CN114713241A - Preparation method and application of molybdate intercalated hydrotalcite of heterogeneous Fenton catalyst - Google Patents
Preparation method and application of molybdate intercalated hydrotalcite of heterogeneous Fenton catalyst Download PDFInfo
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- CN114713241A CN114713241A CN202210466229.9A CN202210466229A CN114713241A CN 114713241 A CN114713241 A CN 114713241A CN 202210466229 A CN202210466229 A CN 202210466229A CN 114713241 A CN114713241 A CN 114713241A
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- intercalated hydrotalcite
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 38
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 38
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 8
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 8
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 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 abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 230000000593 degrading effect Effects 0.000 claims abstract description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 230000015556 catabolic process Effects 0.000 claims description 10
- 238000006731 degradation reaction Methods 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 20
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910015667 MoO4 Inorganic materials 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a preparation method of molybdate intercalated hydrotalcite of an out-of-phase Fenton catalyst, which comprises the following steps: dissolving ferric nitrate, magnesium nitrate and sodium molybdate in deionized water, mixing, adjusting the pH to 9-10, magnetically stirring for 40-60min, transferring into a high-pressure reaction kettle lined with polytetrafluoroethylene, carrying out hydrothermal synthesis for 24h, centrifuging by a centrifuge, collecting lower-layer precipitates, washing by using deionized water and ethanol, and drying to obtain an out-phase Fenton catalyst molybdate intercalated hydrotalcite; the invention also provides application of the molybdate intercalated hydrotalcite of the heterogeneous Fenton catalyst in degrading trichlorophenol. The heterogeneous Fenton catalyst is prepared by a simple one-step hydrothermal method, has a good layered structure and a stable structure, can effectively generate singlet oxygen in a hydrogen peroxide existing system, and has excellent Fenton catalytic performance in a complex water quality background.
Description
Technical Field
The invention relates to the field of water treatment of trichlorophenol pollutants. More specifically, the invention relates to a preparation method and application of a heterogeneous Fenton catalyst molybdate intercalated hydrotalcite.
Background
In recent years, with the rapid development of economy in China, organic pollutants, particularly persistent organic pollutants represented by chlorinated organic pesticides, are difficult to remove by the traditional water treatment method due to the characteristics of biological accumulation and high toxicity. Advanced oxidation technologies (AOPs) represented by fenton oxidation technology are one of the most promising technologies due to their advantages of high efficiency, universality, complete degradation, etc.
While the most dominant active oxygen species in most fenton systems is OH, which has a high redox potential (Φ ═ 2.8V). And various Fenton catalysts have been shown to activate H2O2OH is generated to degrade TCP with high efficiency. In the past decades, Fenton's advanced oxidation processes for treating chlorinated organic pollutants (TCP) water have mostly focused on the use of OH to degrade organic pollutants. But the water pollution gradually presents the characteristics of diversification, complication and the like. The components of industrial and agricultural wastewater and human domestic wastewater are increasingly complex, and complex water quality parameters such as various coexisting ions, Natural Organic Matters (NOM), different pH values and the like in water bring new challenges for treating TCP pollutant water by OH. Although highly active OH can effectively degrade TCP, the complexity of water quality environmental parameters greatly influences the degradation efficiency of OH on TCP due to the short survival time (half-life period is 10-3 mus) and short migration distance of OH. While studies have less focus on non-free radical singlet oxygen: (1O2) And the method has wide application prospect in the field of environmental pollution control for insensitivity of water quality parameters. Non-radical with respect to free-radical OH which is susceptible to quenching1O2Can be adapted to complex water quality environment. And is1O2Has long half-life (2-4 mus)) And has a strong oxidation-reduction potential (Φ ═ 2.2V).
