A porous organic copper phosphonate framework material and its preparation method and application in hydrocarbon adsorption and separation

Abstract

The present invention relates to the technical field of crystal material preparation and hydrocarbon adsorption and separation, and specifically to a porous organic copper phosphonate framework material and a preparation method thereof and application in hydrocarbon adsorption and separation. The method comprises reacting an organic ligand monoesterified with phosphoric acid with a copper salt to prepare the porous organic copper phosphonate framework material. The present invention adopts an organic ligand monoesterified with a phosphoric acid functional group to reduce the coordination number of phosphoric acid, and constructs a porous organic copper phosphonate framework material with a metal copper salt having catalytic performance.

Description

Technical Field

[0001] The invention relates to the technical field of crystal material preparation and hydrocarbon adsorption and separation, and in particular to a porous organic copper phosphonate framework material and a preparation method thereof and application thereof in hydrocarbon adsorption and separation. Background Art

[0002] Porous materials are a type of functional materials that consist of interconnected or closed pores forming a network structure. For example, early activated carbon and zeolite are widely used in water purification, catalytic cracking and catalytic hydrogenation of crude oil, storage and separation of gas molecules, and other fields. In recent years, emerging crystalline porous materials such as Metal-Organic Frameworks (MOFs), Covalent Organic Frameworks (COFs), and Hydrogen-Bonded Organic Frameworks (HOFs) have developed rapidly due to their atomically clear single crystal structures. MOFs are the most reported. MOFs are crystalline porous materials formed by coordination bonds between metal ions and organic ligands. They have the characteristics of structural adjustability, composition diversity, and pore structure complexity. They have good applications in gas adsorption and separation, environmental pollution, photocatalysis, electrocatalysis, medical treatment, and fluorescence sensing. So far, researchers have prepared more than 20,000 different MOFs materials.

[0003] As a type of phosphoric acid functionalized MOFs, organic phosphonic acid MOFs have some special advantages: compared with carboxylic acid, sulfonic acid, and hydroxyl functional groups, organic ligands functionalized with phosphoric acid can form stronger coordination bonds and coordination patterns with metal nodes or metal cluster nodes, which makes organic phosphonic acid MOFs have high thermal stability, chemical stability, and physical stability, ensuring that they can still be used in photocatalysis, electrocatalysis, ion exchange, proton conductors, corrosion protection, and selective adsorption / separation under harsh conditions. However, since the phosphoric acid functional group has more connection sites, the obtained organic phosphonic acid MOFs are mostly dense structures with no or only small pore structures, which is not conducive to the adsorption and separation of gas molecules. The dense structure is also not conducive to exposing more active sites and the transmission of reactants and substrates. Summary of the invention

[0004] In order to improve the above technical problems, the present invention provides a method for preparing a porous organic copper phosphonate framework material, the preparation method comprising: reacting a phosphoric acid monoesterified organic ligand with a copper salt to prepare a porous organic copper phosphonate framework material.

[0005] According to an embodiment of the present invention, the monophosphate-esterified organic ligand can be selected from 4-HOOC-C6H4-CH2-NHCH2PO3H-CH3 (abbreviated as L-CH3), 4-HOOC-C6H4-CH2-NHCH2PO3H-Et (abbreviated as L-Et), 4-HOOC-C6H4-CH2-NHCH2PO3H-iPr (abbreviated as L-iPr) or 4-HOOC-C6H4-CH2-NHCH2PO3H-Bu (abbreviated as L-Bu).

[0006] According to an embodiment of the present invention, the copper salt may be selected from one, two or more of copper acetate, copper chloride, copper nitrate, copper sulfate, basic copper carbonate and copper acetylacetonate.

[0007] According to an embodiment of the present invention, the reaction of the phosphoric acid monoesterified organic ligand with the copper salt is carried out in a solvent, and the solvent is selected from water, or a mixture of water and alcohol.

[0008] According to an embodiment of the present invention, when the solvent is selected from a mixture of water and alcohol, the volume ratio of water to alcohol is (4-10):(0.1-3), preferably (4-6):(2-3), for example, 5:3, 5:2 or 4:3.

[0009] According to an embodiment of the present invention, the alcohol may be selected from one, two or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, neopentyl alcohol, n-hexanol and cyclohexanol.

