CN115634699B - Nickel-doped CoFe composite oxide/molybdenum disulfide supported catalyst and preparation and application thereof - Google Patents
Nickel-doped CoFe composite oxide/molybdenum disulfide supported catalyst and preparation and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 229910003321 CoFe Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title description 5
- 239000002131 composite material Substances 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000008367 deionised water Substances 0.000 claims abstract description 38
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 38
- 230000003197 catalytic effect Effects 0.000 claims abstract description 37
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 31
- 239000013067 intermediate product Substances 0.000 claims abstract description 28
- 239000002351 wastewater Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 230000001105 regulatory effect Effects 0.000 claims abstract description 19
- 239000002738 chelating agent Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 150000002815 nickel Chemical class 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 238000010525 oxidative degradation reaction Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 27
- 239000007800 oxidant agent Substances 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 12
- 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 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 4
- 235000018417 cysteine Nutrition 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 4
- 229940039790 sodium oxalate Drugs 0.000 claims description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- 235000007686 potassium Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 68
- 239000006228 supernatant Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000011943 nanocatalyst Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- -1 nickel modified molybdenum disulfide Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000003622 immobilized catalyst Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 238000007142 ring opening reaction Methods 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
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Classifications
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Catalysts (AREA)
Abstract
The invention discloses a Ni-doped CoFe 2 O 4 /MoS 2 A supported catalyst, a preparation method thereof and application thereof in catalytic oxidative degradation of organic wastewater. The preparation method comprises the following steps: dissolving a molybdenum source and a sulfur source in water, adding a chelating agent and a template guiding agent, stirring and dissolving, and regulating the pH value to be 2-7 to obtain a solution A; adding the solution A into a reaction kettle for hydrothermal reaction, and washing with absolute ethyl alcohol and deionized water after the reaction is finished to obtain an intermediate product B; ultrasonically dispersing the intermediate product B into water, adding cobalt salt, ferric salt and nickel salt, stirring and dissolving, and regulating the pH value to be 8-14 to obtain a solution C; adding the solution C into a reaction kettle for hydrothermal reaction, washing with absolute ethyl alcohol and deionized water after the reaction is finished, and drying to obtain Ni-doped CoFe 2 O 4 /MoS 2 Supported catalysts.
Description
Technical Field
The invention relates to the field of treating industrial wastewater by an advanced oxidation method, in particular to a high-efficiency Ni-doped CoFe 2 O 4 /MoS 2 A supported catalyst, a preparation method and application thereof.
Background
With the rapid development of the medical industry, the related environmental problems are more and more brought into social attention, and medical wastewater has the characteristics of more organic species, high concentration, complex components, poor biodegradability and the like, so that the effective treatment of the medical wastewater is always a difficult problem puzzling the high-quality development of the industry.
Advanced catalytic oxidation technology generates extremely active free radicals through chemical reaction, and mineralizes the free radicals into CO by utilizing oxidation reaction processes such as ring opening, bond breaking, addition, substitution, electron transfer and the like of the free radicals and nondegradable organic pollutants 2 And H 2 O fundamentally eliminates organic pollutants, and is widely applied to degradation treatment of industrial wastewater difficult to treat. The classical Fenton reaction has wide application in the field of industrial wastewater treatment due to the advantages of high reaction activity, high speed, simple operation and the like, but has certain defects, such as the reaction condition is limited in an acidic environment, and has higher activity at about pH 3, and the acidic condition is unfavorable for chemical equipment; catalyst Fe 2+ After the reaction is finished, the Fe is converted into Fe 3+ A large amount of solid waste is generated, and efficient recycling of the catalyst cannot be realized.
CoFe 2 O 4 Has a Fe-like structure 3 O 4 Has an inverse spinel structure with the formula Fe 3 O 4 Similar catalytic activity is a highly efficient heterogeneous catalyst. But due to its own magnetism it is prone to agglomeration, especially on the nano scale of CoFe 2 O 4 It is difficult to maintain a stable structure, resulting in a rapid decrease in catalytic oxidation efficiency as the reaction proceeds.
MoS 2 The two-dimensional lamellar structure layer and layer are maintained by relatively weak van der Waals force, show excellent performances in various aspects, and are widely applied to the fields of semiconductors, lubricants, catalysts and the like, and the lamellar nano MoS 2 Has a forbidden bandwidth of about 1.2eV, has catalytic activity under visible light, and has MoS with nano lamellar structure 2 The catalyst has larger specific surface area, can provide more active sites, and is a good catalyst carrier.
To sum up, consider nano CoFe 2 O 4 Carried on MoS with high specific surface area 2 On the lamellar support, the magnetic CoFe is limited due to the binding of the active site 2 O 4 Is due to agglomeration of MoS 2 Is promoted by CoFe 2 O 4 Is a compound of formula (I).
