CN113649012B - Preparation method and application of carbon-coated zinc ferrite catalyst - Google Patents
Preparation method and application of carbon-coated zinc ferrite catalyst Download PDFInfo
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- CN113649012B CN113649012B CN202110970136.5A CN202110970136A CN113649012B CN 113649012 B CN113649012 B CN 113649012B CN 202110970136 A CN202110970136 A CN 202110970136A CN 113649012 B CN113649012 B CN 113649012B
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- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 114
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 title claims abstract description 114
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 63
- 230000001699 photocatalysis Effects 0.000 claims abstract description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 17
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 11
- 239000008103 glucose Substances 0.000 claims abstract description 11
- 230000033444 hydroxylation Effects 0.000 claims abstract description 11
- 239000012692 Fe precursor Substances 0.000 claims abstract description 10
- 238000007146 photocatalysis Methods 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 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 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 5
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 22
- 230000033558 biomineral tissue development Effects 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 19
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 17
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 230000003647 oxidation Effects 0.000 abstract description 14
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 14
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 10
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 9
- 235000006408 oxalic acid Nutrition 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 5
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000006385 ozonation reaction Methods 0.000 description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 5
- 229960004889 salicylic acid Drugs 0.000 description 5
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- -1 glucosyl mesoporous carbon Chemical compound 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000036299 sexual function Effects 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a carbon-coated zinc ferrite catalyst, a preparation method thereof and application thereof in preparation of phenol by photocatalysis and hydroxylation of benzene, and photocatalysis and ozone oxidation degradation and mineralization of organic pollutants. Dissolving and mixing an iron precursor and a zinc precursor in proportion, adding glucose, adjusting the pH value, and carrying out hydrothermal treatment to obtain the carbon-coated zinc ferrite catalyst. The carbon-coated zinc ferrite nano-particles prepared by the invention can improve the reaction activity by utilizing the adsorption and activation of the carbon layer on benzene in the benzene hydroxylation reaction, prevent the metal from dissolving out in the reaction process and improve the stability of the catalyst; in the process of photocatalytic ozone oxidation degradation and organic pollutant mineralization, the zinc ferrite coated with carbon on the surface improves the photoproduction electron-hole separation efficiency, improves the ozone utilization rate, accelerates the removal and mineralization of organic matters, solves the problem of metal dissolution in the zinc ferrite reaction process, can prevent secondary pollution to the environment, and has certain industrial application prospect.
Description
Technical Field
The invention belongs to the field of inorganic material preparation, and particularly relates to a carbon-coated zinc ferrite catalyst, a preparation method thereof and application thereof in preparation of phenol by photocatalytic benzene hydroxylation and photocatalytic ozone oxidative degradation and mineralization of organic pollutants.
Background
The zinc ferrite is an inorganic semiconductor material with visible light response, has the advantages of low price, easy obtaining, simple synthesis and the like, and is a common photocatalyst. But the method has the defects of low separation efficiency and poor stability of photogenerated carriers, and the like, which limits the application of the method in the field of photocatalysis. The carbon coating modification is carried out on the surface of the zinc ferrite nano particle, so that the photocatalytic activity and the stability of the zinc ferrite can be effectively improved.
Phenol is an important basic organic chemical raw material and is widely applied to the chemical industry. At present, the industrial production of phenolic compounds is mainly based on an isopropyl benzene method, and the problems of multiple steps, low yield, low atom utilization rate, high energy consumption, serious pollution and the like exist. The method takes hydrogen peroxide as an oxidant, hydroxylates benzene to generate phenol at one step, has the advantages of simple steps, environmental protection and the like, and meets the requirement of sustainable development.
The effective removal of organic pollutants in water is an important problem which needs to be solved urgently today. The traditional water treatment process comprises a physical method, a biological method and a chemical method, and has the problems of high cost, low efficiency, high energy consumption and the like. Photocatalytic oxidation technology and ozone oxidation technology are two emerging wastewater treatment technologies in recent years. At present, the photocatalytic oxidation technology is limited to a certain extent due to high recombination rate of photo-generated electrons and holes, and the ozone oxidation technology also has the problems of slow oxidation, high power consumption, high industrial operation cost and the like. The combination of the two methods greatly increases the yield of active species in the reaction process, has strong synergistic effect on the deep degradation of organic pollutants difficult to degrade and intermediate products, and has great significance in the aspects of energy conservation, environmental protection, sustainable development realization and the like.
