CN114106352A - Cobalt-based metal-hydrogen bond-organic framework material and preparation method and application thereof - Google Patents
Cobalt-based metal-hydrogen bond-organic framework material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of composite materials, in particular to a cobalt-based metal-hydrogen bond-organic framework material and a preparation method and application thereof. The chemical formula of the cobalt-based metal-hydrogen bond-organic framework material is Co (M)4‑8CO3·6‑9(H2O), the preparation method comprises the following steps: mixing and contacting an aqueous solution of divalent cobalt ions with an aqueous solution of N' N-carbonyldiimidazole, and after pink crystals are generated, sequentially carrying out sedimentation, solid-liquid separation and drying. The cobalt-based metal-hydrogen bond-organic framework material combines the bonding principle of MOFs, and metalForm coordinate bond and rely on hydrogen bond connection to combine together with HOFs between the organic ligand, formed a novel porous crystal material, this material crystal growth is rapid, when having organic macromolecule in the solvent, the crystal can wrap up organic macromolecule and grow together to the gathering subsides and realizes removing of organic macromolecule in the solvent.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a cobalt-based metal-hydrogen bond-organic framework material and a preparation method and application thereof.
Background
Water quality problems are a major challenge facing mankind in the 21 st century. The main group of aquatic pollutants are chemical pollutants and domestic sewage, in particular inorganic and organic pollutants, including toxic metals, various synthetic organic chemicals and oil-water mixtures. For more than 50 years, persistent organic pollutants have affected water systems worldwide: during this period, geological pollutants, mining operations and hazardous waste sites have been the main sources of long-term regional and local water pollution, and agricultural chemicals and domestic sewage also affect water quality safety; water pollution causes irreparable damage to the natural environment and human health, and has become one of the most urgent global problems. Common sewage treatment methods include various treatment methods such as a precipitation method, a filtration method, an oxidation-reduction method, an adsorption method and the like.
The metal-organic framework Materials (MOFs) are porous crystal materials formed by self-assembling metal ions or metal clusters and organic ligands in a coordination mode, the hydrogen bond-organic frameworks (HOFs) are highly ordered novel porous crystalline materials, and the two materials have the advantages of high porosity, large specific surface area, material size adjustability, material composition diversity, thermal stability and chemical stability, functional modification, mild synthesis conditions and the like, and become novel porous materials which are widely concerned and researched by people.
Disclosure of Invention
The invention aims to provide a cobalt-based metal-hydrogen bond-organic framework material and a preparation method and application thereof, the cobalt-based metal-hydrogen bond-organic framework material has the characteristics of simple synthesis method, short synthesis time, high yield, low cost and the like, the crystal has good aggregation and sedimentation effects on organic macromolecules in a solvent, can efficiently remove the dispersed organic macromolecules in an aqueous solution, and has the characteristics of short time, high removal rate and the like.
In order to accomplish the above objects, according to one aspect of the present invention, there is provided a cobalt-based metal-hydrogen bond-organic framework material having a chemical formula of Co (M)nCO3·m(H2O), wherein M is imidazole, n is 4-8, and M is 6-9.
In a second aspect, the present invention provides a method for preparing the above cobalt-based metal-hydrogen bond-organic framework material, which comprises: mixing and contacting an aqueous solution of divalent cobalt ions with an aqueous solution of N' N-carbonyldiimidazole, and after pink crystals are generated, sequentially carrying out sedimentation, solid-liquid separation and drying.
Preferably, the divalent cobalt ions are provided by at least one of cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetate.
Preferably, in the aqueous solution of the divalent cobalt ions, the molar concentration of the divalent cobalt ions is 0.05-2 mol/L.
Preferably, the aqueous solution of divalent cobalt ions and/or the aqueous solution of N' N-carbonyldiimidazole further contains at least one of N, N-dimethylformamide, N-dimethylacetamide, and N, N-diethylformamide as a solvent in addition to water.
Preferably, the molar ratio of divalent cobalt ions to N' N-carbonyldiimidazole is (0.5-2): (5-10), preferably (0.4-0.8): 5.
preferably, the temperature for mixing and contacting the aqueous solution of divalent cobalt ions and the N' N-carbonyldiimidazole is 25-80 ℃.
