CN116789254A - Water body restoration method - Google Patents
Water body restoration method Download PDFInfo
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- CN116789254A CN116789254A CN202310924875.XA CN202310924875A CN116789254A CN 116789254 A CN116789254 A CN 116789254A CN 202310924875 A CN202310924875 A CN 202310924875A CN 116789254 A CN116789254 A CN 116789254A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 239000002001 electrolyte material Substances 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 claims description 11
- 229960000623 carbamazepine Drugs 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 10
- 239000012425 OXONE® Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229960002135 sulfadimidine Drugs 0.000 claims description 7
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 claims description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000005067 remediation Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 claims description 5
- 229960001259 diclofenac Drugs 0.000 claims description 5
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 5
- 229960001180 norfloxacin Drugs 0.000 claims description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- -1 bisphenol a Chemical compound 0.000 claims description 3
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 claims description 3
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 3
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 3
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 229940106691 bisphenol a Drugs 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 229960001680 ibuprofen Drugs 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 229910021645 metal ion Inorganic materials 0.000 abstract description 13
- 238000002156 mixing Methods 0.000 abstract description 11
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 230000002779 inactivation Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 description 20
- 238000006731 degradation reaction Methods 0.000 description 20
- 238000005868 electrolysis reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001027 hydrothermal synthesis Methods 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 101100382517 Cynara cardunculus cardA gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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Abstract
The application provides a water body restoration method, which comprises the steps of mixing metal doped molybdenum disulfide with monopersulfate according to a molar ratio of 0.5-2: and 0.1 to 6 of the water is put into the polluted water. The water body restoration method provided by the application has the advantages of high metal ion load, good catalytic activity, strong pollutant adsorption capacity, good stability, difficult inactivation and good restoration effect.
Description
Technical Field
The application relates to the field of water body restoration, in particular to a water body restoration method.
Background
MoS 2 As non-part ofThe homogeneous metal catalyst can effectively activate monopersulfate (PMS) to remove refractory organic matters in water. Compared with the traditional Fenton system, moS 2 Sulfate radical (SO) generated by the PMS system 4 - And has the advantages of higher catalytic performance, wider environmental adaptability and the like. In particular supported MoS 2 Monoatomic doping type MoS 2 Catalyst and MoS 2 The appearance of the metal ion coupling system makes up for MoS 2 The disadvantages of low catalytic efficiency, high cost and the like are becoming research hotspots in recent years.
However MoS 2 When the metal ion is coupled with the metal ion, the adding of the metal ion and the dissolution of Mo easily cause the problems of secondary pollution, difficult recovery and the like; moS (MoS) 2 The supported catalyst has the problems of complex preparation process, high cost of carbon-based and metal materials and the like; moS (MoS) 2 The MoS is limited by the problems of insufficient amount of medium-loaded monoatomic catalyst, poor stability in the synthesis and reaction processes and the like 2 Catalytic Activity of the PMS system. Therefore, the preparation technology with high metal ion loading and high stability is explored, and MoS is enhanced 2 Electron transfer ability with PMS, improving MoS 2 The catalytic activity of oxidized PMS is a currently urgent challenge.
The traditional material has poor performance in water body restoration, and the problem of water body restoration is difficult to solve.
Disclosure of Invention
One of the objects of the present application is: aiming at the defects of the prior art, the water body restoration method has the advantages of high metal ion loading capacity, good catalytic activity, strong pollutant adsorption capacity, good stability and difficult inactivation.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a water body restoration method comprises the steps of mixing metal doped molybdenum disulfide with monopersulfate according to a molar ratio of 0.5-2: and 0.1 to 6 of the water is put into the polluted water. The traditional Fenton system has poor catalytic performance and weak environmental adaptability. MoS (MoS) 2 The PMS system also has the problems of secondary Mo leaching pollution and difficult recovery, and the water body restoration effect is poor. The application sets certain mole between the metal doped molybdenum disulfide and monopersulfateThe catalyst has better catalytic removal effect by mixing and adding the catalyst in the molar ratio, and can play a role in activation.
Preferably, the monopersulfate is one or a mixture of several of potassium monopersulfate, sodium monopersulfate and ammonium monopersulfate.
Preferably, the pH value of the polluted water is 4-11. The metal doped molybdenum disulfide and the monopersulfate can be used in different environments, and have wide pH environments and good practicability.
