CN116832787A - Preparation method of ZIF-67 supported potassium ferrocyanide nanoparticle material and application of ZIF-67 supported potassium ferrocyanide nanoparticle material in adsorption strontium removal - Google Patents
Preparation method of ZIF-67 supported potassium ferrocyanide nanoparticle material and application of ZIF-67 supported potassium ferrocyanide nanoparticle material in adsorption strontium removal Download PDFInfo
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- 239000000276 potassium ferrocyanide Substances 0.000 title claims abstract description 70
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 39
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 28
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 title abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003463 adsorbent Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 229910001631 strontium chloride Inorganic materials 0.000 description 5
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 201000008968 osteosarcoma Diseases 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3206—Organic carriers, supports or substrates
- B01J20/3208—Polymeric carriers, supports or substrates
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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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
- C02F2101/006—Radioactive compounds
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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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- High Energy & Nuclear Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a ZIF-67 supported potassium ferrocyanide nanoparticle material and application of the ZIF-67 supported potassium ferrocyanide nanoparticle material in adsorption strontium removal, and aims to solve the problem that the existing adsorbent is low in strontium removal adsorption rate. The preparation method comprises the following steps: 1. cobalt nitrate is dissolved in methanol at room temperature to obtain solution A; dissolving 2-methylimidazole in methanol to obtain a solution B, pouring the solution B into the solution A, and magnetically stirring the mixed solution to obtain a ZIF-67 material; 2. dissolving ZIF-67 in methanol, ultrasonic dispersing to obtain ZIF-67 solution, and injecting potassium ferrocyanide aqueous solutionStirring was continued at room temperature in ZIF-67 solution to give the reaction product. The invention discovers that ZIF-67 loaded with potassium ferrocyanide nano particles is opposite to Sr 2+ Is prepared through surface modification of ZIF-67 with potassium ferrocyanide and optimization of adsorbent preparing condition and adsorption condition 2+ The adsorption rate of (2) is improved to about 90%.
Description
Technical Field
The invention belongs to the field of radionuclide sewage treatment, and particularly relates to a preparation method of a ZIF-67 loaded potassium ferrocyanide nanoparticle material and application of the ZIF-67 loaded potassium ferrocyanide nanoparticle material in efficient adsorption strontium removal.
Background
Strontium isotopes are one of the most dangerous radioactive pollutants in the environment, and radioactive strontium with a half-life of 28 years is produced not only as fission waste of a nuclear power plant, but also for the post-treatment of nuclear fuel. Because of its chemical similarity to calcium, it readily blends into bone and continues to irradiate local tissue with the eventual development of osteosarcomas and leukemias. Thus, sr is removed from the aqueous medium 2+ Is important to prevent harm to the environment and human health. At present, various methods are available for removing Sr from an aqueous solution 2+ The treatment may be by ion exchange adsorption, chemical precipitation or evaporation, reverse osmosis, filtration and solvent extraction. Because of the relatively low cost of adsorption processes, adsorption processes are the simplest, safest and most cost effective methods of treating heavy metal-containing wastewater. Various adsorbents have been reported to adsorb Sr in aqueous solutions to date 2+ Such as zeolites, metal sulfides, metal oxides, silicates, nanofibers, and metal-organic frameworks (MOFs). Metal-organic frameworks (MOFs), also known as porous coordination polymers, are crystalline microporous materials composed of metal nodes bridged by organic linkers. The novel nano material is widely focused due to the characteristics of large surface area, adjustable structure, adjustable aperture and the like.
Disclosure of Invention
The invention aims to solve the problem of low strontium removal adsorption rate of the existing adsorbent, and provides a preparation method of potassium ferrocyanide modified ZIF-67 and application of the potassium ferrocyanide modified ZIF-67 in efficient strontium removal adsorption.
