CN110833818A - Preparation method of hierarchical porous metal-organic framework gas chromatography stationary phase material - Google Patents
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Abstract
The invention relates to a preparation method of a hierarchical porous metal-organic framework gas chromatography stationary phase material, which adopts carboxylic acid organic ligands and tetravalent metal ions as reactants, adds a certain amount of acid regulator and solvent, and reacts at a certain temperature to obtain the hierarchical porous metal-organic framework material. The multi-stage pore metal-organic framework material is used as a stationary phase of gas chromatography, and excellent separation efficiency is obtained in the gas chromatography analysis of low-carbon paraffin/olefin. The chromatographic stationary phase can be used for analysis and detection in multiple fields of petroleum, chemical industry, biochemistry, medicine and health, food industry, environmental protection and the like.
Description
Technical Field
The invention relates to the technical field of analytical chemistry, in particular to a preparation method of a novel hierarchical porous metal-organic framework gas chromatography stationary phase material.
Background
The chromatographic column is a core component of gas chromatography, and has wide application in various fields of petroleum, chemical industry, biochemistry, medicine and health, food industry, environmental protection and the like. The gas chromatography stationary phase is used as a filler of a chromatographic column, is a part for separating mixed gas components, and is also a core material for forming the gas chromatographic column. Most of the existing gas chromatography stationary phases are traditional porous materials such as activated carbon, alumina, molecular sieves, silica gel and the like, and the materials have the advantages of stable property, low price, mature technology and the like. However, since such materials have a certain limitation in the degree of adjustment of the pore structure, they are also limited in the range of application and separation effect.
The Metal Organic Framework (MOF) material is a crystalline state organic-inorganic hybrid framework material formed by coordination self-assembly of organic ligands and metal ions, has the advantages of uniform pore structure, high specific surface area, adjustable pore structure and pore chemical environment and the like, and has wide application prospects in multiple fields of gas storage and separation, catalysis, sensing, drug transmission and the like. Meanwhile, the metal organic framework material is a potential gas chromatography stationary phase material, and has a good application prospect in the analysis of multi-component gases such as alkane/olefin, hydrogen/methane, oxygen/nitrogen and the like. There are also patent documents reporting the use of metal organic framework materials for chromatographic stationary phases, such as: US20100075123a1, DE102011002540a 1. However, the above patent documents concern only certain properties of the metal-organic framework material, such as water-repellent properties; or, the metal organic framework material is prepared into a coating layer to be compounded with the quartz capillary tube only by utilizing the performance of the metal organic framework material in the aspect of porous structure.
At present, metal-organic framework materials adopted in the traditional chromatographic separation stationary phase research are all intrinsic structures, most of the metal-organic framework materials show intrinsic full-microporous structures, and the phenomena of wide peaks, serious tailing and the like can often occur when the metal-organic framework materials are applied to gas chromatographic separation, so that the application range and the separation efficiency are limited to a certain extent.
Disclosure of Invention
Aiming at the defects of the existing metal-organic framework material chromatographic stationary phase, the invention provides a novel metal-organic framework material stationary phase, in particular to a regular hierarchical pore structure in the metal-organic framework material, which not only improves the specific surface area of the stationary phase, but also promotes the adsorption kinetics of gas molecules in the chromatographic stationary phase, thereby greatly improving the separation efficiency of the metal-organic framework stationary phase material on specific components, in particular low-carbon paraffin/olefin. The multi-level hole metal-organic framework material is adopted as the gas chromatography stationary phase, so that the problems of narrow application range and low separation efficiency on certain gases of the current metal-organic framework material chromatography stationary phase can be solved.
The technical scheme of the invention is as follows:
a preparation method of a hierarchical porous metal-organic framework gas chromatography stationary phase material comprises the following steps:
(1) placing an organic ligand and a metal ion compound in a hydrothermal reaction kettle, adding an organic solvent, and adding a certain amount of acid as a regulator to obtain a reaction mixture;
(2) and (2) heating the reaction mixture obtained in the step (1) to react, self-assembling the organic ligand and the metal ions to form a hierarchical porous metal-organic framework compound, and filtering, washing and drying to obtain the hierarchical porous metal-organic framework chromatographic stationary phase material.
