CN113680325A - Preparation method and application of diamine-modified MOF/GO alkene composite adsorbent - Google Patents

Preparation method and application of diamine-modified MOF/GO alkene composite adsorbent Download PDF

Info

Publication number
CN113680325A
CN113680325A CN202110906210.7A CN202110906210A CN113680325A CN 113680325 A CN113680325 A CN 113680325A CN 202110906210 A CN202110906210 A CN 202110906210A CN 113680325 A CN113680325 A CN 113680325A
Authority
CN
China
Prior art keywords
alkene
uio
diamine
composite adsorbent
modified mof
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN202110906210.7A
Other languages
Chinese (zh)
Inventor
曹燕
宋夫交
许琦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yancheng Institute of Technology
Original Assignee
Yancheng Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yancheng Institute of Technology filed Critical Yancheng Institute of Technology
Priority to CN202110906210.7A priority Critical patent/CN113680325A/en
Publication of CN113680325A publication Critical patent/CN113680325A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • 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]
    • 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
    • B01D53/04—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 with stationary adsorbents
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • 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
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • 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)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a preparation method of a diamine group modified MOF/GO alkene composite adsorbent, which comprises the following steps: step 1: using GO as a raw material, dispersing GO in an aqueous solution, then ultrasonically stripping to obtain GO alkene and incompletely stripped GO, removing insoluble substances through centrifugation, continuously centrifuging the rest solution to obtain primarily screened GO alkene, freeze-drying, and then preparing the cut GO alkene by using a chemical cutting method; step 2: adding the product obtained in the step 1 into a cosolvent of N, N-Dimethylformamide (DMF) and ethanol, and uniformly mixing; then ZrCl is added4And carrying out in-situ synthesis of GO alkene/NH by using aminoterephthalic acid through microwave-assisted solvothermal method2-UiO-66 complex with supercritical CO2Dry para GO ene/NH2-activation and solvent removal of the UiO-66 complex; and step 3: adding the product of step 2Adding into anhydrous hexane suspension, adding urea and N2Refluxing for 18h under the atmosphere, filtering, washing with hexane, and finally drying for 24h at 50 ℃ under the vacuum condition to obtain the diamine group modified MOF/GO alkene composite adsorbent.

Description

Preparation method and application of diamine-modified MOF/GO alkene composite adsorbent
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a preparation method of a diamine group modified MOF/GO alkene composite adsorbent and application thereof in carbon dioxide adsorption.
Background
According to data of the International Energy Agency (IEA), the emission of carbon dioxide in 2021 year worldwide is 330 hundred million tons, and the innovation history is high. To improve the shapeUnder the circumstances, countries around the world are actively developing and using clean energy, and are also working on developing efficient carbon dioxide capture, storage and separation (CO)2Capture and Separation, CCS). Currently, ammonia solutions are commonly used in industry to absorb and capture carbon dioxide, but huge energy is consumed in the subsequent desorption process, and environmental pollution is also avoided. Therefore, low energy consumption solid adsorbents are receiving much attention as an alternative.
Compared with traditional porous materials such as zeolite and activated carbon, the metal organic framework compound (MOF) develops rapidly. The MOF new material combines the characteristics of a polymer and a complex, and the MOF new material not only has rich space topological structure and controllable synthesis, but also has the characteristics of structural design, higher specific surface area, higher porosity, convenience in regulating and controlling pore channel environment and the like. Therefore, the MOF new material shows excellent application prospects in the fields of gas adsorption storage, separation and the like, and is also considered to be a most promising platform for carbon dioxide storage and selective capture. In 2010, MOF-210, designed by the subject group of Yaghi professor in los Angeles, California university, was directed to CO at room temperature and a pressure of 50bar2The adsorption capacity can reach 2.4g/g, which is far higher than other solid adsorbents. Among the MOFs, UiO-66 is a mixture of terephthalic acid and Zr4+The prepared carbon dioxide adsorbent has high mechanical, chemical and thermal stability, shows good performance in the aspect of carbon dioxide adsorption, has large specific surface area which is not the only standard of high adsorption capacity, and has proper pore diameter and pore structure which play a determining role in gas adsorption capacity and selectivity. The compounding of MOFs with other materials to achieve structure lifting and functional improvement has become a new research hotspot. Research finds that (professor Bondosz of American City university, etc.), the application of graphene oxide to the porous material can effectively adjust the pore diameter and pore volume to match the molecular diameter of an adsorbed target, avoid the waste of free volume, and improve the adsorption performance of gas, thereby indicating the direction for the subsequent research of the composite adsorbent. Previous studies have also shown that (Stavitski, Pachful, etc.), MOFS materials can significantly increase CO after amino modification2Selectivity of adsorption.