The patent specification with the publication number of CN 112694126A discloses a preparation method of high-dispersion nickel modified molybdenum disulfide, firstly, molybdenum disulfide materials with coordination unsaturated Mo centers are obtained by dispersing molybdenum-containing and sulfur-containing precursors into the same solution according to the atomic ratio of Mo: S=1:4-1:60, transferring the solution into a hydrothermal synthesis kettle, reacting for 6-48 hours at 140-220 ℃, centrifugally separating, washing and vacuum drying; dispersing the obtained molybdenum disulfide material with coordinated unsaturated Mo center in nickel formate aqueous solution according to the atomic ratio of Ni: mo=1:1000-1:20, transferring the mixture into a hydrothermal synthesis kettle, treating for 3-48 h in inert atmosphere at 120-200 ℃, and centrifugally washing to obtain solid, namely the high-dispersion nickel modified molybdenum disulfide.
Patent specification publication No. CN 114570393A discloses CoFe containing oxygen vacancies 2 O 4 -MoS 2 A method for preparing a supported catalyst comprising the steps of: at room temperature, adding an aqueous solution containing Fe salt and Co salt to MoS 2 After being evenly dispersed by ultrasonic, the aqueous solution of (B) is dropwise added with a precipitator, heated and refluxed, dried and calcined, thus obtaining the CoFe containing surface oxygen vacancies 2 O 4 -MoS 2 Supported catalysts.
The invention adopts Ni dopingImpurity modified CoFe 2 O 4 Further enhancing CoFe by electron coordination of (C) 2 O 4 Thus synthesizing Ni-doped CoFe 2 O 4 /MoS 2 The supported catalyst has great application prospect in the technical aspect of advanced catalytic oxidation in the field of industrial water treatment.
Disclosure of Invention
The invention provides a Ni-doped CoFe 2 O 4 /MoS 2 Preparation method of supported catalyst, and synthesis of MoS with auxiliary catalytic activity through hydrothermal reaction 2 Control of MoS by simultaneous introduction of specific chelating agents and template directing agents to a lamellar carrier 2 The size and specific surface area of the sheet; in MoS by in situ-co-precipitation 2 Synthesis of highly active Ni-doped CoFe on a Carrier 2 O 4 A nano-catalyst; ni doped CoFe 2 O 4 /MoS 2 The supported catalyst has good effect on catalytic oxidative degradation of organic wastewater, the immobilization of the catalyst reduces metal ion loss, the cyclic catalytic activity is stable, and the catalyst has certain magnetism and is convenient for recovery of the catalyst; the heterogeneous catalytic oxidation system has wide pH application range and mild reaction conditions, and has important significance for degrading and treating organic wastewater by the heterogeneous catalytic oxidation system.
Ni doped CoFe 2 O 4 /MoS 2 A method for preparing a supported catalyst comprising the steps of:
(1) Dissolving a molybdenum source and a sulfur source in water, adding a chelating agent and a template guiding agent, stirring and dissolving, and regulating the pH value to be 2-7 to obtain a solution A;
the chelating agent comprises at least one of sodium citrate, disodium ethylenediamine tetraacetate and sodium oxalate;
the template guiding agent comprises at least one of polyacrylamide and cetyltrimethylammonium bromide;
(2) Adding the solution A into a reaction kettle for hydrothermal reaction, and washing with absolute ethyl alcohol and deionized water after the reaction is finished to obtain an intermediate product B (molybdenum disulfide);
(3) Ultrasonically dispersing the intermediate product B into water, adding cobalt salt, ferric salt and nickel salt, stirring and dissolving, and regulating the pH value to be 8-14 to obtain a solution C;
the molar ratio of the nickel atoms in the nickel salt is 5-20% based on 100% of the sum of the amounts of cobalt atoms in the cobalt salt and nickel atoms in the nickel salt;
(4) Adding the solution C into a reaction kettle for hydrothermal reaction, washing with absolute ethyl alcohol and deionized water after the reaction is finished, and drying to obtain Ni-doped CoFe 2 O 4 /MoS 2 Supported catalysts.
In step (1), the molybdenum source includes at least one of ammonium molybdate, sodium molybdate, potassium molybdate, and the like.
In step (1), the sulfur source includes at least one of thiourea, thioacetamide, cysteine, and the like.
MoS due to chemical reaction conversion problems 2 In the synthesis process, the proportion of Mo and S is MoS with high-efficiency catalytic activity 2 The key of the carrier. Preferably, in the step (1), the molar ratio of the molybdenum atoms in the molybdenum source to the sulfur atoms in the sulfur source is 1:2-2.5.