The preparation method of the ZIF-67 supported potassium ferrocyanide nanoparticle material is realized according to the following steps:
1. cobalt nitrate is dissolved in methanol at room temperature to obtain solution A; dissolving 2-methylimidazole in methanol to obtain a solution B, pouring the solution B (slowly) into the solution A to form a (purple) mixed solution, magnetically stirring the mixed solution for 20-26 h, washing a solid phase with ethanol, centrifuging, and drying to obtain a ZIF-67 material;
2. dissolving the ZIF-67 obtained in the first step in methanol, performing ultrasonic dispersion to obtain a ZIF-67 solution, injecting 0.08-0.15 mol/L potassium ferrocyanide aqueous solution into the ZIF-67 solution, continuously stirring for 10-16 hours at room temperature, washing with ethanol, centrifuging, and drying to obtain a ZIF-67 supported potassium ferrocyanide nanoparticle material (FCK/ZIF-67);
wherein the molar ratio of potassium ferrocyanide to ZIF-67 in the second step is 0.2-0.4:1.
The application of the ZIF-67 supported potassium ferrocyanide nanoparticle material of the invention is that the ZIF-67 supported potassium ferrocyanide nanoparticle material is taken as an adsorbent to be added into a material containing Sr 2+ Is subjected to strontium removal in water.
ZIF-67 is a subclass of MOF, combines the advantages of zeolite and MOF materials, and has higher chemical and thermal stability. But only the adsorption rate of the ZIF-67 on strontium by means of pore canal adsorption and complexation reaction is almost zero, so that the adsorption rate of the ZIF-67 for adsorbing and removing strontium is improved by modifying the potassium ferrocyanide nano particles.
The potassium ferrocyanide modified ZIF-67 prepared by the invention is connected together by complexing the potassium ferrocyanide and the ZIF-67. Because the ZIF-67 modified by the potassium ferrocyanide has larger specific surface area and more exposed adsorption active sites, sr is obtained from the aqueous solution 2+ Has higher adsorption efficiency.
The invention provides a preparation method of a modified ZIF-67 for efficiently removing strontium adsorbent potassium ferrocyanide, namely, potassium ferrocyanide is modified in the ZIF-67 by adopting a one-step method to obtain an efficient strontium-removing adsorbent FCK/ZIF-67, and the efficiency of removing strontium of the adsorbent can reach 90% after simple potassium ferrocyanide modification by optimizing the preparation conditions and the adsorption conditions of the adsorbent.
The synthesis method and application of the potassium ferrocyanide modified ZIF-67 disclosed by the invention have the following beneficial effects:
the invention discovers that ZIF-67 loaded with potassium ferrocyanide nano particles is opposite to Sr for the first time 2+ Is prepared through surface modification of ZIF-67 with potassium ferrocyanide and optimization of adsorbent preparing condition and adsorption condition 2+ The adsorption rate of (2) is improved to about 90%. The preparation of the high-efficiency strontium-removing adsorbent FCK/ZIF-67The preparation process is simple, the adsorption condition is mild and controllable, the cost is reduced, and the excellent strontium removal rate of up to 90% is realized.
Drawings
FIG. 1 is a scanning electron microscope image of ZIF-67 material;
FIG. 2 is a scanning electron microscope image of ZIF-67 loaded with potassium ferrocyanide nanoparticles synthesized in example II;
FIG. 3 is a scanning electron microscope image of ZIF-67 loaded with potassium ferrocyanide nanoparticles synthesized in example I;
FIG. 4 is a scanning electron microscope image of ZIF-67 loaded with potassium ferrocyanide nanoparticles synthesized in example III;
FIG. 5 is a graph of a strontium removal rate test of an example using a ZIF-67 material loaded with potassium ferrocyanide nanoparticles, wherein ■ represents the ZIF-67 material, T.sub.i represents the FCK (1.0)/ZIF-67 material (example three), T.sub.i represents the FCK (0.4)/ZIF-67 (example one), and T.sub.i represents the FCK (0.2)/ZIF-67 (example two);
FIG. 6 is an XRD pattern of the synthesized FCK/ZIF-67 material of the example, wherein 1 represents ZIF-67 material, 2 represents FCK (0.2)/ZIF-67 (example two), 3 represents FCK (0.4)/ZIF-67 (example one), and 4 represents FCK (1.0)/ZIF-67 material (example three).
