CN116621208A - Double-layer layered metal hydroxide, and preparation method and application thereof - Google Patents
Double-layer layered metal hydroxide, and preparation method and application thereof Download PDFInfo
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- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 96
- 150000004692 metal hydroxides Chemical class 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 84
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002244 precipitate Substances 0.000 claims abstract description 34
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006228 supernatant Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims description 27
- 230000015556 catabolic process Effects 0.000 claims description 23
- 238000006731 degradation reaction Methods 0.000 claims description 23
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 18
- 239000002957 persistent organic pollutant Substances 0.000 claims description 15
- 229940106691 bisphenol a Drugs 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 10
- 229940043267 rhodamine b Drugs 0.000 claims description 10
- 229960005404 sulfamethoxazole Drugs 0.000 claims description 10
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims description 10
- -1 aluminum ions Chemical class 0.000 claims description 9
- 230000007613 environmental effect Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000002351 wastewater Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 55
- 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 16
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000004317 sodium nitrate Substances 0.000 description 5
- 235000010344 sodium nitrate Nutrition 0.000 description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 239000012425 OXONE® Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 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 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The application discloses a double-layer layered metal hydroxide, a preparation method and application thereof, wherein the preparation method comprises the steps of preparing a first solution and a second solution, the first solution comprises divalent metal ions and trivalent metal ions, and the second solution comprises nitrate and formamide; heating the second solution to a reaction temperature, simultaneously dropwise adding the first solution and the sodium hydroxide solution into the second solution, stirring at a constant temperature, centrifugally washing, and collecting a precipitate; placing the precipitate in deionized water, performing ultrasonic treatment, centrifuging, taking supernatant, and drying to obtain the double-layer layered metal hydroxide. According to the application, the metal ion solution and the sodium hydroxide solution are synchronously added into the formamide and the nitrate solution in a dropwise manner, ultrasonic stripping is adopted to prepare the double-layer layered metal hydroxide, and the prepared double-layer layered metal hydroxide is ensured to be of a double-layer structure by controlling reaction conditions and parameters, so that the accurate control of the thickness of the laminate is realized; meanwhile, the preparation process is simple, the yield is high, and the method is suitable for industrial mass production.
Description
Technical Field
The application belongs to the technical field of sewage treatment, and particularly relates to a double-layer layered metal hydroxide, and a preparation method and application thereof.
Background
With the improvement of detection technology and the increasingly strict water quality safety standard, the refractory organic pollutants (such as medicines, endocrine disruptors and the like) in the water body are more concerned and researched, and the exposure risks of the refractory organic pollutants are gradually increased and the refractory organic pollutants are greatly harmful to human bodies. Meanwhile, the conventional water treatment processes such as coagulation, precipitation, filtration and the like are difficult to remove and degrade organic pollutants.
The heterogeneous catalytic activation technology based on the advanced oxidation technology of persulfate has been used for treating refractory organic pollutants because of the advantages of simple operation, high separability recovery rate, no limitation of pH conditions, good recycling stability and the like. However, the existing persulfate has low efficiency of degrading organic pollutants, long degradation time, high cost and incapability of meeting treatment requirements. With the rapid development of economy and industry, the volume of wastewater containing refractory organic pollutants is huge, and development of a high-efficiency and low-cost treatment technology is needed, so that the efficiency of degrading organic matters by persulfate is improved, the degradation time of pollutants is reduced, and the water treatment cost is reduced.
Disclosure of Invention
The application aims to provide a double-layer layered metal hydroxide, a preparation method and application thereof, which are used for solving the technical problems of reduced efficiency and long degradation time of organic pollutants degraded by persulfate in the prior art.
In order to achieve the above purpose, the application adopts a technical scheme that:
provided is a method for producing a double layered metal hydroxide, comprising:
preparing a first solution and a second solution, wherein the first solution comprises divalent metal ions and trivalent metal ions, and the second solution comprises nitrate and formamide;
heating the second solution to a reaction temperature, simultaneously dropwise adding the first solution and the sodium hydroxide solution into the second solution, keeping the second solution constant temperature and continuously stirring in the dropwise adding process, centrifugally washing after the dropwise adding is finished, and collecting a precipitate;
and placing the precipitate in deionized water, performing ultrasonic treatment, centrifuging, taking supernatant, and drying to obtain the double-layer layered metal hydroxide.