The structural form and the specific surface area are important properties of the catalyst support in order to obtain MoS with a high specific surface area 2 Carrier, in MoS 2 In the synthesis process, the invention introduces specific chelating agent and template guiding agent to control the laminated MoS with high specific surface area 2 The carrier is used for providing more loading points for the catalyst.
The amount of chelating agent and template directing agent is relative to highly active MoS 2 Is also of critical importance.
The chelating agent is preferably added in an amount of 0.5 to 5% by mass of the intermediate product B, and more preferably 1 to 3% by mass of the intermediate product B.
The template directing agent is preferably added in an amount of 0.01 to 0.5% by mass of the intermediate product B, and more preferably in an amount of 0.05 to 0.1% by mass of the intermediate product B.
The reaction conditions have an important influence on the synthesis and activity of the cocatalysts.
In step (1), the ph=4 to 6 is preferably adjusted.
In the step (2), the temperature of the hydrothermal reaction is preferably 100 to 200 ℃, more preferably 120 to 160 ℃, and the time is preferably 6 to 48 hours, more preferably 8 to 24 hours.
Intermediate B (MoS) 2 Sheet layer) with a specific surface area of 85-120 m 2 /g，MoS 2 The thickness of the sheet layer is 8-15 nm.
The traditional inorganic catalyst post-treatment method mainly adopts deionized water for cleaning, but reactant which is not reacted completely in the reaction process can not be removed completely, and has certain influence on the activity and the form of the catalyst.
In the preparation method of the invention, in the step (2), absolute ethyl alcohol and deionized water are adopted for washing, preferably absolute ethyl alcohol and deionized water are adopted for alternately washing until the pH value of a washing supernatant is about 7, and the intermediate product B treated by the steps shows higher auxiliary catalytic activity.
The preparation method of the invention utilizes the principle of isomorphous substitution to dope, ni ions partially replace Co ions, and a coprecipitation method is used for synthesizing Ni-doped CoFe 2 O 4 Catalyst, doping of Ni alters CoFe 2 O 4 Not only improve CoFe 2 O 4 Is also broadened by CoFe 2 O 4 In addition, ni and Co metal ions are relatively friendly to the environment, and are high-efficiency and green wastewater treatment catalysts.
The ratio of the sum of the amounts of cobalt atoms in the cobalt salt and the amounts of material of nickel atoms in the nickel salt to the amount of material of iron atoms in the iron salt may be in a stoichiometric ratio of 1:2.
CoFe 2 O 4 Too much or too little Ni doping in the lattice affects the catalytic performance of the catalyst. In the step (3) of the present invention, the molar ratio of the nickel atoms in the nickel salt is 5% to 20% based on 100% of the sum of the amounts of the cobalt atoms in the cobalt salt and the nickel atoms in the nickel salt. NiFe formed too much of Ni 2 O 4 Is free of CoFe 2 O 4 Good catalytic oxidation effect and poor catalytic oxidation effectAnd the loss of metal ions is high. Only the cooperation of Ni and Co in a certain proportion can produce the best effect.
In the step (3), the cobalt salt comprises at least one of cobalt chloride, cobalt nitrate, cobalt sulfate and the like.
In step (3), the iron salt includes at least one of ferric chloride, ferric nitrate, ferric sulfate, and the like.
In the step (3), the nickel salt includes at least one of nickel chloride, nickel nitrate, nickel sulfate, and the like.
The reaction conditions have an important influence on the synthesis and activity of the catalyst.
In step (3), the ph=9 to 12 is preferably adjusted.
In the step (4), the temperature of the hydrothermal reaction is preferably 100 to 200 ℃, more preferably 120 to 160 ℃, and the time is preferably 6 to 48 hours, more preferably 8 to 24 hours.
The traditional inorganic catalyst post-treatment method mainly adopts deionized water for cleaning, but reactant which is not reacted completely in the reaction process can not be removed completely, and has certain influence on the activity of the catalyst.
In the preparation method, in the step (4), absolute ethyl alcohol and deionized water are adopted for washing, preferably, absolute ethyl alcohol and deionized water are adopted for alternately washing until the pH value of a washing supernatant is about 7, and the target product treated by the steps shows higher catalytic activity.
The invention uses MoS 2 The lamellar structure is a carrier, and a specific chelating agent and a template guiding agent are used for obtaining a large specific surface area to provide a catalyst attachment site, and MoS is on the other hand 2 The S with medium negative bivalent has reducibility, is favorable for reducing Co in the catalyst from high valence to low valence, forms circulation and plays a role of a promoter.
