CN115634699A - 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 62
- 229910003321 CoFe Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title description 6
- 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 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 230000003197 catalytic effect Effects 0.000 claims abstract description 38
- 239000008367 deionised water Substances 0.000 claims abstract description 38
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 38
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 32
- 239000013067 intermediate product Substances 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 29
- 239000002351 wastewater Substances 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000002738 chelating agent Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 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
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000010525 oxidative degradation reaction Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 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 10
- 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
- 230000000593 degrading effect Effects 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
- 238000004519 manufacturing process Methods 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 80
- 230000000694 effects Effects 0.000 description 21
- 239000006228 supernatant Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000011943 nanocatalyst Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 241000446313 Lamella Species 0.000 description 3
- 239000007795 chemical reaction product Substances 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
- 239000002135 nanosheet Substances 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
- 230000009286 beneficial effect 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
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 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
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor 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
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000003622 immobilized catalyst Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000696 magnetic material 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
- 239000010815 organic waste Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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 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 adjusting the pH = 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 adjusting the pH = 8-14 to obtain a solution C; adding the solution C into a reaction kettle for hydrothermal reaction, and carrying out a reaction after the reaction is finishedWashing with water ethanol and deionized water, and drying to obtain Ni-doped CoFe 2 O 4 /MoS 2 A supported catalyst.
Description
Technical Field
The invention relates to the field of industrial wastewater treatment by an advanced oxidation method, in particular to 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 and chemical industry, the social attention is more and more aroused to the related environmental problems, and the medical and chemical wastewater has the characteristics of various related organic matters, high concentration, complex components, poor biodegradability and the like, so that the effective treatment of the medical and chemical wastewater is a difficult problem which troubles the high-quality development of the industry all the time.
The advanced catalytic oxidation technology generates free radicals with extremely strong activity through chemical reaction, and utilizes the free radicals and refractory organic pollutants to carry out oxidation reaction processes of ring opening, bond breaking, addition, substitution, electron transfer and the like to mineralize the free radicals into CO 2 And H 2 O, fundamentally eliminating 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 limitation of reaction conditions in an acidic environment and the pH value of about 3The right part has higher activity, and the acidic condition is unfavorable for chemical equipment; catalyst Fe 2+ After the reaction is finished, the reaction product is converted into Fe 3+ A large amount of solid waste is generated, and the efficient cyclic utilization of the catalyst cannot be realized.
CoFe 2 O 4 Having a Fe-like structure 3 O 4 Of inverse spinel structure of and Fe 3 O 4 Similar catalytic activity, is a highly efficient heterogeneous catalyst. But is easy to agglomerate due to the magnetism of the magnetic material, especially CoFe in nanometer level 2 O 4 It is difficult to maintain a stable structure, resulting in rapid decrease in catalytic oxidation efficiency as the reaction proceeds.
MoS 2 The two-dimensional lamellar structure is maintained by relatively weak van der Waals force between layers, shows excellent performances in various aspects, is widely applied to the fields of semiconductors, lubricants, catalysts and the like, and is in the form of layered nano MoS 2 The forbidden band width of the nano-sheet is about 1.2eV, the nano-sheet has catalytic activity under visible light, and the nano-sheet has a MoS structure 2 Has larger specific surface area, can provide more active sites and is a good catalyst carrier.
In conclusion, consider the nano CoFe 2 O 4 Loaded on MoS with high specific surface area 2 On lamellar support, magnetic CoFe is restricted due to active site constraint 2 O 4 Due to MoS 2 The co-catalysis of, increasing CoFe 2 O 4 Activity of (2).
The patent specification with publication number CN 112694126A discloses a preparation method of high-dispersion nickel-modified molybdenum disulfide, which comprises the steps of firstly dispersing a molybdenum-containing precursor and a sulfur-containing precursor into the same solution according to the atomic ratio of Mo: S =1: 4-1: 60, then transferring the solution into a hydrothermal synthesis kettle, reacting for 6-48 h under the condition of 140-220 ℃, centrifugally separating, washing, and vacuum drying to obtain a molybdenum disulfide material with a coordinated unsaturated Mo center; and dispersing the obtained molybdenum disulfide material with the coordination unsaturated Mo center in an aqueous solution of nickel formate according to the atomic ratio of Ni: mo = 1.