However, for1O2The mechanism of formation in the Fenton reaction system is not clear, especially from OH and superoxide radical (O2)·-) to1O2The transformation mechanism of (2) is controversial. From the perspective of the current regulation and control method, the following problems mainly exist: firstly, additional energy is needed, and the process cost is increased; ② high active oxygen species toward1O2Loss in the conversion process and easily cause secondary pollution problems. Therefore, aiming at the complex treatment of the TCP polluted water body, how to regulate and control1O2The generation path of the Fenton is paid more attention by researchers, and the generation path is also the key for promoting the application of the Fenton technology in the actual water body remediation.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing heterogeneous fenton catalyst molybdate intercalated hydrotalcite comprising the steps of:
s1, dissolving ferric nitrate, magnesium nitrate and sodium molybdate in deionized water, and continuously stirring to form a clear solution;
s2, adjusting the pH value of the clear solution to 9-10 at room temperature, magnetically stirring for 40-60min, transferring the clear solution into a high-pressure reaction kettle lined with polytetrafluoroethylene, and carrying out hydrothermal treatment for 24h at the temperature of 110-;
s3, centrifuging the reaction product through a centrifugal machine, collecting the lower precipitate, washing with deionized water and ethanol, and drying to obtain the heterogeneous Fenton catalyst molybdate intercalated hydrotalcite MgFe-2MoO4。
Preferably, the pH adjustment is performed using sodium hydroxide solution.
Preferably, the deionized water in step S1 is boiled for 30min to remove CO in the water2And then standing the cooled deionized water.
Preferably, the molar ratio of the iron nitrate, the magnesium nitrate and the sodium molybdate is 1: 3: 1-3.
Preferably, the drying in step S3 is freeze-drying.
The invention provides application of molybdate intercalated hydrotalcite of an out-of-phase Fenton catalyst in degradation of trichlorophenol.
The invention provides a method for degrading trichlorophenol by using an out-of-phase Fenton catalyst molybdate intercalated hydrotalcite, which comprises the step of carrying out reaction on molybdate intercalated hydrotalcite MgFe-2MoO4Adding into trichlorophenol solution, stirring to make it reach adsorption equilibrium, adding H2O2An aqueous solution.
The invention at least comprises the following beneficial effects:
the invention utilizes a simple one-step hydrothermal method to prepare MgFe-2MoO4The Fenton catalyst is safe and environment-friendly in production process and suitable for industrial production scale. In addition, the Fenton catalyst prepared by the method has a good layered structure and a stable structure, can effectively generate singlet oxygen in a hydrogen peroxide existing system, and has excellent Fenton catalytic performance in water within the pH value range of 5-11. .
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 shows an example of a mono-molybdate intercalated hydrotalcite MgFe-2MoO4An X-ray diffraction (XRD) pattern of the sample;
FIG. 2 shows an example of a molybdate intercalated hydrotalcite MgFe-2MoO4Infrared (FITR) map of the sample;
FIG. 3 is a schematic representation of example mono-molybdate intercalated hydrotalcite MgFe-2MoO4A Scanning Electron Microscope (SEM) image of the sample;
FIG. 4 is the MgFe-2MoO hydrotalcite intercalated with molybdate in example two4The accumulation amount of singlet oxygen generated by disproportionating hydrogen peroxide during catalytic degradation;
FIG. 5 shows a comparative example in which molybdate-intercalated hydrotalcite MgFe-2MoO4The Fenton catalytic performance curve diagram of the sample;
FIG. 6 shows MgFe-2MoO under different pH conditions in example II4Fenton catalytic performance curve diagram of Fenton catalyst.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.