Detailed Description
The first embodiment is as follows: the preparation method of the ZIF-67 supported potassium ferrocyanide nanoparticle material is realized according to the following steps:
1. cobalt nitrate is dissolved in methanol at room temperature to obtain solution A; dissolving 2-methylimidazole in methanol to obtain a solution B, pouring the solution B (slowly) into the solution A to form a (purple) mixed solution, magnetically stirring the mixed solution for 20-26 h, washing a solid phase with ethanol, centrifuging, and drying to obtain a ZIF-67 material;
2. dissolving the ZIF-67 obtained in the first step in methanol, performing ultrasonic dispersion to obtain a ZIF-67 solution, injecting 0.08-0.15 mol/L potassium ferrocyanide aqueous solution into the ZIF-67 solution, continuously stirring for 10-16 hours at room temperature, washing with ethanol, centrifuging, and drying to obtain a ZIF-67 supported potassium ferrocyanide nanoparticle material (FCK/ZIF-67);
wherein the molar ratio of potassium ferrocyanide to ZIF-67 in the second step is 0.2-0.4:1.
In the first step of the embodiment, cobalt nitrate and 2-methylimidazole are used as raw materials to synthesize a ZIF-67 base material, ZIF-67 is modified, and the ZIF-67 loaded with potassium ferrocyanide nano particles is subjected to a one-step surface modification method by adopting potassium ferrocyanide, so that the FCK/ZIF-67 material is prepared.
The second embodiment is as follows: the present embodiment differs from the first embodiment in that the mixed solution is magnetically stirred at room temperature for 24 hours in the first step.
And a third specific embodiment: the present embodiment differs from the first or second embodiment in that the drying in the first step is drying at 60 ℃ for 8 to 12 hours under an atmosphere of air.
The specific embodiment IV is as follows: this embodiment differs from one to three embodiments in that the mass ratio of cobalt nitrate to 2-methylimidazole in step one is 1:1.69.
Fifth embodiment: the fourth difference between this embodiment and the fourth embodiment is that in the first step, the solution B is poured into the solution a to form a mixed solution, wherein the volume ratio of the solution a to the solution B is 3:1.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that stirring is continued at room temperature for 10 hours in the second step.
Seventh embodiment: the difference between this embodiment and one to six embodiments is that the molar ratio of potassium ferrocyanide to ZIF-67 in the reaction system of step two is 0.4:1.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that the drying temperature in the second step is 60 ℃.
Detailed description nine: the application of the ZIF-67 supported potassium ferrocyanide nanoparticle material in the embodiment is that the ZIF-67 supported potassium ferrocyanide nanoparticle material is taken as an adsorbent to be added into the material containing Sr 2+ Is subjected to strontium removal in water.
In the embodiment, the ZIF-67 material loaded with potassium ferrocyanide is used for removing strontium in water, so that the strontium removing efficiency is improved.
Detailed description ten: this embodiment differs from embodiment nine in that the Sr content is regulated 2+ The system pH of water=5 to 9.
Embodiment one: the preparation method of the ZIF-67 supported potassium ferrocyanide nanoparticle material is realized according to the following steps:
1. 0.582g of Co (NO) 3 )·6H 2 O is dissolved in 30ml of methanol to obtain solution A; dissolving 0.984g of 2-methylimidazole in 10ml of methanol to obtain a solution B, slowly pouring the solution B into the solution A to form a purple mixed solution, magnetically stirring the mixed solution for 24 hours, washing a solid phase with ethanol, centrifuging, and drying (drying at 60 ℃ for 8 hours) to obtain a ZIF-67 material (purple solid);
2. 0.14g of ZIF-67 is dissolved in 60mL of methanol, ultrasonic dispersion is carried out for 1min, ZIF-67 solution is obtained, 0.4mL of potassium ferrocyanide aqueous solution with the concentration of 0.1mol/L is injected into the ZIF-67 solution, stirring is continued for 10h at room temperature, ethanol is used for washing, centrifugation and drying (60 ℃) are carried out, and ZIF-67 supported potassium ferrocyanide nanoparticle material FCK (0.4)/ZIF-67 is obtained.
