WO2019057050A1 - Slurry synthesis method for porous composite framework material - Google Patents

Slurry synthesis method for porous composite framework material Download PDF

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WO2019057050A1
WO2019057050A1 PCT/CN2018/106380 CN2018106380W WO2019057050A1 WO 2019057050 A1 WO2019057050 A1 WO 2019057050A1 CN 2018106380 W CN2018106380 W CN 2018106380W WO 2019057050 A1 WO2019057050 A1 WO 2019057050A1
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solvent
porous composite
slurry
copper
synthesis method
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French (fr)
Chinese (zh)
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薛春峰
李晓红
王恩阳
杨复娟
郝晓刚
王俊文
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太原理工大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/307—Monocyclic tricarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic System without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)

Definitions

  • the invention belongs to the technical field of preparation of porous composite materials, and in particular relates to a slurry synthesis method of a porous composite skeleton material.
  • the process uses a very small amount of solvent and the reactants are converted in a slurry state to obtain porous composite materials of different particle sizes.
  • Porous composite materials are a new class of microporous high specific surface functional materials.
  • the surface properties, pore structure and central metal ion coordination form are variable, and specific chemical modifications can be made according to the final application requirements.
  • it has great application potential in the fields of gas storage and separation, drug storage and release, energy storage, optical devices, chromatographic analysis, etc., which has caused competition among domestic and foreign governments, enterprises and university scholars. .
  • methods for synthesizing such materials include hydrothermal method, solvothermal method, ultrasonic assisted synthesis method, microwave synthesis method, electrochemical synthesis method, and grinding method.
  • hydrothermal or solvothermal synthesis of such materials is mainly focused on the use of a large amount of solvent to promote the complete dissolution of the reactants in the synthesis process, so as to obtain a relatively small particle (usually around 10 microns).
  • An unavoidable situation in the reaction process is that the reactants are always dissolved in a large amount of solvent and no crystal product is formed, and finally discharged as a mother liquid or recycled, which greatly reduces the yield and increases the environmental pollution.
  • waste liquid is to avoid waste liquid as much as possible. By improving the production process, it can reduce or eliminate waste liquid from the source.
  • the literature mentions that the porous inorganic metal salt nickel ammonium molybdate is synthesized by the slurry method.
  • the literature uses a high-speed pulverizer to mix the solid reactants, and finally adds an auxiliary agent to form a slurry and crystallize at a certain temperature.
  • the product was obtained.
  • the paper does not specify the type and dosage of the adjuvant, and the reaction mechanism is not yet clear.
  • the shape of the product is commonplace, the length is only 0.8 microns, and the physical and chemical properties are not significantly improved.
  • the existing process for synthesizing the porous inorganic metal salt nickel ammonium molybdate by the slurry method is not mature, and there are still many problems.
  • the object of the present invention is to provide a slurry synthesis method of a porous composite skeleton material, which controls the mass ratio of a solvent to a solid reactant, so that the reactants are at different degrees of saturation, and the inorganic-organic is obtained by heat treatment in a sealed container.
  • the composite framework material controls the grain size and distribution of the composite framework material.
  • the invention is realized by the following technical solution: a slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is an organic solvent or an aqueous organic solvent
  • the molar ratio of the inorganic metal source to the polycarboxylic acid organic compound is: (0.5-10): 2; the ratio of the sum of the mass of the inorganic metal salt or the metal base to the polycarboxylic acid organic compound to the total mass of the solvent is 0.1-3 .
  • the organic solvent in the step (1) is any one or any two of methanol, ethanol, ethylene glycol, dimethyl ether, diethyl ether, acetone, dimethyl sulfoxide, and N,N-dimethylformamide. Mix in any ratio; water is deionized water or distilled water; the volume ratio of water to organic solvent in the aqueous organic solvent is 0-1000.
  • the inorganic metal source described in the step (2) is any one or any two metal sources of iron, cobalt, nickel, copper, chromium, zinc or a base.
  • the inorganic metal source described in the step (2) is preferably: copper nitrate, copper pyrophosphate trihydrate, copper acetate, basic copper carbonate, copper sulfate, copper chloride, copper hydroxide, zinc nitrate, aluminum nitrate, aluminum acetate. Any one or any two of cobalt nitrate, cobalt acetate, nickel nitrate, nickel acetate, nickel hydroxide, cobalt hydroxide, iron nitrate, and ferric chloride are mixed in an arbitrary ratio.
  • the polycarboxylic acid organic compound described in the step (2) is one or a mixture of trimesic acid and terephthalic acid.
  • the prepared porous composite skeleton material has a particle diameter of 0.0002 to 2 mm.
  • the invention adjusts the particle size of the prepared porous composite skeleton material according to the ratio of the sum of the mass of the metal source and the polycarboxylic acid organic compound to the total mass of the solvent, and the particle size distribution is narrower when the ratio is higher, and the particles are uniform;
  • the diameter distribution is wide, and the particle size is different, that is, when the solvent dosage is small, the obtained porous composite skeleton material has a narrow particle size distribution and uniform particles, and when the solvent amount is large, the particle size is different.
  • the volume ratio of water to the organic solvent in the organic solvent contained in the mixed solvent controls the particle size of the prepared porous composite skeleton material, and when the organic solvent content is high, the crystal grain size is small, and conversely, the crystal grain size is larger. .
  • the larger the crystal grain size the longer the microporous channel is, which is convenient for capturing and accommodating more gas molecules, thereby having a higher gas adsorption capacity.
  • a material with a smaller particle exposing more of the outer surface does not have much benefit in capturing the gas.
  • the slurry synthesis method of the present invention does not require sufficient dissolution and is a completely heterogeneous reaction.
  • the synthesis process is completely different from the prior art. Since the solvent used is about 10% of the amount of the conventional solvothermal solvent, the amount of the solvent is greatly reduced, the initial concentration of the reactant is supersaturated, the reaction driving force is larger, and the formation of large crystals is facilitated. In addition, due to the reduction of the amount of solvent, there is no need for washing in the subsequent process, and the waste liquid generated by the whole process is only one tenth or less of the conventional hydrothermal method, and the pressure on the environment is also smaller, and the operation cost is lower.
  • the obtained product has uniform crystal grains, and the micropores of the large crystal are longer, which facilitates adsorption and storage of more gas, and the carbon dioxide adsorption capacity thereof also increases remarkably.
  • the beneficial effects of the present invention are that a high quality target composite framework material is synthesized with a very small amount of solvent.
  • the composite framework material with different particle sizes is grown by slurry crystallization under the condition of using a very small amount of solvent, and the grain controllable is realized, and the composite skeleton material is controlled.
  • the particle size provides a new synthetic route. Due to the large consumption of solvents, especially organic solvents, during the growth of the composite framework material, the mother liquor or waste liquid is rare, the yield is higher, and the washing is avoided, the discharge of metal ions and organic ligands is eliminated, and the operation is greatly reduced.
  • the method has less infrastructure investment, short process flow, low operating cost, easy operation, zero emission, environmental protection, economic feasibility, and easy realization of large-scale intensive production.
  • the obtained large particle composite skeleton material has a higher adsorption capacity in gas adsorption. It also has broad application prospects in the fields of chromatographic packing, optical devices, and green energy.
  • FIG. 1 is an optical photograph of a copper-based composite skeleton material synthesized by hydrothermal method of Experimental Example 1;
  • FIG. 2 is an XRD diffraction diagram of a copper-based composite framework material synthesized by hydrothermal method of Experimental Example 1;
  • FIG. 3 is a hydrothermal example of Experimental Example 1.
  • FIG. 4 is a pore size distribution diagram of the copper-based composite framework material synthesized by the hydrothermal method of the experimental example 1;
  • FIG. 5 is the copper-based composite skeleton synthesized by the hydrothermal method of the experimental example 1.
  • FIG. 6 is an optical photographic diagram of the copper-based composite framework material prepared in Example 1;
  • Figure 7 is an XRD diffraction pattern of the copper-based composite framework material prepared in Example 1, and
  • Figure 8 is a preparation of Example 1.
  • FIG. 9 is a pore size distribution diagram of the copper-based composite skeleton material prepared in Example 1;
  • FIG. 10 is a thermogravimetric curve diagram of the copper-based composite skeleton material prepared in Example 1; 11 is a carbon dioxide adsorption curve of the copper-based composite skeleton material prepared by the present invention.
  • Embodiment 1 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 1.6 ml of deionized water and 1.4 ml of ethanol;
  • the obtained granulated product was photographed, and the optical photograph showed that most of the particles had a size of about 140 ⁇ m (as shown in Fig. 6), and the XRD pattern showed high crystallinity and crystal plane orientation growth (as shown in Fig. 7).
  • Nitrogen isotherm adsorption showed a specific surface area of about 1858 square meters per gram (as shown in Figure 8), a pore volume of about 0.78 cubic centimeters per gram, and most of the pore size was concentrated at 0.62 nanometers (as shown in Figure 9). 87%. Its thermogravimetric curve in nitrogen showed good thermal stability and began to decompose at 623 K (as shown in Figure 10).
  • the carbon dioxide adsorption capacity of the material is about 6.73 kg/mol (as shown in Fig. 11), which is 1.7 times of the adsorption capacity of the material obtained by hydrothermal method (Experimental Example 1), and the product yield is 99.6. %.
  • Embodiment 2 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 1.0 ml of deionized water and 2.0 ml of industrial alcohol;
  • the product was tested to show that the optical image showed a size of about 130 microns, a specific surface area of about 1690 square meters per gram, a pore volume of about 0.53 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 98.9%.