In one or more embodiments, the divalent metal ion is cobalt ion, the trivalent metal ion is aluminum ion, the molar concentration of the divalent metal ion in the first solution is 0.01-10 mol/L, and the molar concentration of the divalent metal ion is 2-4 times that of the trivalent metal ion.
In one or more embodiments, the volume fraction of the formamide in the second solution is 15-25 vt, and the molar concentration of the nitrate is 0.01-50 mol/L.
In one or more embodiments, the concentration of the sodium hydroxide solution is 0.2 to 0.5mol/L.
In one or more embodiments, the reaction temperature is 60 to 80 ℃.
In one or more embodiments, in the step of simultaneously adding the first solution and the sodium hydroxide solution to the second solution, a volume ratio of the first solution to the second solution is (5-100): 10, the volume ratio of the dropwise adding amount of the sodium hydroxide solution to the second solution is (5-100): and 10, the dropping speed of the first solution and the sodium hydroxide solution is 0.1-5 ml/min. In one or more embodiments, the step of collecting the precipitate is performed at least 3 times by centrifugal washing after the completion of the dropping; and placing the precipitate in deionized water, carrying out ultrasonic treatment, wherein the ultrasonic treatment time in the step of centrifuging is 10-100 min.
In order to achieve the above purpose, another technical scheme adopted by the application is as follows:
there is provided a double layered metal hydroxide prepared by the method of any one of the above embodiments.
In order to achieve the above object, another technical scheme adopted by the present application is as follows:
there is provided the use of a double layered metal hydroxide according to any of the embodiments above for catalyzing persulfate degradation of environmental organic pollutants.
In one or more embodiments, the double layered metal hydroxide and persulfate are added to wastewater including environmental organic contaminants including one or more combinations of rhodamine B, bisphenol a, sulfamethoxazole to form a catalytic oxidation reaction system, wherein the concentration of the double layered metal hydroxide in the catalytic oxidation reaction system is 0.1 g/L.
Compared with the prior art, the application has the beneficial effects that:
according to the application, the metal ion solution and the sodium hydroxide solution are synchronously added into the formamide and the nitrate solution in a dropwise manner, the metal ion, the formamide and the nitrate concentration are controlled, the layered metal hydroxide with a double-layer structure grows, then the double-layer layered metal hydroxide is stripped and uniformly dispersed in the supernatant by ultrasonic stripping, the double-layer layered metal hydroxide is obtained after drying, the reactant concentration and the reaction step are controlled, the prepared layered metal hydroxide is ensured to be of a double-layer structure, the accurate control of the thickness of the laminate is realized, and meanwhile, the preparation flow is simple, the yield is high, and the method is suitable for industrial mass production;
the double-layer layered metal hydroxide prepared by the method is of a double-layer structure, has excellent stability in structure, and has a large number of exposed catalytic sites, so that a catalytic oxidation reaction system can be formed by the double-layer layered metal hydroxide and persulfate, and as the double-layer layered metal hydroxide is exposed with a large number of catalytic sites, the persulfate can be obviously promoted to generate more sulfate radicals, hydroxyl radicals and other active oxidants to oxidize and decompose organic pollutants, finally water and carbon dioxide are generated, and under the activation effect of the double-layer layered metal hydroxide, the degradation efficiency of the persulfate on rhodamine B, bisphenol A and sulfamethoxazole can reach 100%, 98.1% and 99.5% respectively.