Preferably, the mode of mixing and contacting the aqueous solution of divalent cobalt ions and the N' N-carbonyl diimidazole is direct mixing, ultrasonic mixing or magnetic stirring mixing.
In a third aspect, the present invention provides a method for removing organic macromolecules from water, the method comprising:
(1) preparing a divalent cobalt ion aqueous solution and an N' N-carbonyl diimidazole aqueous solution;
(2) adding the aqueous solution of divalent cobalt ions obtained in the step (1) and the aqueous solution of N' N-carbonyl diimidazole into water containing organic macromolecules, and mixing and contacting.
Optionally, preparing the aqueous solution of divalent cobalt ions by using the same solvent as the water containing the organic macromolecules in the step (2); and/or, the solvent used for preparing the aqueous solution of the N' N-carbonyl diimidazole is the same as the water containing the organic macromolecules in the step (2).
Preferably, the molar ratio of divalent cobalt ions to N' N-carbonyldiimidazole is (0.5-2): (5-10), preferably (0.4-0.8): 5.
the cobalt-based metal-hydrogen bond-organic framework material (Co-M-HOF) combines the bonding principle of MOFs, and the metal and the organic ligand form a coordination bond and are combined with the HOFs by means of hydrogen bond connection, so that a novel porous crystal material is formed.
Moreover, the Co-M-HOF has the advantages of large pore channels, high specific surface area, good biocompatibility, size structure adjustability and the like, and the Co-M-HOF material has wider application by combining the characteristics of fast crystal growth, repairability and the like of the hydrogen bond-organic framework material.
In the method for removing the organic macromolecules in the water, after the water containing the organic macromolecules (namely the organic macromolecule solution) participates in the reaction, the water containing the organic macromolecules can be quickly wrapped by the Co-M-HOF crystal and settled, so that the organic macromolecules in the water can be removed. Specifically, the organic macromolecules and metal ions or organic ligands generate certain intermolecular acting force in the mixed solution, so that the organic macromolecules are more easily wrapped, aggregated and settled during the rapid growth of the crystal.
The invention has the beneficial effects that:
(1) the cobalt-based metal-hydrogen bond-organic framework material (Co-M-HOF) provided by the invention is of a porous structure, has the characteristics of simple synthesis method, short synthesis time, high yield, low cost and the like, has a good aggregation and sedimentation effect on macromolecular particles in a solvent, can efficiently remove organic macromolecules dispersed in an aqueous solution, and has the characteristics of short time, high removal rate and the like.
(2) The cobalt-based metal-hydrogen bond-organic framework material (Co-M-HOF) provided by the invention is prepared by adopting a solvothermal method, and the method is simple and safe to operate, easy to obtain raw materials and mild in condition.
Drawings
FIG. 1 is a crystal photograph of a cobalt-based metal-hydrogen bond-organic framework material (Co-M-HOF) prepared in example 1;
FIG. 2 is a crystal photograph after removal of albumen powder (i.e., organic macromolecules) using the cobalt-based metal-hydrogen bond-organic framework material (Co-M-HOF) of example 1.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The chemical formula of the cobalt-based metal-hydrogen bond-organic framework material is Co (M)nCO3·m(H2O), wherein M is imidazole, n is 4-8, and M is 6-9. In the text, the cobalt-based metal-hydrogen bond-organic framework material can be referred to as Co-M-HOF for short, is of a porous structure, has the advantages of large pore channel, high specific surface area, good biocompatibility, size structure adjustability and the like, and combines the characteristics of fast crystal growth, repairability and the like of the hydrogen bond-organic framework material, so that the material has wider application. The Co-M-HOF crystal has good aggregation and sedimentation effects on organic macromolecules (such as protein powder) in a solvent, can efficiently remove the organic macromolecules dispersed in water, and has the characteristics of short time, high removal rate and the like.
The method for preparing the cobalt-based metal-hydrogen bond-organic framework material comprises the following steps: mixing and contacting an aqueous solution of divalent cobalt ions with an aqueous solution of N' N-carbonyldiimidazole, and after pink crystals are generated, sequentially carrying out sedimentation, solid-liquid separation and drying.