CN201510155183.9Discloses a metal organic framework material PEI @ UiO-66, a preparation method thereof and a method for adsorbing and separating CO2The use of (1). The method comprises the following steps: (1) dropwise adding absolute ethyl alcohol into Polyethyleneimine (PEI), and ultrasonically mixing until the PEI is completely dissolved; (2) dropwise adding the obtained mixed solution to the pretreated UiO-66 metal organic framework material; (3) mixing the pasty mixture obtained in the step (2) with N2Drying in the atmosphere; (4) and drying the dried material in vacuum to obtain the PEI @ UiO-66 adsorbent. Adsorbing CO by using the PEI @ UiO-66 prepared in the step (4)2The temperature and relative humidity of the feed gas can be adjusted to further increase the adsorption of CO onto the PEI @ UiO-66 adsorbent2The capacity of (c). The PEI @ UiO-66 adsorbent not only has good hydrothermal stability, but also greatly improves the CO content of the UiO-66 material under mild temperature and humid conditions2Adsorption capacity and for CO2/CH4And (4) the separation selectivity of the mixed gas.
CN201811521835.6 discloses a carbon nano tube/UiO-66-NH2The invention belongs to the field of preparation of metal organic framework materials, and relates to a novel adsorbing material carbon nano tube/UiO-66-NH2The preparation method comprises the steps of firstly carrying out acidification treatment on the multi-wall carbon nano tube to functionalize carboxyl at defect sites of the carbon nano tube, then forming coordination bonds with organic ligands and metal ions simultaneously, and self-assembling the nano composite material. The carbon nano-tube not only participates in the UiO-66-NH in the form of physical blending2In the material, carbon nano tube/UiO-66-NH is also formed in the form of chemical bond2A composite material. Due to the addition of the carbon nano tube, the water stability of the metal organic framework material is obviously improved, and the thermal stability, the specific surface area and the pore volume and the pore diameter of the composite material are improved to a certain degree, so that the composite material has more excellent adsorption performance. The preparation method is simple and efficient, and provides a new way for preparing the carbon nano tube/MOFs composite material.
CN201910555824.8 discloses a functionalized zirconium-based metal organic framework/graphene oxide composite material, a preparation method and an application thereof, wherein the composite material takes UiO-66-OH as a carrier, and graphene oxide is doped in the carrier. The preparation method comprises the following steps: preparing organic ligand, soluble zirconium salt, organic solvent, high-boiling-point organic solvent and graphene oxide aqueous solution into reaction matrix solution, reacting the obtained reaction matrix solution, repeatedly soaking and centrifuging the obtained reaction product, washing and drying to obtain the composite material. The composite material has the advantages of low cost, stable structure, strong adsorption capacity, high adsorption rate and the like, can be widely used for treating dye wastewater, can obtain a good removal effect, and has high use value and good application prospect.