Drawings
FIG. 1 is a schematic flow chart of an embodiment of a method for producing a double layered metal hydroxide according to the present application;
FIG. 2 is a schematic reaction diagram showing an embodiment of a method for producing a double layered metal hydroxide according to the present application;
FIG. 3 is an XRD diffraction pattern of the double layered metal hydroxides prepared in example 1 and example 2 of the present application;
FIG. 4 is a TEM image of the double layered metal hydroxide of example 1;
FIG. 5 is a TEM image of the double layered metal hydroxide of example 2;
FIG. 6 is an atomic force microscope scanning analysis chart of a double layered metal hydroxide of example 1 of the present application, wherein a is an AFM scanning chart of the double layered metal hydroxide of example 1, and b is a graph of the results of the height test of the horizontal line area in a;
FIG. 7 is an atomic force microscope scanning analysis chart of a double layered metal hydroxide of example 2 of the present application, wherein a is an AFM scanning chart of the double layered metal hydroxide of example 2, and b is a graph of the results of the height test of the horizontal line area in a;
FIG. 8 is an XPS spectrum of a double layered metal hydroxide according to example 1 of the present application, wherein a is an XPS spectrum of cobalt element and b is an XPS spectrum of aluminum element;
FIG. 9 is a graph of the degradation of organic contaminants by potassium hydrogen peroxymonosulfate catalyzed by a double layered metal hydroxide of example 1 of the present application;
FIG. 10 is a graph of the degradation of organic contaminants by potassium hydrogen peroxymonosulfate catalyzed by a double layered metal hydroxide of example 2 of the present application;
FIG. 11 shows the degradation curve of potassium hydrogen peroxymonosulfate of the control group of effect example 2 of the present application.
Detailed Description
The present application will be described in detail below with reference to the embodiments shown in the drawings. The embodiments are not intended to limit the application, but structural, methodological, or functional modifications of the application from those skilled in the art are included within the scope of the application.
At present, the key of the catalytic persulfate technology is how to improve the efficiency of catalytic degradation of organic matters and reduce the degradation time of pollutants. The two-dimensional material has special physical and chemical properties, and has great application potential, such as a metal layered hydroxide structure, and the layered structure can provide larger specific surface area, so that catalytic sites are more exposed, and the effect of improving the reaction rate is achieved.
However, the number of layers of the existing metal layered hydroxide is large, so that more exposure of catalytic sites is affected. In order to solve the problems, the applicant develops a layered metal hydroxide catalyst with a double-layer structure, which has a stable structure and a small number of layers, can greatly increase the exposure quantity of catalytic sites, thereby remarkably increasing the reaction rate, remarkably catalyzing and increasing the efficiency of persulfate for degrading environmental organic matters and reducing the degradation time when being applied to the field of sewage treatment.
Specifically, referring to fig. 1, fig. 1 is a schematic flow chart of an embodiment of a method for preparing a double layered metal hydroxide according to the present application.
As shown in fig. 1, the preparation method comprises:
s100, preparing a first solution and a second solution.
Wherein the first solution comprises divalent metal ions and trivalent metal ions; the second solution includes a nitrate salt and a formamide.
In one embodiment, the divalent metal ion may be a cobalt ion and the trivalent metal ion may be an aluminum ion.
The molar concentration of the divalent metal ions in the first solution may be 0.01 to 10mol/L, and the molar concentration of the divalent metal ions may be 2 to 4 times the molar concentration of the trivalent metal ions.
In one embodiment, the volume fraction of formamide in the second solution may be 15-25 vt% and the molar concentration of nitrate is 0.01-50 mol/L.
The nitrate may be sodium nitrate, potassium nitrate, or the like, and the effect of the present embodiment can be achieved.
And S200, heating the second solution to a reaction temperature, simultaneously dropwise adding the first solution and the sodium hydroxide solution into the second solution, keeping the second solution constant temperature and continuously stirring in the dropwise adding process, centrifugally washing after the dropwise adding is finished, and collecting a precipitate.
Wherein the reaction temperature may be 60-80 ℃.
In one embodiment, the concentration of the sodium hydroxide solution may be 0.2 to 0.5mol/L, and the volume ratio of the first solution to the second solution may be (5 to 100): 10, the volume ratio of the dropwise adding amount of the sodium hydroxide solution to the second solution can be (5-100): 10, the dropping speed of the first solution and the sodium hydroxide solution can be 0.1-5 ml/min.
The sodium hydroxide solution and the first solution are synchronously added dropwise, and the sodium hydroxide solution is used for ensuring that the pH value of the reaction system is more than 9, thereby being beneficial to the growth of the layered metal hydroxide. The reaction system is kept at a constant temperature and continuously stirred, and when divalent metal ions and trivalent metal ions are added into the second solution in a dropwise manner, layered metal hydroxides begin to grow under alkaline conditions, and nitrate ions serve as interlayer anions to connect the layered structure.
Due to the existence of formamide in the second solution, the formamide can replace nitrate ions to inhibit the Z-axis growth of the layered hydroxide, so that the double-layer layered metal hydroxide with fewer layers is grown, the number of layers is reduced, and the exposure of catalytic sites is improved.