Patent specification CN 114570393A discloses oxygen vacancy-containing CoFe 2 O 4 -MoS 2 The preparation method of the supported catalyst comprises the following steps: adding an aqueous solution containing Fe salt and Co salt to MoS at room temperature 2 After the water solution is dispersed evenly by ultrasonic, a precipitator is dripped, heated, refluxed, dried and calcined, and the CoFe containing surface oxygen vacancy is obtained 2 O 4 -MoS 2 A supported catalyst.
The invention changes CoFe through doping Ni 2 O 4 Further increase the CoFe 2 O 4 Catalytic oxidation activity of (1), thereby synthesizing Ni-doped CoFe 2 O 4 /MoS 2 The supported catalyst has great application prospect in the aspect of advanced catalytic oxidation technology in the field of industrial water treatment.
Disclosure of Invention
The invention provides Ni-doped CoFe 2 O 4 /MoS 2 Preparation method of supported catalyst, synthesis of MoS with catalytic activity by hydrothermal reaction 2 Lamellar support, simultaneous incorporation of specific chelating agents and template directing agents to control MoS 2 The size and specific surface area of the lamellae; in MoS by in-situ-co-mixing precipitation method 2 Synthesis of high activity Ni-doped CoFe on support 2 O 4 A nano-catalyst; ni-doped CoFe 2 O 4 /MoS 2 The loaded catalyst has good effect of degrading the waste water containing organic matters by catalytic oxidation, the immobilization of the catalyst reduces the loss of metal ions, the circulating catalytic activity is stable, and the catalyst has certain magnetism and is convenient for the 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 The preparation method of the supported catalyst comprises 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 adjusting the pH = 2-7 to obtain a solution A;
the chelating agent comprises at least one of sodium citrate, disodium ethylene diamine tetraacetate and sodium oxalate;
the template guiding agent comprises at least one of polyacrylamide and hexadecyl trimethyl ammonium 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 for dissolving, and adjusting the pH to be = 8-14 to obtain a solution C;
the molar ratio of the nickel atoms in the nickel salt is 5-20% by taking the sum of the cobalt atoms in the cobalt salt and the nickel atoms in the nickel salt as 100%;
(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 A supported catalyst.
In the step (1), the molybdenum source comprises at least one of ammonium molybdate, sodium molybdate, potassium molybdate and the like.
In the step (1), the sulfur source comprises at least one of thiourea, thioacetamide, cysteine and the like.
MoS due to conversion problems of chemical reactions 2 In the synthesis process, the ratio of Mo and S is to synthesize the high-efficiency cocatalyst active MoS 2 The key of the vector. Preferably, in the step (1), the molar ratio of molybdenum atoms in the molybdenum source to sulfur atoms in the sulfur source is 1.
The structural form and the specific surface area are important properties of the catalyst carrier in order to obtain MoS with high specific surface area 2 Carrier in MoS 2 In the synthesis process, the invention introduces a specific chelating agent and a template directing agent to control the synthesis of lamellar MoS with high specific surface area 2 Carrier to provide more loading sites for catalyst。
Amounts of chelating agent and template directing agent for high activity MoS 2 Is also of importance.
The addition amount of the chelating agent is preferably 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 addition amount of the template directing agent is preferably 0.01-0.5% of the mass of the intermediate product B, and more preferably 0.05-0.1% of the mass of the intermediate product B.
The reaction conditions have an important influence on the synthesis and activity of the cocatalyst.
In step (1), the pH is preferably adjusted to be 4 to 6.
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 product B (MoS) obtained under the preferred conditions described above 2 Lamellar) specific surface area of 85 to 120m 2 /g，MoS 2 The thickness of the lamella is 8-15 nm.
The traditional inorganic catalyst post-treatment method mainly adopts deionized water for cleaning, but can not completely remove reactants which are not completely reacted in the reaction process, and has certain influence on the activity and the form of the catalyst.
In the preparation method, 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 catalytic activity.
The preparation method of the invention utilizes the principle of isomorphous replacement to dope, partially replaces Co ions with Ni ions, and synthesizes Ni-doped CoFe by a coprecipitation method 2 O 4 Catalyst, doping of Ni modified CoFe 2 O 4 Not only improves CoFe 2 O 4 Also broadens the catalytic activity of CoFe 2 O 4 The proper catalytic pH value range, and the Ni and Co metal ions are relatively friendly to the environment, thus being efficient and green wastewater treatmentA catalyst.