[0010] By way of example, the solvent is a mixture of water and isopropanol, a mixture of water and methanol, or a mixture of water and ethanol.

[0011] According to an embodiment of the present invention, the molar ratio of the monophosphate-esterified organic ligand and the copper salt is (1-3):(1-4), preferably, the molar ratio of the monophosphate-esterified organic ligand and the copper salt is (1-2):(2-3), for example, 1:2, 2:2 or 2:3.

[0012] According to an embodiment of the present invention, the reaction of the phosphoric acid monoesterified organic ligand and the copper salt is, for example, a solvothermal reaction.

[0013] According to an embodiment of the present invention, the reaction temperature may be 60-120°C, preferably, the reaction temperature is 80-100°C, for example, 60°C, 100°C, 120°C.

[0014] According to an embodiment of the present invention, the reaction time may be 2-72 hours, preferably, the reaction time is 20-48 hours, for example, 22 hours, 28 hours, 30 hours, or 48 hours.

[0015] According to an embodiment of the present invention, after the reaction, the steps of cooling, filtering, washing and drying are also included.

[0016] The present invention also provides a method for preparing a compressed copper organic phosphonate framework material, which obtains the compressed copper organic phosphonate framework material by removing water from the porous copper organic phosphonate framework material.

[0017] Preferably, the compressed porous copper organic phosphonate framework material is prepared by the above method.

[0018] According to an embodiment of the present invention, the dehydration is performed by a gas adsorption apparatus under closed conditions.

[0019] According to an embodiment of the present invention, the dehydration temperature is 30-150 degrees, and the dehydration time is 2-24 hours.

[0020] As an example, the porous organic copper phosphonate framework material is sealed in a gas adsorption tube, activated on a gas adsorption instrument, and maintained at 30 degrees for 12 hours.

[0021] According to an embodiment of the present invention, the compressed organic copper phosphonate framework material is a compressed organic copper phosphonate framework material Cu-CH3a, and its preparation method includes: sealing the porous organic copper phosphonate framework material Cu-CH3 in a gas adsorption tube, activating it on a gas adsorption instrument, and removing water from the porous organic copper phosphonate framework material Cu-CH3.

[0022] The present invention also provides a porous organic copper phosphonate framework material, which is prepared by the above-mentioned method for preparing the porous organic copper phosphonate framework material or obtained by soaking the compressed organic copper phosphonate framework material in water.

[0023] According to an embodiment of the present invention, the porous organic copper phosphonate framework material is a crystalline compound.

[0024] According to an embodiment of the present invention, the porous organic copper phosphonate framework material is selected from porous organic copper phosphonate framework material Cu-CH3, porous organic copper phosphonate framework material Cu-Et, porous organic copper phosphonate framework material Cu-iPr or porous organic copper phosphonate framework material Cu-Bu.

[0025] According to an embodiment of the present invention, the pores of the porous organic copper phosphonate framework material Cu-Bu are arranged in a disordered manner (because the butyl chains are too long and extend into the pores, resulting in the pores being arranged in a disordered manner).

[0026] According to an embodiment of the present invention, the molecular formula of the porous organic copper phosphonate framework material Cu-CH3 is C 20 H 46 Cu2N2O21 P2, belongs to the monoclinic system, the space group is C2 / c,

[0027] According to an embodiment of the present invention, the molecular formula of the porous organic copper phosphonate framework material Cu-Et is C 11 H 18 CuNO7P, belongs to the monoclinic system, the space group is C2 / c,

[0028] According to an embodiment of the present invention, the molecular formula of the porous organic copper phosphonate framework material Cu-iPr is C 12 H 18 CuNO6P, belongs to the monoclinic system, the space group is C2 / c,

[0029] According to an embodiment of the present invention, the molecular formula of the porous organic copper phosphonate framework material Cu-Bu is C 13 H 18 CuNO5P, belongs to the monoclinic system, the space group is C2 / c,

[0030] During the preparation of the porous copper organic phosphonate framework material, due to the slight twisting of the monoesterified organic ligand, the unit cell parameters of the obtained crystalline compound have slight differences.

[0031] According to an embodiment of the present invention, the porous organic copper phosphonate framework material Cu-CH3 has substantially Figure 1 Schematic diagram of the X-ray single crystal structure shown: structural unit, one-dimensional copper phosphate chain, three-dimensional pore structure diagram and three-dimensional pore structure diagram filled with water molecules.