In the present invention, the divalent cobalt ion may be provided by a conventional divalent cobalt salt. The divalent cobalt salt may be at least one selected from the group consisting of cobalt nitrate, cobalt sulfate, cobalt chloride, and cobalt acetate. In one embodiment, the divalent cobalt salt is cobalt chloride hexahydrate (CoCl)2·6H2O)。
In the present invention, the molar concentration of the divalent cobalt ions in the aqueous solution of the divalent cobalt ions may be 0.05 to 2mol/L, preferably 0.1 to 1mol/L, and specifically, may be, for example, 0.2mol/L, 0.5mol/L, or 0.8 mol/L.
In the present invention, the solvent in the aqueous solution of divalent cobalt ions may be all water, or water may be used as a main solvent, and a small amount of an organic solvent may be added. The organic solvent may be at least one of N, N-dimethylformamide, N-dimethylacetamide, and N, N-diethylformamide.
In the present invention, the solvent in the aqueous solution of N' N-carbonyldiimidazole may be all water, or water may be used as a main solvent, and a small amount of an organic solvent may be added. The organic solvent may be at least one of N, N-dimethylformamide, N-dimethylacetamide, and N, N-diethylformamide.
In the process of the present invention, the molar ratio of divalent cobalt ions to N' N-carbonyldiimidazole may be (0.5-2): (5-10), preferably (0.4-0.8): specifically, for example, the ratio of 0.5: 5. 0.8: 5. 0.8: 10.
in the method of the present invention, the temperature at which the aqueous solution of divalent cobalt ions is mixed and contacted with N' N-carbonyldiimidazole may be 25 to 80 ℃.
In the method, the mode of mixing and contacting the aqueous solution of the divalent cobalt ions and the N' N-carbonyl diimidazole can be direct mixing, ultrasonic mixing or magnetic stirring and mixing.
The invention also provides a method for removing organic macromolecules in water, which comprises the following steps:
(1) preparing a divalent cobalt ion aqueous solution and an N' N-carbonyl diimidazole aqueous solution;
(2) adding the aqueous solution of divalent cobalt ions obtained in the step (1) and the aqueous solution of N' N-carbonyl diimidazole into water containing organic macromolecules, and mixing and contacting.
In the method for removing the organic macromolecules in the water, after the aqueous solution of divalent cobalt ions and the aqueous solution of N' N-carbonyldiimidazole are added into the water containing the organic macromolecules, the organic macromolecules are wrapped and aggregated by Co-M-HOF crystals along with the rapid growth of the Co-based metal-hydrogen bond-organic framework material (Co-M-HOF) crystals, and then the organic macromolecules can be separated out along with the Co-M-HOF crystals through sedimentation and solid-liquid separation, so that the removal of the organic macromolecules is realized.
In the method for removing the organic macromolecules in the water, a solvent used for preparing the aqueous solution of the divalent cobalt ions can be the same as the water containing the organic macromolecules in the step (2), namely the aqueous solution of the divalent cobalt ions is prepared by using the water containing the organic macromolecules.
In the method for removing organic macromolecules in water, the solvent used for preparing the aqueous solution of N 'N-carbonyl diimidazole and the water containing the organic macromolecules in the step (2) can be the same, namely the aqueous solution of N' N-carbonyl diimidazole is prepared by using the water containing the organic macromolecules.
In the method for removing organic macromolecules in water, the molar ratio of the divalent cobalt ions to the N' N-carbonyldiimidazole can be (0.5-2): (5-10), preferably (0.4-0.8): 5.
in the present invention, the organic macromolecule may be, for example, protein powder, edible oil, flocculant, long carbon chain organic solvent, starch, petroleum, and the like.
In the method for removing the organic macromolecules in the water, the organic macromolecules and bivalent cobalt ions or organic ligand N' N-carbonyl diimidazole generate certain intermolecular acting force in the mixed solution, so that the organic macromolecules are more easily wrapped, gathered and settled when the crystals grow quickly, and the aim of removing the organic macromolecules in the water solution is fulfilled.