  • Embodiment 3 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 1.2 ml of deionized water and 1.8 ml of ethylene glycol;
  • the product was tested to show that the optical image showed a size of about 110 microns, a specific surface area of about 1601 square meters per gram, a pore volume of about 0.50 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99%.
  • Embodiment 4 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 2.0 ml of deionized water and 1.0 ml of crude methanol;
  • the product was tested to show that the optical image showed a size of about 120 microns, a specific surface area of about 1726 square meters per gram, a pore volume of about 0.51 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 98%.
  • Embodiment 5 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 3 ml of N,N-dimethylformamide.
  • 1.5 ml of deionized water can also be mixed with 1.5 ml of N,N-dimethylformamide;
  • step (3) adding copper pyrophosphate trihydrate to the solvent prepared in the step (1) at room temperature, stirring for 15 minutes, then adding trimesic acid, stirring for 3 hours to form a slurry, sealing in a self-pressure reactor, heating The reaction was carried out at 110 ° C for 12 h, and dried at room temperature to obtain a granulated product.
  • the product was tested to show that the optical image showed a size of about 90 microns, a specific surface area of about 1705 square meters per gram, a pore volume of about 0.54 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99%.
  • Embodiment 6 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 1.2 ml of deionized water and 1.8 ml of dimethyl sulfoxide;
  • step (3) adding copper nitrate trihydrate to the solvent prepared in the step (1) at room temperature, stirring for 20 minutes, then adding trimesic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating to The reaction was carried out at 120 ° C for 11 h, and dried at room temperature to obtain a granulated product.
  • the product was tested to show that the optical image showed a size of about 105 microns, a specific surface area of about 1751 square meters per gram, a pore volume of about 0.55 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99%.
  • Embodiment 7 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 2.0 ml of deionized water and 1.0 ml of dimethyl ether;
  • step (3) adding copper nitrate trihydrate to the solvent prepared in the step (1) at room temperature, stirring for 16 minutes, then adding trimesic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating to The reaction was carried out at 120 ° C for 13 h, and dried at room temperature to obtain a granulated product.
  • the product was tested to show that the optical image showed a size of about 120 microns, a specific surface area of about 1850 square meters per gram, a pore volume of about 0.61 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99%.
  • Embodiment 8 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • step (3) adding copper chloride and copper nitrate to the solvent prepared in the step (1) at room temperature, stirring for 15 minutes, then adding trimesic acid, stirring for 2 hours to form a slurry, and sealing in a self-pressure reactor.
  • the mixture was heated to 110 ° C for 9 h, and dried at room temperature to obtain a granulated product.
  • the product was tested to show that the optical image showed a size of about 90 microns, a specific surface area of about 1,523 square meters per gram, a pore volume of about 0.48 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99.1%.
  • Embodiment 9 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 1.5 ml of deionized water and 1.5 ml of diethyl ether;
  • step (3) adding zinc nitrate and copper acetate to the solvent prepared in the step (1) at room temperature, stirring for 25 minutes, then adding trimesic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating The reaction was carried out at 110 ° C for 10 h, and dried at room temperature to obtain a granulated product.
  • the product was tested to show that the optical image showed a size of about 130 microns, a specific surface area of about 1682 square meters per gram, a pore volume of about 0.53 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99.3%.
  • Embodiment 10 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 1.0 ml of deionized water and 2.0 ml of industrial alcohol;
  • the product was tested to show that the optical photograph showed a size of about 90 microns, a specific surface area of about 1580 square meters per gram, a pore volume of about 0.49 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99.2%.
  • Embodiment 11 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • step (3) adding nickel nitrate and copper acetate to the solvent prepared in the step (1) at room temperature, stirring for 30 minutes, then adding trimesic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating The reaction was carried out at 110 ° C for 12 h, and dried at room temperature to obtain a granulated product.
  • the product was tested to show that the optical image showed a size of about 100 microns, a specific surface area of about 1616 square meters per gram, a pore volume of about 0.51 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99%.
  • Embodiment 12 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 3.0 ml of 95% ethanol, in order to save the amount of organic solvent, it can also be mixed with 1.0 ml of deionized water and 2.0 ml of 95% ethanol;
  • step (3) adding copper nitrate trihydrate to the solvent prepared in the step (1) at room temperature, stirring for 10 minutes, then adding trimesic acid, stirring for 1 hour to form a slurry, sealing in a self-pressure reactor, heating to The reaction was carried out at 110 ° C for 15 h, and dried at room temperature to obtain a granulated product.
  • the product was tested to show that the optical image showed a size of about 140 microns, a specific surface area of about 1801 square meters per gram, a pore volume of about 0.58 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99.5%.
  • Embodiment 13 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is mixed with 3.0 ml of deionized water and 3.0 ml of ethanol;
  • the product was tested to show that the optical image showed a size of about 80 microns, a specific surface area of about 1156 square meters per gram, a pore volume of about 0.52 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99%.
  • Embodiment 14 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 1.0 ml of deionized water and 2.0 ml of industrial alcohol;
  • the product was tested to show that the optical image showed a size of about 100 microns, a specific surface area of about 1304 square meters per gram, a pore volume of about 0.51 cubic centimeters per gram, a pore size of about 0.61 nanometers, and a yield of about 99.1%.
  • Embodiment 15 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is mixed with 1.4 ml of deionized water and 1.7 ml of 95% ethanol;
  • the product was tested to show that the optical image showed a size of about 90 microns, a specific surface area of about 1231 square meters per gram, a pore volume of about 0.50 cubic centimeters per gram, a pore size of about 0.62 nanometers, and a yield of about 98.1%.
  • Embodiment 16 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is mixed with 1.2 ml of deionized water and 1.7 ml of acetone;
  • the product was tested to show that the optical image showed a size of about 70 microns, a specific surface area of about 1030 square meters per gram, a pore volume of about 0.47 cubic centimeters per gram, a pore size of about 0.62 nanometers, and a yield of about 98.6%.
  • Embodiment 17 A slurry synthesis method of a porous composite skeleton material, comprising the steps of:
  • solvent is 1.5 ml of deionized water and 3 ml of industrial alcohol
  • step (3) adding basic copper carbonate to the solvent prepared in the step (1) at room temperature, stirring and mixing, then adding trimesic acid, stirring for 3 hours to form a slurry, sealing in a self-pressure reactor, heating to 140
  • the reaction was carried out at ° C for 12 h, and dried at room temperature to obtain a granulated product.
  • the product was tested to show that the optical image showed a size of about 50 microns, a specific surface area of about 1405 square meters per gram, a pore volume of about 0.51 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 97%.
  • Embodiment 18 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 7 ml of deionized water and 8.75 ml of ethanol;
  • the product was tested to show that the optical image showed a size of about 110 microns, a specific surface area of about 1291 square meters per gram, a pore volume of about 0.49 cubic centimeters per gram, a pore size of about 0.61 nanometers, and a yield of about 98.4%.
  • Embodiment 19 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 3 ml of deionized water and 4 ml of ethanol;
  • the product was tested to show that the optical image showed a size of about 60 microns, a specific surface area of about 991 square meters per gram, a pore volume of about 0.42 cubic centimeters per gram, a pore size of about 0.61 nanometers, and a yield of about 88.4%.
  • Embodiment 20 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 0.1 ml of deionized water and 1.224 ml of ethanol;
  • the product was tested to show that the optical image showed a size of about 50 microns, a specific surface area of about 871 square meters per gram, a pore volume of about 0.38 cubic centimeters per gram, a pore size of about 0.61 nanometers, and a yield of about 89.1%.
  • Embodiment 21 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the solvent is 25.0 ml of deionized water and 34.0 ml of ethanol;
  • step (3) adding copper nitrate trihydrate to the solvent prepared in the step (1) at room temperature, stirring for 16 minutes, then adding trimesic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating to The reaction was carried out at 130 ° C for 6 h, and dried at room temperature to obtain a granulated product.
  • the product was tested to show that the optical image showed a size of about 70 microns, a specific surface area of about 1250 square meters per gram, a pore volume of about 0.601 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 79%.
  • Embodiment 22 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • step (3) adding aluminum nitrate nonahydrate to the solvent prepared in the step (1) at room temperature, stirring for 36 minutes, then adding terephthalic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating to The reaction was carried out at 150 ° C for 6 h, and dried at room temperature to obtain a granulated product.
  • the product was tested to show that the optical image showed a white crystal size of about 20 microns, a specific surface area of about 1050 square meters per gram, a pore volume of about 0.43 cubic centimeters per gram, and a yield of about 83%.
  • Embodiment 23 A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
  • the product was tested to show that the optical image showed a white crystal size of about 30 microns, a specific surface area of about 1150 square meters per gram, a pore volume of about 0.44 cubic centimeters per gram, and a yield of about 89%.
  • Experimental Example 1 Synthesis of skeleton material by hydrothermal method: 20.0 ml of deionized water and 20.0 ml of ethanol were mixed, and 0.004 mol of pyromellitic acid was weighed and stirred at room temperature, and then 0.0061 mol of copper nitrate trihydrate was added. After stirring for 1 hour, a mixture was formed, sealed in a reaction vessel, heated at 110 ° C for 12 hours, cooled, washed with an equal amount of deionized water and ethanol, and then dried to obtain a powdery product.
  • the optical photograph showed that the size of most of the powder was about About 10 microns (as shown in Figure 1), the XRD pattern shows that the crystallinity is low, and the crystal face orientation growth is not obvious (as shown in Figure 2).
  • the nitrogen isotherm adsorption results show that the specific surface area is about 1251 square meters per gram ( As shown in Figure 3, the pore volume is about 0.48 cubic centimeters per gram, and most of the pore size is concentrated at 0.62 nm, but a small portion of the pore size is different (as shown in Figure 4), and the yield is about 67%.