After the dropwise addition of the sodium hydroxide solution and the first solution is completed, the precipitate can be centrifuged and washed, and the single-layer layered metal hydroxide which is not connected between the nitrate ion layers is removed with the supernatant of centrifugation, and the double-layer layered hydroxide is precipitated during centrifugation and collected.
S300, placing the precipitate in deionized water, carrying out ultrasonic treatment, centrifuging, taking supernatant, and drying to obtain the double-layer layered metal hydroxide.
In one embodiment, the time of the ultrasound may be 10-100 minutes.
In one embodiment, freeze drying may be used for drying, and in other embodiments, other drying methods may be used, and the effects of this embodiment can be achieved.
Placing the precipitate in deionized water and performing ultrasonic treatment to peel off and uniformly disperse the double-layer layered metal hydroxide in the supernatant, centrifuging, taking the supernatant, and drying to obtain the stable double-layer layered metal hydroxide with two layers.
Referring to fig. 2, fig. 2 is a schematic reaction diagram of an embodiment of a preparation method of a double-layer layered metal hydroxide according to the present application, in which cobalt ions and aluminum ions react with nitrate under the action of formamide under an alkaline condition to grow, and then the double-layer layered metal hydroxide with two layers is obtained through centrifugation, washing, ultrasonic stripping, centrifugation, and drying.
It will be appreciated that as the number of layers of the double layered metal hydroxide increases, the exposure of the catalytic sites thereof decreases, but at the same time the stability increases; when the number of layers of the double layered metal hydroxide is reduced, the exposure of the catalytic site thereof is increased, but at the same time, the stability is reduced; according to the preparation method, the double-layer layered metal hydroxide with two layers can be efficiently grown by precisely controlling the dosage of the reaction materials and the reaction parameters, the double-layer layered metal hydroxide with two layers has balance between stability and catalytic performance, and meanwhile, the double-layer layered metal hydroxide has excellent stability and catalytic performance; the single-layer double-layer layered metal hydroxide with fewer layers is easy to run off in the water treatment process due to poor stability, has poor catalytic effect and is difficult to recycle.
The application also provides the double-layer layered metal hydroxide prepared by the preparation method, the catalyst has a double-layer structure consisting of two layers of double-layer layered metal hydroxide, nitrate anions are arranged between the layers, the catalytic sites are exposed much, the structure is stable, the catalyst is beneficial to improving the degradation rate of pollutants in water treatment, and the catalyst can be recycled.
The application also provides an application of catalyzing persulfate to degrade environmental organic matters by adopting the double-layer layered metal hydroxide.
In the application, the double-layer layered metal hydroxide can form a catalytic oxidation reaction system with persulfate, and because the double-layer layered metal hydroxide with two layers exposes a large number of catalytic sites, the persulfate can be obviously promoted to generate more active oxidants such as sulfate radicals, hydroxyl radicals and the like so as to oxidatively decompose organic pollutants, and finally water and carbon dioxide are generated.
Wherein, in one embodiment, the mass concentration of the total metal in the catalytic oxidation reaction system can be 0.1g/L, and the environmental organic pollutants can comprise one or a combination of a plurality of rhodamine B, bisphenol A and sulfamethoxazole; in other embodiments, the effect of the present embodiment can be achieved by other environmental organic pollutants that can be degraded by persulfate.
The following describes the advantageous effects of the technical scheme of the present application in further detail with reference to specific examples.
Example 1:
a double-layer layered metal hydroxide is prepared by the following method:
10mL of a first solution comprising 0.03mol/L cobalt nitrate and 0.01mol/L aluminum nitrate, 10mL of a second solution comprising 23vt% formamide and 0.01mol/L sodium nitrate, and 10mL of a sodium hydroxide solution having a concentration of 0.25mol/L were prepared.
The second solution was placed in a beaker, the beaker was placed in a constant temperature oil bath to maintain a constant temperature of 80 ℃, the first solution and the sodium hydroxide solution were simultaneously added dropwise to the beaker at a rate of 1mL/min, and after the completion of the dropwise addition, the sample was centrifuged at 10000rpm for 5min.