To make MoS 2 The invention adopts a hydrothermal synthesis method, has no roasting process, and the roasting treatment can destroy MoS 2 The structure of the sheet (breaking it up) and its reducibility (as analyzed above, reducibility is also MoS 2 One of the reasons for exhibiting co-catalytic properties) But also divalent Ni and Co in the catalyst may oxidize them to reduce their catalytic activity. The invention uses a hydrothermal synthesis method to prepare MoS 2 No roasting process, and subsequent continuous hydrothermal reaction on MoS 2 The structure and the catalytic performance are not affected.
The invention also provides Ni-doped CoFe prepared by the preparation method 2 O 4 /MoS 2 Supported catalysts.
In a preferred embodiment, ni-doped CoFe is used to maintain high catalytic activity 2 O 4 /MoS 2 Ni-doped CoFe in supported catalysts 2 O 4 The loading of the catalyst is 20-40 mmol/g.
The invention also provides the Ni-doped CoFe 2 O 4 /MoS 2 The application of the supported catalyst in catalytic oxidative degradation of organic wastewater.
As a general inventive concept, the present invention also provides a method of catalytic oxidative degradation of organic wastewater, comprising: adding oxidant and the Ni doped CoFe into the organic wastewater 2 O 4 /MoS 2 The supported catalyst is subjected to catalytic oxidation by adjusting the pH to be 3-11.
The oxidant comprises potassium hydrogen Persulfate (PMS), hydrogen peroxide (H) 2 O 2 ) Sodium hypochlorite (NaClO), sodium chlorate (NaClO) 3 ) At least one of the following.
The addition amounts of the oxidant and the catalyst have a remarkable influence on the catalytic oxidation effect and the utilization efficiency of the oxidant, and the oxidant and the Ni-doped CoFe 2 O 4 /MoS 2 The molar ratio of the supported catalyst to the catalyst is preferably 0.5 to 20:1, more preferably 5 to 20:1. In the range of the feeding ratio, the catalytic oxidation has better degradation effect and higher utilization efficiency of the oxidant. Wherein Ni is doped with CoFe 2 O 4 /MoS 2 The amount of the supported catalyst is measured as the sum of the amounts of the substances of Co, fe and Ni metal ions.
The reaction temperature of the catalytic oxidation is preferably 20-50 ℃, and the reaction time is preferably 1-10 h.
The organic wastewater is wastewater containing organic matters; further preferably, the organic wastewater is medical wastewater containing toluene, aniline, heterocyclic compounds, halogenated hydrocarbons and other refractory organic matters, and the COD range of the wastewater is 200-1000 mg/L.
The invention adopts the isomorphous replacement principle to adopt an in-situ-blending precipitation method to carry out MoS 2 Synthesis of highly active Ni-doped CoFe on support 2 O 4 Nanocatalyst, ni doping altering CoFe 2 O 4 To enhance CoFe by electron coordination of (C) 2 O 4 Is a MoS with large specific surface area 2 The lamellar carrier provides active site limiting nano Ni doped CoFe 2 O 4 The catalyst has agglomeration, certain auxiliary catalytic activity, low loss rate of immobilized catalyst metal ions, stable catalyst multi-cycle catalytic activity, wide pH application range and great practical application value and wide industrial application prospect in the field of degrading and treating organic wastewater by a heterogeneous catalytic oxidation system.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention adopts the isomorphous substitution principle in situ-coprecipitation method to synthesize Ni-doped CoFe in one step 2 O 4 Catalyst, ni doping changes electron coordination, improves CoFe 2 O 4 The catalytic activity of the catalyst is improved, and the catalytic oxidation efficiency is further improved;
2) Ni doped CoFe 2 O 4 Nano catalyst supported on MoS 2 On the carrier, the agglomeration of the nano catalyst is limited, the catalytic activity of the catalyst is improved, and the MoS prepared by the calcination-free hydrothermal synthesis method is prepared 2 The lamellar carrier has a certain catalysis assisting effect, and the catalysis activity is further improved by the cooperation of the lamellar carrier and the lamellar carrier;
3) Ni doped CoFe 2 O 4 /MoS 2 The supported catalyst has a wider pH application range, avoids the acid or alkali regulating process for keeping the optimal reaction condition, saves the operation cost, simplifies the process steps, greatly reduces the use of acid and alkali, and reduces the potential harm to the environment;
4) In the application of refractory organic wasteNi doped CoFe during advanced oxidation reaction of water 2 O 4 /MoS 2 The supported catalyst has the advantages of high catalytic activity, low metal ion loss rate, stable multiple circulation effect and easy recovery of magnetism, is a novel heterogeneous catalyst with high efficiency and green, and has wide application prospect in the field of organic wastewater treatment.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
Example 1
9.8g (0.05 mol) of ammonium molybdate and 7.6g (0.1 mol) of thiourea are taken and dissolved in 100mL of deionized water, and 0.24g (3.0%wt) of sodium citrate and 0.008g (0.1%wt) of polyacrylamide are added to regulate the pH value to be about 6, so as to obtain solution A; pouring the solution A into a hydrothermal reaction kettle, reacting for 8 hours at 160 ℃, and after the reaction is finished, alternately washing with absolute ethyl alcohol and deionized water until the pH value of the supernatant is 7 to obtain an intermediate product B (the specific surface area is 115m 2 /g, thickness of the platelet 8 nm); dispersing the intermediate product B into an aqueous solution by ultrasonic, adding 17.6g (0.135 mol) of cobalt chloride, 48.6g (0.3 mol) of ferric chloride and 2.0g (0.015 mol) of nickel chloride, stirring and dissolving, and regulating the pH value to be about 12 to obtain a solution C; adding the solution C into a hydrothermal reaction kettle, reacting for 12 hours at 120 ℃, alternately washing with absolute ethyl alcohol and deionized water until the pH value of the supernatant is about 7 after the reaction is finished, drying in a 60 ℃ oven for 4 hours, and obtaining a target product D, and grinding for later use.