  • the material has a carbon dioxide adsorption capacity of about 3.9 kg/mol (as shown in Figure 5).
  • Example 1 Compared with Example 1, this experimental example clearly shows that the slurry synthesis method of the present invention can synthesize high-quality target composite skeleton materials by using less solvent, has less waste liquid, and has higher yield and eliminates metal ions. And the discharge of organic ligands, greatly reducing operating energy consumption and cost, and more importantly, avoiding environmental pollution, direct drying, making the product easier to collect. In addition, the adsorption capacity for carbon dioxide is higher, and it is apparent that the large particle composite skeleton material obtained by the slurry synthesis method of the present invention has a higher adsorption capacity in gas adsorption.

Abstract

The present invention relates to the technical field of porous composite material preparation, and provides a slurry synthesis method for a porous composite framework material. A mass ratio of a solvent to a solid reactant is controlled, so that the reactant is at different saturation levels, an inorganic-organic composite framework material is obtained by heating in a sealed container, and the grain size and distribution of the composite framework material are regulated and controlled. At room temperature, an inorganic metal source is dispersed into the solvent, and then mixed with a polycarboxylic acid organic compound to form slurry, the slurry is sealed in a self-pressurized reaction kettle, and heated to 70-170ºC, reaction is performed for 0.5-240 h, drying is performed at room temperature, and therefore the porous composite framework material is obtained. According to the method, the grain size is controllable, and the method provides a novel synthesis route for controlling the grin size of the composite framework material. The yield is increased, washing is not required, operating costs are low, the operation is easy, zero emission is implemented, the method is environmentally friendly and economically feasible, and it is easy to implement large-scale intensive production. The obtained large-grain composite framework material has a larger adsorption capacity in the aspect of gas adsorption.

Description

一种多孔复合骨架材料的浆态合成方法Slurry synthesis method of porous composite skeleton material 技术领域Technical field
本发明属于多孔复合材料制备技术领域，具体涉及一种多孔复合骨架材料的浆态合成方法。该方法使用极少量的溶剂，反应物在浆态中转化，得到不同粒径的多孔复合材料。The invention belongs to the technical field of preparation of porous composite materials, and in particular relates to a slurry synthesis method of a porous composite skeleton material. The process uses a very small amount of solvent and the reactants are converted in a slurry state to obtain porous composite materials of different particle sizes.
背景技术Background technique
多孔复合材料是一类新型微孔高比表面功能材料，表面性质、孔道结构、中心金属离子配位形式多变，可根据最终应用需求进行特定的化学修饰。随着近年来的研究，其在气体储存与分离、药物储运与释放、能源储存、光学器件、色谱分析等领域拥有巨大的应用潜力，引起了国内外政府、企业、高校学者的争相研究。Porous composite materials are a new class of microporous high specific surface functional materials. The surface properties, pore structure and central metal ion coordination form are variable, and specific chemical modifications can be made according to the final application requirements. With the recent research, it has great application potential in the fields of gas storage and separation, drug storage and release, energy storage, optical devices, chromatographic analysis, etc., which has caused competition among domestic and foreign governments, enterprises and university scholars. .
目前合成该类材料的方法有水热法、溶剂热法、超声波辅助合成法，微波合成法、电化学合成法、研磨法等。以水热或者溶剂热法合成该类材料为例，主要在合成过程中侧重于使用大量的溶剂促使反应物的充分溶解，以便均相反应，得到颗粒较小(通常在10微米左右)的产物。反应过程中一个不可避免的情况是始终有反应物溶解在大量溶剂中未形成晶体产物，最后以母液形式排放或进行回收处理，大大降低了产率和增加了环境污染。其他方法在合成或者后处理中同样需要消耗大量的溶剂，增加了生产运行成本和对环境的污染，回收利用将会产生额外成本。处理废液最好的办法是尽量不产生废液，可以通过改进生产工艺，从源头上削减或者杜绝废液的产生。At present, methods for synthesizing such materials include hydrothermal method, solvothermal method, ultrasonic assisted synthesis method, microwave synthesis method, electrochemical synthesis method, and grinding method. For example, hydrothermal or solvothermal synthesis of such materials is mainly focused on the use of a large amount of solvent to promote the complete dissolution of the reactants in the synthesis process, so as to obtain a relatively small particle (usually around 10 microns). . An unavoidable situation in the reaction process is that the reactants are always dissolved in a large amount of solvent and no crystal product is formed, and finally discharged as a mother liquid or recycled, which greatly reduces the yield and increases the environmental pollution. Other methods also require a large amount of solvent to be consumed in the synthesis or after-treatment, which increases production operation costs and environmental pollution, and recycling will incur additional costs. The best way to dispose of waste liquid is to avoid waste liquid as much as possible. By improving the production process, it can reduce or eliminate waste liquid from the source.
针对上述类似的问题，文献提到用浆态法合成了多孔无机金属盐钼酸镍铵，该文献采用高速粉碎机混合各固体反应物，最后添加助剂形成浆态并在一定温度下晶化得到产物。该论文并没有明确助剂的种类和剂量,反应机理也尚不明确。产物形态司空见惯，长度只有0.8微米，物化性能也没有明显改善。显然现有采用浆态法合成多孔无机金属盐钼酸镍铵的工艺并未成熟，仍然存在诸多问题。In view of the above similar problems, the literature mentions that the porous inorganic metal salt nickel ammonium molybdate is synthesized by the slurry method. The literature uses a high-speed pulverizer to mix the solid reactants, and finally adds an auxiliary agent to form a slurry and crystallize at a certain temperature. The product was obtained. The paper does not specify the type and dosage of the adjuvant, and the reaction mechanism is not yet clear. The shape of the product is commonplace, the length is only 0.8 microns, and the physical and chemical properties are not significantly improved. Obviously, the existing process for synthesizing the porous inorganic metal salt nickel ammonium molybdate by the slurry method is not mature, and there are still many problems.
作为一种需要溶剂参与晶化的无机-有机复合骨架材料，针对制备过程中溶 剂的消耗和晶体尺寸的控制尚处于空白阶段，并没有采用浆态法合成无机-有机复合骨架材料的文献。As an inorganic-organic composite framework material which requires solvent to participate in crystallization, the consumption of solvent and the control of crystal size in the preparation process are still in a blank stage, and there is no literature on the synthesis of inorganic-organic composite framework materials by slurry method.
发明内容Summary of the invention
本发明的目的在于提供一种多孔复合骨架材料的浆态合成方法，控制溶剂与固态反应物的质量比，使反应物处在不同的饱和度，通过在密封的容器中加热处理得到无机-有机复合骨架材料，并调控复合骨架材料的晶粒大小及其分布。The object of the present invention is to provide a slurry synthesis method of a porous composite skeleton material, which controls the mass ratio of a solvent to a solid reactant, so that the reactants are at different degrees of saturation, and the inorganic-organic is obtained by heat treatment in a sealed container. The composite framework material controls the grain size and distribution of the composite framework material.
本发明由如下技术方案实现的：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：The invention is realized by the following technical solution: a slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为有机溶剂或含水的有机溶剂；(1) selecting a solvent: the solvent is an organic solvent or an aqueous organic solvent;
(2)选择固体反应原料：无机金属盐或金属碱作为多孔复合骨架材料中的配位无机金属源，多羧酸有机化合物作为多孔复合骨架材料的有机配体；(2) selecting a solid reaction raw material: an inorganic metal salt or a metal base as a coordination inorganic metal source in the porous composite skeleton material, and a polycarboxylic acid organic compound as an organic ligand of the porous composite skeleton material;
(3)室温下，将无机金属源分散于溶剂中，然后与多羧酸有机化合物混合形成浆料，密封于自压反应釜中，加热至70-170℃反应0.5-240h，室温干燥即可；(3) Dispersing the inorganic metal source in a solvent at room temperature, then mixing with the polycarboxylic acid organic compound to form a slurry, sealing in a self-pressure reactor, heating to 70-170 ° C for 0.5-240 h, drying at room temperature ;
所述无机金属源与多羧酸有机化合物的摩尔比为：(0.5-10):2；无机金属盐或金属碱与多羧酸有机化合物的质量之和与溶剂总质量的比值为0.1-3。The molar ratio of the inorganic metal source to the polycarboxylic acid organic compound is: (0.5-10): 2; the ratio of the sum of the mass of the inorganic metal salt or the metal base to the polycarboxylic acid organic compound to the total mass of the solvent is 0.1-3 .
步骤(1)中的有机溶剂为：甲醇、乙醇、乙二醇、二甲醚、乙醚、丙酮、二甲基亚砜、N，N—二甲基甲酰胺中的任意一种或者任意两种以任意比例混合；水为去离子水或蒸馏水；含水的有机溶剂中水与有机溶剂的体积比为0-1000。The organic solvent in the step (1) is any one or any two of methanol, ethanol, ethylene glycol, dimethyl ether, diethyl ether, acetone, dimethyl sulfoxide, and N,N-dimethylformamide. Mix in any ratio; water is deionized water or distilled water; the volume ratio of water to organic solvent in the aqueous organic solvent is 0-1000.
步骤(2)中所述的无机金属源为铁、钴、镍、铜、铬、锌的盐或碱中的任意一种或任意两种金属源。The inorganic metal source described in the step (2) is any one or any two metal sources of iron, cobalt, nickel, copper, chromium, zinc or a base.