Taking precipitate in the centrifugal tube after centrifugation, cleaning the precipitate by deionized water, centrifuging the precipitate for 5min at 10000rpm after cleaning, repeating the process for three times, and collecting the precipitate.
The precipitate was placed in 30mL of deionized water, after which it was sonicated with an sonicator at 25000Hz for 10 min.
Centrifuging the suspension obtained by ultrasonic treatment at 10000rpm for 5min, collecting supernatant, and drying to obtain double-layer layered metal hydroxide (D-CoAl-LDH).
Example 2:
a double-layer layered metal hydroxide is prepared by the following method:
10mL of a first solution, 10mL of a second solution and 10mL of a sodium hydroxide solution with a concentration of 0.25mol/L were prepared, wherein the first solution comprises 0.03mol/L cobalt nitrate and 0.015mol/L aluminum nitrate, and the second solution comprises 18vt% formamide and a concentration of 0.01mol/L sodium nitrate.
The second solution was placed in a beaker, the beaker was placed in a constant temperature oil bath to maintain a constant temperature of 80 ℃, the first solution and the sodium hydroxide solution were simultaneously added dropwise to the beaker at a rate of 1mL/min, and after the completion of the dropwise addition, the sample was centrifuged at 10000rpm for 5min.
Taking precipitate in the centrifugal tube after centrifugation, cleaning the precipitate by deionized water, centrifuging the precipitate for 5min at 10000rpm after cleaning, repeating the process for three times, and collecting the precipitate.
The precipitate was placed in 30mL of deionized water, after which it was sonicated with an sonicator at 25000Hz for 10 min.
Centrifuging the suspension obtained by ultrasonic treatment at 10000rpm for 5min, collecting supernatant, and drying to obtain double-layer layered metal hydroxide (D-CoAl-LDH).
Example 3:
a double-layer layered metal hydroxide is prepared by the following method:
5mL of a first solution, 10mL of a second solution and 5mL of a sodium hydroxide solution with a concentration of 0.50mol/L were prepared, wherein the first solution comprises a first solution of 10mol/L cobalt nitrate and 2.5mol/L aluminum nitrate, and the second solution comprises 25vt% formamide and a concentration of 50mol/L sodium nitrate.
The second solution was placed in a beaker, the beaker was placed in a constant temperature oil bath to maintain a constant temperature of 60 ℃, the first solution and the sodium hydroxide solution were simultaneously added dropwise to the beaker at a rate of 0.1mL/min, and after the addition was completed, the sample was centrifuged at 10000rpm for 5min.
Taking precipitate in the centrifugal tube after centrifugation, cleaning the precipitate by deionized water, centrifuging the precipitate for 5min at 10000rpm after cleaning, repeating the process for three times, and collecting the precipitate.
The precipitate was placed in 30mL of deionized water, and then sonicated with an sonicator at 20000Hz for 50 min.
Centrifuging the suspension obtained by ultrasonic treatment at 10000rpm for 5min, collecting supernatant, and drying to obtain double-layer layered metal hydroxide (D-CoAl-LDH).
Example 4:
a double-layer layered metal hydroxide is prepared by the following method:
100mL of a first solution comprising 0.01mol/L cobalt nitrate and 0.005mol/L aluminum nitrate, 10mL of a second solution comprising 15vt% formamide and 5mol/L sodium nitrate, and 100mL of a sodium hydroxide solution having a concentration of 0.20mol/L were prepared.
The second solution was placed in a beaker, the beaker was placed in a constant temperature oil bath to maintain a constant temperature of 70 ℃, the first solution and the sodium hydroxide solution were simultaneously added dropwise to the beaker at a rate of 5mL/min, and after the completion of the dropwise addition, the sample was centrifuged at 10000rpm for 5min.
Taking precipitate in the centrifugal tube after centrifugation, cleaning the precipitate by deionized water, centrifuging the precipitate for 5min at 10000rpm after cleaning, repeating the process for three times, and collecting the precipitate.
The precipitate was placed in 30mL of deionized water, after which it was sonicated with an sonicator at a frequency of 15000Hz for 100min.
Centrifuging the suspension obtained by ultrasonic treatment at 10000rpm for 5min, collecting supernatant, and drying to obtain double-layer layered metal hydroxide (D-CoAl-LDH).