The XRD pattern of ZIF-67 loaded with potassium ferrocyanide nano particles obtained in the embodiment is shown in figure 6, figure 6 shows that the material has characteristic peaks of ZIF-67, the structure of ZIF-67 cannot be changed by modifying the ZIF-67 with potassium ferrocyanide, and the material is prepared by an electron microscope scanning pattern of FCK/ZIF-67 material, and has uneven surface and more active sites.
Embodiment two: this example differs from example one in that step two, 0.2mL of 0.1mol/L aqueous potassium ferrocyanide solution was injected into ZIF-67 solution, and stirring was continued at room temperature for 10 hours, and the solid precipitate was obtained by washing three times with ethanol, and then dried overnight in an oven at 60℃to obtain adsorbent FCK (0.2)/ZIF-67.
Embodiment III: this example differs from example one in that step two, 1.0mL of a 0.1mol/L aqueous potassium ferrocyanide solution was injected into a ZIF-67 solution, and stirring was continued at room temperature for 10 hours, and the solid precipitate was obtained by washing three times with ethanol, and then dried overnight in an oven at 60℃to obtain the adsorbent FCK (1.0)/ZIF-67.
From the strontium removal rate graph of FIG. 5, the FCK (0.4)/ZIF-67 strontium removal rate was highest in all samples. The method shows that the sample has more active sites and the strontium removal rate is highest, so that the ideal adsorption activity is obtained.
Application example one: in this example, 0.05g of the potassium ferrocyanide nano-ion-supported ZIF-67 obtained in example one was placed in 50mL of strontium chloride solution, sr 2+ The concentration of (2) was 50mg/L, and the pH of the system was 7, and the adsorption was equilibrated by magnetic stirring adsorption.
In this example, the reaction mixture was subjected to removal of the adsorbent by a water filter head (0.22 μm), and the remainder of Sr was measured by an atomic absorption spectrometer using a Sr hollow cathode lamp 2+ Concentration. The strontium removal rates were measured to be 51.3%, 73.9%, 88.0%, 94.1% and 96.9% in each of the reaction time intervals of 15min, 30min, 60min, 90min and 120min, respectively.
Application example two: in this example, 0.05g of the potassium ferrocyanide nano-ion-loaded ZIF-67 obtained in example two was placed in 50mL of strontium chloride solution, sr 2+ The concentration of (2) was 50mg/L, and the pH of the system was 7, and the adsorption was equilibrated by magnetic stirring adsorption.
In this example, the reaction mixture was subjected to removal of the adsorbent by a water filter head (0.22 μm), and the remainder of Sr was measured by an atomic absorption spectrometer using a Sr hollow cathode lamp 2+ Concentration. The strontium removal rates were 54.0%, 76.2%, 85.5%, 89.3%, 92.1% respectively in each of the reaction time intervals of 15min, 30min, 60min, 90min, 120 min.
Application example three: in this example, 0.05g of the potassium ferrocyanide nano-ion-loaded ZIF-67 obtained in example three was placed in 50mL of strontium chloride solution, sr 2+ The concentration of (2) was 50mg/L, and the pH of the system was 7, and the adsorption was equilibrated by magnetic stirring adsorption.
In this example, the reaction mixture was subjected to removal of the adsorbent by a water filter head (0.22 μm), and the remainder of Sr was measured by an atomic absorption spectrometer using a Sr hollow cathode lamp 2+ Concentration. The strontium removal rate measured in each reaction time interval of 15min, 30min, 60min, 90min and 120min is 43.2%、66.1％、81.9％、86.7％、90.8％。
Application example four: in this example, 0.05g of the potassium ferrocyanide nano-ion-supported ZIF-67 obtained in example one was placed in 50mL of strontium chloride solution, sr 2+ The concentration of (2) is 50mg/L, the pH value of the system is regulated to be=5 by adopting a dilute hydrochloric acid solution, and the magnetic stirring adsorption is carried out to balance the adsorption.