According to the present invention, it is preferable that the organic ligand described in the step (1) is a carboxylic acid ligand having a rigid structure; further preferred is fumaric acid, terephthalic acid or naphthalenedicarboxylic acid;
preferably, the metal ion is a 4-valent metal ion, and more preferably zirconium (Zr)4+) Hafnium (Hf)4+) Ions;
preferably, the molar ratio of organic ligand to metal ion compound is 1: (0.5-1).
According to the present invention, it is preferable that the organic solvent described in step (1) is N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA), or N, N-Diethylformamide (DEF).
According to the present invention, it is preferred that the acid in step (1) is hydrochloric acid, formic acid, acetic acid, trifluoroacetic acid, benzoic acid or o-fluorobenzoic acid.
According to the present invention, it is preferred that the molar ratio of the acid to the organic ligand in step (1) is (5-45): 1, further preferably (10-42): 1.
according to the present invention, it is preferred that the temperature of the reaction in step (2) is 90 to 140 ℃.
According to the present invention, it is preferable that the reaction time in the step (2) is 6 to 72 hours
According to the present invention, it is preferable that the washing agent used in the washing process in step (2) is an organic solvent such as methanol, ethanol, acetone, dichloromethane, chloroform, etc.
According to the present invention, it is preferable that the drying temperature in the drying process in the step (2) is 80 to 130 ℃.
According to the invention, the step (2) self-assembly to form the hierarchical porous metal-organic framework compound is preferably MOF-801(Zr), MOF-801(Hf), UiO-66(Zr) or UiO-66 (Hf).
According to the invention, the multi-stage pore metal-organic framework chromatographic stationary phase material has remarkable separation efficiency of low-carbon alkane/olefin, especially the separation between C1-C3 alkane and C2-C3 olefin. Including not only the separation between alkenes and alkanes, but also the separation between alkenes and alkenes (such as ethylene/propylene), alkanes and alkanes (methane/ethane, ethane/propane).
The principle of the invention is as follows:
the invention constructs the hierarchical porous metal-organic framework material based on specific metal ions, and adjusts the pore size and the pore structure of the metal-organic framework material by using acid to form the uniform mesoporous hierarchical porous metal-organic framework material. By constructing the multi-level pores, the adsorption kinetics of gas molecules in the pores are improved, so that the peak shape of a chromatographic peak is improved, and the trailing phenomenon in the traditional microporous metal-organic framework material is solved. The proportion of the acid regulator and the organic ligand (namely the concentration of the acid in the reaction mixture) has important influence on the pore structure of the stationary phase of the hierarchical pore metal-organic framework gas chromatography, and the pore diameter of the hierarchical pore metal-organic framework material can be reduced under the condition of higher acid concentration. When the concentration of the acid is adjusted to a certain concentration, ink bottle-shaped mesopores with the pore diameter of about 4-6 nanometers are formed in the generated metal-organic framework material, and the mesopores are communicated with intrinsic micropores of the metal-organic framework material to form the hierarchical pore metal-organic framework material. When the concentration of the acid is reduced to a certain degree, the size distribution of mesopores in the formed hierarchical porous metal-organic framework material is wider. Therefore, the pore channel size and the pore channel structure of the stationary phase of the hierarchical porous metal-organic framework gas chromatography can be adjusted by adjusting the concentration of the acid regulator.
By constructing the multi-level porous metal-organic framework material, the dynamics of adsorption and diffusion of gas molecules in the pores of the metal-organic framework material can be improved, and the adsorption rate is increased. If the material is used as a chromatographic stationary phase, excellent separation effect can be obtained through the difference of adsorption acting force of the intrinsic microporous structure of the stationary phase material on different gas molecules and the rapid adsorption rate.
The invention has the following beneficial effects:
1. the present invention provides a novel hierarchical porous metal-organic framework gas chromatography stationary phase, and such stationary phase has excellent separation efficiency with respect to lower alkanes and alkenes. The method has important significance for expanding the application range of the metal-organic framework gas chromatography stationary phase and improving the separation efficiency of the chromatography stationary phase.