CN201911335820.5 discloses a preparation method and application of a graphene oxide-loaded UiO-66 composite material. Adding graphite powder and sodium nitrate into concentrated sulfuric acid, uniformly stirring, adding an oxidant at the temperature of 0-10 ℃, reacting at the temperature of 20-30 ℃, placing in an ice-water bath, and adding deionized water; placing at room temperature, adding excessive hydrogen peroxide, reacting for 0.5-2h, washing, and drying to obtain graphene oxide nanosheets; purifying the graphene oxide nanosheets to obtain a graphene oxide turbid liquid; dissolving zirconium chloride and terephthalic acid in N' N-dimethylformamide, adding acetic acid and hydrochloric acid, and reacting under stirring to obtain a UiO-66 precursor solution; and adding the graphene oxide suspension into the UiO-66 precursor solution, uniformly mixing, reacting at the temperature of 100-120 ℃, washing, and drying in vacuum to obtain the graphene oxide loaded UiO-66 composite material. The composite material can be used for adsorbing and removing hexavalent chromium ions in wastewater.
Disclosure of Invention
Aiming at the problems of the prior art, the invention aims to provide a preparation method of a diamine group modified MOF/GO alkene composite adsorbent and an application thereof in carbon dioxide adsorption,
in order to solve the problems of the prior art, the invention adopts the technical scheme that:
a preparation method of a diamine group modified MOF/GO alkene composite adsorbent comprises the following steps:
step 1: using GO as a raw material, ultrasonically stripping GO after the GO is dispersed in an aqueous solution, wherein the ultrasonic frequency and the ultrasonic time are respectively 300W and 2h to obtain GO alkene and incompletely stripped GO, removing insoluble substances through centrifugation, continuously centrifuging the rest solution to obtain primarily screened GO alkene, freeze-drying, and then preparing GO alkene with 1-3 layers and 60-150nm of surface size by using a chemical cutting method; in this application go (graphite oxide) stands for graphite oxide.
Step 2: adding the product obtained in the step 1 into a cosolvent of N, N-Dimethylformamide (DMF) and ethanol, and uniformly mixing; then ZrCl is added4Amino terephthalic acid, ZrCl4The mass ratio of the amino terephthalic acid to the GO alkene is 1.4:1:0.05, and GO alkene/NH is synthesized in situ by a microwave-assisted solvothermal method2-UiO-66 complex with supercritical CO2Dry para GO ene/NH2-activation and solvent removal of the UiO-66 complex; the composite material synthesized by the microwave-assisted solvothermal method has shorter time, larger specific surface area and supercritical CO (carbon monoxide) than the composite material synthesized by the hydrothermal method2Drying and activating are more sufficient, and the coordinated water and the bound water in the material are removed, so that the adsorption of carbon dioxide is facilitated.
And step 3: adding the product obtained in the step 2 into anhydrous hexane suspension, and then adding urea, urea and GO alkene/NH2The mass ratio of the-UiO-66 complex is (0.05-0.15):1, N2Refluxing for 18h under the atmosphere, filtering, washing with hexane, and finally drying for 24h at 50 ℃ under the vacuum condition to obtain the diamine group modified MOF/GO alkene composite adsorbent. And (2) carrying out amine modification on the MOF material after synthesis, carrying out pore channel functional modification on the product in the step (2) based on the fact that the amino group can be coordinated to an unsaturated metal site, improving the adsorption selectivity and water resistance of the composite material, and providing richer hydrogen bond binding sites for carbon dioxide molecules while reducing the reduction of the specific surface area as much as possible. Urea is selected as diamine, one end of the amine group is linked with the metal center, and the other end of the amine group is suspended in the pore channel and can be selectively linked with CO2Reaction occurs to increase the carbon dioxide adsorption capacity and CO at low concentrations2/N2And (4) selectivity.
The detailed operation of the chemical cutting method comprises the following steps: dissolving the preliminarily screened and freeze-dried GO in mixed acid, wherein the mixed acid is prepared from concentrated nitric acid/concentrated sulfuric acid according to the volume ratio of 1:3, performing ultrasonic treatment for 3h at 300W, heating in a water bath for 90 ℃ after complete dispersion, and keeping for 48 h; cooling to room temperature, and diluting; dialyzing with dialysis bag until the dialysate is neutral to obtain yellow solution, and obtaining GO alkene with 1-3 layers and 60-150nm surface size.