步骤(2)中所述的无机金属源优选为：硝酸铜、三水合焦磷酸铜、醋酸铜、碱式碳酸铜、硫酸铜、氯化铜、氢氧化铜、硝酸锌、硝酸铝、醋酸铝、硝酸钴、醋酸钴、硝酸镍、醋酸镍、氢氧化镍、氢氧化钴、硝酸铁、氯化铁中的任意一种或任意两种以任意比例混合。The inorganic metal source described in the step (2) is preferably: copper nitrate, copper pyrophosphate trihydrate, copper acetate, basic copper carbonate, copper sulfate, copper chloride, copper hydroxide, zinc nitrate, aluminum nitrate, aluminum acetate. Any one or any two of cobalt nitrate, cobalt acetate, nickel nitrate, nickel acetate, nickel hydroxide, cobalt hydroxide, iron nitrate, and ferric chloride are mixed in an arbitrary ratio.
步骤(2)中所述的多羧酸有机化合物为均苯三甲酸、对苯二甲酸中的一种或者混合。所制备的多孔复合骨架材料粒径为0.0002-2毫米。The polycarboxylic acid organic compound described in the step (2) is one or a mixture of trimesic acid and terephthalic acid. The prepared porous composite skeleton material has a particle diameter of 0.0002 to 2 mm.
本发明根据金属源和多羧酸有机化合物的质量之和与溶剂总质量的比值来调节所制备的多孔复合骨架材料的粒径，比值较高时粒径分布较窄，颗粒均一；反之，粒径分布较宽，颗粒大小不一，即溶剂用量小时，获得的多孔复合骨架材料的粒径分布较窄，颗粒均一，而溶剂用量大时，颗粒大小不一。The invention adjusts the particle size of the prepared porous composite skeleton material according to the ratio of the sum of the mass of the metal source and the polycarboxylic acid organic compound to the total mass of the solvent, and the particle size distribution is narrower when the ratio is higher, and the particles are uniform; The diameter distribution is wide, and the particle size is different, that is, when the solvent dosage is small, the obtained porous composite skeleton material has a narrow particle size distribution and uniform particles, and when the solvent amount is large, the particle size is different.
另外，混合溶剂中含水的有机溶剂中水与有机溶剂的体积比控制所制备的多孔复合骨架材料的粒径大小，有机溶剂含量较高时，晶体粒径较小，反之，晶体粒径较大。而晶体粒径越大，微孔孔道就越长，便于捕获和容纳更多的气体分子，从而有更高的气体吸附容量。反之颗粒越小的材料暴露了更多的外表面，对捕获气体并没有太大的好处。In addition, the volume ratio of water to the organic solvent in the organic solvent contained in the mixed solvent controls the particle size of the prepared porous composite skeleton material, and when the organic solvent content is high, the crystal grain size is small, and conversely, the crystal grain size is larger. . The larger the crystal grain size, the longer the microporous channel is, which is convenient for capturing and accommodating more gas molecules, thereby having a higher gas adsorption capacity. Conversely, a material with a smaller particle exposing more of the outer surface does not have much benefit in capturing the gas.
本发明所述的浆态合成法并不需要充分溶解，是完全的非均相反应。合成工艺与现有技术完全不同,由于所用溶剂约为传统溶剂热法溶剂用量的10％，溶剂用量大大减少，反应物起始浓度过饱和，反应推动力更大，便于形成大晶体。另外，由于溶剂用量的减少，后续无须洗涤，整个过程产生的废液仅为传统水热法的十分之一或者更少，对环境的压力也更小，同时运行成本更低。所得产品的晶粒均匀，大晶体的微孔孔道更长，便于吸附储存更多气体，其二氧化碳吸附容量也明显增加。The slurry synthesis method of the present invention does not require sufficient dissolution and is a completely heterogeneous reaction. The synthesis process is completely different from the prior art. Since the solvent used is about 10% of the amount of the conventional solvothermal solvent, the amount of the solvent is greatly reduced, the initial concentration of the reactant is supersaturated, the reaction driving force is larger, and the formation of large crystals is facilitated. In addition, due to the reduction of the amount of solvent, there is no need for washing in the subsequent process, and the waste liquid generated by the whole process is only one tenth or less of the conventional hydrothermal method, and the pressure on the environment is also smaller, and the operation cost is lower. The obtained product has uniform crystal grains, and the micropores of the large crystal are longer, which facilitates adsorption and storage of more gas, and the carbon dioxide adsorption capacity thereof also increases remarkably.
本发明的有益效果在于：以极少量的溶剂合成高质量的目标复合骨架材料。通过调控体系溶剂与固体反应物的质量比，在使用极少量的溶剂的条件下，经过浆态晶化法生长出不同粒径的复合骨架材料，实现了晶粒可控，为控制复合骨架材料的粒径提供了新的合成途径。由于在复合骨架材料生长过程中避免了溶剂尤其是有机溶剂的大量消耗，母液或者废液极少，产率更高，免于洗涤，杜绝了金属离子和有机配体的排放，极大地减少运行能耗和成本，更重要的是，避免了对环境的污染，直接干燥，使得产物更加容易收集。该方法设备基建投资少，工艺流程简短，运行成本低，操作容易，零排放，绿色环保，经济可行，易于实现大规模集约化生产。所获得的大颗粒复合骨架材料在气体吸附方面有更高的吸附容量。在色谱填料、光学器件、绿 色能源等领域同样具有广阔的应用前景。The beneficial effects of the present invention are that a high quality target composite framework material is synthesized with a very small amount of solvent. By controlling the mass ratio of the solvent to the solid reactant in the system, the composite framework material with different particle sizes is grown by slurry crystallization under the condition of using a very small amount of solvent, and the grain controllable is realized, and the composite skeleton material is controlled. The particle size provides a new synthetic route. Due to the large consumption of solvents, especially organic solvents, during the growth of the composite framework material, the mother liquor or waste liquid is rare, the yield is higher, and the washing is avoided, the discharge of metal ions and organic ligands is eliminated, and the operation is greatly reduced. Energy consumption and cost, and more importantly, avoid environmental pollution and direct drying, making the product easier to collect. The method has less infrastructure investment, short process flow, low operating cost, easy operation, zero emission, environmental protection, economic feasibility, and easy realization of large-scale intensive production. The obtained large particle composite skeleton material has a higher adsorption capacity in gas adsorption. It also has broad application prospects in the fields of chromatographic packing, optical devices, and green energy.
附图说明DRAWINGS
图1为实验例1水热法合成的铜基复合骨架材料的光学照片图；图2为实验例1水热法合成的铜基复合骨架材料的XRD衍射图；图3为实验例1水热法合成的铜基复合骨架材料的氮气吸附曲线图；图4为实验例1水热法合成的铜基复合骨架材料的孔径分布图；图5为实验例1水热法合成的铜基复合骨架材料的二氧化碳吸附曲线图；图6为实施例1制备的铜基复合骨架材料的光学照片图；图7为实施例1制备的铜基复合骨架材料的XRD衍射图；图8为实施例1制备的铜基复合骨架材料的氮气吸附曲线图；图9为实施例1制备的铜基复合骨架材料的孔径分布图；图10为实施例1制备的铜基复合骨架材料的热重曲线图；图11为实施例1本发明制备的铜基复合骨架材料的二氧化碳吸附曲线图。1 is an optical photograph of a copper-based composite skeleton material synthesized by hydrothermal method of Experimental Example 1; FIG. 2 is an XRD diffraction diagram of a copper-based composite framework material synthesized by hydrothermal method of Experimental Example 1; and FIG. 3 is a hydrothermal example of Experimental Example 1. The nitrogen adsorption curve of the copper-based composite framework material synthesized by the method; FIG. 4 is a pore size distribution diagram of the copper-based composite framework material synthesized by the hydrothermal method of the experimental example 1; FIG. 5 is the copper-based composite skeleton synthesized by the hydrothermal method of the experimental example 1. Figure 6 is an optical photographic diagram of the copper-based composite framework material prepared in Example 1; Figure 7 is an XRD diffraction pattern of the copper-based composite framework material prepared in Example 1, and Figure 8 is a preparation of Example 1. FIG. 9 is a pore size distribution diagram of the copper-based composite skeleton material prepared in Example 1; FIG. 10 is a thermogravimetric curve diagram of the copper-based composite skeleton material prepared in Example 1; 11 is a carbon dioxide adsorption curve of the copper-based composite skeleton material prepared by the present invention.
具体实施方式Detailed ways
下述实施例是对于本发明内容的进一步说明，并作为对本发明技术内容的解释。但本发明的实质内容不受下述实施例所述内容所限，本领域的技术人员可以且应当知悉任何基于本发明实质精神的简单变化或替换均应属于本发明所要求的保护范围。The following examples are a further description of the contents of the present invention and are intended to explain the technical contents of the present invention. However, the essence of the invention is not limited by the following examples, and those skilled in the art can and should understand that any simple changes or substitutions based on the spirit of the invention should fall within the scope of the invention.
实施例1：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 1: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为1.6毫升去离子水和1.4毫升乙醇混合；(1) selecting a solvent: the solvent is 1.6 ml of deionized water and 1.4 ml of ethanol;
(2)准确称取0.0061摩尔三水合硝酸铜为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) Accurately weigh 0.0061 moles of copper nitrate trihydrate as a metal precursor, and accurately weigh 0.004 moles of pyromellitic acid as an organic ligand of the porous composite framework material;
(3)室温下，将三水合硝酸铜加入到步骤(1)制备的溶剂中，搅拌10min，然后加入均苯三甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至110℃反应10h，室温干燥即可获得颗粒状产物。(3) adding copper nitrate trihydrate to the solvent prepared in the step (1) at room temperature, stirring for 10 min, then adding trimesic acid, stirring for 2 h to form a slurry, sealing in a self-pressure reactor, heating to 110 The reaction was carried out for 10 hours at ° C, and dried at room temperature to obtain a granulated product.