2. The concentration of the acid regulator has important influence on the pore structure of the stationary phase of the hierarchical pore metal-organic framework gas chromatography, and the pore diameter of the stationary phase of the hierarchical pore metal-organic framework gas chromatography can be reduced under higher acid concentration. Therefore, the pore channel size and the pore channel structure of the stationary phase of the hierarchical porous metal-organic framework gas chromatography can be adjusted by adjusting the concentration of the acid regulator.
3. The multi-stage pore metal-organic framework gas chromatography stationary phase prepared by the invention has excellent separation efficiency in the fields of separation of low-carbon alkane/olefin, especially separation of methane/ethane/ethylene/propane/propylene and the like. The principle is that through constructing a multi-level hole, the adsorption kinetics of gas molecules in the hole is improved, so that the peak shape of a chromatographic peak is improved, and the trailing phenomenon in the traditional microporous metal-organic framework material is solved.
Drawings
FIG. 1 is a schematic structural diagram of a hierarchical porous metal-organic framework gas chromatography stationary phase material obtained in example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of the multi-stage porous metal-organic framework gas chromatography stationary phase materials obtained in examples 1 to 4 of the present invention and comparative example 1.
FIG. 3 is a nitrogen adsorption curve and a pore size distribution of the multi-stage pore metal-organic framework gas chromatography stationary phase materials obtained in examples 1-4 and comparative example 1 of the present invention, wherein a is a nitrogen adsorption curve and b is a pore size distribution diagram.
FIG. 4 is a scanning electron microscope image of the multi-stage porous metal-organic framework gas chromatography stationary phase material obtained in example 1 of the present invention.
FIG. 5 is a transmission electron microscope image of the multi-stage porous metal-organic framework gas chromatography stationary phase material obtained in example 1 of the present invention. Wherein, the upper right hand inset is an aperture size distribution plot.
FIG. 6 is a gas chromatogram of a mixed gas of 5 components of MOF-801-49.5, which is a gas chromatogram fixed phase separation, methane/ethane/ethylene/propane/propylene in experimental example 4 of the present invention.
FIG. 7 is a gas chromatogram of a mixed gas of 5 components of methane/ethane/ethylene/propane/propylene, in which MOF-801-33.0 in Experimental example 4 of the present invention is a gas chromatogram stationary phase.
FIG. 8 is a graph showing that MOF-801-16.5, MOF-801-24.8, MOF-801-33.0 and MOF-801-41.3 in Experimental example 4 of the present invention are gas chromatography stationary phases, and methane/ethane/ethylene (left) and propane/propylene (right) are separated, respectively.
FIG. 9 is a gas chromatogram of a mixed gas of methane/ethane/ethylene 3 components separated at different column box temperatures (40, 60, 80, 100 ℃) when MOF-801-33.0 in Experimental example 4 of the present invention is a gas chromatography stationary phase.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
Example 1
A preparation method of a hierarchical porous metal-organic framework gas chromatography stationary phase material comprises the following steps:
(1) adding 0.293g of fumaric acid and 0.809g of zirconium oxychloride into a reaction kettle with a polytetrafluoroethylene lining, adding 16.5 molar times of formic acid and 10mL of DMF, stirring for dissolving, and sealing;
(2) and (3) placing the reaction kettle in an oven to react for 24 hours at 130 ℃, then filtering, washing with ethanol, and drying at 100 ℃ to obtain the hierarchical porous metal-organic framework gas chromatography stationary phase material. Labeled as MOF-801-16.5.
Examples 2 to 4
As described in example 1, except that:
formic acid was added in 24.8 times, 33.0 times, and 41.3 times molar amounts of fumaric acid. After the steps as shown in example 1, the hierarchical porous metal-organic framework gas chromatography stationary phase material is obtained. Respectively marked as MOF-801-24.8, MOF-801-33.0 and MOF-801-41.3.
