CN117619437A - Beta-cyclodextrin loaded cobalt-nickel composite catalyst and preparation method and application thereof - Google Patents
Beta-cyclodextrin loaded cobalt-nickel composite catalyst and preparation method and application thereof Download PDFInfo
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- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 93
- 229960004853 betadex Drugs 0.000 title claims abstract description 93
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 title claims abstract description 52
- 239000001116 FEMA 4028 Substances 0.000 title claims abstract description 50
- 235000011175 beta-cyclodextrine Nutrition 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 title claims abstract 9
- 239000002086 nanomaterial Substances 0.000 claims abstract description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 claims abstract description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229960003376 levofloxacin Drugs 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 150000001868 cobalt Chemical class 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 12
- 239000002351 wastewater Substances 0.000 claims abstract description 11
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 230000000593 degrading effect Effects 0.000 claims abstract description 5
- 229910003266 NiCo Inorganic materials 0.000 claims abstract 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 21
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 31
- 238000006731 degradation reaction Methods 0.000 abstract description 31
- 238000000034 method Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 8
- 238000011068 loading method Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000003911 water pollution Methods 0.000 abstract description 2
- 239000013049 sediment Substances 0.000 abstract 3
- 239000000047 product Substances 0.000 description 40
- 238000002474 experimental method Methods 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000000725 suspension Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 8
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 5
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910018916 CoOOH Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a beta-cyclodextrin supported cobalt-nickel composite catalyst, and a preparation method and application thereof, and relates to the field of water pollution control. The preparation method comprises the following steps: (1) Slowly adding sodium hydroxide solution containing beta-cyclodextrin into solution containing cobalt salt and nickel salt; then dropwise adding citric acid, uniformly stirring, and reacting to obtain blue precipitate; (2) The blue sediment is subjected to hydrothermal reaction to obtain light green sediment, the light green sediment is washed with water and centrifuged to be neutral, the excessive beta-cyclodextrin is removed by washing, and the NiCo is obtained by drying 2 O 4 @ beta-CD nanomaterials. The invention adopts a simple covalent immobilization mode, takes beta-CD as a carrier and adopts a method of bonding and coprecipitationMaking NiCo 2 O 4 Directly loading on beta-CD in the hydrothermal reaction process to form a stable composite structure, and preparing NiCo 2 O 4 The @ beta-CD nano material is applied to degrading organic pollutants in wastewater, the degradation rate of levofloxacin after 40min can reach 96.7%, the degradation rate of orange II can reach more than 98%, and the degradation efficiency and the degradation effect are excellent.
Description
Technical Field
The invention relates to the field of water pollution control, in particular to a beta-cyclodextrin supported cobalt-nickel composite catalyst and a preparation method and application thereof.
Background
Advanced oxidation has become a research hotspot in industrial wastewater treatment technologies in recent years. The Fenton oxidation technology is widely applied due to low cost and simple operation mode, but has the defects of narrow pH application range, easiness in secondary pollution and the like. The persulfate advanced oxidation technology can not only retain many advantages of a heterogeneous Fenton system, but also further improve the degradation rate of pollutants, thereby achieving better removal effect. Meanwhile, the method has wider pH application range and better pollutant universality. Therefore, research on new materials and new technical systems aiming at persulfate advanced oxidation technology is carried out, and the method has important theoretical significance and practical value.
Generally, persulfates can be activated by ultraviolet light, heat, transition metals, and the like. Transition metal activation has the advantage of being effective and controllable compared to other methods. Among various transition metal catalysts, co-based catalysts have good compatibility with persulfates. Meanwhile, co and Ni can be combined through Ni 3+ /Ni 2+ And Co 3+ /Co 2+ Mutually protects, thereby obtaining higher persulfate activation efficiency. Compared with the single metal oxide, the double metal oxide nano material can show large specific surface area, multiple active sites and good catalytic activity. For example, patent CN 112138661A adopts a grinding-calcining method, but the time consumption and energy consumption involved are long, although nano NiO is successfully obtained. Meanwhile, patent CN 115386909A adopts a homogeneous precipitation-calcination method, and NiCo is successfully prepared 2 O 4 Catalyst, but at a temperature during the preparation for homogeneous reactionsAnd the calcination temperature is strictly controlled, the morphology and structure of the product can be influenced by improper control, and the energy consumption can be excessive.