获得的颗粒状产物照相，光学照片显示大部分颗粒的尺寸约为140微米左右(如图6所示)，XRD图谱显示其结晶度高，而且晶面取向生长明显(如图7所示)，氮气等温吸附结果显示其比表面积约为1858平方米每克(如图8所示)，孔容约为0.78立方厘米每克，大部分孔径集中在0.62纳米(如图9所示)，产率87％。其在氮气中的热重曲线显示其热稳定性较好， 在623K开始分解(如图10所示)。在295K、一个大气压下，该材料的二氧化碳吸附容量约约为6.73kg/mol(如图11所示)，是水热法所得材料(实验例1)的吸附容量的1.7倍，产品产率99.6％。The obtained granulated product was photographed, and the optical photograph showed that most of the particles had a size of about 140 μm (as shown in Fig. 6), and the XRD pattern showed high crystallinity and crystal plane orientation growth (as shown in Fig. 7). Nitrogen isotherm adsorption showed a specific surface area of about 1858 square meters per gram (as shown in Figure 8), a pore volume of about 0.78 cubic centimeters per gram, and most of the pore size was concentrated at 0.62 nanometers (as shown in Figure 9). 87%. Its thermogravimetric curve in nitrogen showed good thermal stability and began to decompose at 623 K (as shown in Figure 10). At 295 K and one atmosphere, the carbon dioxide adsorption capacity of the material is about 6.73 kg/mol (as shown in Fig. 11), which is 1.7 times of the adsorption capacity of the material obtained by hydrothermal method (Experimental Example 1), and the product yield is 99.6. %.
实施例2：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 2: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为1.0毫升去离子水和2.0毫升工业酒精混合；(1) Select solvent: the solvent is 1.0 ml of deionized water and 2.0 ml of industrial alcohol;
(2)准确称取0.0061摩尔硫酸铜为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) accurately weigh 0.0061 mol of copper sulfate as a metal precursor, accurately weigh 0.004 mol of pyromellitic acid as an organic ligand of the porous composite framework material;
(3)室温下，将硫酸铜加入到步骤(1)制备的溶剂中，搅拌10min，然后加入均苯三甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至100℃反应16h，室温干燥即可获得颗粒状产物。(3) Add copper sulfate to the solvent prepared in the step (1) at room temperature, stir for 10 min, then add trimesic acid, stir for 2 h to form a slurry, seal in a autoclave, and heat to 100 ° C. After 16 h, drying at room temperature gave a granular product.
产物经检测显示：光学照片显示其尺寸约为130微米左右，比表面积约为1690平方米每克，孔容约为0.53立方厘米每克，孔径约为0.6纳米，产率约为98.9％。The product was tested to show that the optical image showed a size of about 130 microns, a specific surface area of about 1690 square meters per gram, a pore volume of about 0.53 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 98.9%.
实施例3：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 3: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为1.2毫升去离子水和1.8毫升乙二醇混合；(1) selecting a solvent: the solvent is 1.2 ml of deionized water and 1.8 ml of ethylene glycol;
(2)准确称取0.0061摩尔氯化铜为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) accurately weigh 0.0061 moles of copper chloride as a metal precursor, and accurately weigh 0.004 moles of trimesic acid as an organic ligand of the porous composite framework material;
(3)室温下，将氯化铜加入到步骤(1)制备的溶剂中，搅拌10min，然后加入均苯三甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至110℃反应13h，室温干燥即可获得颗粒状产物。(3) adding copper chloride to the solvent prepared in the step (1) at room temperature, stirring for 10 min, then adding trimesic acid, stirring for 2 h to form a slurry, sealing in a self-pressure reactor, heating to 110 ° C The reaction was carried out for 13 hours and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸为110微米左右，比表面积约为1601平方米每克，孔容约为0.50立方厘米每克，孔径约为0.6纳米，产率约为99％。The product was tested to show that the optical image showed a size of about 110 microns, a specific surface area of about 1601 square meters per gram, a pore volume of about 0.50 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99%.
实施例4：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 4: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为2.0毫升去离子水和1.0毫升粗甲醇混合；(1) selecting a solvent: the solvent is 2.0 ml of deionized water and 1.0 ml of crude methanol;
(2)准确称取0.0061摩尔氢氧化铜为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) accurately weigh 0.0061 moles of copper hydroxide as a metal precursor, accurately weigh 0.004 moles of pyromellitic acid as an organic ligand of the porous composite framework material;
(3)室温下，将氢氧化铜加入到步骤(1)制备的溶剂中，搅拌0.5h，然后加入均苯三甲酸，搅拌3h混合形成浆料，密封于自压反应釜 中，加热至110℃反应140h，室温干燥即可获得颗粒状产物。(3) adding copper hydroxide to the solvent prepared in the step (1) at room temperature, stirring for 0.5 h, then adding trimesic acid, stirring for 3 h to form a slurry, sealing in a self-pressure reactor, heating to 110 The reaction was carried out at ° C for 140 h, and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸为120微米左右，比表面积约为1726平方米每克，孔容约为0.51立方厘米每克，孔径约为0.6纳米，产率约为98％。The product was tested to show that the optical image showed a size of about 120 microns, a specific surface area of about 1726 square meters per gram, a pore volume of about 0.51 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 98%.
实施例5：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 5: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为3毫升N，N—二甲基甲酰胺，为节约有机溶剂用量，也可以采用1.5毫升去离子水与1.5毫升毫升N，N—二甲基甲酰胺混合；(1) Select solvent: the solvent is 3 ml of N,N-dimethylformamide. In order to save the organic solvent, 1.5 ml of deionized water can also be mixed with 1.5 ml of N,N-dimethylformamide;
(2)准确称取0.00305摩尔三水合焦磷酸铜为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) accurately weigh 0.00305 moles of copper pyrophosphate trihydrate as a metal precursor, and accurately weigh 0.004 moles of pyromellitic acid as an organic ligand of the porous composite framework material;
(3)室温下，将三水合焦磷酸铜加入到步骤(1)制备的溶剂中，搅拌15分钟，然后加入均苯三甲酸，搅拌3h混合形成浆料，密封于自压反应釜中，加热至110℃反应12h，室温干燥即可获得颗粒状产物。(3) adding copper pyrophosphate trihydrate to the solvent prepared in the step (1) at room temperature, stirring for 15 minutes, then adding trimesic acid, stirring for 3 hours to form a slurry, sealing in a self-pressure reactor, heating The reaction was carried out at 110 ° C for 12 h, and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸为90微米左右，比表面积约为1705平方米每克，孔容约为0.54立方厘米每克，孔径约为0.6纳米，产率约为99％。The product was tested to show that the optical image showed a size of about 90 microns, a specific surface area of about 1705 square meters per gram, a pore volume of about 0.54 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99%.
实施例6：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 6: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为1.2毫升去离子水和1.8毫升二甲基亚砜混合；(1) selecting a solvent: the solvent is 1.2 ml of deionized water and 1.8 ml of dimethyl sulfoxide;
(2)准确称取0.0061摩尔三水合硝酸铜为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) Accurately weigh 0.0061 moles of copper nitrate trihydrate as a metal precursor, and accurately weigh 0.004 moles of pyromellitic acid as an organic ligand of the porous composite framework material;
(3)室温下，将三水合硝酸铜加入到步骤(1)制备的溶剂中，搅拌20分钟，然后加入均苯三甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至120℃反应11h，室温干燥即可获得颗粒状产物。(3) adding copper nitrate trihydrate to the solvent prepared in the step (1) at room temperature, stirring for 20 minutes, then adding trimesic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating to The reaction was carried out at 120 ° C for 11 h, and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸为105微米左右，比表面积约为1751平方米每克，孔容约为0.55立方厘米每克，孔径约为0.6纳米，产率约为99％。The product was tested to show that the optical image showed a size of about 105 microns, a specific surface area of about 1751 square meters per gram, a pore volume of about 0.55 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99%.
实施例7：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 7: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为2.0毫升去离子水和1.0毫升二甲醚混合；(1) selecting a solvent: the solvent is 2.0 ml of deionized water and 1.0 ml of dimethyl ether;
(2)准确称取0.0061摩尔三水合硝酸铜为金属前驱体，准确称取 0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) Accurately weigh 0.0061 moles of copper nitrate trihydrate as a metal precursor, and accurately weigh 0.004 moles of pyromellitic acid as an organic ligand of the porous composite framework material;
(3)室温下，将三水合硝酸铜加入到步骤(1)制备的溶剂中，搅拌16分钟，然后加入均苯三甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至120℃反应13h，室温干燥即可获得颗粒状产物。(3) adding copper nitrate trihydrate to the solvent prepared in the step (1) at room temperature, stirring for 16 minutes, then adding trimesic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating to The reaction was carried out at 120 ° C for 13 h, and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸为120微米左右，比表面积约为1850平方米每克，孔容约为0.61立方厘米每克，孔径约为0.6纳米，产率约为99％。The product was tested to show that the optical image showed a size of about 120 microns, a specific surface area of about 1850 square meters per gram, a pore volume of about 0.61 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99%.
实施例8：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 8: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为1.2毫升去离子水和1.8毫升工业酒精混合；(1) Select solvent: the solvent is mixed with 1.2 ml of deionized water and 1.8 ml of industrial alcohol;
(2)准确称取0.003摩尔氯化铜和0.0031摩尔硝酸铜为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) accurately weigh 0.003 moles of copper chloride and 0.0031 moles of copper nitrate as metal precursors, and accurately weigh 0.004 moles of trimesic acid as an organic ligand of the porous composite framework material;
(3)室温下，将氯化铜和硝酸铜加入到步骤(1)制备的溶剂中，搅拌15分钟，然后加入均苯三甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至110℃反应9h，室温干燥即可获得颗粒状产物。(3) adding copper chloride and copper nitrate to the solvent prepared in the step (1) at room temperature, stirring for 15 minutes, then adding trimesic acid, stirring for 2 hours to form a slurry, and sealing in a self-pressure reactor. The mixture was heated to 110 ° C for 9 h, and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸为90微米左右，比表面积约为1523平方米每克，孔容约为0.48立方厘米每克，孔径约为0.6纳米，产率约为99.1％。The product was tested to show that the optical image showed a size of about 90 microns, a specific surface area of about 1,523 square meters per gram, a pore volume of about 0.48 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99.1%.