Example 1: preparation of molybdate intercalated hydrotalcite catalyst MgFe-2MoO4
6mmol of magnesium nitrate hexahydrate, 2mmol of ferric nitrate nonahydrate and 4mmol of sodium molybdate were dispersed in 120mL of water and stirred continuously to form a clear solution. 2M NaOH solution was added dropwise at room temperature to adjust pH to 10 and magnetic stirring was continued for 40 min. The mixture was then transferred to a 200mL autoclave and reacted at 120 ℃ for 24 h. Centrifuging the product obtained after the reaction for 5min at the centrifugal rate of 4000rpm by a centrifugal machine, pouring out the upper solution, washing the obtained lower precipitate with water and ethanol for at least 3 times, and freeze-drying the product for 24h to obtain the heterogeneous Fenton catalyst molybdate intercalated hydrotalcite MgFe-2MoO4。
FIG. 1 is an X-ray diffraction (XRD) pattern of the product of this example after hydrothermal treatment at 120 deg.C for 24h, from which it can be seen that the product is hydrotalcite MgFe-2MoO with obvious layered structure4And no other impurity phases are present.
Fig. 2 and 3 are respectively an infrared (FITR) image and a Scanning Electron Microscope (SEM) image of the product of this example, from which it can be seen that molybdate successfully intercalates into the hydrotalcite layers, and the prepared catalyst is in the form of stacked sheets, uniform in size, and uniform in distribution.
Example 2: preparation of molybdate intercalated hydrotalcite catalyst MgFe-2MoO4
6mmol magnesium nitrate hexahydrate, 2mmol ferric nitrate nonahydrate and 2mmol sodium molybdate were dispersed in 120mL water and stirred continuously to form a clear solution. 2M NaOH solution was added dropwise to the mixture at room temperature to adjust the pH of the mixture to 9, and magnetic stirring was continued for 60 min. The mixture was then transferred to a 200mL reaction kettleAnd reacting for 24 hours at 110 ℃. Centrifuging the product obtained after the reaction for 5min at the centrifugal rate of 4000rpm by a centrifugal machine, pouring out the upper solution, washing the obtained lower precipitate with water and ethanol for at least 3 times, and freeze-drying the product for 24h to obtain the heterogeneous Fenton catalyst molybdate intercalated hydrotalcite MgFe-2MoO4。
Example 3: preparation of molybdate intercalated hydrotalcite catalyst MgFe-2MoO4
6mmol magnesium nitrate hexahydrate, 2mmol iron nitrate nonahydrate and 6mmol sodium molybdate were dispersed in 120mL water and stirred continuously to form a clear solution. 2M NaOH solution was added dropwise at room temperature to adjust the pH of the mixture to 10, and magnetic stirring was continued for 50 min. The mixture was then transferred to a 200mL autoclave and reacted at 130 ℃ for 24 h. Centrifuging the product obtained after the reaction for 5min at the centrifugal rate of 4000rpm by a centrifugal machine, pouring out the upper solution, washing the obtained lower precipitate with water and ethanol for at least 3 times, and freeze-drying the product for 24h to obtain the heterogeneous Fenton catalyst molybdate intercalated hydrotalcite MgFe-2MoO4。
Example 4: test of molybdate intercalated hydrotalcite catalyst MgFe-2MoO4Catalytic performance of
30mg of MgFe-2MoO from example 14Adding a catalyst into 50mL of trichlorophenol solution with the concentration of 10ppm, adjusting the pH of the solution to 5-11, magnetically stirring the mixture solution for 30min to reach adsorption balance, and adding 0.2mLH2O2The fenton catalytic reaction was performed. 2mL of suspended sample is taken out at certain time intervals in the reaction process, then filtered by a 0.45-micrometer organic filter membrane, 20 mu L of sodium thiosulfate is added to quench unreacted hydrogen peroxide, and the corresponding concentration of the obtained solution is measured by high performance liquid chromatography.
Comparative example 1: in the examples, the catalyst Na without intercalation treatment is added2MoO4The other steps are the same as in example 4.
Furfuryl Alcohol (FFA) can react with singlet oxygen specifically, so that the catalytic degradation rate can be quantitatively analyzed by detecting the change of concentration in the catalytic process of furfuryl alcohol, and then the decomposition efficiency and the decomposition amount of FFA are measured by HPLC (high performance liquid chromatography)Is calculated to obtain1O2The rate of generation and the cumulative amount. Steady state1O2The concentration can be converted from the following formula.