Disclosure of Invention
The invention mainly aims at providing a high-stability beta-cyclodextrin supported cobalt-nickel composite catalyst NiCo aiming at the problems and the defects existing in the prior art 2 O 4 The @ beta-CD can activate persulfate to realize the efficient degradation of organic pollutants in wastewater, has good catalytic activity and stability, can be recycled, is environment-friendly, has relatively low cost, and has good application prospect.
In order to achieve the technical aim, the invention adopts a simple covalent immobilization mode, uses beta-cyclodextrin (beta-CD) as a carrier and leads NiCo to be prepared by a bonding and coprecipitation method 2 O 4 Directly supported on beta-CD in the hydrothermal reaction process to form a stable composite structure. The technical scheme is mainly as follows:
in a first aspect, the invention discloses a beta-cyclodextrin supported cobalt-nickel composite catalyst NiCo 2 O 4 The preparation method of the @ beta-CD comprises the following steps:
(1) Slowly adding sodium hydroxide solution containing beta-cyclodextrin into solution containing cobalt salt and nickel salt; then dropwise adding citric acid, uniformly stirring, and reacting to obtain blue precipitate;
(2) Performing hydrothermal reaction on the blue precipitate obtained in the step (1) to obtain light green precipitate, washing and centrifuging the light green precipitate to be neutral, washing to remove redundant beta-cyclodextrin, and drying to obtain NiCo 2 O 4 @ beta-CD nanomaterials.
In a preferred embodiment of the present invention, in the step (1), the amount of the beta-cyclodextrin added is 0.1-3g, the concentration of the sodium hydroxide solution is 1.2mol/L, and the volume of the sodium hydroxide solution is 100ml.
In a preferred embodiment of the present invention, in the step (1), the cobalt salt and the nickel salt are cobalt nitrate and nickel nitrate, respectively, and the molar ratio of the cobalt salt to the nickel salt is 1-4:1-2, and the cobalt salt and the nickel salt are respectively dissolved in 100ml of water to prepare Co 2+ The concentration is0.15mol/L of solution and 0.15-0.3mol/L of Ni+.
In a preferred embodiment of the present invention, in the step (1), the amount of citric acid added is 1ml.
In a preferred embodiment of the present invention, in the step (1), the stirring time is 2 hours, and the reaction temperature is 30 ℃; in the step (2), the hydrothermal reaction temperature is 100-160 ℃ and the time is 12 hours; the drying temperature is 80 ℃, and the drying time is 6 hours.
In a second aspect, the invention also discloses a beta-cyclodextrin supported cobalt-nickel composite catalyst NiCo prepared by the preparation method in the first aspect 2 O 4 @beta-CD, the composite catalyst NiCo 2 O 4 The @ beta-CD is in a laminated form and consists of hexagonal particles with the average diameter of 30-100nm, and the surface of the hexagonal particles is uneven.
In a third aspect, the invention also discloses a beta-cyclodextrin supported cobalt-nickel composite catalyst NiCo as described in the second aspect 2 O 4 The application of @ beta-CD in degrading organic pollutants in wastewater.
In a preferred embodiment of the invention, the application comprises the following steps: niCo is prepared 2 O 4 After the @ beta-CD nano material is mixed with the wastewater containing the organic pollutants, persulfate and carbonate are added to initiate reaction, so that the organic pollutants in the wastewater are degraded.
In a preferred embodiment of the present invention, the potassium persulfate is potassium persulfate and the carbonate is sodium carbonate.
In a preferred embodiment of the invention, the organic contaminant in the wastewater is levofloxacin or orange II.
Compared with the prior art, the invention has the following beneficial effects:
1. the carrier beta-cyclodextrin (beta-CD) used in the invention has a slightly conical hollow cylinder three-dimensional ring structure, is harmless to human body, is easy to obtain and has biodegradability, and various compounds can be embedded in the hydrophobic cavity of the carrier beta-cyclodextrin (beta-CD) to form an inclusion compound. The invention uses beta-CD as carrier to make it pass through citric acid and NiCo 2 O 4 Formation ofCovalent bond, and preparing beta-cyclodextrin supported cobalt-nickel composite catalyst NiCo 2 O 4 And @ beta-CD, a stable composite structure is formed, so that the stability of the catalyst is improved, the agglomeration and passivation phenomena of transition metal are reduced, and the catalytic degradation effect of a reaction system is improved.