实施例9：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 9: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为1.5毫升去离子水和1.5毫升乙醚混合；(1) selecting a solvent: the solvent is 1.5 ml of deionized water and 1.5 ml of diethyl ether;
(2)准确称取0.002摩尔硝酸锌和0.0041摩尔醋酸铜为金属前驱体，准确称取0.00404摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) accurately weigh 0.002 mol of zinc nitrate and 0.0041 mol of copper acetate as a metal precursor, accurately weigh 0.00404 mol of pyromellitic acid as an organic ligand of the porous composite framework material;
(3)室温下，将硝酸锌和醋酸铜加入到步骤(1)制备的溶剂中，搅拌25分钟，然后加入均苯三甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至110℃反应10h，室温干燥即可获得颗粒状产物。(3) adding zinc nitrate and copper acetate to the solvent prepared in the step (1) at room temperature, stirring for 25 minutes, then adding trimesic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating The reaction was carried out at 110 ° C for 10 h, and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸为130微米左右，比表面积约为1682平方米每克，孔容约为0.53立方厘米每克，孔径约为0.6纳米，产率约为99.3％。The product was tested to show that the optical image showed a size of about 130 microns, a specific surface area of about 1682 square meters per gram, a pore volume of about 0.53 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99.3%.
实施例10：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 10: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为1.0毫升去离子水和2.0毫升工业酒精混合；(1) Select solvent: the solvent is 1.0 ml of deionized water and 2.0 ml of industrial alcohol;
(2)准确称取0.00203摩尔硝酸钴和0.00407摩尔醋酸铜为金属前驱体，准确称取0.00405摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) accurately weigh 0.00203 moles of cobalt nitrate and 0.00407 moles of copper acetate as metal precursors, accurately weigh 0.00405 moles of trimesic acid as the organic ligand of the porous composite framework material;
(3)室温下，将硝酸钴和醋酸铜加入到步骤(1)制备的溶剂中，搅拌10分钟，然后加入均苯三甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至170℃反应0.5h，室温干燥即可获得颗粒状产物。(3) adding cobalt nitrate and copper acetate to the solvent prepared in the step (1) at room temperature, stirring for 10 minutes, then adding trimesic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating The reaction was carried out at 170 ° C for 0.5 h, and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸为90微米左右，比表面积约为1580平方米每克，孔容约为0.49立方厘米每克，孔径约为0.6纳米，产率约为99.2％。The product was tested to show that the optical photograph showed a size of about 90 microns, a specific surface area of about 1580 square meters per gram, a pore volume of about 0.49 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99.2%.
实施例11：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 11: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为1.2毫升去离子水和1.8毫升工业酒精混合；(1) Select solvent: the solvent is mixed with 1.2 ml of deionized water and 1.8 ml of industrial alcohol;
(2)准确称取0.00303摩尔硝酸镍和0.00305摩尔醋酸铜为金属前驱体，准确称取0.00402摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) Accurately weigh 0.00303 moles of nickel nitrate and 0.00305 moles of copper acetate as metal precursors, and accurately weigh 0.00402 moles of trimesic acid as the organic ligand of the porous composite framework material;
(3)室温下，将硝酸镍和醋酸铜加入到步骤(1)制备的溶剂中，搅拌30分钟，然后加入均苯三甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至110℃反应12h，室温干燥即可获得颗粒状产物。(3) adding nickel nitrate and copper acetate to the solvent prepared in the step (1) at room temperature, stirring for 30 minutes, then adding trimesic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating The reaction was carried out at 110 ° C for 12 h, and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸为100微米左右，比表面积约为1616平方米每克，孔容约为0.51立方厘米每克，孔径约为0.6纳米，产率约为99％。The product was tested to show that the optical image showed a size of about 100 microns, a specific surface area of about 1616 square meters per gram, a pore volume of about 0.51 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99%.
实施例12：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 12: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为3.0毫升95％乙醇，为节约有机溶剂用量，也可以采用1.0毫升去离子水和2.0毫升95％乙醇混合；(1) Select solvent: the solvent is 3.0 ml of 95% ethanol, in order to save the amount of organic solvent, it can also be mixed with 1.0 ml of deionized water and 2.0 ml of 95% ethanol;
(2)准确称取0.0061摩尔三水合硝酸铜为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) Accurately weigh 0.0061 moles of copper nitrate trihydrate as a metal precursor, and accurately weigh 0.004 moles of pyromellitic acid as an organic ligand of the porous composite framework material;
(3)室温下，将三水合硝酸铜加入到步骤(1)制备的溶剂中，搅拌10分钟，然后加入均苯三甲酸，搅拌1h混合形成浆料，密封于自压反应釜中，加热至110℃反应15h，室温干燥即可获得颗粒状产物。(3) adding copper nitrate trihydrate to the solvent prepared in the step (1) at room temperature, stirring for 10 minutes, then adding trimesic acid, stirring for 1 hour to form a slurry, sealing in a self-pressure reactor, heating to The reaction was carried out at 110 ° C for 15 h, and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸为140微米左右，比表面积约为1801平方米每克，孔容约为0.58立方厘米每克，孔径约为0.6纳米，产率约为99.5％。The product was tested to show that the optical image showed a size of about 140 microns, a specific surface area of about 1801 square meters per gram, a pore volume of about 0.58 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99.5%.
实施例13：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 13: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为3.0毫升去离子水和3.0毫升乙醇混合；(1) selecting a solvent: the solvent is mixed with 3.0 ml of deionized water and 3.0 ml of ethanol;
(2)准确称取0.0061摩尔三水合硝酸铜为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) Accurately weigh 0.0061 moles of copper nitrate trihydrate as a metal precursor, and accurately weigh 0.004 moles of pyromellitic acid as an organic ligand of the porous composite framework material;
(3)室温下，将三水合硝酸铜加入到步骤(1)制备的溶剂中，搅拌混合，然后加入均苯三甲酸，搅拌3h混合形成浆料，密封于自压反应釜中，加热至70℃反应240h，室温干燥即可获得颗粒状产物。(3) adding copper nitrate trihydrate to the solvent prepared in the step (1) at room temperature, stirring and mixing, then adding trimesic acid, stirring for 3 hours to form a slurry, sealing in a self-pressure reactor, heating to 70 The reaction was carried out at ° C for 240 h, and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸为80微米左右，比表面积约为1156平方米每克，孔容约为0.52立方厘米每克，孔径约为0.6纳米，产率约为99％。The product was tested to show that the optical image showed a size of about 80 microns, a specific surface area of about 1156 square meters per gram, a pore volume of about 0.52 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 99%.
实施例14：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 14: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为1.0毫升去离子水和2.0毫升工业酒精混合；(1) Select solvent: the solvent is 1.0 ml of deionized water and 2.0 ml of industrial alcohol;
(2)准确称取0.0061摩尔醋酸钴为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) accurately weigh 0.0061 moles of cobalt acetate as a metal precursor, accurately weigh 0.004 moles of trimesic acid as an organic ligand of the porous composite framework material;
(3)室温下，将醋酸钴加入到步骤(1)制备的溶剂中，搅拌混合，然后加入均苯三甲酸，搅拌1h混合形成浆料，密封于自压反应釜中，加热至110℃反应14h，室温干燥即可获得颗粒状产物。(3) Add cobalt acetate to the solvent prepared in the step (1) at room temperature, stir and mix, then add trimesic acid, stir for 1 hour to form a slurry, seal in a self-pressure reactor, and heat to 110 ° C. After 14 h, drying at room temperature gave a granular product.
产物经检测显示：光学照片显示其尺寸为100微米左右，比表面积约为1304平方米每克，孔容约为0.51立方厘米每克，孔径约为0.61纳米，产率约为99.1％。The product was tested to show that the optical image showed a size of about 100 microns, a specific surface area of about 1304 square meters per gram, a pore volume of about 0.51 cubic centimeters per gram, a pore size of about 0.61 nanometers, and a yield of about 99.1%.
实施例15：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 15: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为1.4毫升去离子水和1.7毫升95％乙醇混合；(1) selecting a solvent: the solvent is mixed with 1.4 ml of deionized water and 1.7 ml of 95% ethanol;
(2)准确称取0.00605摩尔醋酸镍为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) accurately weigh 0.00605 moles of nickel acetate as a metal precursor, and accurately weigh 0.004 moles of trimesic acid as an organic ligand of the porous composite framework material;
(3)室温下，将醋酸镍加入到步骤(1)制备的溶剂中，搅拌混合，然后加入均苯三甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至110℃反应13h，室温干燥即可获得颗粒状产物。(3) Add nickel acetate to the solvent prepared in the step (1) at room temperature, stir and mix, then add trimesic acid, stir for 2 hours to form a slurry, seal in a autoclave, and heat to 110 ° C. After 13 h, drying at room temperature gave a granular product.
产物经检测显示：光学照片显示其尺寸为90微米左右，比表面积约为1231平方米每克，孔容约为0.50立方厘米每克，孔径约为0.62纳米，产 率约为98.1％。The product was tested to show that the optical image showed a size of about 90 microns, a specific surface area of about 1231 square meters per gram, a pore volume of about 0.50 cubic centimeters per gram, a pore size of about 0.62 nanometers, and a yield of about 98.1%.