A double-amino modified MOF/GO alkene composite adsorbent is used for adsorbing carbon dioxide.
A device for adsorbing carbon dioxide comprises a gas inlet device, a gas outlet device and a filtering channel, wherein an adsorbent filling layer is arranged in the filtering channel, and the adsorbent filling layer is adhered with the diamine modified MOF/GO alkene composite adsorbent prepared by the preparation method of the diamine modified MOF/GO alkene composite adsorbent disclosed by claim 1 or 2.
The adsorption layer is more than one, and the adsorption layer is vertically arranged in the filtering channel, and the filtering channel is trumpet-shaped, and the diameter of the cross section of the filtering channel is gradually increased.
Aiming at the problems of insufficient pore volume utilization, poor selectivity, poor water resistance and the like existing in the process of carbon dioxide adsorption, the invention synthesizes the double-amine-group modified MOF/GO composite material, the macroporous structure of the MOF is adjusted by embedding lamellar GO, the gas storage capacity of the MOF is enlarged, and meanwhile, the amine group carried by diamine and the amine group in a ligand provide CO2Selectively adsorbing active sites. Firstly, the volume and the pore size distribution of pores are adjusted through embedding so as to improve the physical adsorption quantity and selectivity of the material to carbon dioxide; secondly, the chemical environment of the site is changed, structural defects and unsaturated coordinated metal centers are also generated, and adsorption sites are increased; and thirdly, the amino group is bonded to the metal ion, so that the water resistance of the MOF is improved.
Drawings
FIG. 1 is an SEM topography of the synthesized sorbent of example 1;
FIG. 2 is an SEM topography of the synthesized sorbent of example 2;
fig. 3 is an SEM topography of the sorbent synthesized in example 3.
Detailed Description
The invention is further described below with reference to the accompanying drawings and specific embodiments.
Example 1
A preparation method of a diamine group modified MOF/GO alkene composite adsorbent comprises the following steps:
(1) taking GO (synthesized by a Hummers method) as a raw material, dispersing GO in an aqueous solution, carrying out ultrasonic stripping (ultrasonic frequency and ultrasonic time are respectively 300W and 2h) to obtain GO with a wider size range and GO which is not completely stripped, removing insoluble substances by centrifugation (centrifugal rotation speed and centrifugal time are respectively 5000rpm and 5min), continuously centrifuging the rest solution (10000rpm and 2h) to obtain primary screened GO, and carrying out freeze drying. Then the small size GO alkene is prepared by chemical clipping (concentrated acid clipping). 100mg of the GO alkene prepared above is dissolved in 25mL of mixed acid (concentrated nitric acid/concentrated sulfuric acid, v/v 1:3), ultrasonic treatment is carried out (300W and 3h), after complete dispersion, water bath heating is carried out for 90 ℃, and the temperature is kept for 48 h. After cooling to room temperature, the solution was diluted to 100 mL. Dialyzing with 1000Da dialysis bag until the dialysate is neutral to obtain yellow solution, and obtaining 1-3 layers of GO alkene with surface size of 60-150 nm.
(2) Adding the product obtained in the step 1 into a cosolvent of N, N-Dimethylformamide (DMF) and ethanol, uniformly mixing, and then adding ZrCl4Amino terephthalic acid (ZrCl)4And the mass ratio of the amino terephthalic acid to GO is 1.4:1: 0.05). In-situ synthesis of GO alkene/NH by microwave-assisted solvothermal method2-UiO-66 complex with supercritical CO2Drying activates the composite and removes the solvent.
(3) Adding the product of step 2 into anhydrous hexane suspension, and adding urea (urea and GO alkene/NH)2Mass ratio of-UiO-66 Complex 0.05:1), N2Refluxing under atmosphere for 18h, filtering, washing with hexane, and drying under vacuum at 50 deg.C for 24 h. The resulting adsorbent is labeled N0.5GO/NH2UiO-66, SEM picture of product shown in FIG. 1.