Disclosure of Invention
Aiming at the problems, the invention provides a carbon-coated zinc ferrite catalyst, a preparation method thereof and application thereof in preparation of phenol by photocatalysis and hydroxylation of benzene, and photocatalysis of oxidative degradation of ozone and mineralization of organic pollutants. The method has the advantages of simple synthesis technology, easy operation, good yield, high selectivity and cycling stability, and potential application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first purpose of the invention is to protect a preparation method of a carbon-coated zinc ferrite catalyst, which comprises the following steps:
(1) At normal temperature, dissolving a certain amount of iron precursor and zinc precursor in water, adding a certain amount of glucose after the iron precursor and the zinc precursor are uniformly mixed, and uniformly stirring;
(2) Adjusting the pH value of the solution obtained in the step (1) by using a NaOH solution, and uniformly stirring;
(3) And (3) carrying out hydrothermal treatment on the solution obtained in the step (2), and then washing, centrifuging and drying in vacuum to obtain the carbon-coated zinc ferrite catalyst.
Further, the molar ratio of the iron precursor to the zinc precursor used in step (1) is 2:1. The iron precursor is any one of ferric chloride, ferric nitrate and ferric sulfate, and the zinc precursor is any one of zinc chloride, zinc nitrate and zinc sulfate.
Further, the molar ratio of the iron precursor to the glucose used in the step (1) is 1-90. If the glucose is used in too much amount, znFe will be generated 2 O 4 A too thick carbon layer is formed on the catalyst, so that the surface catalytic reaction is hindered, and the catalytic activity is obviously inhibited; if the dosage of glucose is too small, the dosage is not enough in ZnFe 2 O 4 A compact carbon layer which is completely covered is formed on the surface, so that the catalyst cannot be protected, and the purpose of inhibiting the loss of metal components is achieved.
Further, in the step (2), the pH of the solution is adjusted to 8-10.
Further, the temperature of the hydrothermal treatment in the step (3) is 150-200 ℃ and the time is 5-36 h.
The second purpose of the invention is to protect the carbon-coated zinc ferrite catalyst prepared by the method, and the carbon-coated layer on the surface of the carbon-coated zinc ferrite catalyst is dense and nonporous.
The third purpose of the invention is to protect the application of the carbon-coated zinc ferrite catalyst.
One application of the method is that benzene is used as a substrate, hydrogen peroxide is used as an oxidant, and in the presence of the carbon-coated zinc ferrite catalyst, the hydroxylation reaction is driven by visible light in an acetonitrile-water system to generate phenol.
Further, the volume ratio of hydrogen peroxide to benzene used is 1-17.
Further, the volume ratio of acetonitrile to water in the acetonitrile-water system is 1-4:1.
Further, the hydroxylation reaction time is 4 h-12 h.
The second application is that under the condition of ozone, the carbon-coated zinc ferrite catalyst is used for carrying out photocatalytic degradation and mineralization reaction on organic pollutants in water so as to remove the organic pollutants in the solution.
Further, the organic pollutant is any one or more of oxalic acid, tetracycline hydrochloride, phenol, bisphenol A, salicylic acid or golden orange.
Patent CN 105565792a provides a glucose-based mesoporous carbon coated ferrite and a preparation method thereof, which specifically comprises the steps of preparing ferrite (ZnFeO) particles, coating glucose on the surface of the ferrite, and performing heat treatment to prepare the mesoporous carbon coated ferrite. But because it is in ZnFeO (not ZnFe) 2 O 4 ) The surface of the catalyst is coated with a porous carbon layer, which cannot form good protection on nano particles in the heterogeneous catalytic reaction process, thereby inhibiting the loss of metal components.
The invention has the beneficial effects that: the invention coats carbon on zinc ferrite (ZnFe) by a hydrothermal method 2 O 4 ) On the surface, zinc ferrite nano-particles (ZnFe) coated by a compact carbon layer are prepared 2 O 4 @ C). In the reaction for preparing phenol by photo-catalytic benzene hydroxylation, the obtained ZnFe 2 O 4 @ C can not only utilize the carbon layer to adsorb and activate the benzene, improve the reaction activity, but also prevent the metal from dissolving out in the reaction process and improve the stability of the catalyst. The test result shows that the obtained ZnFe 2 O 4 The yield of @ C in the preparation of phenol by photocatalytic benzene hydroxylation is 15.8%, and the activity remains stable through 5 rounds of reaction. In the process of photocatalytic ozone oxidation degradation and mineralization of organic pollutants, znFe 2 O 4 @ C improves the photoproduction electron-hole separation efficiency, improves the ozone utilization rate, accelerates the removal and mineralization of organic pollutants, solves the problem of metal dissolution in the zinc ferrite reaction process, and can prevent secondary pollution to the environment. The test results show thatZnFe 2 O 4 The mineralization rate of the oxalic acid under the condition of the @ C photocatalytic ozonation is 87%, and the activity of the oxalic acid still keeps stable after 4 rounds of reaction. Therefore, the ZnFe obtained by the invention 2 O 4 @ C has certain industrial application prospects in the fields.