实施例16：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 16: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为1.2毫升去离子水和1.7毫升丙酮混合；(1) selecting a solvent: the solvent is mixed with 1.2 ml of deionized water and 1.7 ml of acetone;
(2)准确称取0.00401摩尔氯化铁为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) Accurately weigh 0.00401 mol of ferric chloride as a metal precursor, and accurately weigh 0.004 mol of pyromellitic acid as an organic ligand of the porous composite framework material;
(3)室温下，将氯化铁加入到步骤(1)制备的溶剂中，搅拌混合，然后加入均苯三甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至100℃反应16h，室温干燥即可获得颗粒状产物。(3) adding ferric chloride to the solvent prepared in the step (1) at room temperature, stirring and mixing, then adding trimesic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating to 100 ° C The reaction was carried out for 16 hours and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸约为70微米左右，比表面积约为1030平方米每克，孔容约为0.47立方厘米每克，孔径约为0.62纳米，产率约为98.6％。The product was tested to show that the optical image showed a size of about 70 microns, a specific surface area of about 1030 square meters per gram, a pore volume of about 0.47 cubic centimeters per gram, a pore size of about 0.62 nanometers, and a yield of about 98.6%.
实施例17：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 17: A slurry synthesis method of a porous composite skeleton material, comprising the steps of:
(1)选择溶剂：溶剂为1.5毫升去离子水和3毫升工业酒精；(1) Select solvent: solvent is 1.5 ml of deionized water and 3 ml of industrial alcohol;
(2)准确称取0.00301摩尔碱式碳酸铜为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) Accurately weigh 0.00301 moles of basic copper carbonate as a metal precursor, and accurately weigh 0.004 moles of pyromellitic acid as an organic ligand of the porous composite framework material;
(3)室温下，将碱式碳酸铜加入到步骤(1)制备的溶剂中，搅拌混合，然后加入均苯三甲酸，搅拌3h混合形成浆料，密封于自压反应釜中，加热至140℃反应12h，室温干燥即可获得颗粒状产物。(3) adding basic copper carbonate to the solvent prepared in the step (1) at room temperature, stirring and mixing, then adding trimesic acid, stirring for 3 hours to form a slurry, sealing in a self-pressure reactor, heating to 140 The reaction was carried out at ° C for 12 h, and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸为50微米左右，比表面积约为1405平方米每克，孔容约为0.51立方厘米每克，孔径约为0.6纳米，产率约为97％。The product was tested to show that the optical image showed a size of about 50 microns, a specific surface area of about 1405 square meters per gram, a pore volume of about 0.51 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 97%.
实施例18：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 18: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为7毫升去离子水和8.75毫升乙醇混合；(1) selecting a solvent: the solvent is 7 ml of deionized water and 8.75 ml of ethanol;
(2)准确称取0.00602摩尔氢氧化镍为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) accurately weigh 0.00602 moles of nickel hydroxide as a metal precursor, and accurately weigh 0.004 moles of trimesic acid as an organic ligand of the porous composite framework material;
(3)室温下，将氢氧化镍加入到步骤(1)制备的溶剂中，搅拌混合，然后加入均苯三甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至130℃反应30h，室温干燥即可获得颗粒状产物。(备注:氢氧化镍与均苯三甲酸的质量之和与溶剂总质量的比值为0.1)(3) adding nickel hydroxide to the solvent prepared in the step (1) at room temperature, stirring and mixing, then adding trimesic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating to 130 ° C The reaction was carried out for 30 hours and dried at room temperature to obtain a granulated product. (Note: The ratio of the mass of nickel hydroxide to trimesic acid to the total mass of the solvent is 0.1)
产物经检测显示：光学照片显示其尺寸为110微米左右，比表面积约为1291平方米每克，孔容约为0.49立方厘米每克，孔径约为0.61纳米，产率约为98.4％。The product was tested to show that the optical image showed a size of about 110 microns, a specific surface area of about 1291 square meters per gram, a pore volume of about 0.49 cubic centimeters per gram, a pore size of about 0.61 nanometers, and a yield of about 98.4%.
实施例19：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 19: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为3毫升去离子水和4毫升乙醇混合；(1) Select solvent: the solvent is 3 ml of deionized water and 4 ml of ethanol;
(2)准确称取0.00102摩尔氢氧化钴为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) accurately weigh 0.00102 moles of cobalt hydroxide as a metal precursor, accurately weigh 0.004 moles of pyromellitic acid as an organic ligand of the porous composite framework material;
(3)室温下，将氢氧化钴加入到步骤(1)制备的溶剂中，搅拌混合，然后加入均苯三甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至120℃反应36h，室温干燥即可获得颗粒状产物。(3) Add cobalt hydroxide to the solvent prepared in the step (1) at room temperature, stir and mix, then add trimesic acid, stir for 2 hours to form a slurry, seal in a self-pressure reactor, and heat to 120 ° C The reaction was carried out for 36 hours and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸为60微米左右，比表面积约为991平方米每克，孔容约为0.42立方厘米每克，孔径约为0.61纳米，产率约为88.4％。The product was tested to show that the optical image showed a size of about 60 microns, a specific surface area of about 991 square meters per gram, a pore volume of about 0.42 cubic centimeters per gram, a pore size of about 0.61 nanometers, and a yield of about 88.4%.
实施例20：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 20: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为0.1毫升去离子水和1.224毫升乙醇混合；(1) selecting a solvent: the solvent is 0.1 ml of deionized water and 1.224 ml of ethanol;
(2)准确称取0.008摩尔九水合硝酸铁为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) accurately weighing 0.008 mol of iron nitrate nonahydrate as a metal precursor, and accurately weighing 0.004 mol of pyromellitic acid as an organic ligand of the porous composite framework material;
(3)室温下，将九水合硝酸铁加入到步骤(1)制备的溶剂中，搅拌混合，然后加入均苯三甲酸，搅拌4h混合形成浆料，密封于自压反应釜中，加热至110℃反应46h，室温干燥即可获得颗粒状产物。(备注:九水合硝酸铁与均苯三甲酸的质量之和与溶剂总质量的比值为3)(3) adding ferric nitrate nonahydrate to the solvent prepared in the step (1) at room temperature, stirring and mixing, then adding trimesic acid, stirring for 4 hours to form a slurry, sealing in a self-pressure reactor, heating to 110 The reaction was carried out at ° C for 46 h, and dried at room temperature to obtain a granulated product. (Remarks: The ratio of the sum of the mass of ferric nitrate to pyromellitic acid and the total mass of the solvent is 3)
产物经检测显示：光学照片显示其尺寸为50微米左右，比表面积约为871平方米每克，孔容约为0.38立方厘米每克，孔径约为0.61纳米，产率约为89.1％。The product was tested to show that the optical image showed a size of about 50 microns, a specific surface area of about 871 square meters per gram, a pore volume of about 0.38 cubic centimeters per gram, a pore size of about 0.61 nanometers, and a yield of about 89.1%.
实施例21：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 21: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为25.0毫升去离子水和34.0毫升乙醇混合；(1) selecting a solvent: the solvent is 25.0 ml of deionized water and 34.0 ml of ethanol;
(2)准确称取0.0200摩尔三水合硝酸铜为金属前驱体，准确称取0.004摩尔均苯三甲酸作为多孔复合骨架材料的有机配体；(2) accurately weigh 0.0200 moles of copper nitrate trihydrate as a metal precursor, accurately weigh 0.004 moles of trimesic acid as an organic ligand of the porous composite framework material;
(3)室温下，将三水合硝酸铜加入到步骤(1)制备的溶剂中，搅拌 16分钟，然后加入均苯三甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至130℃反应6h，室温干燥即可获得颗粒状产物。(3) adding copper nitrate trihydrate to the solvent prepared in the step (1) at room temperature, stirring for 16 minutes, then adding trimesic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating to The reaction was carried out at 130 ° C for 6 h, and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示其尺寸为70微米左右，比表面积约为1250平方米每克，孔容约为0.601立方厘米每克，孔径约为0.6纳米，产率约为79％。The product was tested to show that the optical image showed a size of about 70 microns, a specific surface area of about 1250 square meters per gram, a pore volume of about 0.601 cubic centimeters per gram, a pore size of about 0.6 nanometers, and a yield of about 79%.
实施例22：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 22: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为17.0毫升二甲基甲酰胺和4.0毫升乙醇混合；(1) selecting a solvent: a solvent of 17.0 ml of dimethylformamide and 4.0 ml of ethanol;
(2)准确称取0.0106摩尔九水合硝酸铝为金属前驱体，准确称取0.0314摩尔对苯二甲酸作为多孔复合骨架材料的有机配体；(2) Accurately weigh 0.0106 moles of aluminum nitrate nonahydrate as the metal precursor, and accurately weigh 0.0314 moles of terephthalic acid as the organic ligand of the porous composite framework material;
(3)室温下，将九水合硝酸铝加入到步骤(1)制备的溶剂中，搅拌36分钟，然后加入对苯二甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至150℃反应6h，室温干燥即可获得颗粒状产物。(3) adding aluminum nitrate nonahydrate to the solvent prepared in the step (1) at room temperature, stirring for 36 minutes, then adding terephthalic acid, stirring for 2 hours to form a slurry, sealing in a self-pressure reactor, heating to The reaction was carried out at 150 ° C for 6 h, and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示该白色晶体尺寸为20微米左右，比表面积约为1050平方米每克，孔容约为0.43立方厘米每克，产率约为83％。The product was tested to show that the optical image showed a white crystal size of about 20 microns, a specific surface area of about 1050 square meters per gram, a pore volume of about 0.43 cubic centimeters per gram, and a yield of about 83%.