Effect example 1: characterization analysis
XRD diffractometry was performed on the double layered metal hydroxides prepared in examples 1 and 2 to obtain fig. 3, and fig. 3 is an XRD diffractogram of the double layered metal hydroxides prepared in examples 1 and 2 according to the present application.
As shown, the XRD diffractograms of the double layered metal hydroxides of example 1 and example 2 each have diffraction peaks at (003), (006), and (012), which correspond to cobalt-aluminum layered hydroxide crystal phases, indicating that examples 1 and 2 produced cobalt-aluminum layered hydroxide CoAl-LDH.
Transmission electron microscopy analysis was performed on the double layered metal hydroxides of examples 1 and 2 to obtain fig. 4 and 5, wherein fig. 4 is a TEM image of the double layered metal hydroxide of example 1 and fig. 5 is a TEM image of the double layered metal hydroxide of example 2.
As shown in FIG. 4, the hexagonal long diameter of the double layered metal hydroxide prepared in example 1 was 56.44nm; as shown in FIG. 5, the hexagonal long diameter of the double layered metal hydroxide prepared in example 2 was 50.0nm.
Atomic force microscope scanning analysis was performed on the double layered metal hydroxides of example 1 and example 2, resulting in fig. 6 and 7.
Referring to fig. 6, fig. 6 is an atomic force microscope scanning analysis chart of a double layered metal hydroxide according to example 1 of the present application, wherein a is an AFM scanning chart of the double layered metal hydroxide according to example 1, and b is a graph of a height test result of a horizontal line region in a.
As shown in FIG. 6, the double layered metal hydroxide prepared in example 1 has a two-dimensional planar structure with a thickness of 1.55nm, and since the hydrotalcite single layer has a thickness of about 0.78. 0.78 nm, it is proved that it has two metal laminates, which have a double layered structure.
Referring to fig. 7, fig. 7 is an atomic force microscope scanning analysis chart of a double layered metal hydroxide according to example 2 of the present application, wherein a is an AFM scanning chart of the double layered metal hydroxide according to example 2, and b is a graph of a height test result of a horizontal line region in a.
As shown in FIG. 7, the double layered metal hydroxide prepared in example 2 has a two-dimensional planar structure with a thickness of 1.53nm, and since the hydrotalcite single layer has a thickness of about 0.78. 0.78 nm, it is proved that it has two metal laminates, which have a double layered structure.
XPS spectroscopy analysis was performed on the double layered metal hydroxide of example 1, resulting in FIG. 8.
Referring to fig. 8, fig. 8 is an XPS spectrum of a double layered metal hydroxide according to example 1 of the present application, wherein a is an XPS spectrum of cobalt element and b is an XPS spectrum of aluminum element.
As shown in fig. 8, the valence state of aluminum in the double layered metal hydroxide of example 1 was +3, and the valence states of cobalt were +2 and +3.
As can be seen from the above characterization experiments, example 1 and example 2 both prepared double layered metal hydroxides.
Effect example 2: catalytic performance experiments
The catalytic performance was verified by using the double layered metal hydroxides prepared in example 1 and example 2, respectively, as catalysts.
The specific experimental process comprises the following steps:
three kinds of simulated wastewater comprising 10mg/L rhodamine B, 10mg/L bisphenol A and 10mg/L sulfamethoxazole are respectively prepared, 100mL of the three kinds of simulated wastewater are respectively placed in three triangular beakers, 0.01g of the catalyst prepared in the above example is added into the triangular beakers, then 0.015g of potassium peroxymonosulfate is added to start catalytic degradation, at the same time, stirring for 300 revolutions per minute is carried out, 3mL of water sample is sampled at a specific reaction time, 0.1mL of 0.5mol/L sodium sulfite is added to terminate the reaction, and the concentration of pollutants in the simulated wastewater is detected, so that FIG. 9 and FIG. 10 are obtained, and meanwhile, an experiment without adding the catalyst is taken as a control group, so that FIG. 11 is obtained.
Referring to fig. 9 to 11, fig. 9 is a degradation curve of the double layered metal hydroxide catalyzed potassium hydrogen peroxymonosulfate of example 1 of the present application, fig. 10 is a degradation curve of the double layered metal hydroxide catalyzed potassium hydrogen peroxymonosulfate of example 2 of the present application, and fig. 11 is a degradation curve of the potassium peroxymonosulfate of the control group of example 2 of the present application.