Preferably, the contaminants contained in the contaminated water include one or more of diclofenac, norfloxacin, sulfamethazine, nitrobenzene, bisphenol a, ibuprofen, and carbamazepine. The water body restoration method disclosed by the application can treat more pollutants.
Preferably, the preparation method of the metal doped molybdenum disulfide comprises the steps of mixing a metal salt material, an electrolyte material, a sulfur source and a molybdenum source according to the weight ratio of 0.5-5: 150-200: 20-50: 10-40, and then placing the mixture into an electrolytic furnace for heating and melting to obtain the metal doped molybdenum disulfide.
The traditional method mostly adopts a hydrothermal method to prepare the metal doped molybdenum disulfide material, but the preparation process is generally complex, the technical difficulty is high, the equipment requirement is high, the safety performance is poor, and the material performance is relatively high. Compared with the traditional hydrothermal method, the method for preparing the metal doped molybdenum disulfide by adopting the fused salt electrolysis method has the advantages that the prepared metal doped molybdenum disulfide has high metal ion load, high catalytic activity, good stability and difficult deactivation. The fused salt electrolysis method has the characteristics of low equipment cost, easily available raw materials, easy operation and good controllability. Wherein, when mixing, the metal salt material, the electrolyte material, the sulfur source and the molybdenum source are mixed in a crucible, and are put in a vacuum drying oven for drying. And (3) when the mixed material is heated and melted, placing the mixed material in a muffle furnace for heating and melting, taking a molybdenum wire as a cathode and a glassy carbon electrode as an anode, and electrolyzing to obtain the metal doped molybdenum disulfide material. Doped incorporation of metal atoms can result in MoS near impurity atoms 2 The lattice is distorted, so that the adsorption stability of Mo bits is stronger than that of S bits. Specifically, a metal salt material, an electrolyte material, a sulfur source and a molybdenum source are mixedThe weight portion ratio is 0.5-5: 150-200: 20-50: 10-40, and the material prepared by metal doping by using the mixture ratio has better and more stable performance. In particular the molybdenum source comprises (NH 4 ) 6 Mo 7 O 24 、K 2 MoO 4 ·H 2 O、CaMoO 4 One or more of them.
Preferably, the temperature of the heating and melting is 500-1000 ℃, and the time of the heating and melting is 0.5-5 h. Preferably, the temperature of the heating and melting is 500 to 900 ℃, 600 to 800 ℃, specifically 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃; the heating and melting time is 0.5-4 h, 0.5-3 h, 1-3 h and 2-3 h, specifically, the heating and melting time is 0.5h, 0.8h, 1h, 1.5h, 2h, 2.5h, 2.8h and 3h.
Preferably, the temperature of the heating and drying is 300-500 ℃, and the time of the heating and drying is 5-8 h. Specifically, the temperature of heating and drying is 300 ℃, 350 ℃, 400 ℃, 450 ℃ and 500 ℃; the heating and drying time is 5h, 5.5h, 6h, 6.5h, 7h, 7.5h and 8h.
Preferably, the metal salt material comprises Fe (NO 3 ) 2 、Cu(NO 3 ) 2 、Ni(NO 3 ) 2 And Pd (NO) 3 ) 2 One or more of them. Heating and doping by using soluble metal salt to form a polymer cluster, and electrolyzing to obtain metal doped MoS 2 . Soluble metal salts include nitrates, chlorides, and the like, and may also include divalent metal salts.
Preferably, the electrolyte material comprises LiCl, KCl, liF-KF, naCl-KCl, li 2 CO 3 -K 2 CO 3 One or more of them. The electrolyte material is added to play a role in conducting electricity, so that the conductivity of the material is improved.
Preferably, the sulfur source comprises one or two of potassium thiocyanate, sodium thiocyanate, thiourea and sulfur dioxide.
Compared with the prior art, the application has the beneficial effects that:
1. the application enablesIn the catalytic activation of the monopersulfate by using the metal doped molybdenum disulfide, the electron transfer effect between the material and the persulfate is enhanced, the electron efficiency is 70% -87%, and the problem of secondary pollution caused by metal ion dissolution in the repairing process is avoided. Can realize complete degradation of 0-10 mg/L pollutant in 30min, and the first-order reaction kinetic constant is simple MoS 2 7 to 10 times of the total weight of the steel sheet.