Drawings
FIG. 1 shows ZnFe prepared in example and comparative example 1 2 O 4 @ C and ZnFe 2 O 4 XRD pattern of (a);
FIG. 2 shows ZnFe prepared in example and comparative example 1 2 O 4 @ C and ZnFe 2 O 4 Raman spectrogram of (a);
FIG. 3 shows ZnFe prepared in example and comparative example 1 2 O 4 @ C and ZnFe 2 O 4 SEM picture of (1);
FIG. 4 is the ZnFe prepared in the example 2 O 4 TEM image of @ C;
FIG. 5 shows ZnFe obtained in example 2 O 4 、ZnFe 2 O 4 And the ultraviolet-visible diffuse reflection spectrums of the particles of ZnFeO and the particles of ZnFeO @ meso-C obtained in the comparative example 2 are shown.
FIG. 6 shows ZnFe in application example 1 2 O 4 And ZnFe 2 O 4 A performance comparison graph of @ C in preparation of phenol by multi-round photocatalytic benzene hydroxylation;
FIG. 7 shows ZnFe in application example 1 2 O 4 A performance comparison graph of @ C and ZnFeO @ meso-C in two-round photocatalytic reaction for preparing phenol by benzene hydroxylation;
FIG. 8 shows ZnFe in application example 1 2 O 4 、ZnFe 2 O 4 @ C and ZnFe 2 O 4 A performance comparison diagram of @ C (multi-step method) in two-round reaction for preparing phenol by photocatalysis and benzene hydroxylation;
FIG. 9 shows ZnFe in example 2 2 O 4 、ZnFe 2 O 4 @C、ZnFeO@Meso-C、ZnFe 2 O 4 A graph for comparing the performance of @ C (multi-step method) in the oxidation and mineralization of oxalic acid by photocatalytic ozone;
FIG. 10 shows ZnFe in example 2 2 O 4 And ZnFe 2 O 4 @ C photocatalytic ozonation mineralizationA performance comparison graph of oxalic acid;
FIG. 11 shows ZnFe in example 2 2 O 4 And ZnFe 2 O 4 A performance comparison graph of the @ C photocatalytic ozonation mineralization tetracycline hydrochloride;
FIG. 12 shows ZnFe in example 2 2 O 4 And ZnFe 2 O 4 A comparison graph of performances of the @ C photocatalytic ozone oxidation mineralized methyl orange;
FIG. 13 shows ZnFe in application example 2 2 O 4 And ZnFe 2 O 4 Comparison graph of performances of the @ C photocatalytic ozonation mineralization salicylic acid.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Examples
1.35 g (5 mmol) FeCl 3 ·6H 2 O and 0.34 g (2.5 mmol) ZnCl 2 Dispersing in deionized water, stirring 0.5 h to make them fully dissolved and mixed, adding 20 mg (0.11 mmol) glucose, adjusting solution pH to 9 with NaOH solution, continuing stirring 1 h, and heating the resulting solution at 180 deg.C with water 10 h. Washing, centrifuging and vacuum drying the obtained sample to obtain ZnFe 2 O 4 @C。
Comparative example 1
1.35 g (5 mmol) FeCl 3 ·6H 2 O and 0.34 g (2.5 mmol) ZnCl 2 Dispersing in deionized water, stirring 0.5 h to fully dissolve and mix the two, adjusting the pH of the solution to 9 by using NaOH solution, continuously stirring 1 h, and then heating the obtained solution by water at 180 ℃ to 10 h. Washing, centrifuging and vacuum drying the obtained sample to obtain ZnFe 2 O 4 。
FIG. 1 shows ZnFe obtained in examples and comparative example 1 2 O 4 @ C and ZnFe 2 O 4 X-ray diffraction pattern of (a). As can be seen from the figure, znFe 2 O 4 The @ C only has a zinc ferrite phase, which shows that ZnFe is not changed after carbon coating 2 O 4 A crystalline form of (a).
FIG. 2 shows ZnFe obtained in example and comparative example 1 2 O 4 @ C and ZnFe 2 O 4 A raman spectrum of (a). As can be seen from the figure, znFe 2 O 4 @ C has a carbon structure in both amorphous and graphitic forms.