Example 2
(1) Taking GO (synthesized by a Hummers method) as a raw material, dispersing GO in an aqueous solution, carrying out ultrasonic stripping (ultrasonic frequency and ultrasonic time are respectively 300W and 2h) to obtain GO with a wider size range and GO which is not completely stripped, removing insoluble substances by centrifugation (centrifugal rotation speed and centrifugal time are respectively 5000rpm and 5min), continuously centrifuging the rest solution (10000rpm and 2h) to obtain primary screened GO, and carrying out freeze drying. Then the small size GO alkene is prepared by chemical clipping (concentrated acid clipping). 100mg of the GO alkene prepared above is dissolved in 25mL of mixed acid (concentrated nitric acid/concentrated sulfuric acid, v/v 1:3), ultrasonic treatment (such as 300W and 3h) is carried out, after complete dispersion, water bath heating is carried out for 90 ℃, and the temperature is kept for 48 h. After cooling to room temperature, the solution was diluted to 100 mL. Dialyzing with 1000Da dialysis bag until the dialysate is neutral to obtain yellow solution, and obtaining 1-3 layers of GO alkene with surface size of 60-150 nm.
(2) Adding the product obtained in the step (1) into a cosolvent of N, N-Dimethylformamide (DMF) and ethanol, uniformly mixing, and then adding ZrCl4Amino terephthalic acid (ZrCl)4And the mass ratio of the amino terephthalic acid to GO is 1.4:1: 0.05). In-situ synthesis of GO alkene/NH by microwave-assisted solvothermal method2-UiO-66 complex with supercritical CO2Drying activates the composite and removes the solvent.
(3) Adding the product of step (2) into anhydrous hexane suspension, and adding urea (urea and GO alkene/NH)2Mass ratio of-UiO-66 Complex 0.1:1, N2Refluxing under atmosphere for 18h, filtering, washing with hexane, and drying under vacuum at 50 deg.C for 24 h. The resulting adsorbent is labeled N1.0GO/NH2UiO-66, SEM picture of product shown in FIG. 2.
Example 3
(1) Taking GO (synthesized by a Hummers method) as a raw material, dispersing GO in an aqueous solution, carrying out ultrasonic stripping (ultrasonic frequency and ultrasonic time are respectively 300W and 2h) to obtain GO with a wider size range and GO which is not completely stripped, removing insoluble substances by centrifugation (centrifugal rotation speed and centrifugal time are respectively 5000rpm and 5min), continuously centrifuging the rest solution (10000rpm and 2h) to obtain primary screened GO, and carrying out freeze drying. Then the small size GO alkene is prepared by chemical clipping (concentrated acid clipping). 100mg of the GO alkene prepared above is dissolved in 25mL of mixed acid (concentrated nitric acid/concentrated sulfuric acid, v/v 1:3), ultrasonic treatment (such as 300W and 3h) is carried out, after complete dispersion, water bath heating is carried out for 90 ℃, and the temperature is kept for 48 h. After cooling to room temperature, the solution was diluted to 100 mL. Dialyzing with 1000Da dialysis bag until the dialysate is neutral to obtain yellow solution, and obtaining 1-3 layers of GO alkene with surface size of 60-150 nm.
(2) Adding the product obtained in the step (1) into a cosolvent of N, N-Dimethylformamide (DMF) and ethanol, uniformly mixing, and then adding ZrCl4Amino terephthalic acid (ZrCl)4And the mass ratio of the amino terephthalic acid to GO is 1.4:1: 0.05). In-situ synthesis of GO alkene/NH by microwave-assisted solvothermal method2-UiO-66 complex with supercritical CO2Drying activates the composite and removes the solvent.
(3) Adding the product of step (2) into anhydrous hexane suspension, and adding urea (urea and GO alkene/NH)2Mass ratio of-UiO-66 Complex 0.15:1), N2Refluxing under atmosphere for 18h, filtering, washing with hexane, and drying under vacuum at 50 deg.C for 24 h. The resulting adsorbent is labeled N1.5GO/NH2UiO-66, SEM picture of product shown in FIG. 3.