In the formula, k1O2 and FFA are the reaction rate constants of singlet oxygen and furfuryl alcohol.
Molybdate intercalated hydrotalcite in example 4 and Na in comparative example 12MoO4The accumulation of singlet oxygen produced by disproportionating hydrogen peroxide is shown in FIG. 4, and MgFe-2MoO of example 44The degradation effect of trichlorophenol is shown in fig. 5, and the degradation effect of trichlorophenol under different pH conditions is shown in fig. 6. As can be seen from FIG. 4, when the catalyst without intercalation treatment is added, trichlorophenol is hardly degraded under the condition of adding hydrogen peroxide, while in the molybdate intercalated hydrotalcite reaction system, 0.2mLH is added in the reaction system2O2And then, the degradation of trichlorophenol reaches more than 99%, and the molybdate intercalated hydrotalcite can effectively disproportionate hydrogen peroxide to stably and efficiently generate more singlet oxygen. As can be seen from FIGS. 5 and 6, the molybdate intercalated hydrotalcite shows better pollutant degradation effect under different pH conditions.
As can be seen, MgFe-2MoO4Can disproportionate hydrogen peroxide to generate singlet oxygen and has good catalytic performance. The catalyst not only can disproportionate hydrogen peroxide to generate singlet oxygen under the conventional acidic condition of Fenton reaction, but also can disproportionate hydrogen peroxide under the alkaline condition, and has good catalytic performance. The method lays a good foundation for the application of the Fenton technology in the complex water body environment under the alkaline condition.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the embodiments shown and described without departing from the generic concept as defined by the claims and their equivalents.
Claims (7)
1. A preparation method of molybdate intercalated hydrotalcite of a heterogeneous Fenton catalyst is characterized by comprising the following steps:
s1, dissolving ferric nitrate, magnesium nitrate and sodium molybdate in deionized water, and continuously stirring to form a clear solution;
s2, adjusting the pH value of the clear solution to 9-10 at room temperature, magnetically stirring for 40-60min, transferring the clear solution into a high-pressure reaction kettle lined with polytetrafluoroethylene, and carrying out hydrothermal treatment for 24h at the temperature of 110-;
s3, centrifuging the reaction product through a centrifugal machine, collecting the lower precipitate, washing with deionized water and ethanol, and drying to obtain the heterogeneous Fenton catalyst molybdate intercalated hydrotalcite MgFe-2MoO4。
2. The method of preparing the heterogeneous fenton catalyst molybdate intercalated hydrotalcite of claim 1 wherein the pH adjustment is performed with sodium hydroxide solution.
3. The method of preparing the heterogeneous Fenton' S catalyst molybdate intercalated hydrotalcite of claim 1, wherein the deionized water in step S1 is boiled for 30min to remove CO in the water2And then standing the cooled deionized water.
4. The method of preparing a heterogeneous fenton catalyst molybdate intercalated hydrotalcite according to claim 1 wherein the molar ratio of said iron nitrate, said magnesium nitrate and said sodium molybdate is 1: 3: 1-3.
5. The method for preparing the heterogeneous fenton catalyst molybdate intercalated hydrotalcite of claim 1, wherein the drying in step S3 is freeze drying.
6. Use of the heterogeneous Fenton catalyst molybdate intercalated hydrotalcite prepared by the preparation method according to any one of claims 1 to 5 in degradation of trichlorophenol.
7. The method for degrading trichlorophenol by using the heterogeneous Fenton catalyst molybdate intercalated hydrotalcite prepared by the preparation method of any one of claims 1 to 5, wherein the molybdate intercalated hydrotalcite MgFe-2MoO4Adding into trichlorophenol-containing solution, stirring to reach adsorption balance, adding H2O2An aqueous solution.
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