Example 5
A preparation method of a multistage pore metal-organic framework gas chromatography stationary phase comprises the following steps:
(1) adding 0.293g of fumaric acid and 0.794g of hafnium chloride into a reaction kettle with a polytetrafluoroethylene lining, adding trifluoroacetic acid in an amount which is 5 times the molar amount of the fumaric acid, adding 10mL of DMF, stirring for dissolving, and sealing;
(2) and (3) placing the reaction kettle in an oven to react for 48 hours at 130 ℃, then filtering, washing with methanol, and drying at 100 ℃ to obtain the hierarchical porous metal-organic framework gas chromatography stationary phase material. The label is: MOF-801 (Hf).
Example 6
A preparation method of a multistage pore metal-organic framework gas chromatography stationary phase comprises the following steps:
(1) adding 0.111g of terephthalic acid and 0.155g of anhydrous zirconium tetrachloride into a reaction kettle with a polytetrafluoroethylene lining, adding 1mL of formic acid and 10mL of DMF, stirring for dissolving, and sealing;
(2) and (3) placing the reaction kettle in an oven to react for 24 hours at 130 ℃, then filtering, washing with ethanol, and drying at 100 ℃ to obtain the hierarchical porous metal-organic framework gas chromatography stationary phase material. Labeled UiO-66 (Zr).
Example 7
A preparation method of a multistage pore metal-organic framework gas chromatography stationary phase comprises the following steps:
(1) adding 0.111g of terephthalic acid and 0.210g of hafnium chloride into a reaction kettle with a polytetrafluoroethylene lining, adding 1mL of formic acid and 10mL of DMF, stirring for dissolving, and sealing;
(2) and (3) placing the reaction kettle in an oven to react for 24 hours at 130 ℃, then filtering, washing with ethanol, and drying at 100 ℃ to obtain the hierarchical porous metal-organic framework gas chromatography stationary phase material. Labeled UiO-66 (Hf).
Comparative example 1
As described in example 1, except that: when the amount of formic acid added was 49.5 times, the resulting metal-organic framework material was designated as MOF-801-49.5, which is a microporous metal-organic framework. As a comparative example.
Comparative example 2
As described in example 1, except that: copper ions are adopted as metal ions, and the multilevel porous metal-organic framework material cannot be obtained after reaction.
Comparative example 3
As described in example 1, except that: the nickel ions are adopted as the metal ions, and the hierarchical porous metal-organic framework material cannot be obtained after the reaction.
Comparative example 4
As described in example 1, except that: sulfuric acid is used as an acid regulator, and the multilevel porous metal-organic framework material cannot be obtained after reaction.
Test example 1
The structure schematic diagram of the hierarchical porous metal-organic framework gas chromatography stationary phase material obtained in example 1 is shown in fig. 1.
The X-ray diffraction patterns of the hierarchical porous metal-organic framework gas chromatography stationary phase materials obtained in examples 1 to 4 and comparative example 1 were tested, as shown in fig. 2.
Test example 2
The multistage pore metal-organic framework gas chromatography stationary phase materials obtained in examples 1 to 4 and comparative example 1 were tested for nitrogen adsorption curve and pore size distribution, as shown in fig. 3. Wherein a is a nitrogen adsorption curve diagram and b is a pore diameter distribution diagram.
As can be seen from FIG. 3, the obtained metal-organic framework materials MOF-801-16.5, MOF-801-24.8, MOF-801-33.0 and MOF-801-41.3 are hierarchical porous materials. With the increase of the addition of formic acid, the mesoporous rate of the obtained metal-organic framework material is gradually reduced, and when the formic acid content is high, the obtained metal-organic framework material approaches to a full microporous material.
Test example 3
Scanning electron micrographs of the hierarchical porous metal-organic framework gas chromatography stationary phase material obtained in example 1 were tested and shown in fig. 4.
As can be seen from fig. 4, the obtained hierarchical porous metal-organic framework material has an appearance of a polyhedron with a regular polyhedron morphology of a crystalline material.
The transmission electron microscope image of the hierarchical porous metal-organic framework gas chromatography stationary phase material obtained in example 1 was tested and shown in fig. 5. Wherein, the picture inserted at the upper right corner is a mesoporous size distribution diagram.
As can be seen from fig. 5, the obtained hierarchical porous metal-organic framework material contains mesopores having a uniform structure and an average size of 6 nm.