Comparative example 1
(1) Zirconium chloride (ZrCl)4) Adding the amino terephthalic acid and the dimethyl formamide (DMF) solvent according to the mass ratio of 1.4:1, uniformly stirring, and transferring the mixed solution to a polytetrafluoroethylene lining reaction kettle;
(2) and (2) covering and sealing the stainless steel reaction kettle in the step (1), transferring the stainless steel reaction kettle into a homogeneous reactor, and reacting for 20 hours at 120 ℃ and 300r/min, wherein the homogeneous reactor is adopted to ensure that the materials are fully contacted.
(3) Cooling the product obtained in the step (2), repeatedly washing the product with DMF and ethanol, drying the product at 120 ℃ to obtain yellow crystals, and marking the obtained adsorbent as NH2-UiO-66-raw, wherein raw represents NH without modification2-UiO-66 precursor.
Comparative example 2
(1) Zirconium chloride (ZrCl)4) Adding the amino terephthalic acid and the dimethyl formamide (DMF) solvent according to the mass ratio of 1.4:1, and uniformly mixing by ultrasonic;
(2) and (2) transferring the solution in the step (1) into a microwave hydrothermal reactor, and reacting for 30 minutes at 120 ℃ and 150r/min, wherein the microwave hydrothermal reactor is adopted to ensure that materials are fully contacted, and the whole reaction time is reduced.
(3) Cooling the product obtained in the step (3) and then adopting supercritical CO2Drying to activate and remove solvent, and removing coordinated water and bound water in the material. The resulting adsorbent is labeled WNH2-UiO-66。
Comparative example 3
(1) Taking GO (synthesized by a Hummers method) as a raw material, dispersing GO in an aqueous solution, carrying out ultrasonic stripping (ultrasonic frequency and ultrasonic time are respectively 300W and 2h) to obtain GO with a wider size range and GO which is not completely stripped, removing insoluble substances by centrifugation (centrifugal rotation speed and centrifugal time are respectively 5000rpm and 5min), continuously centrifuging the rest solution (10000rpm and 2h) to obtain primary screened GO, and carrying out freeze drying. Then the small size GO alkene is prepared by chemical clipping (concentrated acid clipping). 100mg of the GO alkene prepared above is dissolved in 25mL of mixed acid (concentrated nitric acid/concentrated sulfuric acid, v/v 1:3), ultrasonic treatment is carried out (300W and 3h), after complete dispersion, water bath heating is carried out for 90 ℃, and the temperature is kept for 48 h. After cooling to room temperature, it is diluted (e.g., to 100 mL). Dialyzing with 1000Da dialysis bag until the dialysate is neutral to obtain yellow solution, and obtaining 1-3 layers of GO alkene with surface size of 60-150 nm.
(2) Adding the product obtained in the step (1) into a cosolvent of N, N-Dimethylformamide (DMF) and ethanol, uniformly mixing, and then adding ZrCl4Amino terephthalic acid (ZrCl)4And the mass ratio of the amino terephthalic acid to GO is 1.4:1: 0.05).
(3) And (3) transferring the solution in the step (2) into a microwave hydrothermal reactor, and reacting for 30 minutes at 120 ℃ and 150r/min, wherein the microwave hydrothermal reactor is adopted to ensure that the materials are fully contacted, and the whole reaction time is reduced.
(4) Cooling the product obtained in the step (3) and then adopting supercritical CO2Drying to activate and remove solvent, and removing coordinated water and bound water in the material. The resulting adsorbent was labeled GO/NH2-UiO-66。
The specific surface area and the pore volume of the composite adsorbent are measured by an ASAP2020M full-automatic specific surface area and porosity analyzer manufactured by Michk instruments of America, samples are measured at a liquid nitrogen temperature (-196 ℃), and the specific surface area and the pore volume of the samples are calculated by using a BET equation.