2. Preparation of NiCo according to the invention 2 O 4 The method of the @ beta-CD nano material has the advantages of simple flow, easy operation, low energy consumption, high stability of the obtained product, no rare noble metal and low cost.
3. NiCo prepared by the invention 2 O 4 The @ beta-CD nano material is applied to degrading organic pollutants in wastewater, the degradation rate of levofloxacin after 40min can reach 96.7%, the degradation rate of orange II can reach more than 98%, and the degradation efficiency and the degradation effect are excellent.
4. NiCo prepared by the invention 2 O 4 After 5 times of cyclic use, the removal rate of the @ beta-CD nano material to the levofloxacin is still up to more than 85%, which shows that NiCo 2 O 4 The @ beta-CD nano material has good catalytic activity and stability and can be recycled.
Drawings
FIG. 1 is an SEM image of the products obtained in example 1 and comparative example 2 of the present invention; in the figure, a is an SEM image of the product obtained in example 1; b is an SEM image of the product of comparative example 2;
FIG. 2 is an XRD pattern of the products obtained in examples 1-2 and comparative examples 1-2 of the present invention;
FIG. 3 is a graph showing the application of the product obtained in example 1 of the present invention to the degradation of levofloxacin by activating persulfate;
FIG. 4 is a graph showing the cyclic stability of the product obtained in example 1 of the present invention in the degradation of levofloxacin by activating persulfate;
FIG. 5 is a graph showing the application of the product obtained in example 1 of the present invention to the degradation of orange II by means of activated persulphate.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and the described embodiments are only some embodiments of the present invention, but not all embodiments. The embodiments and the protection scope of the present invention are not limited thereto.
Example 1
NiCo 2 O 4 The preparation method of the @ beta-CD nano material comprises the following steps:
1) 1g of β -CD was added to 100mL of a 1.2mol/L NaOH solution and stirred at 30℃until completely dissolved, designated as suspension A; adding cobalt salt (cobalt nitrate hexahydrate) and nickel salt (nickel nitrate hexahydrate) into 100ml of water at a molar ratio of 1:1, stirring at room temperature for 10min to completely dissolve, and preparing Co 2+ And Ni+ concentration was 0.15mol/L, designated as solution B. Dropwise adding the solution B into the suspension A at a speed of 5mL/min, and dropwise adding 1mL of citric acid into the suspension A at a speed of 1 mL/min; then, mechanical stirring was carried out at 30℃for 2h to give a blue product.
2) Transferring the obtained blue product into a hydrothermal reaction kettle, reacting for 12 hours at 140 ℃ to obtain a light green product, washing the product with water at a rotating speed of 400rpm, and centrifuging to be neutral; washing with ethanol to remove redundant beta-CD in the product; then drying at 80 ℃ for 6 hours to obtain NiCo 2 O 4 @ beta-CD nanomaterials.
The scanning electron microscope of the product obtained in this example is shown in FIG. 1 a, and it can be seen that NiCo prepared by the present invention 2 O 4 The @ beta-CD nanoparticles exhibit a regular, lamellar morphology, consisting of hexagonal particles with an average diameter of 30-100 nm. And the surface of the catalyst immobilized by the beta-CD is rugged, which is probably caused by inclusion structures formed by beta-CD loading.
The product obtained in this example was subjected to X-ray diffraction analysis, the results of which are shown in FIG. 2, in which NiCo is the product 2 O 4 Characteristic peak of @ beta-CD and NiCo 2 O 4 In contrast, with NiCo 2 O 4 Characteristic diffraction peaks at the same positions, which indicate that beta-CD can be successfully loaded and NiCo can be obtained by adopting the scheme 2 O 4 @ beta-CD nanomaterials. But when NiCo 2 O 4 After the beta-CD is immobilized, the peak intensity of each XRD is reduced to a certain extent, whichMainly due to the fact that beta-CD belongs to non-magnetic substances.