FIG. 3 shows ZnFe obtained in example and comparative example 1 2 O 4 @ C and ZnFe 2 O 4 Scanning electron micrograph (c). As can be seen from the figure, the shapes of the two are similar, the particle size is basically about 20nm, and the ZnFe is not changed after the carbon coating 2 O 4 The basic morphology and dimensions of (a).
FIG. 4 shows ZnFe obtained in example 2 O 4 Transmission electron micrograph of @ C. As can be seen from the figure, the surface of the zinc ferrite nano-particle is uniformly coated by the dense carbon layer.
Comparative example 2
ZnFeO particles and glucosyl mesoporous carbon coated ferrites (ZnFeO @ meso-C) were prepared as described in patent CN 105565792A.
FIG. 5 shows ZnFe obtained in example 2 O 4 、ZnFe 2 O 4 And the ultraviolet-visible diffuse reflection spectrums of the particles of ZnFeO and the particles of ZnFeO @ meso-C obtained in the comparative example 2 are shown. As can be seen from the figure, znFeO and ZnFeO @ meso-C exhibit a 2-step type light absorption, while ZnFe 2 O 4 、ZnFe 2 O 4 @ C has a single typical semiconductor absorption, which is consistent with a zinc ferrite material for its semiconductor characteristic absorption. Thus, it is proved that ZnFeO, znFeO @ C and ZnFe 2 O 4 、ZnFe 2 O 4 @ C is a different class of materials that exhibit distinct light absorption characteristics.
Comparative example 3
0.6g of ZnFe prepared in comparative example 1 was weighed 2 O 4 Dispersing in deionized water, adding 0.2mL of 0.5M glucose solution, performing ultrasonic dispersion for 30min, performing hydrothermal reaction at 180 ℃ for 4 h, centrifugally separating the obtained product, washing with distilled water and ethanol, drying, and keeping the temperature at 500 ℃ for 6h under the protection of nitrogen to obtain ZnFe 2 O 4 @ C (multi-step process).
Application example 1
ZnFe obtained in examples and comparative examples was used 2 O 4 @C、ZnFe 2 O 4 、ZnFeO@Meso-C、ZnFe 2 O 4 @ C (Multi-step method) 10 mg were each charged into a reactor containing 3 mL water and 3 mL acetonitrile, respectively, and 0.1 mL benzene and 0.5 mL H 2 O 2 4 h was illuminated with a 420 nm LED lamp. After the reaction, 2mL ethanol was injected into the mixture to quench the reaction and convert the two-phase system into a single phase, followed by addition of toluene as an internal standard, the reaction system was centrifuged, and the reaction solution was analyzed by liquid chromatography. And simultaneously collecting the catalyst for multiple rounds of reactions.
FIG. 6 is ZnFe 2 O 4 @ C and ZnFe 2 O 4 The activity in the reaction for preparing phenol by multiple rounds of photocatalysis and benzene hydroxylation is compared. As can be seen from the figure, in the first round of reaction, the catalyst ZnFe 2 O 4 、ZnFe 2 O 4 The phenol conversion of @ C was 8.6% and 9.4%, respectively. After five rounds of reaction, the catalyst ZnFe 2 O 4 Significant deactivation occurred, while ZnFe 2 O 4 The activity of @ C is obviously increased after the second round, and in the fifth round, znFe 2 O 4 、ZnFe 2 O 4 The yield of the phenol of @ C is 4.7 percent and 15.8 percent respectively, and the carbon coating is proved to have obvious enhancement effect on the activity and the stability of the catalyst.
FIG. 7 is ZnFe 2 O 4 And the activity comparison graphs of @ C and ZnFeO @ meso-C in two-round photocatalytic reaction for preparing phenol by benzene hydroxylation. As can be seen from the figure, the catalytic activity of ZnFeO @ meso-C is significantly lower than that of ZnFe 2 O 4 @ C, which may be due to a surface carbon layer that is too thick to impede the catalytic reaction.
FIG. 8 is ZnFe 2 O 4 、ZnFe 2 O 4 @ C and ZnFe 2 O 4 Comparison of the activity of @ C (multi-step process) in two-pass photocatalytic benzene hydroxylation reaction for preparing phenol. As can be seen from the figure, znFe 2 O 4 The catalytic performance of @ C (multi-step process) is also lower than that of ZnFe 2 O 4 @ C, which may be due to the carbon layer prepared by the fractional step method with ZnFe 2 O 4 The surface contact is not tight enough and additional ZnFe destruction or even destruction is possible during the multi-stage treatment 2 O 4 Resulting in a decrease in its activity.