2. The metal doped molybdenum disulfide is prepared by adopting a fused salt electrolysis method, and the prepared metal doped molybdenum disulfide has the advantages of high metal ion load, high catalytic activity, good stability and difficult inactivation. Compared with the traditional hydrothermal method for preparing the metal doped molybdenum disulfide material, the molten salt electrolysis method has the characteristics of low equipment cost, easily available raw materials, easy operation and good controllability.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of metal doped molybdenum disulfide.
FIG. 2 is a Ni/MoS obtained by the preparation method of the present application 2 Is an enlarged schematic view of (a).
FIG. 3 is MoS 2 Ni/MoS obtained by the preparation method of the application 2 Is a graph of the charge transfer impedance curve.
FIG. 4 is MoS 2 、Ni 0.96 S、NiClO 4 With Ni/MoS 2 Is a contrast chart of X-ray diffraction spectrum of (C).
FIG. 5 is MoS 2 、Ni/MoS 2 And a reaction rate comparison graph of PMS.
FIG. 6 is a bar graph of the degradation rate of diclofenac, norfloxacin, sulfamethazine, nitrobenzene, bisphenol A, carbamazepine by the water remediation method of the present application.
FIG. 7 is a schematic representation of the use of PMS, moS 2 And the application prepares Ni/MoS 2 Is a comparative graph of the carbamazepine polluted water restoration process.
FIG. 8 is a schematic representation of the use of PMS, moS 2 And the application prepares Pd/MoS 2 Is a comparison graph of the remediation process of the sulfa-methyl pyrimidine polluted water.
FIG. 9 is a Ni/MoS prepared by a conventional hydrothermal method and a molten salt electrolysis method 2 Is matched with the cardA comparative graph of the repair process of the malaysin polluted water.
FIG. 10 is a Ni/MoS produced by the molten salt electrolysis method of the present application 2 Effect graph in four cycle degradation experiments.
Detailed Description
In order to make the technical solution and advantages of the present application more apparent, the present application and its advantageous effects will be described in further detail below with reference to the specific embodiments, but the embodiments of the present application are not limited thereto.
Example 1
A water body restoration method comprises the steps of mixing metal doped molybdenum disulfide with potassium peroxymonosulfate oxidant according to a molar ratio of 1:3, putting the metal doped molybdenum disulfide into polluted water to repair the water body, wherein the preparation method of the metal doped molybdenum disulfide comprises the following steps:
the method comprises the steps of mixing a metal salt material, an electrolyte material, a sulfur source and a molybdenum source according to a weight part ratio of 1:160:30:20, mixing, vacuum heating and drying, and putting into an electrolytic furnace for heating and melting to obtain the metal doped molybdenum disulfide.
Wherein the temperature of heating and melting is 950 ℃, and the time of heating and melting is 4 hours;
wherein the temperature of heating and drying is 400 ℃, and the time of heating and drying is 6 hours;
wherein the metal salt material is Ni (NO) 3 ) 2 ；
Wherein the electrolyte material is LiCl and KCl with the mass ratio of 80:80 mixing;
wherein the sulfur source is potassium thiocyanate;
wherein the molybdenum source is Na 2 MoO 4 。
Example 2
Unlike the above-described embodiment 1, the following is: the molar ratio of the metal doped molybdenum disulfide to the potassium peroxymonosulfate oxidant is 0.5:1.
the remainder is the same as embodiment 1 and will not be described here again.
Example 3
Unlike example 1, the following is: the molar ratio of the metal doped molybdenum disulfide to the potassium peroxymonosulfate oxidant is 2:5.
the remainder is the same as embodiment 1 and will not be described here again.
Example 4
Unlike example 1, the following is: the molar ratio of the metal doped molybdenum disulfide to the potassium peroxymonosulfate oxidant is 1:6.
the remainder is the same as embodiment 1 and will not be described here again.
Example 5
Unlike example 1, the following is: the metal salt material, the electrolyte material, the sulfur source and the molybdenum source are mixed according to the weight part ratio of 2:170:30:30.
the remainder is the same as embodiment 1 and will not be described here again.
Example 6
Unlike example 1, the following is: the metal salt material, the electrolyte material, the sulfur source and the molybdenum source are mixed according to the weight part ratio of 2:180:35:32.
the remainder is the same as embodiment 1 and will not be described here again.
Example 7
Unlike example 1, the following is: the metal salt material, the electrolyte material, the sulfur source and the molybdenum source are mixed according to the weight part ratio of 4:185:40:38.
the remainder is the same as embodiment 1 and will not be described here again.