实施例23：一种多孔复合骨架材料的浆态合成方法，包括如下步骤：Embodiment 23: A slurry synthesis method of a porous composite skeleton material, comprising the following steps:
(1)选择溶剂：溶剂为8.0毫升二甲基甲酰胺和2.0毫升乙醇混合；(1) selecting a solvent: a solvent of 8.0 ml of dimethylformamide and 2.0 ml of ethanol;
(2)准确称取0.0102摩尔醋酸铝为金属前驱体，准确称取0.0204摩尔对苯二甲酸作为多孔复合骨架材料的有机配体；(2) accurately weigh 0.0102 moles of aluminum acetate as a metal precursor, and accurately weigh 0.0204 moles of terephthalic acid as an organic ligand of the porous composite framework material;
(3)室温下，将醋酸铝加入到步骤(1)制备的溶剂中，搅拌40分钟，然后加入对苯二甲酸，搅拌2h混合形成浆料，密封于自压反应釜中，加热至140℃反应18h，室温干燥即可获得颗粒状产物。(3) At room temperature, aluminum acetate is added to the solvent prepared in the step (1), stirred for 40 minutes, then terephthalic acid is added, stirred for 2 hours to form a slurry, sealed in a self-pressure reactor, heated to 140 ° C The reaction was carried out for 18 hours and dried at room temperature to obtain a granulated product.
产物经检测显示：光学照片显示该白色晶体尺寸为30微米左右，比表面积约为1150平方米每克，孔容约为0.44立方厘米每克，产率约为89％。The product was tested to show that the optical image showed a white crystal size of about 30 microns, a specific surface area of about 1150 square meters per gram, a pore volume of about 0.44 cubic centimeters per gram, and a yield of about 89%.
实验例1：采用水热法合成骨架材料：选取20.0毫升去离子水和20.0毫升乙醇混合，加入称取好的0.004摩尔均苯三甲酸，室温搅拌溶解后，再加入0.0061摩尔三水合硝酸铜，搅拌1小时后形成混合物，密封在反应釜中，在110摄氏度加热12小时，冷却后用等量的去离子水和乙醇洗涤，然后干燥得到粉末状产物，光学照片显示大部分粉末的尺寸约为10微米左右(如图1所示)，XRD图谱显示其结晶度低，而且晶面取向生长不明显(如图 2所示)，氮气等温吸附结果显示其比表面积约为1251平方米每克(如图3所示)，孔容约为0.48立方厘米每克，大部分孔径集中在0.62纳米，但有少部分孔径不同(如图4所示)，产率约为67％。在295K、一个大气压下，该材料的二氧化碳吸附容量约为3.9kg/mol(如图5所示)。Experimental Example 1: Synthesis of skeleton material by hydrothermal method: 20.0 ml of deionized water and 20.0 ml of ethanol were mixed, and 0.004 mol of pyromellitic acid was weighed and stirred at room temperature, and then 0.0061 mol of copper nitrate trihydrate was added. After stirring for 1 hour, a mixture was formed, sealed in a reaction vessel, heated at 110 ° C for 12 hours, cooled, washed with an equal amount of deionized water and ethanol, and then dried to obtain a powdery product. The optical photograph showed that the size of most of the powder was about About 10 microns (as shown in Figure 1), the XRD pattern shows that the crystallinity is low, and the crystal face orientation growth is not obvious (as shown in Figure 2). The nitrogen isotherm adsorption results show that the specific surface area is about 1251 square meters per gram ( As shown in Figure 3, the pore volume is about 0.48 cubic centimeters per gram, and most of the pore size is concentrated at 0.62 nm, but a small portion of the pore size is different (as shown in Figure 4), and the yield is about 67%. At 295 K, one atmosphere, the material has a carbon dioxide adsorption capacity of about 3.9 kg/mol (as shown in Figure 5).
本实验例与实施例1对比，明显得出：本发明浆态合成方法采用较少的溶剂，能够合成高质量的目标复合骨架材料，废液极少，且产率更高，杜绝了金属离子和有机配体的排放，极大地减少运行能耗和成本，更重要的是，避免了对环境的污染，直接干燥，使得产物更加容易收集。另外对二氧化碳的吸附容量更高，显然本发明浆态合成方法所获得的大颗粒复合骨架材料在气体吸附方面有更高的吸附容量。Compared with Example 1, this experimental example clearly shows that the slurry synthesis method of the present invention can synthesize high-quality target composite skeleton materials by using less solvent, has less waste liquid, and has higher yield and eliminates metal ions. And the discharge of organic ligands, greatly reducing operating energy consumption and cost, and more importantly, avoiding environmental pollution, direct drying, making the product easier to collect. In addition, the adsorption capacity for carbon dioxide is higher, and it is apparent that the large particle composite skeleton material obtained by the slurry synthesis method of the present invention has a higher adsorption capacity in gas adsorption.

Claims (6)

  1. 一种多孔复合骨架材料的浆态合成方法，其特征在于：包括如下步骤：A slurry synthesis method for a porous composite skeleton material, comprising: the following steps:
    (1)选择溶剂：溶剂为有机溶剂或含水的有机溶剂；(1) selecting a solvent: the solvent is an organic solvent or an aqueous organic solvent;
    (2)选择固体反应原料：无机金属盐或金属碱作为多孔复合骨架材料中的配位无机金属源，多羧酸有机化合物作为多孔复合骨架材料的有机配体；(2) selecting a solid reaction raw material: an inorganic metal salt or a metal base as a coordination inorganic metal source in the porous composite skeleton material, and a polycarboxylic acid organic compound as an organic ligand of the porous composite skeleton material;
    (3)室温下，将无机金属源分散于溶剂中，然后与多羧酸有机化合物混合形成浆料，密封于自压反应釜中，加热至70-170℃反应0.5-240h，室温干燥即可；(3) Dispersing the inorganic metal source in a solvent at room temperature, then mixing with the polycarboxylic acid organic compound to form a slurry, sealing in a self-pressure reactor, heating to 70-170 ° C for 0.5-240 h, drying at room temperature ;
    所述无机金属源与多羧酸有机化合物的摩尔比为：(0.5-10):2；无机金属盐或金属碱与多羧酸有机化合物的质量之和与溶剂总质量的比值为0.1-3。The molar ratio of the inorganic metal source to the polycarboxylic acid organic compound is: (0.5-10): 2; the ratio of the sum of the mass of the inorganic metal salt or the metal base to the polycarboxylic acid organic compound to the total mass of the solvent is 0.1-3 .
  2. 根据权利要求1所述的一种多孔复合骨架材料的浆态合成方法，其特征在于：步骤(1)中的有机溶剂为：甲醇、乙醇、乙二醇、二甲醚、乙醚、丙酮、二甲基亚砜、N，N—二甲基甲酰胺中的任意一种或者任意两种以任意比例混合；水为去离子水或蒸馏水；含水的有机溶剂中水与有机溶剂的体积比为0-1000。The slurry synthesis method of a porous composite skeleton material according to claim 1, wherein the organic solvent in the step (1) is: methanol, ethanol, ethylene glycol, dimethyl ether, diethyl ether, acetone, and Any one or any two of methyl sulfoxide and N,N-dimethylformamide are mixed in any ratio; water is deionized water or distilled water; and the volume ratio of water to organic solvent in the aqueous organic solvent is 0. -1000.
  3. 根据权利要求1所述的一种多孔复合骨架材料的浆态合成方法，其特征在于：步骤(2)中所述的无机金属源为铁、钴、镍、铜、铬、锌的盐或碱中的任意一种或任意两种金属源。The slurry synthesis method of a porous composite skeleton material according to claim 1, wherein the inorganic metal source in the step (2) is a salt or a base of iron, cobalt, nickel, copper, chromium or zinc. Any one or any two of the metal sources.
  4. 根据权利要求3所述的一种多孔复合骨架材料的浆态合成方法，其特征在于：步骤(2)中所述的无机金属源为硝酸铜、三水合焦磷酸铜、醋酸铜、碱式碳酸铜、硫酸铜、氯化铜、氢氧化铜、硝酸锌、硝酸铝、醋酸铝、硝酸钴、醋酸钴、硝酸镍、醋酸镍、氢氧化镍、氢氧化钴、硝酸铁、氯化铁中的任意一种或任意两种以任意比例混合。The slurry synthesis method of a porous composite skeleton material according to claim 3, wherein the inorganic metal source in the step (2) is copper nitrate, copper pyrophosphate trihydrate, copper acetate, basic carbonic acid. Copper, copper sulfate, copper chloride, copper hydroxide, zinc nitrate, aluminum nitrate, aluminum acetate, cobalt nitrate, cobalt acetate, nickel nitrate, nickel acetate, nickel hydroxide, cobalt hydroxide, iron nitrate, ferric chloride Any one or any two of them may be mixed in any ratio.
  5. 根据权利要求1所述的一种多孔复合骨架材料的浆态合成方法，其特征在于：步骤(2)中所述的多羧酸有机化合物为均苯三甲酸、对苯二甲酸中的任意一种。The slurry synthesis method of a porous composite skeleton material according to claim 1, wherein the polycarboxylic acid organic compound in the step (2) is any one of trimesic acid and terephthalic acid. Kind.
  6. 根据权利要求1所述的一种多孔复合骨架材料的浆态合成方法，其特征在 于：所制备的多孔复合骨架材料粒径为0.002-2毫米。A slurry synthesis method for a porous composite skeleton material according to claim 1, wherein the porous composite skeleton material has a particle diameter of from 0.002 to 2 mm.
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