Taking 100mL of a toluene-containing medical wastewater solution, adding H according to the ratio of 10:1 of the oxidant to the catalyst substances, wherein the COD is 480mg/L, the pH value is 8.5 2 O 2 And Ni doped CoFe 2 O 4 /MoS 2 Reacting at 25 ℃ for 2h, H 2 O 2 And adding the COD equivalent of the target substrate, measuring the COD of the solution after the reaction, and calculating the COD removal rate of the solution to be 75.2%.
Example 2
10.3g of sodium molybdate (0.05 mol) and 9.4g (0.125 mol) of thioacetamide are taken and dissolved in 100mL of deionized water, and 0.08g (1.0 wt%) of disodium ethylenediamine tetraacetate and 0.004g (0.05 wt%) of cetyltrimethylammonium bromide are added to adjust the pH value to about 4 to obtain solution A; pouring the solution A into a hydrothermal reaction kettle, reacting for 24 hours at 120 ℃, and after the reaction is finished, alternately washing with absolute ethyl alcohol and deionized water until the pH value of the supernatant is 7 to obtain an intermediate product B; dispersing the intermediate product B into an aqueous solution by ultrasonic, adding 37.2g of cobalt sulfate (0.24 mol), 120.0g of ferric sulfate (0.3 mol) and 9.3g of nickel sulfate (0.06 mol), stirring and dissolving, and regulating the pH value to be about 9 to obtain a solution C; adding the solution C into a hydrothermal reaction kettle, reacting for 8 hours at 160 ℃, alternately washing with absolute ethyl alcohol and deionized water until the pH value of the supernatant is about 7 after the reaction is finished, drying in a 50 ℃ oven for 6 hours, and obtaining a target product D, and grinding for later use.
Taking 100mL of a certain aniline-containing medical wastewater solution, adding PMS and Ni doped CoFe according to the ratio of the oxidant to the catalyst material of 20:1, wherein the COD is 390mg/L and the pH value is 11 2 O 4 /MoS 2 The reaction is carried out for 1h at 50 ℃, the COD equivalent of PMS and target substrate is added, the COD of the solution after the reaction is measured, and the removal rate of the solution COD is calculated to be 73.5%.
Example 3
Dissolving 11.9g of potassium molybdate (0.05 mol) and 13.6g (0.1125 mol) of cysteine in 100mL of deionized water, stirring and dissolving, adding 0.16g (2.0%wt) of sodium oxalate and 0.006g (0.075%wt) of polyacrylamide, and regulating the pH value to about 4 to obtain a solution A; pouring the solution A into a hydrothermal reaction kettle, reacting for 6 hours at 200 ℃, and after the reaction is finished, alternately washing with absolute ethyl alcohol and deionized water until the pH value of the supernatant is 7 to obtain an intermediate product B; dispersing the intermediate product B into an aqueous solution by ultrasonic, adding 20.9g of cobalt nitrate (0.114 mol), 58.1g of ferric nitrate (0.24 mol) and 1.1g of nickel nitrate (0.006 mol), stirring and dissolving, and regulating the pH value to be about 9 to obtain a solution C; adding the solution C into a hydrothermal reaction kettle, reacting for 24 hours at 100 ℃, alternately washing with absolute ethyl alcohol and deionized water until the pH value of the supernatant is about 7 after the reaction is finished, drying in a 50 ℃ oven for 6 hours, and obtaining a target product D, and grinding for later use.