Example 2
NiCo 2 O 4 The preparation method of the @ beta-CD nano material comprises the following steps:
1) 1g of β -CD was added to 100mL of a 1.2mol/L NaOH solution and stirred at 30℃until completely dissolved, designated as suspension A; adding cobalt salt (cobalt nitrate hexahydrate) and nickel salt (nickel nitrate hexahydrate) into 100ml of water at a molar ratio of 1:1, stirring at room temperature for 10min to completely dissolve, and preparing Co 2+ And Ni + The solution having a concentration of 0.15mol/L was designated as solution B. Dropwise adding the solution B into the suspension A at a speed of 5mL/min, and dropwise adding 1mL of citric acid into the suspension A at a speed of 1 mL/min; mechanical stirring at 30 ℃ for 2h gave a blue product.
2) Transferring the obtained blue product into a hydrothermal reaction kettle, reacting for 12 hours at 160 ℃ to obtain a light green product, washing the product with water at a rotating speed of 400rpm, and centrifuging to be neutral; washing with ethanol to remove redundant beta-CD in the product; drying at 80deg.C for 6 hr to obtain NiCo 2 O 4 @ beta-CD nanomaterials.
The product obtained in this example was subjected to X-ray diffraction analysis, the results are shown in FIG. 2, in which characteristic peaks of the product obtained are shown together with NiCo 2 O 4 In contrast, there are corresponding characteristic diffraction peaks.
Example 3
NiCo 2 O 4 The preparation method of the @ beta-CD nano material comprises the following steps:
1) 1g of β -CD was added to 100mL of a 1.2mol/L NaOH solution and stirred at 30℃until completely dissolved, designated as suspension A; adding cobalt salt (cobalt nitrate hexahydrate) and nickel salt (nickel nitrate hexahydrate) into 100ml of water at a molar ratio of 1:2, stirring at room temperature for 10min to completely dissolve, and preparing Co 2+ The concentration is 0.15mol/L, ni + The solution having a concentration of 0.3mol/L was designated as solution B. Dropwise adding the solution B into the suspension A at a speed of 5mL/min, and dropwise adding 1mL of citric acid into the suspension A at a speed of 1 mL/min; mechanical stirring at 30 ℃ for 2h gave a blue product.
Will result inTransferring the blue product of (2) into a hydrothermal reaction kettle, reacting for 12 hours at 140 ℃ to obtain a light green product, washing the product with water at 400rpm, and centrifuging to be neutral; washing with ethanol to remove redundant beta-CD in the product; then drying at 80 ℃ for 6 hours to obtain NiCo 2 O 4 @ beta-CD nanomaterials.
Application example 1
NiCo obtained in example 1 2 O 4 The @ beta-CD nanomaterial is applied to degrading organic pollutant levofloxacin in water by activating potassium hydrogen persulfate, and the specific operation comprises the following steps of:
(1)NiCo 2 O 4 the procedure for the preparation of @ beta-CD nanomaterials is as described in example 1.
(2) 5mg of NiCo obtained in example 1 was weighed out 2 O 4 Putting @ beta-CD nano material into 250mL of 10mg/L levofloxacin solution, and placing the solution on a magnetic stirrer to stir for 5min at a speed of 200rpm/min, so that the catalyst is uniformly distributed in the solution; then adding a certain amount of potassium hydrogen persulfate and sodium carbonate; the degradation rate of levofloxacin was measured by sampling at predetermined time intervals (0, 5, 10, 15, 20, 25, 30, 40 min) and the results are shown in fig. 3.
As shown in FIG. 3, in NiCo alone 2 O 4 In the @ beta-CD system, the adsorption removal rate of the levofloxacin on the surface of the catalyst is less than 4%, which indicates that the adsorption capacity of the catalyst on the levofloxacin is very weak. When potassium hydrogen Persulfate (PMS) is used alone, the concentration of the levofloxacin is not changed obviously, which indicates that the potassium hydrogen Persulfate (PMS) has weak self-oxidizing capability and is difficult to directly oxidize and degrade the levofloxacin. Thus, the oxidation capacity of the potassium hydrogen persulfate itself and the adsorptivity of the catalyst were negligible in this experiment. After adding sodium carbonate to the potassium hydrogen persulfate system (potassium hydrogen persulfate system containing sodium carbonate is abbreviated as PC), the removal rate of levofloxacin is 10.1%, which indicates that sodium carbonate alone may produce a small amount of active species to degrade levofloxacin. With NiCo alone 2 O 4 Compared with potassium hydrogen persulfate oxidation, the adsorption of the @ beta-CD nano material is carried out on NiCo 2 O 4 Sodium carbonate (NiCo) was added to the @ beta-CD/Potassium hydrogen persulfate System 2 O 4 @ beta-CD/PC system), the degradation effect of the levofloxacin is obviously improved, the degradation rate reaches 96.7%, which indicates that NiCo 2 O 4 The @ beta-CD nano material has good catalytic activity under the conditions of potassium hydrogen persulfate and sodium carbonate.