The present invention will be described in detail below by way of examples.
Example 1
This example illustrates a cobalt-based metal-hydrogen bond-organic framework material and a method for preparing the same according to the present invention.
(1) 118mg of cobalt chloride hexahydrate (CoCl)2·6H2O) is dissolved in 1mL of water to prepare CoCl with the molar concentration of 0.5mol/L2An aqueous solution.
(2) 811mg of N' N-carbonyldiimidazole was dissolved in 4mL of water to prepare an organic ligand solution having a molar concentration of 1.25 mol/L.
(3) 1mL of the above CoCl2Mixing the aqueous solution with the 4mL of organic ligand solution, stirring and mixing at room temperature to quickly generate pink crystals, and then sequentially settling, carrying out solid-liquid separation and drying to finally obtain the cobalt-based metal-hydrogen bond-organic framework material (Co-M-HOF) with a chemical formula of Co (M)6CO3·8(H2O), wherein M is imidazole. A crystal picture of the resulting cobalt-based metal-hydrogen bond-organic framework material is shown in FIG. 1.
Application example 1
This example illustrates the method of the present invention for removing organic macromolecules from water.
(1) 118mg of cobalt chloride hexahydrate (CoCl)2·6H2O) is dissolved in 1mL of water to prepare CoCl with the molar concentration of 0.5mol/L2An aqueous solution.
(2) 811mg of N' N-carbonyldiimidazole was dissolved in 4mL of water to prepare an organic ligand solution having a molar concentration of 1.25 mol/L.
(3) Protein powder is taken as organic macromolecule, 10mg of protein powder is weighed and added into 5mL of water to prepare 2g/L protein powder turbid liquid.
(4) 1mL of the above CoCl2Mixing the aqueous solution with 1mL of protein powder turbid liquid to prepare mixed liquid a; mixing the 4mL of organic ligand solution with 4mL of protein powder turbid liquid to prepare mixed liquid b; mixing the mixed solution a and the mixed solution b under the condition of room temperature, standing for a period of time to find that the upper layer solvent is in a clear state,has no suspended matter. Then the protein powder (organic macromolecule) is separated out along with the Co-M-HOF crystal through sedimentation and solid-liquid separation. A crystal pattern of the isolated Co-M-HOF crystals is shown in FIG. 2.
It can be seen from the above application example 1 that after the protein powder turbid liquid (i.e. organic macromolecular solution) participates in the reaction, the protein powder turbid liquid is quickly wrapped by the crystal and settled, so that the organic macromolecules in the water are removed. By comparing the turbidity degrees of the solution before and after the reaction (i.e. the turbidity degrees of the protein powder turbid liquid before and after the reaction), the solution after the reaction becomes clear and has no Tyndall effect, which indicates that the organic macromolecules in the solution are removed.
As can be seen from a comparison of FIGS. 1 and 2, the Co-M-HOF crystals prepared in example 1 did not exhibit crystal aggregation (see FIG. 1), whereas the Co-M-HOF crystals separated from application example 1 exhibited significant aggregation. Therefore, the Co-M-HOF can aggregate and settle the organic macromolecules in the water in the synthesis process, so that the organic macromolecules in the water can be removed.
Example 2
This example illustrates a cobalt-based metal-hydrogen bond-organic framework material and a method for preparing the same according to the present invention.
(1) 190mg of cobalt chloride hexahydrate (CoCl)2·6H2O) is dissolved in 1mL of water to prepare CoCl with the molar concentration of 0.8mol/L2An aqueous solution.
(2) 811mg of N' N-carbonyldiimidazole was dissolved in 4mL of an aqueous solution to prepare an organic ligand solution having a molar concentration of 1.25 mol/L.
(3) 1mL of the above CoCl2Mixing the aqueous solution with the 4mL of organic ligand solution, stirring and mixing at room temperature to quickly generate pink crystals, and then sequentially settling, carrying out solid-liquid separation and drying to finally obtain the cobalt-based metal-hydrogen bond-organic framework material (Co-M-HOF) with a chemical formula of Co (M)6CO3·8(H2O), wherein M is imidazole.