The ratio of the sum of the amount of cobalt atoms in the cobalt salt and the amount of nickel atoms in the nickel salt to the amount of iron atoms in the iron salt may be in a stoichiometric ratio of 1.
CoFe 2 O 4 Too much or too little doping amount of Ni in the crystal 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 with excessive Ni formation 2 O 4 Without CoFe 2 O 4 Good catalytic oxidation effect and high metal ion loss. Only a certain proportion of Ni and Co can produce the best effect by synergy.
In the step (3), the cobalt salt includes at least one of cobalt chloride, cobalt nitrate, cobalt sulfate, and the like.
In the step (3), the ferric 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 the step (3), the pH is preferably adjusted to be 9 to 12.
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 can not completely remove unreacted reactants in the reaction process, 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 a target product treated by the steps shows higher catalytic activity.
The invention uses MoS 2 The lamellar structure is a carrier, a large specific surface area is obtained through a specific chelating agent and a template directing agent, a catalyst attachment site is provided, and on the other hand, moS 2 The S with middle negative bivalence has reducibility, is beneficial to reducing Co in the catalyst from high valence to low valence, forms circulation and plays a role of a catalyst promoter.
To make MoS 2 The lamellar structure keeps good cocatalyst effect, the invention adopts a hydrothermal synthesis method, has no roasting process, and MoS can be damaged by roasting treatment 2 Lamellar Structure (fragmentation) and reducibility (as analyzed above, reducibility is also MoS 2 One of the reasons for the Co-catalysis) and may oxidize the divalent Ni and Co in the catalyst to lower the catalytic activity thereof. The invention uses hydrothermal synthesis method to prepare MoS 2 Without roasting process, the subsequent hydrothermal reaction on MoS 2 The structure and the cocatalyst have no influence.
The invention also provides Ni-doped CoFe prepared by the preparation method 2 O 4 /MoS 2 A supported catalyst.
In a preferred embodiment, to maintain high catalytic activity, ni-doped CoFe 2 O 4 /MoS 2 Ni-doped CoFe in supported catalysts 2 O 4 The loading amount 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 oxidation degradation of organic wastewater.
As a general inventive concept, the present invention also provides a method for catalytic oxidative degradation of organic wastewater, comprising: adding oxidant and Ni-doped CoFe into organic waste water 2 O 4 /MoS 2 The supported catalyst is adjusted to have a pH of 3 to 11, and is subjected to catalytic oxidation.
The oxidant comprises potassium hydrogen Persulfate (PMS) and hydrogen peroxide (H) 2 O 2 ) Sodium hypochlorite (NaClO), sodium chlorate (NaClO) 3 ) And the like.
Addition of oxidizing agent and catalystThe influence of the input amount on the catalytic oxidation effect and the utilization efficiency of an oxidant and the Ni-doped CoFe is obvious 2 O 4 /MoS 2 The molar ratio of the supported catalyst to be fed is preferably 0.5 to 20. Within the range of the feed 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 three metal ions of Co, fe and Ni.
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; more preferably, the organic wastewater is medical wastewater containing refractory organic matters such as toluene, aniline, heterocyclic compounds, halogenated hydrocarbons and the like, and the COD range of the wastewater is 200-1000 mg/L.
The invention adopts an in-situ-blending precipitation method to MoS by utilizing the isomorphous replacement principle 2 Synthesis of high-activity Ni-doped CoFe on carrier 2 O 4 Nanocatalyst, ni doping modified CoFe 2 O 4 Thereby increasing CoFe 2 O 4 Catalytic activity of (2), moS of large specific surface area 2 Lamellar carrier for providing active site to limit nano Ni-doped CoFe 2 O 4 The catalyst has certain cocatalyst activity, the loss rate of metal ions of the immobilized catalyst is low, the multi-cycle catalytic activity of the catalyst is stable, the pH application range is wide, and the catalyst has great practical application value and wide industrial application prospect in the field of organic wastewater degradation treatment by a heterogeneous catalytic oxidation system.