[0032] According to an embodiment of the present invention, the porous organic copper phosphonate framework material Cu-Et has substantially Figure 2 Schematic diagram of the X-ray single crystal structure shown: structural unit, one-dimensional copper phosphate chain, three-dimensional pore structure diagram and three-dimensional pore structure diagram filled with water molecules.

[0033] According to an embodiment of the present invention, the porous organic copper phosphonate framework material Cu-iPr has substantially Figure 3 Schematic diagram of the X-ray single crystal structure shown: structural unit, one-dimensional copper phosphate chain and three-dimensional pore structure.

[0034] According to an embodiment of the present invention, the porous organic copper phosphonate framework material Cu-Bu has substantially Figure 4 Schematic diagram of the X-ray single crystal structure shown: structural unit and three-dimensional pore structure.

[0035] According to the embodiment of the present invention, the topological structure of the porous organic copper phosphonate framework material is basically as follows: Figure 6 Schematic diagram shown, in which the binuclear copper is simplified to 6 connected nodes and the organic ligand is simplified to 3 connected nodes.

[0036] According to an embodiment of the present invention, the porous organic copper phosphonate framework material has substantially the following Figure 7 The X-ray powder diffraction pattern is shown.

[0037] According to an embodiment of the present invention, the porous organic copper phosphonate framework material has substantially the following Fig. 9 Infrared graph shown.

[0038] According to an embodiment of the present invention, the porous organic copper phosphonate framework material has substantially the following Fig.10 Thermogravimetric curve shown.

[0039] According to an embodiment of the present invention, the porous organic copper phosphonate framework material has substantially the following Fig.11 The N2 adsorption curve at 77K is shown.

[0040] According to an embodiment of the present invention, the porous organic copper phosphonate framework material has substantially the following Fig.12 CO2 adsorption curves at 298K and 273K are shown.

[0041] According to an embodiment of the present invention, the porous organic copper phosphonate framework material Cu-CH3 has substantially the following Fig.13 The hydrocarbon adsorption curves at 298K and 273K are shown.

[0042] According to an embodiment of the present invention, the porous organic copper phosphonate framework material Cu-Et has substantially the following characteristics: Fig.14 The hydrocarbon adsorption curves at 298K and 273K are shown.

[0043] The present invention also provides a compressed organic copper phosphonate framework material, which is prepared by the method for preparing the compressed organic copper phosphonate framework material, or is obtained by dehydrating the porous organic copper phosphonate framework material.

[0044] According to an embodiment of the present invention, the compressed copper organic phosphonate framework material is a crystalline compound.

[0045] According to an embodiment of the present invention, the compressed copper organic phosphonate framework material is selected from the compressed copper organic phosphonate framework material Cu-CH3a.

[0046] According to an embodiment of the present invention, the molecular formula of the compressed copper organic phosphonate framework material Cu-CH3a is C10 H 12 CuNO5P, belongs to the triclinic system, space group P-1,

[0047] According to an embodiment of the present invention, the compressed copper organic phosphonate framework material Cu-CH3a has substantially Figure 5 Schematic diagram of the X-ray single crystal structure shown: structural unit, one-dimensional copper phosphate chain and three-dimensional pore structure.

[0048] The present invention also provides a method for dynamically transforming a porous copper organic phosphonate framework material and a compressed copper organic phosphonate framework material, comprising removing moisture from the porous copper organic phosphonate framework material and transforming it into a compressed copper organic phosphonate framework material, or immersing the compressed copper organic phosphonate framework material in water and then transforming it into a porous copper organic phosphonate framework material.

[0049] According to an embodiment of the present invention, the porous copper organic phosphonate framework material is Cu-CH3, and the compressed copper organic phosphonate framework material is Cu-CH3a.

[0050] According to an embodiment of the present invention, the porous copper organic phosphonate framework material Cu-CH3 and the compressed copper organic phosphonate framework material Cu-CH3a have substantially the following Figure 8 The transformable X-ray powder diffraction pattern is shown.