Application example 2
This example illustrates the method of the present invention for removing organic macromolecules from water.
(1) 190mg of cobalt chloride hexahydrate (CoCl)2·6H2O) is dissolved in 1mL of water to prepare CoCl with the molar concentration of 0.8mol/L2An aqueous solution.
(2) 811mg of N' N-carbonyldiimidazole was dissolved in 4mL of an aqueous solution to prepare an organic ligand solution having a molar concentration of 1.25 mol/L.
(3) Protein powder is used as an organic macromolecule, 20mg of protein powder is weighed and added into 5mL of water to prepare 4g/L protein powder turbid liquid.
(5) 1mL of the above CoCl2Mixing the aqueous solution with 1mL of protein powder turbid liquid to prepare mixed liquid a; mixing the 4mL of organic ligand solution with 4mL of protein powder turbid liquid to prepare mixed liquid b; and mixing the mixed solution a and the mixed solution b under a stirring state at room temperature, and standing for a period of time to find that the upper layer solvent is in a clear state and has no suspended matters. Then the protein powder (organic macromolecule) is separated out along with the Co-M-HOF crystal through sedimentation and solid-liquid separation. The separated Co-M-HOF crystals have obvious aggregation phenomenon.
It can be seen that the organic macromolecules in the protein cloud (i.e., protein powder) have been removed.
Example 3
This example illustrates a cobalt-based metal-hydrogen bond-organic framework material and a method for preparing the same according to the present invention.
(1) 118mg of cobalt chloride hexahydrate (CoCl)2·6H2O) is dissolved in 1mL of water to prepare CoCl with the molar concentration of 0.8mol/L2An aqueous solution.
(2) 1621mg of N' -N-carbonyldiimidazole was dissolved in 4mL of an aqueous solution to prepare an organic ligand solution having a molar concentration of 2.5 mol/L.
(3) 1mL of the above CoCl2Mixing the aqueous solution with the 4mL of organic ligand solution, stirring and mixing at room temperature to quickly generate pink crystals, and then sequentially settling, carrying out solid-liquid separation and drying to finally obtain the cobalt-based metal-hydrogen bond-organic framework material (Co-M-HOF) with a chemical formula of Co (M)6CO3·8(H2O) in whichAnd M is imidazole.
Application example 3
This example illustrates the method of the present invention for removing organic macromolecules from water.
(1) 118mg of cobalt chloride hexahydrate (CoCl)2·6H2O) is dissolved in 1mL of water to prepare CoCl with the molar concentration of 0.8mol/L2An aqueous solution.
(2) 1621mg of N' -N-carbonyldiimidazole was dissolved in 4mL of an aqueous solution to prepare an organic ligand solution having a molar concentration of 2.5 mol/L.
(3) Taking edible oil as organic macromolecule, weighing 0.5mL of edible oil, adding into 5mL of water, and stirring to prepare emulsion.
(4) 1mL of the above CoCl2Mixing the aqueous solution with 1mL of emulsion to prepare a mixed solution a; mixing the 4mL of organic ligand solution with 4mL of emulsion to prepare a mixed solution b; and mixing the mixed solution a and the mixed solution b under a stirring state at room temperature, and standing for a period of time to find that an oil layer in an upper layer solvent almost disappears and obvious irregular large particles appear in a precipitate.
It can be seen that the organic macromolecules (i.e., the edible oil) in the emulsion have been removed.
Example 4
This example illustrates a cobalt-based metal-hydrogen bond-organic framework material and a method for preparing the same according to the present invention.
(1) 118mg of cobalt chloride hexahydrate (CoCl)2·6H2O) is dissolved in 1mL of water to prepare CoCl with the molar concentration of 0.5mol/L2An aqueous solution.
(2) 811mg of N' N-carbonyldiimidazole was dissolved in 4mL of an aqueous solution to prepare an organic ligand solution having a molar concentration of 1.25 mol/L.
