then adds
The methanol solution 200ml for entering the melamine of a concentration of 2mol/L reacts 6-8h at 100-120 DEG C, is finally placed in closed earthenware
It calcines 4-6h in crucible at 550-600 DEG C under nitrogen atmosphere, room temperature is cooled to after calcining, it is dry after absolute ethyl alcohol washing
The graphite phase carbon nitride nano particle of zinc oxide load is obtained, the graphite phase carbon nitride nano particle of the zinc oxide load is abbreviated as
ZnO@g-C3N4；
2）Titania oxide supported process：The tetraisopropyl titanate of 10mmol is dissolved in isopropanol, and ZnO@g-C are added3N4It is dispersed with stirring
It is even, the aqueous solution of nitric acid 20ml of 0.5mol/L is then added dropwise, stirs 8-10h after completion of dropwise addition at 60-70 DEG C, removes solvent, obtains
Yellow gum object；Jelly is calcined under argon atmosphere under high temperature, and room temperature is cooled to after calcining, is existed through toluene
Filtration drying obtains carbon-nitrogen doped zinc titanium bimetal nano particles after ultrasound 10-12h at 60-70 DEG C.
2. preparation method according to claim 1, it is characterised in that：Step 2）Middle ZnO@g-C3N4Addition be 15-
25g。
3. preparation method according to claim 1, it is characterised in that：Step 2）The jelly is under argon atmosphere in height
The temperature calcined under temperature is 600-700 DEG C.
4. the purposes of carbon-nitrogen doped zinc titanium bimetal nano particles described in a kind of claim 1, it is characterised in that：In ultraviolet light
And/or for arylamine waste water of degrading under the irradiation of visible light.
5. purposes according to claim 4, it is characterised in that：The arylamine waste water is bis- (trifluoromethyl) aniline of 2,5-.
6. purposes according to claim 5, it is characterised in that：The specific steps are：In bis- (trifluoromethyl) aniline of 2,5-
In waste water, carbon-nitrogen doped zinc titanium bimetal nano particles are added and are dispersed with stirring, under conditions of aeration, using ultraviolet light and/
Or visible light pair 2, the waste water of bis- (trifluoromethyl) aniline of 5- carry out photodissociation, HPLC detects the drop of bis- (trifluoromethyl) aniline of 2,5-
When solution rate no longer changes, carbon-nitrogen doped zinc titanium bimetal nano particles are recycled by filtering with microporous membrane.
7. purposes according to claim 6, it is characterised in that：The pH of the waste water of bis- (trifluoromethyl) aniline of 2,5- is 6.0
±0.5。
8. purposes according to claim 6, it is characterised in that：Using ultraviolet light and/or visible light to the bis- (fluoroforms of 2,5-
Base) aniline waste water carry out photodissociation, photodissociation temperature be 40-45 DEG C.
9. purposes according to claim 7, it is characterised in that：Bis- (trifluoromethyl) aniline of 2,5- that pH is 6.0 ± 0.5
The initial concentration of waste water is 80-100mg/L, is added in the waste water for bis- (trifluoromethyl) aniline of 2,5- that every liter of pH is 6.0 ± 0.5
The weight of carbon-nitrogen doped zinc titanium bimetal nano particles is 0.04-0.2g.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050226761A1 (en) * | 2004-04-07 | 2005-10-13 | Kronos International Inc. | Titanium dioxide photocatalyst containing carbon and method for its production |
| CN102463130A (en) * | 2010-11-19 | 2012-05-23 | 北京佳盛世纪科技有限公司 | Method for preparing modified TiO2 coatings by sol-gel method |
| CN104084228A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | Oxygen-doped carbon nitride/zinc oxide photo-catalyst as well as preparation method and application thereof |
| CN105195195A (en) * | 2015-08-14 | 2015-12-30 | 阜阳师范学院 | Photocatalyst CN-ZnO and preparation method and application thereof |
| CN105797763A (en) * | 2016-04-22 | 2016-07-27 | 华南师范大学 | Method for preparing carbon and nitrogen-doped titanium dioxide |
| CN107715906A (en) * | 2017-11-24 | 2018-02-23 | 南昌航空大学 | A kind of preparation method of the direct Z-type heterojunction composite photocatalyst of carbonitride/zinc titanate/titanium oxide sandwich-like |
-
2018
- 2018-04-28 CN CN201810398529.1A patent/CN108654670B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050226761A1 (en) * | 2004-04-07 | 2005-10-13 | Kronos International Inc. | Titanium dioxide photocatalyst containing carbon and method for its production |
| CN102463130A (en) * | 2010-11-19 | 2012-05-23 | 北京佳盛世纪科技有限公司 | Method for preparing modified TiO2 coatings by sol-gel method |
| CN104084228A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | Oxygen-doped carbon nitride/zinc oxide photo-catalyst as well as preparation method and application thereof |
| CN105195195A (en) * | 2015-08-14 | 2015-12-30 | 阜阳师范学院 | Photocatalyst CN-ZnO and preparation method and application thereof |
| CN105797763A (en) * | 2016-04-22 | 2016-07-27 | 华南师范大学 | Method for preparing carbon and nitrogen-doped titanium dioxide |
| CN107715906A (en) * | 2017-11-24 | 2018-02-23 | 南昌航空大学 | A kind of preparation method of the direct Z-type heterojunction composite photocatalyst of carbonitride/zinc titanate/titanium oxide sandwich-like |
Non-Patent Citations (2)
| Title |
|---|
| DONG JIANG ET AL.: "Modified g-C3N4/TiO2 nanosheets/ZnO ternary facet coupled heterojunction for photocatalytic degradation of p-toluenesulfonic acid (p-TSA) under visible light", 《PHYSICA E》 * |
| 彭富昌等: "g-C3N4/TiO2复合材料的制备及其可见光催化性能", 《中国陶瓷》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114522711A (en) * | 2022-02-22 | 2022-05-24 | 徐林 | Preparation method, product and application of visible light photocatalytic composite material |
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Effective date of registration: 20211220 Address after: 510000 201 and 301, block 2, No. 367, Fuyi Road, Dalong street, Panyu District, Guangzhou, Guangdong Patentee after: GUANGDONG ANNA DETECTION TECHNOLOGY Co.,Ltd. Address before: 277500 Anju community, Xueyuan Middle Road, Tengzhou City, Zaozhuang City, Shandong Province Patentee before: Liu Shuzhen |