Example 8
Unlike example 1, the following is: the metal salt material, the electrolyte material, the sulfur source and the molybdenum source are mixed according to the weight part ratio of 0.5:150:20:10.
the remainder is the same as embodiment 1 and will not be described here again.
Example 9
Unlike example 1, the following is: the temperature of heating and melting is 950 ℃, and the time of heating and melting is 4 hours.
The remainder is the same as embodiment 1 and will not be described here again.
Example 10
Unlike example 1, the following is: the temperature of heating and melting is 950 ℃, and the time of heating and melting is 4 hours.
The remainder is the same as embodiment 1 and will not be described here again.
Example 11
Unlike example 1, the following is: the temperature of heating and melting is 950 ℃, and the time of heating and melting is 4 hours.
The remainder is the same as embodiment 1 and will not be described here again.
Comparative example 1
The traditional hydrothermal method is adopted to prepare the metal doped molybdenum disulfide, and the preparation steps are as follows:
1.1, adding ammonium molybdate and thiourea into water according to a molar ratio of 1:2, and performing ultrasonic treatment for 1-2 hours to obtain a uniformly mixed reaction solution;
1.2, transferring the reaction solution into a polytetrafluoroethylene high-pressure reaction kettle, and reacting for 24 hours at 160-200 ℃; after the reaction kettle is cooled to room temperature, the reaction liquid is removed and centrifugally separated, and then washed by deionized water and centrifugally separated for a plurality of times; the product is moved to a baking oven at the temperature of 40-60 ℃ to be dried for 12-18h; obtaining the MoS with mixed valence state 2 ；
1.3 mixing 30mL of water with 40mg of the synthesized MoS in the valence state 2 Adding the mixture into a three-neck flask, and performing ultrasonic treatment for 1-2 hours to fully and uniformly mix the mixture to obtain a mixed solution;
1.4 preparing 50mL of 0.001-0.002 mol of metal ion aqueous solution, mixing the metal ion aqueous solution with the mixed solution after ultrasonic treatment, and fully stirring under reflux;
1.5 after the solution in the step 1.4 is cooled, carrying out suction filtration, cleaning and freeze drying to obtain metal ion doped MoS 2 。
The molar ratio of the prepared metal doped molybdenum disulfide to the potassium peroxymonosulfate oxidant is 1: and 3, putting the water into polluted water to repair the water body.
Comparative example 2
Directly using potassium monopersulfate oxidant to restore the polluted water.
Comparative example 3
And the molybdenum disulfide is directly used for repairing the water body of the polluted water.
The restoration effect of the water restoration of the above embodiment is recorded, the restoration effect is recorded with the overall degradation rate as a reference index, and table 1 is recorded. Wherein the polluted water contains diclofenac, norfloxacin, sulfamethazine, nitrobenzene, bisphenol A, carbamazepine and the like.
TABLE 1
| Project | Degradation rate% | Project | Degradation rate% |
| Example 1 | 96 | Example 2 | 94 |
| Example 3 | 94 | Example 4 | 95 |
| Example 5 | 94 | Example 6 | 93 |
| Example 7 | 93 | Example 8 | 94 |
| Example 9 | 94 | Example 10 | 93 |
| Example 11 | 94 | Comparative example 1 | 70 |
| Comparative example 2 | 20 | Comparative example 3 | 60 |
By comparing the examples 1-11 with the comparative examples 1-3, the metal doped molybdenum disulfide prepared by the application has higher active sites, is not easy to inactivate, has good stability, and has good effect when being applied to polluted water for water body restoration.