Compared with the prior art, the invention has the following beneficial effects:
1) The Ni-doped CoFe is synthesized in one step by adopting an in-situ-coprecipitation method based on isomorphous replacement principle 2 O 4 Catalyst, doping of Ni changes electron coordination, increasing 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 The nano catalyst is loaded onMoS 2 On the carrier, the agglomeration of the nano catalyst is limited, the catalytic activity of the catalyst is improved, and simultaneously the MoS prepared by the non-roasting hydrothermal synthesis method is adopted 2 The lamellar carrier has a certain cocatalyst effect, and the cocatalyst effect and the lamellar carrier are cooperated to further improve the catalytic activity;
3) Ni-doped CoFe 2 O 4 /MoS 2 The supported catalyst shows a wider pH application range, avoids the processes of adjusting acid or alkali for keeping the optimal reaction condition, saves the operation cost, simplifies the process steps, greatly reduces the use of acid and alkali, and lightens the potential harm to the environment;
4) Ni-doped CoFe in advanced oxidation reaction of refractory organic wastewater 2 O 4 /MoS 2 The supported catalyst has the advantages of high catalytic activity, low metal ion loss rate, stable multi-cycle effect and easy recovery of magnetism, is a novel high-efficiency green heterogeneous catalyst, and has wide application prospect in the field of organic wastewater treatment.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
Dissolving 9.8g (0.05 mol) of ammonium molybdate and 7.6g (0.1 mol) of thiourea in 100mL of deionized water, stirring for dissolution, adding 0.24g (3.0 percent by weight) of sodium citrate and 0.008g (0.1 percent by weight) of polyacrylamide, and adjusting the pH value to about 6 to obtain a solution A; pouring the solution A 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 7 after the reaction is finished, and obtaining an intermediate product B (the specific surface area is 115 m) 2 (iv)/g, lamella thickness 8 nm); ultrasonically dispersing the intermediate product B into an aqueous solution, 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 for dissolving, and adjusting the pH value to be about 12 to obtain a solution C; adding the solution C into water for heatingAnd (3) reacting for 12 hours at 120 ℃ in a reaction kettle, alternately washing the reaction product with absolute ethyl alcohol and deionized water after the reaction is finished until the pH value of the supernatant is about 7, drying the reaction product in a drying oven at 60 ℃ for 4 hours to obtain a target product D, and grinding the target product D for later use.
Taking 100mL of a toluene-containing medical wastewater solution, adding H according to the ratio of an oxidant to a catalyst substance of 10 according to the COD of 480mg/L and the pH value of 8.5 2 O 2 And Ni-doped CoFe 2 O 4 /MoS 2 Reaction at 25 ℃ for 2h, H 2 O 2 Adding the solution into a target substrate in equivalent of COD, measuring the COD of the reacted solution, and calculating the removal rate of the COD in the solution to be 75.2%.
Example 2
Dissolving 10.3g of sodium molybdate (0.05 mol) and 9.4g (0.125 mol) of thioacetamide in 100mL of deionized water, stirring to dissolve, adding 0.08g (1.0 wt%) of disodium ethylenediaminetetraacetate and 0.004g (0.05 wt%) of cetyltrimethylammonium bromide, and adjusting pH 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 the solution A with absolute ethyl alcohol and deionized water until the pH value of the supernatant is 7 to obtain an intermediate product B; ultrasonically dispersing the intermediate product B into an aqueous solution, 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 for dissolving, and adjusting the pH value to be about 9 to obtain a solution C; and adding the solution C into a hydrothermal reaction kettle, reacting for 8 hours at 160 ℃, alternately washing with absolute ethyl alcohol and deionized water after the reaction is finished until the pH value of the supernatant is about 7, drying for 6 hours in a 50 ℃ oven to obtain a target product D, and grinding for later use.
Taking 100mL of a certain aniline-containing hospital wastewater solution, adding PMS and Ni-doped CoFe according to the ratio of an oxidant to a catalyst substance of 20 2 O 4 /MoS 2 Reacting at 50 ℃ for 1h, adding PMS and a target substrate and the like into the solution, measuring the COD of the solution after the reaction, and calculating the removal rate of the COD of the solution to be 73.5 percent.