(2) 1mL of the above CoCl2Mixing the aqueous solution with the 4mL of organic ligand solution, stirring and mixing at room temperature to quickly generate pink crystals, and then sequentially settling, carrying out solid-liquid separation and drying to finally obtain the cobalt-based metal-hydrogen bond-organic framework material (Co-M-HOF) with a chemical formula of Co (M)6CO3·8(H2O), wherein M isImidazole.
Application example 4
This example illustrates the method of the present invention for removing organic macromolecules from water.
(1) 118mg of cobalt chloride hexahydrate (CoCl)2·6H2O) is dissolved in 1mL of water to prepare CoCl with the molar concentration of 0.5mol/L2An aqueous solution.
(2) 811mg of N' N-carbonyldiimidazole was dissolved in 4mL of an aqueous solution to prepare an organic ligand solution having a molar concentration of 1.25 mol/L.
(3) The flocculant is used as a macromolecular particle, 10mg of flocculant is weighed and added into 500mL of water to prepare 0.02g/L flocculant solution.
(4) 1mL of the above CoCl2Mixing the aqueous solution with 1mL of flocculant solution to prepare a mixed solution a; mixing the 4mL of organic ligand solution with 4mL of flocculant solution to prepare mixed solution b; and mixing the mixed solution a and the mixed solution b under a stirring state at room temperature, standing for a period of time, absorbing the upper-layer solvent by using a disposable suction tube, and dripping the liquid downwards, wherein the viscosity of the upper-layer solvent is obviously reduced, and the falling of the liquid drops is not poor to that of water.
It can be seen that the organic macromolecules (i.e., the flocculants) in the flocculant solution have been removed.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A cobalt-based metal-hydrogen bond-organic framework material is characterized in that the chemical formula of the cobalt-based metal-hydrogen bond-organic framework material is Co (M)nCO3·m(H2O), wherein M is imidazole, n is 4-8, and M is 6-9.
2. A method for preparing a cobalt-based metal-hydrogen bond-organic framework material of claim 1, comprising: mixing and contacting an aqueous solution of divalent cobalt ions with an aqueous solution of N' N-carbonyldiimidazole, and after pink crystals are generated, sequentially carrying out sedimentation, solid-liquid separation and drying.
3. The method of claim 2, wherein the divalent cobalt ions are provided by at least one of cobalt nitrate, cobalt sulfate, cobalt chloride, and cobalt acetate.
4. The method according to claim 2 or 3, wherein the molar concentration of the divalent cobalt ions in the aqueous solution of divalent cobalt ions is 0.05-2 mol/L.
5. The method according to claim 2, wherein the aqueous solution of divalent cobalt ions and/or the aqueous solution of N' N-carbonyldiimidazole further comprises at least one of N, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide as a solvent in addition to water.
6. The process according to claim 2, 3 or 5, characterized in that the molar ratio of divalent cobalt ions to N' N-carbonyldiimidazole is (0.5-2): (5-10), preferably (0.4-0.8): 5.
7. the method according to claim 2, 3 or 5, wherein the temperature of the mixed contact of the aqueous solution of divalent cobalt ions and the N' N-carbonyldiimidazole is 25-80 ℃;
preferably, the mode of mixing and contacting the aqueous solution of divalent cobalt ions and the N' N-carbonyl diimidazole is direct mixing, ultrasonic mixing or magnetic stirring mixing.
8. A method for removing organic macromolecules from water, the method comprising:
(1) preparing a divalent cobalt ion aqueous solution and an N' N-carbonyl diimidazole aqueous solution;
(2) adding the aqueous solution of divalent cobalt ions obtained in the step (1) and the aqueous solution of N' N-carbonyl diimidazole into water containing organic macromolecules, and mixing and contacting.
9. The method according to claim 8, wherein the aqueous solution of divalent cobalt ions is prepared using the same solvent as the water containing the organic macromolecule in step (2); and/or
The solvent used to prepare the aqueous solution of N' N-carbonyldiimidazole is the same as the water containing the organic macromolecule used in step (2).
10. The process according to claim 8 or 9, characterized in that the molar ratio of divalent cobalt ions to N' N-carbonyldiimidazole is (0.5-2): (5-10), preferably (0.4-0.8): 5.
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