From FIG. 1, it can be obtained that the molten salt electrolysis method of the application is used to heat an electrolyte material, a metal salt material, a molybdenum source and a sulfur source to form a cluster, and then the metal doped MoS is obtained by electrolysis 2 . FIG. 2 shows a metal-doped MoS prepared by doping with Ni metal element 2 A material. As can be seen from FIG. 3, ni/MoS 2 Possess smaller charge transfer impedance (Rct), indicate that the electron can participate in the charge transfer process more easily, faster, improve PMS activation efficiency, also can further prove that doping Ni can promote electron transfer kinetics process simultaneously. As can be seen from FIG. 4, ni/MoS 2 XRD diffraction peaks of (2) and NiClO 4 、Ni 0.96 S、MoS 2 Has good corresponding relation, which shows that Ni is successfully doped into MoS by substituting Mo and forming coordination bond with S 2 In the crystal lattice. From FIG. 5, it can be derived that Ni/MoS 2 The first order reaction rate constants are PMS and MoS 2 5.96 and 6.68 times, ni/MoS of the application 2 Has higher reactivity. As can be seen from FIG. 6, the Ni/MoS of the present application 2 Has good degradation rate to diclofenac, norfloxacin, sulfamethazine, nitrobenzene, bisphenol A and carbamazepine, the degradation rate is more than 73 percent, and the degradation rate to carbamazepine is as high as92%, the water body restoration effect is good. As can be seen from the comparison of FIG. 7, the water body is repaired by adopting the traditional PDS system, the degradation rate of carbamazepine is 75 percent, the water body is directly repaired by adopting molybdenum disulfide, the degradation rate of carbamazepine is 60 percent, but the Ni/MoS prepared by the application 2 The repairing effect is higher when repairing, and the repairing effect reaches 95% within one hour. As can be seen from the comparison of FIG. 8, the conventional PDS system is adopted to repair the water body, the degradation rate of the sulfamethazine is 75%, the molybdenum disulfide is directly adopted to repair the water body, the degradation rate of the sulfamethazine is 60%, but the Pd/MoS prepared by the application 2 The repairing effect is higher when repairing, and the repairing effect reaches 95% within one hour. As can be seen from FIG. 9, the metal doped molybdenum disulfide prepared by the fused salt electrolysis method has better catalytic degradation effect than the metal doped molybdenum disulfide prepared by the traditional hydrothermal method, the degradation rate of the metal doped molybdenum disulfide prepared by the fused salt electrolysis method on carbamazepine is up to 97%, and the degradation rate of the metal doped molybdenum disulfide prepared by the traditional hydrothermal method on carbamazepine is only 70%. As can be seen from FIG. 10, ni/MoS 2 The degradation efficiency can reach more than 70% in the degradation experiment for 4 times, and only tiny reduction occurs in the degradation experiment for the second time, and the degradation performance tends to be stable and has good stability after 2 times of circulation.
In summary, the metal doped molybdenum disulfide prepared by the preparation method provided by the application has better catalytic performance and stability compared with the metal doped molybdenum disulfide prepared by the traditional hydrothermal method.
Variations and modifications of the above embodiments will occur to those skilled in the art to which the application pertains from the foregoing disclosure and teachings. Therefore, the present application is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in light of the present teachings. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present application in any way.
Claims (10)
1. A water body restoration method is characterized in that metal doped molybdenum disulfide and monopersulfate are mixed according to the mole ratio of 0.5-2: and 0.1 to 6 of the water is put into the polluted water.
2. The method for restoring water according to claim 1, wherein the monopersulfate is one or a mixture of several of potassium monopersulfate, sodium monopersulfate and ammonium monopersulfate.
3. The method for restoring water according to claim 1, wherein the ph of the polluted water is 4 to 11.
4. The method of water remediation according to claim 1 wherein the contaminants contained in the contaminated water include one or more of diclofenac, norfloxacin, sulfamethazine, nitrobenzene, bisphenol a, ibuprofen, and carbamazepine.
5. The water body restoration method according to claim 1, wherein the preparation method of the metal doped molybdenum disulfide is characterized in that a metal salt material, an electrolyte material, a sulfur source and a molybdenum source are mixed according to the weight ratio of 0.5-5: 150-200: 20-50: 10-40, and then placing the mixture into an electrolytic furnace for heating and melting to obtain the metal doped molybdenum disulfide.
6. The method for repairing a water body according to claim 5, wherein the temperature of the heating and melting is 500-1000 ℃ and the time of the heating and melting is 0.5-5 h.
7. The water restoration method according to claim 5, wherein the temperature of heating and drying is 300-500 ℃ and the time of heating and drying is 5-8 hours.
8. The method of water remediation of claim 5 wherein the metal salt material includes Fe (NO 3 ) 2 、Cu(NO 3 ) 2 、Ni(NO 3 ) 2 And Pd (NO) 3 ) 2 One or more of them.
9. The method of water remediation according to claim 5 wherein the electrolyte material comprises LiCl, KCl, liF-KF, naCl-KCl, li 2 CO 3 -K 2 CO 3 One or more of them.
10. The method of water remediation according to claim 5 wherein the source of sulfur comprises one or both of potassium thiocyanate, sodium thiocyanate, thiourea, sulfur dioxide.
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