[0051] The present invention also provides a use of the porous organic copper phosphonate framework material in hydrocarbon adsorption and separation, photocatalysis and electrocatalysis, for example, in the adsorption and separation of methane, ethane, ethylene, acetylene, propane, propylene and propyne.

[0052] As an example, the use of the invention in the adsorption of ethane, ethylene, acetylene, propane, propylene and propyne, and the use of the invention in the separation of methane and C2 and C3 hydrocarbons, wherein the C2 and C3 hydrocarbons include one, two or more of ethane, ethylene, acetylene, propane, propylene and propyne.

[0053] Beneficial Effects

[0054] The porous organic copper phosphonate framework material of the present invention is a porous organic copper phosphonate framework material obtained by adopting an organic ligand monoesterified with a phosphoric acid functional group, which can reduce the coordination number of phosphoric acid, and constructing it with a metal copper salt having catalytic performance. The organic ligand monoesterified with a phosphoric acid functional group of the present invention can adjust the size of the pores in the obtained material by changing the length of the ester chain on the phosphoric acid functional group, thereby changing the hydrocarbon adsorption amount and adsorption capacity, wherein Cu-CH3 and Cu-Et basically do not adsorb methane, but have good adsorption capacity for other hydrocarbon gases (such as C2, C3), and the porous organic copper phosphonate framework material has great application prospects in hydrocarbon adsorption separation and photo- and electro-catalysis.

[0055] The synthesis method of the porous organic copper phosphonate framework material of the invention is simple, has a short operation cycle, is easy to process, has a low cost, and is suitable for large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 Schematic diagram of the X-ray single crystal structure of the porous organic copper phosphonate framework material Cu-CH3 prepared in Example 1: structural unit, one-dimensional copper phosphate chain, three-dimensional pore structure diagram and three-dimensional pore structure diagram filled with water molecules;

[0057] Figure 2 Schematic diagram of the X-ray single crystal structure of the porous organic copper phosphonate framework material Cu-Et prepared in Example 2: structural unit, one-dimensional copper phosphate chain, three-dimensional pore structure diagram and three-dimensional pore structure diagram filled with water molecules;

[0058] Figure 3 Schematic diagram of the X-ray single crystal structure of the porous organic copper phosphonate framework material Cu-iPr prepared in Example 3: structural unit, one-dimensional copper phosphate chain and three-dimensional pore structure;

[0059] Figure 4 Schematic diagram of the X-ray single crystal structure of the porous organic copper phosphonate framework material Cu-Bu prepared in Example 4: structural unit, three-dimensional pore structure diagram;

[0060] Figure 5 Schematic diagram of the X-ray single crystal structure of the compressed organic copper phosphonate framework material Cu-CH3a prepared in Example 5: structural unit, one-dimensional copper phosphate chain and three-dimensional pore structure;

[0061] Figure 6 Schematic diagram of the topological structure of Cu-CH3, Cu-Et, Cu-iPr, and Cu-Bu prepared in Examples 1-4

[0062] Figure 7 X-ray powder diffraction patterns of Cu-CH3, Cu-Et, Cu-iPr and Cu-Bu prepared in Examples 1-4;

[0063] Figure 8 The X-ray powder diffraction patterns of Cu-CH3 and Cu-CH3a prepared in Example 1 and Example 5 are transformable;

[0064] Fig. 9 The infrared curves of Cu-CH3, Cu-Et, Cu-iPr and Cu-Bu prepared in Examples 1-4 are shown in FIG.

[0065] Fig.10 Thermogravimetric curves of Cu-CH3, Cu-Et, Cu-iPr and Cu-Bu prepared in Examples 1-4;

[0066] Fig.11 N2 adsorption curves of Cu-CH3, Cu-Et, Cu-iPr and Cu-Bu prepared in Examples 1-4;

[0067] Fig.12 CO2 adsorption curves of Cu-CH3, Cu-Et, Cu-iPr and Cu-Bu prepared in Examples 1-4;

[0068] Fig.13 The adsorption curve of Cu-CH3 prepared in Example 1 and different hydrocarbon gases;

[0069] Fig.14 This is the adsorption curve diagram of Cu-Et prepared in Example 2 and different hydrocarbon gases. DETAILED DESCRIPTION

[0070] The organic framework material of the present invention and its preparation method and application will be described in further detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope of protection that the present invention is intended to protect.