Test example 4
The separation performance of the column for separating 5-component mixed gas of methane/ethane/ethylene/propane/propylene was tested by using the hierarchical pore metal-organic framework materials prepared in examples 1 to 4 and comparative example 1 as the stationary phase of the gas chromatography column. The results are shown in FIGS. 6-8.
Wherein, FIG. 6 is a gas chromatography spectrum of MOF-801-49.5 for separating 5 component mixed gas of methane/ethane/ethylene/propane/propylene by gas chromatography fixed phase. FIG. 7 is a gas chromatogram of MOF-801-33.0, which is a gas chromatogram stationary phase, for separating a methane/ethane/ethylene/propane/propylene 5 component mixed gas. FIG. 8 is a graph of MOF-801-16.5, MOF-801-24.8, MOF-801-33.0 and MOF-801-41.3 as gas chromatographic stationary phases, respectively separating methane/ethane/ethylene (left) and separating propane/propylene (right). FIG. 9 is a gas chromatogram of a mixture gas of methane/ethane/ethylene 3 components separated at different column box temperatures (40, 60, 80, 100 ℃) with MOF-801-33.0 being a gas chromatogram stationary phase.
As can be seen from fig. 6, when the microporous metal-organic framework MOF-801-49.5 is used as a stationary phase of gas chromatography, the separation effect is very poor when separating the 5-component gas mixture of methane/ethane/ethylene/propane/propylene, the five gases are difficult to separate, and the tailing and peak broadening phenomena are very serious.
As can be seen from fig. 7, the multilevel porous metal-organic framework MOF-801-33.0 is a stationary phase of gas chromatography, and has a good separation effect when separating a 5-component gas mixture of methane/ethane/ethylene/propane/propylene, and peaks of five gases are clearly shown in a spectrum, and have good peak shapes and no tailing phenomenon.
As can be seen from fig. 8, the multi-stage porous metal-organic framework materials with different pore size distributions have different separation effects on methane/ethane/ethylene and propane/propylene. If the multistage pore content is small, the separation effect on the C1 and C2 components is good, but the separation effect on ethane/ethylene in C2 and propane/propylene in C3 is poor. When the mesoporous content in the hierarchical porous metal-organic framework material is moderate and the distribution of the mesopores is relatively uniform, the corresponding metal-organic framework material has a good separation effect on C1 and C2, and a good separation effect on ethane/ethylene in C2 and propane/propylene in C3. Further, when the mesoporous ratio in the hierarchical porous metal-organic framework material is large and the pore size distribution is not uniform, the corresponding metal-organic framework material has a good separation effect on C1, C2 and C3, but has a poor separation effect on ethane/ethylene in C2 and propane/propylene in C3.
As can be seen from FIG. 9, the multi-level porous metal-organic framework MOF-801-33.0 has better separation effect at different column box temperatures. Particularly low, and has good separation effect at low temperature of 40 ℃. The property shows that the metal-organic framework material has wide application range.
Claims (10)
1. A preparation method of a hierarchical porous metal-organic framework gas chromatography stationary phase material comprises the following steps:
(1) placing an organic ligand and a metal ion compound in a hydrothermal reaction kettle, adding an organic solvent, and adding a certain amount of acid as a regulator to obtain a reaction mixture;
(2) and (2) heating the reaction mixture obtained in the step (1) to react, self-assembling the organic ligand and the metal ions to form a hierarchical porous metal-organic framework compound, filtering, washing and drying to obtain the hierarchical porous metal-organic framework chromatographic stationary phase material.
2. The method for preparing a hierarchical porous metal-organic framework gas chromatography stationary phase material according to claim 1, wherein the organic ligand in step (1) is a carboxylic acid ligand having a rigid structure.
3. The method for preparing a hierarchical porous metal-organic framework gas chromatography stationary phase material according to claim 1, wherein the organic ligand in step (1) is fumaric acid, terephthalic acid or naphthalenedicarboxylic acid.
4. The method for preparing a hierarchical porous metal-organic framework gas chromatography stationary phase material according to claim 1, wherein the metal ion in step (1) is a 4-valent metal ion, preferably zirconium (Zr)4+) Or hafnium (Hf)4+) Ions.