Application example 2
ZnFe obtained in working examples and comparative examples was used 2 O 4 @C、ZnFe 2 O 4 、ZnFeO@Meso-C、ZnFe 2 O 4 @ C (Multi-step method) 30 mg are respectively taken and added into a reactor filled with 130 mL water and 20 mL, 2 g/L oxalic acid solution, or 135 mL water and 15 mL, 0.5 g/L tetracycline hydrochloride solution, or 135 mL water and 15 mL, 0.5 g/L methyl orange solution, or 135 mL water and 15 mL 0.5 g/L salicylic acid solution, and O with the concentration of 10 mg/L is continuously introduced into the reactor at the flow rate of 40 mL/min 3 And a 500W xenon lamp is used as a simulated light source for carrying out photocatalytic ozone oxidation reaction. Sampling is carried out at specific time intervals, and solution samples are 0.22µm, filtering with a microporous filter membrane, and adding a small amount of 0.1 mol/L Na into the solution sample 2 S 2 O 3 Solution to remove residual O 3 And finally, detecting and analyzing the solution sample by using a TOC analyzer.
FIG. 9 is ZnFe 2 O 4 、ZnFe 2 O 4 @C、ZnFeO@Meso-C、ZnFe 2 O 4 The activity result graph of @ C (multi-step method) in the oxidation and mineralization of oxalic acid by photocatalytic ozone. As can be seen from the figure, znFe 2 O 4 The catalytic activity of @ C is the most preferred.
FIG. 10 is ZnFe 2 O 4 @ C and ZnFe 2 O 4 The activity result of the oxidation and mineralization of oxalic acid by photocatalytic ozone is shown in the figure. As can be seen from the figure, in the first round of reaction, the catalyst ZnFe 2 O 4 、ZnFe 2 O 4 The mineralization rates of @ C on oxalic acid are 56% and 87%, respectively, which proves that the carbon coating is on ZnFe 2 O 4 The photocatalysis ozone oxidation degradation and the improvement of the performance of mineralizing the organic pollutants have certain promotion effect. After four-wheel reaction, the catalyst ZnFe 2 O 4 The activity of (B) is reduced, and ZnFe 2 O 4 The activity of @ C remained stable, demonstrating that the carbon coating is stable to the catalystHas obvious effect of strengthening sexual function.
FIGS. 11, 12 and 13 are ZnFe 2 O 4 And ZnFe 2 O 4 The results of the activity of @ C in photocatalytic ozonation mineralization of tetracycline hydrochloride, methyl orange and salicylic acid are shown in the figure. As can be seen from the figure, the catalyst ZnFe 2 O 4 、ZnFe 2 O 4 The mineralization rates of @ C to tetracycline hydrochloride are respectively 35% and 70%, the mineralization rates to methyl orange are respectively 39% and 89%, and the mineralization rates to salicylic acid are respectively 11.2% and 26.7%, so that the carbon coating has a certain promotion effect on the promotion of the performance of the catalyst in photocatalytic ozone oxidation degradation and mineralization of organic pollutants.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (5)
1. An application of a carbon-coated zinc ferrite catalyst in preparing phenol by photocatalysis and benzene hydroxylation is characterized in that: dissolving an iron precursor and a zinc precursor in water according to a certain proportion, uniformly mixing, adding glucose as a carbon source, adjusting the pH of the solution to 8-10 by using a NaOH solution, carrying out hydrothermal treatment, washing, centrifuging and drying;
the temperature of the hydrothermal treatment is 150-200 ℃, and the time is 5-36 h;
benzene is used as a substrate, hydrogen peroxide is used as an oxidant, and in the presence of the carbon-coated zinc ferrite catalyst, a hydroxylation reaction is driven by visible light in an acetonitrile-water system to generate phenol.
2. Use according to claim 1, characterized in that: the molar ratio of iron precursor to zinc precursor used was 2:1.
3. Use according to claim 1, characterized in that: the iron precursor is any one of ferric chloride, ferric nitrate and ferric sulfate; the zinc precursor is any one of zinc chloride, zinc nitrate and zinc sulfate.
4. Use according to claim 1, characterized in that: the molar ratio of the iron precursor to glucose used is 1-90.
5. Use according to claim 1, characterized in that: the volume ratio of the hydrogen peroxide to the benzene is 1-17; the volume ratio of acetonitrile to water in the acetonitrile-water system is 1-4:1; the hydroxylation reaction time is 4 h-12 h.
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