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 for dissolution, adding 0.16g (2.0% wt) of sodium oxalate and 0.006g (0.075% wt) of polyacrylamide, and adjusting 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 to obtain an intermediate product B; ultrasonically dispersing the intermediate product B into an aqueous solution, 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 for dissolving, and adjusting the pH value to be about 9 to obtain a solution C; and adding the solution C into a hydrothermal reaction kettle, reacting for 24 hours at 100 ℃, alternately washing with absolute ethyl alcohol and deionized water after the reaction is finished until the pH value of the supernatant is about 7, drying for 6 hours in a 50 ℃ oven to obtain a target product D, and grinding for later use.
Taking 100mL of certain chlorinated hydrocarbon-containing medical wastewater solution, adding NaClO according to the proportion that the amount ratio of an oxidant to a catalyst substance is 0.5, wherein the COD is 1000mg/L and the pH value is 6.2 3 And Ni-doped CoFe 2 O 4 /MoS 2 Reaction at 40 ℃ for 10h, naClO 3 Adding the solution and a target substrate with equal COD equivalent, measuring the COD of the reacted solution, and calculating the removal rate of the COD 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 for dissolution, adding 0.04g (0.5% wt) of sodium citrate and 0.0008g (0.01% wt) of hexadecyl trimethyl ammonium bromide, and adjusting 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 the solution A with absolute ethyl alcohol and deionized water until the pH value of the supernatant is 7 to obtain an intermediate product B; ultrasonically dispersing the intermediate product B into an aqueous solution, 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 for dissolving, and adjusting the pH value to be about 14 to obtain a solution C; and adding the solution C into a hydrothermal reaction kettle, reacting for 48 hours at 100 ℃, alternately washing with absolute ethyl alcohol and deionized water after the reaction is finished until the pH value is about 7, drying for 6 hours in a 45 ℃ oven to obtain a target product D, and grinding for later use.
Taking 100mL of a certain heterocyclic compound-containing hospital wastewater solution, adding NaClO and Ni-doped CoFe according to the proportion of 0.5 2 O 4 /MoS 2 Reacting at 25 ℃ for 2h, adding NaClO and a target substrate and other COD equivalent, measuring the COD of the solution after the reaction, and calculating the removal rate of the COD of the solution to be 76.3%.
COMPARATIVE EXAMPLE 1 (without Ni doping)
This comparative example was run under the same conditions as example 1 except that there was no Ni doping.
Dissolving 9.8g (0.05 mol) of ammonium molybdate and 7.6g (0.1 mol) of thiourea in 100mL of deionized water, stirring for dissolution, adding 0.24g (3.0 percent by weight) of sodium citrate and 0.008g (0.1 percent by weight) of polyacrylamide, and adjusting the pH value to about 6 to obtain a 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 the solution A with absolute ethyl alcohol and deionized water until the pH value of the supernatant is 7 to obtain an intermediate product B; ultrasonically dispersing the intermediate product B into an aqueous solution, adding 19.5g (0.15 mol) of cobalt chloride and 48.6g (0.3 mol) of ferric chloride, stirring for dissolving, and adjusting the pH value to be about 12 to obtain a solution C; and adding the solution C into a hydrothermal reaction kettle, reacting for 12 hours at 120 ℃, alternately washing with absolute ethyl alcohol and deionized water after the reaction is finished until the pH value of the supernatant is about 7, drying for 4 hours in a 60 ℃ oven to obtain 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 an oxidant to a catalyst substance of 10 according to the COD of 480mg/L and the pH value of 8.5 2 O 2 And CoFe 2 O 4 /MoS 2 Reaction at 25 ℃ for 2h, H 2 O 2 Adding the solution and a target substrate in equivalent amount of COD, measuring the COD of the solution after reaction, and calculating the removal rate of the COD in the solution to be 62.3%.
Comparative example 2 (MoS free) 2 Carrier)
This comparative example was run under the same conditions as example 2, except that there was no MoS 2 And (3) 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 for dissolving, and adjusting the pH value to be about 9 to obtain a solution C; and adding the solution C into a hydrothermal reaction kettle, reacting for 8 hours at 160 ℃, alternately washing with absolute ethyl alcohol and deionized water after the reaction is finished until the pH value of the supernatant is about 7, drying for 6 hours in a 50 ℃ oven to obtain 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 proportion that the quantity ratio of an oxidant to a catalyst substance is 20 2 O 4 And (3) reacting at 50 ℃ for 1h, adding PMS and a target substrate in equivalent amount, measuring the COD of the solution after the reaction, and calculating the removal rate of the COD of the solution to be 53.5%.