5. The method for preparing a hierarchical porous metal-organic framework gas chromatography stationary phase material according to claim 1, wherein the molar ratio of the organic ligand to the metal ion compound in step (1) is 1: (0.5-1).
6. The method for preparing a hierarchical porous metal-organic framework gas chromatography stationary phase material according to claim 1, wherein the organic solvent in step (1) is N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA), or N, N-Diethylformamide (DEF).
7. The method for preparing a hierarchical porous metal-organic framework gas chromatography stationary phase material according to claim 1, wherein the acid in step (1) is hydrochloric acid, formic acid, acetic acid, trifluoroacetic acid, benzoic acid, or o-fluorobenzoic acid.
8. The method for preparing the hierarchical porous metal-organic framework gas chromatography stationary phase material according to claim 1, wherein the molar ratio of the acid to the organic ligand in step (1) is (5-45): 1, preferably (10-42): 1.
9. the method for preparing a hierarchical porous metal-organic framework gas chromatography stationary phase material according to claim 1, wherein the temperature of the reaction in step (2) is 90-140 ℃;
preferably, the reaction time in the step (2) is 6 to 72 hours;
preferably, the washing agent adopted in the washing process in the step (2) is an organic solvent such as methanol, ethanol, acetone, dichloromethane, trichloromethane and the like;
preferably, the drying temperature in the drying process in the step (2) is 80-130 ℃.
10. The method for preparing a hierarchical porous metal-organic framework gas chromatography stationary phase material according to claim 1, wherein the step (2) self-assembly to form the hierarchical porous metal-organic framework compound is MOF-801(Zr), MOF-801(Hf), UiO-66(Zr), UiO-66 (Hf).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111187423A (en) * | 2020-01-20 | 2020-05-22 | 山西大学 | Novel stable zirconium-based metal organic framework material, and preparation method and application thereof |
| CN111359668A (en) * | 2020-04-23 | 2020-07-03 | 浙江大学 | Preparation method of metal organic framework single-site catalyst for simulating peroxidase |
| CN112979978A (en) * | 2021-02-22 | 2021-06-18 | 中山大学 | Ultramicropore hydrophobic UiO-66 zirconium metal organic framework material and preparation method and application thereof |
| CN113801334A (en) * | 2021-08-27 | 2021-12-17 | 中国科学院重庆绿色智能技术研究院 | Preparation method of small-size MOF-801 material |
| CN114917885A (en) * | 2022-06-10 | 2022-08-19 | 南京师范大学 | Capillary gas chromatographic column for realizing xylene isomer baseline separation and preparation method and application thereof |
| CN116351405A (en) * | 2023-04-18 | 2023-06-30 | 大连中汇达科学仪器有限公司 | Gas-phase capillary column using UiO-66 as adsorbent and manufacturing method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111187423A (en) * | 2020-01-20 | 2020-05-22 | 山西大学 | Novel stable zirconium-based metal organic framework material, and preparation method and application thereof |
| CN111359668A (en) * | 2020-04-23 | 2020-07-03 | 浙江大学 | Preparation method of metal organic framework single-site catalyst for simulating peroxidase |
| CN112979978A (en) * | 2021-02-22 | 2021-06-18 | 中山大学 | Ultramicropore hydrophobic UiO-66 zirconium metal organic framework material and preparation method and application thereof |
| CN112979978B (en) * | 2021-02-22 | 2022-06-07 | 中山大学 | Ultramicropore hydrophobic UiO-66 zirconium metal organic framework material and preparation method and application thereof |
| CN113801334A (en) * | 2021-08-27 | 2021-12-17 | 中国科学院重庆绿色智能技术研究院 | Preparation method of small-size MOF-801 material |
| CN114917885A (en) * | 2022-06-10 | 2022-08-19 | 南京师范大学 | Capillary gas chromatographic column for realizing xylene isomer baseline separation and preparation method and application thereof |
| CN116351405A (en) * | 2023-04-18 | 2023-06-30 | 大连中汇达科学仪器有限公司 | Gas-phase capillary column using UiO-66 as adsorbent and manufacturing method and application thereof |
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