Take 100mL of a certain containerThe chlorinated hydrocarbon medical wastewater solution, corresponding to COD of 1000mg/L and pH value of 6.2, is added with NaClO according to the ratio of the oxidant to the catalyst material of 0.5:1 3 And Ni doped CoFe 2 O 4 /MoS 2 Reacting for 10h at 40 ℃ with NaClO 3 And adding the COD equivalent of the target substrate and the like, measuring the COD of the solution after the reaction, and calculating the COD removal rate of the solution to be 81.7%.
Example 4
Dissolving 11.9g of potassium molybdate (0.05 mol) and 7.6g of thiourea (0.1 mol) in 100mL of deionized water, stirring and dissolving, adding 0.04g (0.5%wt) of sodium citrate and 0.0008g (0.01%wt) of cetyltrimethylammonium bromide, and regulating the pH value to about 5 to obtain a solution A; pouring the solution A into a hydrothermal reaction kettle, reacting for 6 hours at 200 ℃, and after the reaction is finished, alternately washing with absolute ethyl alcohol and deionized water until the pH value of the supernatant is 7 to obtain an intermediate product B; dispersing the intermediate product B into an aqueous solution by ultrasonic, adding 17.6g of cobalt chloride (0.135 mol), 60.0g of ferric sulfate (0.15 mol) and 2.7g of nickel nitrate (0.015 mol), stirring and dissolving, and regulating the pH value to be about 14 to obtain a solution C; adding the solution C into a hydrothermal reaction kettle, reacting for 48 hours at 100 ℃, alternately washing with absolute ethyl alcohol and deionized water until the pH is about 7 after the reaction is finished, drying for 6 hours in a 45 ℃ oven to obtain a target product D, and grinding for later use.
Taking 100mL of a heterocyclic compound-containing medical wastewater solution, adding NaClO and Ni doped CoFe according to the ratio of the oxidant to the catalyst material of 0.5:1, wherein the COD is 250mg/L and the pH value is 3.5 2 O 4 /MoS 2 And (3) reacting for 2 hours at 25 ℃, adding COD equivalent of NaClO and a target substrate, measuring the COD of the reacted solution, and calculating the COD removal rate of the solution to be 76.3%.
Comparative example 1 (no Ni doping)
This comparative example was operated under the same conditions as example 1, except that no Ni doping was present.
9.8g (0.05 mol) of ammonium molybdate and 7.6g (0.1 mol) of thiourea are taken and dissolved in 100mL of deionized water, and 0.24g (3.0%wt) of sodium citrate and 0.008g (0.1%wt) of polyacrylamide are added to regulate the pH value to be about 6, so as to obtain solution A; pouring the solution A into a hydrothermal reaction kettle, reacting for 8 hours at 160 ℃, and after the reaction is finished, alternately washing with absolute ethyl alcohol and deionized water until the pH value of the supernatant is 7 to obtain an intermediate product B; dispersing the intermediate product B into an aqueous solution by ultrasonic, adding 19.5g (0.15 mol) of cobalt chloride and 48.6g (0.3 mol) of ferric chloride, stirring and dissolving, and regulating the pH value to about 12 to obtain a solution C; adding the solution C into a hydrothermal reaction kettle, reacting for 12 hours at 120 ℃, alternately washing with absolute ethyl alcohol and deionized water until the pH value of the supernatant is about 7 after the reaction is finished, drying in a 60 ℃ oven for 4 hours, and obtaining a target product D, and grinding for later use.
Taking 100mL of a toluene-containing medical wastewater solution, adding H according to the ratio of 10:1 of the oxidant to the catalyst substances, wherein the COD is 480mg/L, the pH value is 8.5 2 O 2 And CoFe 2 O 4 /MoS 2 Reacting at 25 ℃ for 2h, H 2 O 2 And adding the COD equivalent of the target substrate, measuring the COD of the solution after the reaction, and calculating the COD removal rate of the solution to be 62.3%.
Comparative example 2 (no MoS) 2 Carrier (C)
This comparative example is operated under the same conditions as example 2, except that no MoS was present 2 A carrier.
Taking 37.2g of cobalt sulfate (0.24 mol), 120.0g of ferric sulfate (0.3 mol) and 9.3g of nickel sulfate (0.06 mol), stirring and dissolving, and regulating the pH value to be about 9 to obtain a solution C; adding the solution C into a hydrothermal reaction kettle, reacting for 8 hours at 160 ℃, alternately washing with absolute ethyl alcohol and deionized water until the pH value of the supernatant is about 7 after the reaction is finished, drying in a 50 ℃ oven for 6 hours, and obtaining a target product D, and grinding for later use.
Taking 100mL of a certain aniline-containing medical wastewater solution, adding PMS and Ni doped CoFe according to the ratio of the oxidant to the catalyst material of 20:1, wherein the COD is 390mg/L and the pH value is 11 2 O 4 The reaction is carried out for 1h at 50 ℃, the COD equivalent of PMS and target substrate is added, the COD of the solution after the reaction is measured, and the removal rate of the solution COD is calculated to be 53.5%.