Comparative example 3 (Synthesis of Ni-doped CoFe 2 O 4 Resynthesis of MoS 2 )
This comparative example was run under the same conditions as example 3, except that Ni-doped CoFe was synthesized first 2 O 4 Reloading at MoS 2 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 for dissolving, and adjusting the pH value to be about 9 to obtain a solution C; and adding the solution C into a hydrothermal reaction kettle, reacting for 24 hours at 100 ℃, alternately washing with absolute ethyl alcohol and deionized water after the reaction is finished until the pH value of the supernatant is about 7, 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 to dissolve, adding 0.16g (2.0% by weight) of sodium oxalate and 0.006g (0.075% by weight) of polyacrylamide, adding the intermediate D prepared as described above, and adjusting pH to about 4 to obtain a solution A; and 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 to obtain a target product B.
Taking 100mL of certain chlorinated hydrocarbon-containing medical wastewater solution, adding NaClO according to the proportion that the amount ratio of an oxidant to a catalyst substance is 0.5, wherein the COD is 1000mg/L and the pH value is 6.2 3 And Ni-doped CoFe 2 O 4 /MoS 2 Reaction at 40 ℃ for 10h, naClO 3 Adding the solution and a target substrate in equivalent amount of COD, measuring the COD of the solution after reaction, and calculating the removal rate of the COD in the solution to be 64.7 percent.
Comparative example 4 (different product working-up method)
This comparative example was conducted under the same conditions as example 4 except that the intermediate and product workup was cleaned 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 for dissolution, adding 0.04g (0.5% wt) of sodium citrate and 0.0008g (0.01% wt) of hexadecyl trimethyl ammonium bromide, and adjusting 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, washing the solution A with deionized water until the pH value of the supernatant is 7 to obtain an intermediate product B; ultrasonically dispersing the intermediate product B into an aqueous solution, 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 for dissolving, and adjusting the pH value to be about 14 to obtain a solution C; and adding the solution C into a hydrothermal reaction kettle, reacting for 48 hours at 100 ℃, washing with deionized water until the pH value 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 certain heterocyclic compound-containing hospital wastewater solution, wherein the COD is 250mg/L, the pH value is 3.5, and the ratio of the oxidant to the catalyst substance is 0.5:1, adding NaClO and Ni-doped CoFe 2 O 4 /MoS 2 Reacting at 25 ℃ for 2h, adding NaClO and a target substrate and other COD equivalent, measuring the COD of the solution after the reaction, and calculating the removal rate of the COD of the solution to be 68.8%.
Comparative example 5 (No chelating agent and template directing agent)
Dissolving 9.8g (0.05 mol) of ammonium molybdate and 7.6g (0.1 mol) of thiourea in 100mL of deionized water, stirring for dissolving, and adjusting the pH value to be about 6 to obtain a solution A; pouring the solution A 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 7 after the reaction is finished, and obtaining an intermediate product B (the specific surface area is 57 m) 2 (g), lamella thickness 36 nm); ultrasonically dispersing the intermediate product B into an aqueous solution, 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 for dissolving, and adjusting the pH value to be about 12 to obtain a solution C; and adding the solution C into a hydrothermal reaction kettle, reacting for 12 hours at 120 ℃, alternately washing with absolute ethyl alcohol and deionized water after the reaction is finished until the pH value of the supernatant is about 7, drying for 4 hours in a 60 ℃ oven to obtain a target product D, and grinding for later use.
Taking 100mL of a toluene-containing medical wastewater solution, and performing corresponding treatmentCOD is 480mg/L, pH value is 8.5, H is added according to the proportion that the quantity ratio of an oxidant to a catalyst substance is 10 2 O 2 And Ni-doped CoFe 2 O 4 /MoS 2 Reaction at 25 ℃ for 2h, H 2 O 2 Adding the solution and a target substrate with equal COD equivalent, measuring the COD of the solution after reaction, and calculating the removal rate of the COD of the solution to be 58.3%.
Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention defined by the appended claims.
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 directing agent, stirring for dissolving, and adjusting the pH = 2-7 to obtain a solution A;
the chelating agent comprises at least one of sodium citrate, disodium ethylene diamine tetraacetate and sodium oxalate;
the template guiding agent comprises at least one of polyacrylamide and hexadecyl trimethyl ammonium 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 adjusting the pH = 8-14 to obtain a solution C;
the molar ratio of the nickel atoms in the nickel salt is 5-20% by taking the sum of the cobalt atoms in the cobalt salt and the nickel atoms in the nickel salt as 100%;
(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 A supported catalyst.
2. The method according to claim 1, wherein in the 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 molar ratio of molybdenum atoms in the molybdenum source to sulfur atoms in the sulfur source is 1;
the addition amount of the chelating agent is 0.5 to 5 percent 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 preparation method according to claim 1, wherein in the step (2), the temperature of the hydrothermal reaction is 100-200 ℃ and the time is 6-48 h.
4. The production method according to claim 1, wherein in 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 6 to 48 hours.
6. Ni-doped CoFe prepared by the method of any one of claims 1 to 5 2 O 4 /MoS 2 A supported catalyst.
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 degrading organic wastewater by catalytic oxidation is characterized by comprising the following steps: adding an oxidizing agent and the Ni-doped CoFe of claim 6 to organic wastewater 2 O 4 /MoS 2 The supported catalyst is adjusted to have a pH of 3 to 11, and is subjected to catalytic oxidation.
9. The method of claim 8, wherein the oxidant comprises at least one of potassium hydrogen persulfate, hydrogen peroxide, sodium hypochlorite, and sodium chlorate;
the oxidant and the Ni-doped CoFe 2 O 4 /MoS 2 The feeding molar ratio of the supported catalyst is 0.5-20.
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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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413921A (en) * | 2013-08-26 | 2013-11-27 | 中国科学技术大学 | Spinel magnetic ferrite/molybdenum disulfide nanometer composite material as well as preparation method and application thereof |
| CN107029801A (en) * | 2017-05-08 | 2017-08-11 | 宁夏大学 | A kind of mimetic enzyme catalyst for catalytic degradation phenol |
| CN107464652A (en) * | 2017-08-25 | 2017-12-12 | 河北工程大学 | A kind of MoS2/MFe2O4Composite aqueous magnetic flow liquid and preparation method thereof |
| CN112430829A (en) * | 2020-11-18 | 2021-03-02 | 葛宗义 | MoS2Preparation method of/S-NiCoCr-LDH composite material |
| CN114570393A (en) * | 2022-03-01 | 2022-06-03 | 南京先进生物材料与过程装备研究院有限公司 | Oxygen vacancy-containing CoFe2O4-MoS2Supported catalyst and preparation method and application thereof |
-
2022
- 2022-11-07 CN CN202211384577.8A patent/CN115634699B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413921A (en) * | 2013-08-26 | 2013-11-27 | 中国科学技术大学 | Spinel magnetic ferrite/molybdenum disulfide nanometer composite material as well as preparation method and application thereof |
| CN107029801A (en) * | 2017-05-08 | 2017-08-11 | 宁夏大学 | A kind of mimetic enzyme catalyst for catalytic degradation phenol |
| CN107464652A (en) * | 2017-08-25 | 2017-12-12 | 河北工程大学 | A kind of MoS2/MFe2O4Composite aqueous magnetic flow liquid and preparation method thereof |
| CN112430829A (en) * | 2020-11-18 | 2021-03-02 | 葛宗义 | MoS2Preparation method of/S-NiCoCr-LDH composite material |
| CN114570393A (en) * | 2022-03-01 | 2022-06-03 | 南京先进生物材料与过程装备研究院有限公司 | Oxygen vacancy-containing CoFe2O4-MoS2Supported catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| J. REVATHI ET AL.,: "Synthesis and characterization of CoFe2O4 and Ni-doped CoFe2O4 nanoparticles by chemical Co-precipitation technique for photo-degradation of organic dyestuffs under direct sunlight", PHYSICA B: PHYSICS OF CONDENSED MATTER * |
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