Application example 2
This application example examined the NiCo obtained in example 1 2 O 4 The @ beta-CD nanomaterial degrades the recycling performance and the stability of the levofloxacin by activating potassium hydrogen persulfate, and the specific operation comprises the following steps:
(1)NiCo 2 O 4 the procedure for the preparation of the @ beta-CD nanomaterial is described in example 1.
(2) First cycle experiments. 5mg of NiCo obtained in example 1 was weighed out 2 O 4 Dispersing @ beta-CD nano material into 250mL of 10mg/L levofloxacin solution, and placing the solution on a magnetic stirrer to stir for 5min at a speed of 200rpm/min so that the catalyst is uniformly distributed in the solution; then adding a certain amount of potassium hydrogen persulfate and sodium carbonate; the degradation rate of levofloxacin was measured by sampling at predetermined time intervals (0, 5, 10, 15, 20, 25, 30, 40 min).
(3) And (3) performing a second cycle experiment. The solution after the first cycle experiment was centrifuged at 10000rpm for 2min to separate the catalyst, and the catalyst recovered for the first time was collected, washed with ethanol and water, and dried, and then used for the second cycle experiment. 5mg of NiCo recovered for the first time 2 O 4 Dispersing @ beta-CD nano material into 250mL of 10mg/L levofloxacin solution, and placing the solution on a magnetic stirrer to stir for 5min at a speed of 200rpm/min so that the catalyst is uniformly distributed in the solution; then adding a certain amount of potassium hydrogen persulfate and sodium carbonate; the degradation rate of levofloxacin was measured by sampling at predetermined time intervals (0, 5, 10, 15, 20, 25, 30, 40 min).
(4) And (3) carrying out third cycle experiments. Centrifuging the solution after the second circulation experiment at 10000rpm for 2min to separate catalyst, collecting the catalyst recovered for the second time, washing with ethanol and water, and dryingAnd (5) drying, and continuing to use for a third cycle experiment. 5mg of NiCo recovered for the second time 2 O 4 The @ beta-CD nanomaterial was dispersed into 250mL of 10mg/L levofloxacin solution and the other steps were the same as in the second cycle experiment.
(5) Fourth cycle experiment. And centrifuging the solution subjected to the third circulation experiment at 10000rpm for 2min to separate the catalyst, collecting the catalyst recovered for the third time, washing with ethanol and water, drying, and continuing to use for the fourth circulation experiment. 5mg of NiCo recovered by the third time 2 O 4 The @ beta-CD nanomaterial was dispersed into 250mL of 10mg/L levofloxacin solution and the other steps were the same as in the second cycle experiment.
(4) Fifth cycle experiment. The solution after the fourth cycle test was centrifuged at 10000rpm for 2min to separate the catalyst, and the fourth recovered catalyst was collected, washed with ethanol and water, dried, and continued for the fifth cycle test. 5mg of NiCo recovered by the fourth time 2 O 4 The @ beta-CD nanomaterial was dispersed into 250mL of 10mg/L levofloxacin solution and the other steps were the same as in the second cycle experiment.
The results of the first to fifth cycle experiments are shown in fig. 4.
As can be seen from FIG. 4, the degradation rate of levofloxacin is hardly affected in the previous two repeated use, and can reach more than 96%; after the third use, the degradation rate of the levofloxacin is reduced to 92.1 percent, and after the fourth and fifth repeated use, the removal rate of the levofloxacin is reduced from 97.1 percent to 85.3 percent, which is related to oxidation and dissolution of metal ions or NiCo 2 O 4 Loss of surface active sites in @ beta-CD nanomaterials is related. Meanwhile, five cycle experiments further prove that NiCo 2 O 4 The @ beta-CD nano material has good catalytic activity and stability and can be recycled.