Comparative example 3 (first Synthesis of Ni-doped CoFe) 2 O 4 Synthesizing MoS again 2 )
This comparative example is identical to example 3 in terms of operating conditions, except that Ni-doped CoFe is first synthesized 2 O 4 Then load on MoS 2 And (3) on a carrier.
Taking 20.9g of cobalt nitrate (0.114 mol), 58.1g of ferric nitrate (0.24 mol) and 1.1g of nickel nitrate (0.006 mol), stirring and dissolving, and regulating the pH value to about 9 to obtain a solution C; adding the solution C into a hydrothermal reaction kettle, reacting for 24 hours at 100 ℃, alternately washing with absolute ethyl alcohol and deionized water until the pH value of the supernatant is about 7 after the reaction is finished, drying for 6 hours in a 50 ℃ oven to obtain an intermediate product D, and grinding for later use. Dissolving 11.9g of potassium molybdate (0.05 mol) and 13.6g (0.1125 mol) of cysteine in 100mL of deionized water, stirring and dissolving, adding 0.16g (2.0%wt) of sodium oxalate and 0.006g (0.075%wt) of polyacrylamide, adding the prepared intermediate D, and regulating the pH value to about 4 to obtain a solution A; pouring the solution A into a hydrothermal reaction kettle, reacting for 6 hours at 200 ℃, and after the reaction is finished, alternately washing the solution A with absolute ethyl alcohol and deionized water until the pH value of the supernatant is 7, thus obtaining a target product B.
Taking 100mL of a chlorinated hydrocarbon-containing medical wastewater solution, adding NaClO according to the ratio of the oxidant to the catalyst material of 0.5:1, wherein the COD is 1000mg/L and the pH value is 6.2 3 And Ni doped CoFe 2 O 4 /MoS 2 Reacting for 10h at 40 ℃ with NaClO 3 And adding the COD equivalent of the target substrate, measuring the COD of the solution after the reaction, and calculating the COD removal rate of the solution to be 64.7%.
Comparative example 4 (different product work-up methods)
This comparative example was run under the same conditions as example 4, except that the intermediate and product post treatments were rinsed with deionized water only.
Dissolving 11.9g of potassium molybdate (0.05 mol) and 7.6g of thiourea (0.1 mol) in 100mL of deionized water, stirring and dissolving, adding 0.04g (0.5%wt) of sodium citrate and 0.0008g (0.01%wt) of cetyltrimethylammonium bromide, and regulating the pH value to about 5 to obtain a solution A; pouring the solution A into a hydrothermal reaction kettle, reacting for 6 hours at 200 ℃, and washing with deionized water until the pH value of the supernatant is 7 after the reaction is finished to obtain an intermediate product B; dispersing the intermediate product B into an aqueous solution by ultrasonic, adding 17.6g of cobalt chloride (0.135 mol), 60.0g of ferric sulfate (0.15 mol) and 2.7g of nickel nitrate (0.015 mol), stirring and dissolving, and regulating the pH value to be about 14 to obtain a solution C; adding the solution C into a hydrothermal reaction kettle, reacting for 48 hours at 100 ℃, washing with deionized water until the pH is about 7 after the reaction is finished, drying for 6 hours in a 45 ℃ oven to obtain a target product D, and grinding for later use.
Taking 100mL of a heterocyclic compound-containing medical wastewater solution, wherein the corresponding COD is 250mg/L, the pH value is 3.5, and the ratio of the oxidant to the catalyst is 0.5:1 ratio of NaClO and Ni doped CoFe 2 O 4 /MoS 2 And (3) reacting for 2 hours at 25 ℃, adding COD equivalent of NaClO and a target substrate, measuring the COD of the reacted solution, and calculating the removal rate of the solution COD to be 68.8%.
Comparative example 5 (no chelating agent and template directing agent)
9.8g (0.05 mol) of ammonium molybdate and 7.6g (0.1 mol) of thiourea are taken and dissolved in 100mL of deionized water, and the solution A is obtained by stirring and dissolving and adjusting the pH value to about 6; pouring the solution A into a hydrothermal reaction kettle, reacting for 8 hours at 160 ℃, and after the reaction is finished, alternately washing with absolute ethyl alcohol and deionized water until the pH value of the supernatant is 7 to obtain an intermediate product B (the specific surface area is 57m 2 /g, thickness of the platelet 36 nm); dispersing the intermediate product B into an aqueous solution by ultrasonic, adding 17.6g (0.135 mol) of cobalt chloride, 48.6g (0.3 mol) of ferric chloride and 2.0g (0.015 mol) of nickel chloride, stirring and dissolving, and regulating the pH value to be about 12 to obtain a solution C; adding the solution C into a hydrothermal reaction kettle, reacting for 12 hours at 120 ℃, alternately washing with absolute ethyl alcohol and deionized water until the pH value of the supernatant is about 7 after the reaction is finished, drying in a 60 ℃ oven for 4 hours, and obtaining a target product D, and grinding for later use.