As shown in FIG. 9, the double layered metal hydroxide of example 1 reached degradation efficiencies of 99.2%, 98.0% and 99.5% for rhodamine B, bisphenol A and sulfamethoxazole, respectively, in 2.5min by activating potassium hydrogen peroxymonosulfate.
As shown in FIG. 10, the double layered metal hydroxide of example 2 reached 100%, 98.1% and 99.5% degradation efficiencies of rhodamine B, bisphenol A and sulfamethoxazole, respectively, in 2.5min by activating potassium hydrogen peroxymonosulfate.
As shown in FIG. 11, the degradation efficiency of rhodamine B, bisphenol A and sulfamethoxazole at 20min was only 7.14%, 8.09% and 7.04%, respectively, by using potassium hydrogen peroxymonosulfate as a control group to directly degrade the organic micropollutants.
Comparing example 1 with the control group, under the catalytic activation of the double layered metal hydroxide of example 1, the degradation efficiency of potassium hydrogen peroxymonosulfate to rhodamine B, bisphenol A and sulfamethoxazole is respectively improved by 12.89 times, 11.11 times and 13.13 times.
Comparing example 2 with the control group, under the catalytic activation of the double-layer layered metal hydroxide of example 2, the degradation efficiency of potassium hydrogen peroxymonosulfate to rhodamine B, bisphenol A and sulfamethoxazole is respectively improved by 13.01 times, 11.12 times and 13.13 times.
The above experiments demonstrate that the double layered metal hydroxides prepared in example 1 and example 2 are effective in catalyzing persulfate degradation of environmental organic pollutants.
The previous description of the disclosure is provided to enable any person skilled in the art to make or use the disclosure. Various modifications to the disclosure will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other variations without departing from the scope of the disclosure. Thus, the disclosure is not limited to the examples and designs described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A method for preparing a double layered metal hydroxide, comprising:
preparing a first solution and a second solution, wherein the first solution comprises divalent metal ions and trivalent metal ions, and the second solution comprises nitrate and formamide;
heating the second solution to a reaction temperature, simultaneously dropwise adding the first solution and the sodium hydroxide solution into the second solution, keeping the second solution constant temperature and continuously stirring in the dropwise adding process, centrifugally washing after the dropwise adding is finished, and collecting a precipitate;
placing the precipitate in deionized water, performing ultrasonic treatment, centrifuging, taking supernatant, and drying to obtain double-layer layered metal hydroxide;
the divalent metal ions are cobalt ions, the trivalent metal ions are aluminum ions, the molar concentration of the divalent metal ions in the first solution is 0.01-10 mol/L, and the molar concentration of the divalent metal ions is 2-4 times that of the trivalent metal ions;
the volume fraction of the formamide in the second solution is 15-25 vt percent, and the molar concentration of the nitrate is 0.01-50 mol/L;
the concentration of the sodium hydroxide solution is 0.2-0.5 mol/L;
in the step of simultaneously dropwise adding the first solution and the sodium hydroxide solution into the second solution, the volume ratio of the dropwise adding amount of the first solution to the volume ratio of the second solution is (5-100): 10, the volume ratio of the dropwise adding amount of the sodium hydroxide solution to the second solution is (5-100): and 10, the dropping speed of the first solution and the sodium hydroxide solution is 0.1-5 ml/min.
2. The method according to claim 1, wherein the reaction temperature is 60 to 80 ℃.
3. The method according to claim 1, wherein the step of collecting the precipitate is performed at least 3 times by centrifugal washing after completion of the dropping; and placing the precipitate in deionized water, carrying out ultrasonic treatment, wherein the ultrasonic treatment time in the step of centrifuging is 10-100 min.
4. A double layered metal hydroxide prepared by the preparation method of any one of claims 1 to 3.
5. Use of the double layered metal hydroxide according to claim 4 for catalyzing persulfate degradation of environmental organic pollutants.
6. The use according to claim 5, wherein the double layered metal hydroxide and persulfate are added to wastewater containing environmental organic contaminants including rhodamine B, bisphenol a, sulfamethoxazole in a concentration of 0.1g/L to form a catalytic oxidation reaction system.
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