Application example 3
NiCo obtained in example 1 2 O 4 Application of @ beta-CD nanomaterial in degradation of organic pollutant orange II in water by activating potassium hydrogen persulfate, and specific operations thereof comprise the following stepsThe steps are as follows:
(1)NiCo 2 O 4 the procedure for the preparation of the @ beta-CD nanomaterial is described in example 1.
(2) 0.1mg of NiCo obtained in example 1 was weighed out 2 O 4 Putting @ beta-CD nano material into 250mL of 0.04mM orange II solution, and placing the solution on a magnetic stirrer to stir at a speed of 300rpm/min for 5min so that the catalyst is uniformly distributed in the solution; then adding a certain amount of potassium hydrogen persulfate and sodium carbonate; the degradation rate of orange II was measured by sampling at predetermined time intervals (0, 5, 10, 15, 20, 25, 30, 40 min) and the results are shown in FIG. 5.
As shown in FIG. 5, niCo 2 O 4 After sodium carbonate is added into the @ beta-CD/potassium hydrogen persulfate system, the degradation rate of the orange II reaches more than 98 percent. Indicating that NiCo 2 O 4 The @ beta-CD has good degradation effect on orange II.
Comparative example 1
NiCo prepared by mechanical stirring method 2 O 4 The preparation method of the beta-CD nano material comprises the following steps:
1) 1g of β -CD was added to 100mL of a 1.2mol/L NaOH solution and stirred at 30℃until completely dissolved, designated as suspension A; adding cobalt salt (cobalt nitrate hexahydrate) and nickel salt (nickel nitrate hexahydrate) into 100ml of water at a molar ratio of 1:1, stirring at room temperature for 10min to completely dissolve, and preparing Co 2+ And Ni + The solution having a concentration of 0.15mol/L was designated as solution B. Dropwise adding the solution B into the suspension A at a speed of 5mL/min, and dropwise adding 1mL of citric acid into the suspension A at a speed of 1 mL/min; then, mechanical stirring was carried out at 30℃for 2h to give a blue product.
2) Mechanically stirring the obtained blue product for 3 hours at 30 ℃ to obtain a dark green product, washing the dark green product with water at 400rpm, and centrifuging to be neutral; washing with ethanol to remove redundant beta-CD in the product; drying at 80deg.C for 6 hr to obtain NiCo 2 O 4 beta-CD nanomaterials.
The product obtained in the comparative example is applied to the degradation of the levofloxacin in water by activating potassium hydrogen persulfate, and the degradation rate is 83.7%. It can be seen that NiCo prepared by mechanical stirring method 2 O 4 The degradation effect of the beta-CD nano material is lower than that of NiCo prepared by a hydrothermal method 2 O 4 beta-CD nanomaterials.
The product obtained in this example was subjected to X-ray diffraction analysis, the results are shown in FIG. 2, and the characteristic peaks and NiCo of the product obtained in FIG. 2 2 O 4 In contrast, almost no corresponding characteristic diffraction peak appears, which may be attributed to NiCo 2 O 4 NiCo in beta-CD 2 O 4 Is amorphous, has no crystalline structure (as shown in fig. 1), and has low crystallinity resulting in no distinct characteristic diffraction peak signals.
Comparative example 2
NiCo 2 O 4 The preparation method of the nanomaterial comprises the following steps:
1) Adding cobalt salt (cobalt nitrate hexahydrate) and nickel salt (nickel nitrate hexahydrate) into 100ml of water respectively at a molar ratio of 2:1, stirring at room temperature for 10min to completely dissolve, and preparing into Co 2+ And Ni + Solutions with the concentration of 0.2mol/L and 0.1mol/L are respectively marked as solutions A and B; preparing 100ml of 1.2mol/L sodium hydroxide solution, slowly adding the solution into the solution A, and reacting the solution A in an alkaline environment to obtain CoOOH; the resulting CoOOH solution was then slowly added to solution B and stirred continuously at room temperature for 30min to allow for uniform mixing while maintaining the pH of the mixture above 12.
2) Transferring the stirred mixture into a hydrothermal reaction kettle, reacting for 12 hours at 140 ℃ to obtain a product, washing the product with water at 400rpm, and centrifuging to be neutral; drying at 80deg.C for 6 hr to obtain NiCo 2 O 4 A nanomaterial.