Taking 100mL of a toluene-containing medical wastewater solution, adding H according to the ratio of 10:1 of the oxidant to the catalyst substances, wherein the COD is 480mg/L, the pH value is 8.5 2 O 2 And Ni doped CoFe 2 O 4 /MoS 2 Reacting at 25 ℃ for 2h, H 2 O 2 And adding the COD equivalent of the target substrate, measuring the COD of the solution after the reaction, and calculating the COD removal rate of the solution to be 58.3%.
Further, it will be understood that various changes and modifications may be made by those skilled in the art after reading the foregoing description of the invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Claims (10)
1. Ni doped CoFe 2 O 4 /MoS 2 The preparation method of the supported catalyst is characterized by comprising the following steps:
(1) Dissolving a molybdenum source and a sulfur source in water, adding a chelating agent and a template guiding agent, stirring and dissolving, and regulating the pH value to be 2-7 to obtain a solution A;
the chelating agent comprises at least one of sodium citrate, disodium ethylenediamine tetraacetate and sodium oxalate;
the template guiding agent comprises at least one of polyacrylamide and cetyltrimethylammonium bromide;
(2) Adding the solution A into a reaction kettle for hydrothermal reaction, and washing with absolute ethyl alcohol and deionized water after the reaction is finished to obtain an intermediate product B;
(3) Ultrasonically dispersing the intermediate product B into water, adding cobalt salt, ferric salt and nickel salt, stirring and dissolving, and regulating the pH value to be 8-14 to obtain a solution C;
the molar ratio of the nickel atoms in the nickel salt is 5-20% based on 100% of the sum of the amounts of cobalt atoms in the cobalt salt and nickel atoms in the nickel salt;
(4) Adding the solution C into a reaction kettle for hydrothermal reaction, washing with absolute ethyl alcohol and deionized water after the reaction is finished, and drying to obtain Ni-doped CoFe 2 O 4 /MoS 2 Supported catalysts.
2. The method according to claim 1, wherein in step (1):
the molybdenum source comprises at least one of ammonium molybdate, sodium molybdate and potassium molybdate;
the sulfur source comprises at least one of thiourea, thioacetamide and cysteine;
the mol ratio of the molybdenum atoms in the molybdenum source to the sulfur atoms in the sulfur source is 1:2-2.5;
the addition amount of the chelating agent is 0.5-5% of the mass of the intermediate product B;
the addition amount of the template guiding agent is 0.01-0.5% of the mass of the intermediate product B.
3. The method according to claim 1, wherein in the step (2), the hydrothermal reaction is carried out at a temperature of 100 to 200 ℃ for a time of 6 to 48 hours.
4. The method according to claim 1, wherein in the step (3):
the cobalt salt comprises at least one of cobalt chloride, cobalt nitrate and cobalt sulfate;
the ferric salt comprises at least one of ferric chloride, ferric nitrate and ferric sulfate;
the nickel salt comprises at least one of nickel chloride, nickel nitrate and nickel sulfate.
5. The method according to claim 1, wherein in the step (4), the hydrothermal reaction is carried out at a temperature of 100 to 200 ℃ for a time of 6 to 48 hours.
6. Ni-doped CoFe prepared by the preparation method according to any one of claims 1-5 2 O 4 /MoS 2 Supported catalysts.
7. The Ni-doped CoFe of claim 6 2 O 4 /MoS 2 The application of the supported catalyst in catalytic oxidative degradation of organic wastewater.
8. A method for catalytic oxidative degradation of organic wastewater, comprising: adding oxidant and Ni-doped CoFe according to claim 6 into organic wastewater 2 O 4 /MoS 2 The supported catalyst is subjected to catalytic oxidation by adjusting the pH to be 3-11.
9. The method of claim 8, wherein the oxidizing agent comprises at least one of potassium hydrogen persulfate, hydrogen peroxide, sodium hypochlorite, sodium chlorate;
the oxidant and the Ni-doped CoFe 2 O 4 /MoS 2 The feeding mole ratio of the supported catalyst is 0.5-20:1.
10. The method according to claim 8 or 9, wherein the catalytic oxidation is carried out at a reaction temperature of 20 to 50 ℃ for a reaction time of 1 to 10 hours.
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