[0071] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0072] In this embodiment, the monoesterified organic ligands of the phosphoric acid functional group are recorded as L-CH3, L-Et, L-iPr, and L-Bu; the corresponding porous organic copper phosphonate framework materials are recorded as Cu-CH3, Cu-Et, Cu-iPr, and Cu-Bu. For example, the porous organic copper phosphonate framework material Cu-CH3 is represented as being prepared by the reaction of the organic ligand L-CH3 with copper salt and heating the reaction at 80 degrees in water and methanol.

[0073] The chemical structural formula of the phosphate monoesterified organic ligand (L-CH3, L-Et, L-iPr, L-Bu) in the following embodiments is:

[0074]

[0075] In the following embodiments, the building units, one-dimensional hydrogen bond chains and three-dimensional structural schematics of porous organic copper phosphonate framework materials (Cu-CH3, Cu-Et, Cu-iPr, Cu-Bu) and organic copper phosphonate framework materials (Cu-CH3a) are characterized by single crystal diffractometer.

[0076] In the following examples, the X-ray powder diffraction patterns of the porous copper organic phosphonate framework materials (Cu-CH3, Cu-Et, Cu-iPr, Cu-Bu) and the copper organic phosphonate framework materials (Cu-CH3a) were characterized by a MiniFlex II powder diffractometer.

[0077] In the following examples, the infrared curves of the porous organic copper phosphonate framework materials (Cu-CH3, Cu-Et, Cu-iPr, Cu-Bu) were characterized by a PerkinElmer Spextrum 100 infrared analyzer.

[0078] In the following examples, the thermogravimetric curves of the porous organic copper phosphonate framework materials (Cu-CH3, Cu-Et, Cu-iPr, Cu-Bu) were characterized by a STA 449F3 thermogravimetric analyzer.

[0079] In the following examples, the N2 adsorption and hydrocarbon adsorption of porous organic copper phosphonate framework materials (Cu-CH3, Cu-Et, Cu-iPr, Cu-Bu) were characterized by ASAP2020 gas adsorption instrument.

[0080] Example 1: Porous organic copper phosphonate framework material Cu-CH3 and preparation method thereof

[0081] Add 5 mL of water and 3 mL of isopropanol into a 20 mL reactor, then add 0.2 mmol of L-CH3 and 0.2 mmol of copper chloride, heat in an oven at 100 degrees for 48 hours, take out, cool, filter, wash, and dry to obtain a porous organic copper phosphonate framework material, recorded as Cu-CH3 crystals.

[0082] Example 2: Porous organic copper phosphonate framework material Cu-Et and preparation method thereof

[0083] Add 5 mL of water and 2 mL of methanol into a 20 mL reactor, then add 0.2 mmol of L-Et and 0.1 mmol of copper chloride, heat in an oven at 120 degrees for 22 hours, take out, cool, filter, wash, and dry to obtain a porous organic copper phosphonate framework material, recorded as Cu-Et crystals.

[0084] Example 3: Porous organic copper phosphonate framework material Cu-iPr and preparation method thereof

[0085] Add 4 mL of water and 2 mL of ethanol into a 20 mL reactor, then add 0.2 mmol of L-Et and 0.1 mmol of copper nitrate, heat in a 60 degree oven for 30 hours, take out, cool, filter, wash, and dry to obtain a porous organic copper phosphonate framework material, recorded as Cu-iPr crystal.

[0086] Example 4: Porous organic copper phosphonate framework material Cu-Bu and preparation method thereof

[0087] Add 4 mL of water and 3 mL of ethanol into a 20 mL reactor, then add 0.2 mmol of L-Et and 0.3 mmol of copper nitrate, heat in a 60 degree oven for 28 hours, take out, cool, filter, wash, and dry to obtain a porous organic copper phosphonate framework material, recorded as Cu-Bu crystals.

[0088] Example 5: Transformation of the structure of porous copper organophosphonate framework material Cu-CH3 and compressed copper organophosphonate Cu-CH3a

[0089] 100 mg of the porous copper organophosphonate framework material Cu-CH3 was sealed in a gas adsorption tube and activated on an ASAP2020 gas adsorption instrument at 30 degrees for 24 hours to remove water molecules in the pores. The crystal was taken out and the crystal structure was recorded on a single crystal diffractometer to obtain Cu-CH3a. Cu-CH3a was soaked in water. Figure 8 As shown, the powder diffraction pattern of the test is similar to that of Cu-CH3 Figure 1 This indicates that Cu-CH3 can be converted into Cu-CH3a by dehydration and can be converted back into Cu-CH3 by absorbing water. Cu-CH3 has a dynamic framework.