The product obtained in the comparative example 2 is applied to the degradation of the levofloxacin in water by the potassium hydrogen persulfate through activation, and the degradation rate is 84.3%. It can be seen that beta-CD loaded NiCo 2 O 4 The degradation effect of the beta-CD nano material is higher than that of NiCo 2 O 4 A material. The description shows that the proper increase of the addition amount of the carrier beta-CD is beneficial to NiCo 2 O 4 Covalent bond formation, such that the beta-CD is found in NiCo 2 O 4 Covalent immobilization on particles, thereby improving catalyst stability and increasing NiCo 2 O 4 Surface active sites, thereby enhancing the catalytic performance of the catalytic material.
The above examples are presented for clarity of illustration only and are not limiting of the embodiments. Other variations and modifications of the above description will be apparent to those of ordinary skill in the art, and it is not necessary or obvious to all embodiments herein to be exemplified, and it is intended that all such variations and modifications be considered to be within the scope of the invention.
Claims (10)
1. Beta-cyclodextrin loaded cobalt-nickel composite catalyst NiCo 2 O 4 The preparation method of the @ beta-CD is characterized by comprising the following steps:
(1) Slowly adding sodium hydroxide solution containing beta-cyclodextrin into solution containing cobalt salt and nickel salt; then dropwise adding citric acid, uniformly stirring, and reacting to obtain blue precipitate;
(2) Performing hydrothermal reaction on the blue precipitate obtained in the step (1) to obtain light green precipitate, washing and centrifuging the light green precipitate to be neutral, washing to remove redundant beta-cyclodextrin, and drying to obtain NiCo 2 O 4 @ beta-CD nanomaterials.
2. The beta-cyclodextrin supported cobalt-nickel composite catalyst NiCo according to claim 1 2 O 4 The preparation method of @ beta-CD is characterized by comprising the following steps: in the step (1), the adding amount of the beta-cyclodextrin is 0.1-3g, the concentration of the sodium hydroxide solution is 1.2mol/L, and the volume of the sodium hydroxide solution is 100ml.
3. The beta-cyclodextrin supported cobalt-nickel composite catalyst NiCo according to claim 1 2 O 4 The preparation method of @ beta-CD is characterized by comprising the following steps: in the step (1), the cobalt salt and the nickel salt are respectively cobalt nitrate and nickel nitrate, the molar ratio of the cobalt salt to the nickel salt is 1-4:1-2, and the cobalt salt and the nickel salt are respectively dissolved in 100ml of water to prepare Co 2+ 0.15mol/L solution, 0.15-0.3mol/L Ni+ solutionAnd (3) liquid.
4. The beta-cyclodextrin supported cobalt-nickel composite catalyst NiCo according to claim 1 2 O 4 The preparation method of @ beta-CD is characterized by comprising the following steps: in the step (1), the addition amount of the citric acid is 1ml.
5. The beta-cyclodextrin supported cobalt-nickel composite catalyst NiCo according to claim 1 2 O 4 The preparation method of @ beta-CD is characterized by comprising the following steps: in the step (1), the stirring time is 2 hours, and the reaction temperature is 30 ℃; in the step (2), the hydrothermal reaction temperature is 100-160 ℃ and the time is 12 hours; the drying temperature is 80 ℃, and the drying time is 6 hours.
6. A beta-cyclodextrin supported cobalt-nickel composite catalyst NiCo prepared by the preparation method of any one of claims 1 to 5 2 O 4 @beta-CD, the composite catalyst NiCo 2 O 4 The @ beta-CD is in a laminated form and consists of hexagonal particles with the average diameter of 30-100nm, and the surface of the hexagonal particles is uneven.
7. The beta-cyclodextrin supported cobalt-nickel composite catalyst NiCo according to claim 6 2 O 4 The application of @ beta-CD in degrading organic pollutants in wastewater.
8. The use according to claim 7, characterized by the steps of: niCo is prepared 2 O 4 After the @ beta-CD nano material is mixed with the wastewater containing the organic pollutants, persulfate and carbonate are added to initiate reaction, so that the organic pollutants in the wastewater are degraded.
9. The use according to claim 7, characterized in that: the persulfate potassium hydrogen persulfate and the carbonate are sodium carbonate.
10. The use according to claim 7, characterized in that: the organic pollutant in the wastewater is levofloxacin or orange II.
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