In this example, the reaction mixture was subjected to removal of the adsorbent by a water filter head (0.22 μm), and the remainder of Sr was measured by an atomic absorption spectrometer using a Sr hollow cathode lamp 2+ Concentration. The strontium removal rates were measured to be 45.7%, 69.2%, 84.4%, 90.3%, 93.4% in each of the reaction time intervals of 15min, 30min, 60min, 90min, 120min, respectively.
Application example four: in this example, 0.05g of the potassium ferrocyanide nano-ion-supported ZIF-67 obtained in example one was placed in 50mL of strontium chloride solution, sr 2+ The concentration of (2) is 50mg/L, the pH value of the system is regulated to be 9 by adopting a dilute hydrochloric acid solution, and the magnetic stirring adsorption is carried out to balance the adsorption.
In this example, the reaction mixture was subjected to removal of the adsorbent by a water filter head (0.22 μm), and the remainder of Sr was measured by an atomic absorption spectrometer using a Sr hollow cathode lamp 2+ Concentration. The strontium removal rates were measured to be 49.7%, 71.8%, 86.3%, 91.2%, 94.5% in each of the reaction time intervals of 15min, 30min, 60min, 90min, 120min, respectively.
Claims (10)
- The preparation method of the ZIF-67 supported potassium ferrocyanide nanoparticle material is characterized by comprising the following steps of:1. cobalt nitrate is dissolved in methanol at room temperature to obtain solution A; dissolving 2-methylimidazole in methanol to obtain a solution B, pouring the solution B into the solution A to form a mixed solution, magnetically stirring the mixed solution for 20-26 h, washing a solid phase with ethanol, centrifuging, and drying to obtain a ZIF-67 material;2. dissolving the ZIF-67 obtained in the first step in methanol, performing ultrasonic dispersion to obtain a ZIF-67 solution, injecting 0.08-0.15 mol/L potassium ferrocyanide aqueous solution into the ZIF-67 solution, continuously stirring for 10-16 hours at room temperature, washing with ethanol, centrifuging, and drying to obtain a ZIF-67 loaded potassium ferrocyanide nanoparticle material;wherein the molar ratio of potassium ferrocyanide to ZIF-67 in the second step is 0.2-0.4:1.
- 2. The method for preparing the ZIF-67 supported potassium ferrocyanide nanoparticle material according to claim 1, wherein the mixed solution is magnetically stirred for 24 hours at room temperature in the first step.
- 3. The method for preparing a ZIF-67 supported potassium ferrocyanide nanoparticle material according to claim 1, wherein the drying in the step one is drying at 60 ℃ for 8-12 hours in an air atmosphere.
- 4. The method for preparing a ZIF-67 supported potassium ferrocyanide nanoparticle material according to claim 1, wherein the mass ratio of cobalt nitrate to 2-methylimidazole in the step one is 1:1.69.
- 5. The method for preparing a ZIF-67 supported potassium ferrocyanide nanoparticle material according to claim 4, wherein in the first step, the solution B is poured into the solution a to form a mixed solution, wherein the volume ratio of the solution a to the solution B is 3:1.
- 6. The method for preparing the ZIF-67 supported potassium ferrocyanide nanoparticle material according to claim 1, wherein in the second step, stirring is continued at room temperature for 10 hours.
- 7. The method for preparing the ZIF-67 supported potassium ferrocyanide nanoparticle material according to claim 1, wherein the molar ratio of potassium ferrocyanide to ZIF-67 in the second reaction system is 0.4:1.
- 8. The method for preparing a ZIF-67 supported potassium ferrocyanide nanoparticle material according to claim 1, wherein the drying temperature in the second step is 60 ℃.
- 9. The use of the ZIF-67 supported potassium ferrocyanide nanoparticle material as claimed in claim 1, characterized in that the ZIF-67 supported potassium ferrocyanide nanoparticle material is added as an adsorbent to Sr-containing materials 2+ Is subjected to strontium removal in water.
- 10. The use of the ZIF-67 supported potassium ferrocyanide nanoparticle material according to claim 9, characterized by regulating Sr-containing 2+ The system pH of water=5 to 9.
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