[0090] Test Example 1: Crystal Parameter Test

[0091] The crystal parameters of the porous copper organic phosphonate framework materials (Cu-CH3, Cu-Et, Cu-iPr, Cu-Bu) prepared in Examples 1-4 and the compressed copper organic phosphonate framework material Cu-CH3a prepared in Example 5 were analyzed by single crystal X-ray, see Table 1:

[0092] Table 1 Crystal parameters of Cu-CH3, Cu-Et, Cu-iPr, Cu-Bu, and Cu-CH3a

[0093]

[0094]

[0095] Test Example 2: N2 and CO2 gas adsorption test

[0096] The porous copper organic phosphonate framework materials (Cu-CH3, Cu-Et, Cu-iPr, Cu-Bu) prepared in Examples 1-4 were sealed in a gas adsorption tube and activated on an ASAP2020 gas adsorption instrument at 30 degrees for 24 hours to remove water molecules in the pores. The N2 adsorption was tested at 77K. Fig.11 As shown, according to the N2 adsorption data, the specific surface areas of Examples 1-4 are 460.8 m 2 / g,421.1m 2 / g,302.4m 2 / g and 30.4m 2 / g. Then the CO2 gas adsorption was tested at 298K and 273K, respectively. Fig.12 As the alkane chain grows, the amount of CO2 adsorbed decreases, indicating that as the alkyl chain grows, the specific surface area decreases and the pore volume also decreases. Since Cu-Bu has a longer chain of butyl groups, there is a greater steric hindrance, which greatly reduces the pore volume and blocks the window. At 77K, only a small amount of N2 can be adsorbed, and the measured specific surface area is small.

[0097] Test Example 3: Hydrocarbon gas adsorption test of porous copper organic phosphonate framework materials (Cu-CH3 and Cu-Et)

[0098] The activated porous copper organic phosphonate framework materials (Cu-CH3 and Cu-Et) were tested for the adsorption of different hydrocarbon gases at 298K and 273K. Figure 13 to Figure 14 It can be seen that the porous organic copper phosphonate framework materials (Cu-CH3 and Cu-Et) prepared in Examples 1 and 2 of the present invention have good hydrocarbon adsorption performance, especially for C2 and C3, but basically do not adsorb methane. It can be seen that the porous organic copper phosphonate framework materials (Cu-CH3 and Cu-Et) have gas separation effects on C1 / C2 and C1 / C3.

[0099] According to the above results, the porous organic copper phosphonate framework material prepared in the embodiment of the present invention has an adjustable pore structure and good hydrocarbon adsorption and separation ability, and can be applied to the field of hydrocarbon adsorption and separation technology.

[0100] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a porous organic copper phosphonate framework material, characterized in that: The preparation method comprises: subjecting a phosphate monoesterified organic ligand to a solvothermal reaction with a copper salt to prepare a porous organic copper phosphonate framework material, wherein the reaction temperature is 60-120° C., the reaction time is 2-72 hours, and the molar ratio of the phosphate monoesterified organic ligand to the copper salt is (1-3):(1-4); The monophosphate-esterified organic ligand is selected from 4-HOOC-C6H4-CH2-NHCH2PO3H-CH3, 4-HOOC-C6H4-CH2-NHCH2PO3H-Et, 4-HOOC-C6H4-CH2-NHCH2PO3H-iPr or 4-HOOC-C6H4-CH2-NHCH2PO3H-Bu; the copper salt is selected from one, two or more of copper acetate, copper chloride, copper nitrate, copper sulfate, basic copper carbonate and copper acetylacetonate; The reaction of the phosphoric acid monoesterified organic ligand and the copper salt is carried out in a solvent, and the solvent is selected from water or a mixture of water and alcohol.

2. A method for preparing a compressed organic copper phosphonate framework material, characterized in that: The preparation method comprises: removing water from the porous organic copper phosphonate framework material prepared by the preparation method of the porous organic copper phosphonate framework material according to claim 1 to obtain a compressed organic copper phosphonate framework material.

3. A porous organic copper phosphonate framework material, characterized in that: The compressed organic copper phosphonate framework material prepared by the preparation method according to claim 2 is obtained by adsorbing water.

4. A porous organic copper phosphonate framework material, characterized in that: The method is prepared according to claim 1.

5. The porous organic copper phosphonate framework material according to claim 4, characterized in that: The porous organic copper phosphonate framework material is selected from the group consisting of porous organic copper phosphonate framework material Cu-CH3, porous organic copper phosphonate framework material Cu-Et, porous organic copper phosphonate framework material Cu-iPr, and porous organic copper phosphonate framework material Cu-Bu.

6. The porous organic copper phosphonate framework material according to claim 4, characterized in that: The porous organic copper phosphonate framework material is a crystalline compound.

7. The porous organic copper phosphonate framework material according to claim 5, characterized in that: The molecular formula of the porous organic copper phosphonate framework material Cu-CH3 is C 20 H 46 Cu2N2O 21 P2, belongs to the monoclinic system, and its space group is C2 / c , a =16.929±0.02 Å, b =15.074±0.02 Å, c =4.105±0.02 Å.

8. The porous organic copper phosphonate framework material according to claim 5, characterized in that: The molecular formula of the porous organic copper phosphonate framework material Cu-Et is C 11 H 18 CuNO7P, belongs to the monoclinic system, and its space group is C2 / c , a =18.425±0.02 Å, b =12.570±0.02 Å, c =13.782±0.02 Å.

9. The porous organic copper phosphonate framework material according to claim 5, characterized in that: The molecular formula of the porous organic copper phosphonate framework material Cu-iPr is C 12 H 18 CuNO6P, belongs to the monoclinic system, and its space group is C2 / c , a =18.443±0.02 Å, b =12.569±0.02 Å, c =14.064±0.02 Å.

10. The porous organic copper phosphonate framework material according to claim 5, characterized in that: The molecular formula of the porous organic copper phosphonate framework material Cu-Bu is C 13 H 18 CuNO5P, belongs to the monoclinic system, and its space group is C2 / c , a =17.933±0.02 Å, b =13.433±0.02 Å, c =14.052±0.02 Å.

11. A compressed copper organic phosphonate framework material, which is obtained by the preparation method of the compressed copper organic phosphonate framework material according to claim 2 or by dehydrating the porous copper organic phosphonate framework material according to any one of claims 4 to 10.

12. The compressed porous copper organic phosphonate framework material according to claim 11, characterized in that: The compressed porous organic copper phosphonate framework material is a compressed organic copper phosphonate framework material Cu-CH3a.

13. A method for dynamically transforming a porous copper organic phosphonate framework material and a compressed copper organic phosphonate framework material, characterized in that: The dynamic transformation method comprises converting the compressed copper organic phosphonate framework material obtained by the preparation method of the compressed copper organic phosphonate framework material according to claim 2 or dehydrating the porous copper organic phosphonate framework material according to any one of claims 4 to 10 into a compressed copper organic phosphonate framework material, or converting the compressed copper organic phosphonate framework material according to claim 11 or 12 into a porous copper organic phosphonate framework material after absorbing water.

14. The method for dynamic transformation of the porous copper organic phosphonate framework material and the compressed copper organic phosphonate framework material according to claim 13, characterized in that: The dynamically transformable porous copper organic phosphonate framework material is Cu-CH3, and the compressed copper organic phosphonate framework material is Cu-CH3a.

15. The method for dynamic transformation of porous copper organic phosphonate framework material and compressed copper organic phosphonate framework material according to claim 13, characterized in that: The porous copper organic phosphonate framework material Cu-CH3 and the compressed copper organic phosphonate framework material Cu-CH3a have transformable X-ray powder diffraction patterns as shown in FIG. 8 .

16. Use of the porous organic copper phosphonate framework material according to any one of claims 4 to 10 in the adsorption and separation of hydrocarbons.

17. The use of the porous organic copper phosphonate framework material according to claim 16, wherein the hydrocarbon adsorption separation is selected from the adsorption separation of methane, ethane, ethylene, acetylene, propane, propylene and propyne.

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