The carbon dioxide adsorption performance test of the composite adsorbent is also carried out in a specific surface area and porosity analyzer, the test pressure is controlled between 0-0.12MPa through a steel cylinder pressure reducing valve and an electromagnetic valve, the temperature is controlled at 0 ℃, 25 ℃ and 45 ℃ by soaking the sample tube in a constant-temperature water bath, and the carbon dioxide and nitrogen adsorption isotherm and the adsorption quantity are measured under the conditions. CO is calculated by combining a DSLF adsorption model with an Ideal Adsorption Solution Theory (IAST)2/N2And (4) adsorption selectivity.
The results of the carbon dioxide adsorption performance test of each adsorbent prepared in the above examples are shown in table 1.
TABLE 1 adsorbent CO at 1bar for each sample at 0 deg.C, 25 deg.C and 45 deg.C2Amount of adsorption
Figure BDA0003201718970000071

Claims (5)

1. A preparation method of a diamine group modified MOF/GO alkene composite adsorbent is characterized by comprising the following steps:
step 1: using GO as a raw material, ultrasonically stripping GO after the GO is dispersed in an aqueous solution, wherein the ultrasonic frequency and the ultrasonic time are respectively 300W and 2h to obtain GO alkene and incompletely stripped GO, removing insoluble substances through centrifugation, continuously centrifuging the rest solution to obtain primarily screened GO alkene, freeze-drying, and then preparing GO alkene with 1-3 layers and 60-150nm of surface size by using a chemical cutting method;
step 2: adding the product obtained in the step 1 into a cosolvent of N, N-Dimethylformamide (DMF) and ethanol, and uniformly mixing; then ZrCl is added4Amino terephthalic acid, ZrCl4The mass ratio of the amino terephthalic acid to the GO alkene is 1.4:1:0.05, and GO alkene/NH is synthesized in situ by a microwave-assisted solvothermal method2-UiO-66 complex with supercritical CO2Dry para GO ene/NH2-activation and solvent removal of the UiO-66 complex;
and step 3: adding the product obtained in the step 2 into anhydrous hexane suspension, and then adding urea, urea and GO alkene/NH2The mass ratio of the-UiO-66 complex is (0.05-0.15):1, N2And (3) refluxing for 18h in the atmosphere, filtering, washing with hexane, and finally drying at 50 ℃ for 24h under a vacuum condition to obtain the diamine group modified MOF/GO alkene composite adsorbent.
2. The method for preparing the diamine-modified MOF/GO alkene composite adsorbent according to claim 1, wherein the detailed operation of the chemical tailoring method is as follows: dissolving the preliminarily screened and freeze-dried GO in mixed acid, wherein the mixed acid is prepared from concentrated nitric acid/concentrated sulfuric acid according to the volume ratio of 1:3, performing ultrasonic treatment for 3h at 300W, heating in a water bath for 90 ℃ after complete dispersion, and keeping for 48 h; cooling to room temperature, and diluting; dialyzing with dialysis bag until the dialysate is neutral to obtain yellow solution, and obtaining GO alkene with 1-3 layers and 60-150nm surface size.
3. A diamine-modified MOF/GO alkene composite adsorbent prepared by the method for preparing the same according to claim 1 or 2, characterized by being used for adsorption of carbon dioxide.
4. A device for adsorbing carbon dioxide, which is characterized by comprising a gas inlet device, a gas outlet device and a filtering channel, wherein an adsorbent filling layer is arranged in the filtering channel, and the adsorbent filling layer is attached with the diamine modified MOF/GO alkene composite adsorbent prepared by the preparation method of the diamine modified MOF/GO alkene composite adsorbent according to claim 1 or 2.
5. The apparatus according to claim 4, wherein the number of the adsorption layers is more than one, the adsorption layers are vertically arranged in the filtering channel, the filtering channel is trumpet-shaped, and the diameter of the cross section of the filtering channel is gradually increased.
CN202110906210.7A 2021-08-09 2021-08-09 Preparation method and application of diamine-modified MOF/GO alkene composite adsorbent Withdrawn CN113680325A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110906210.7A CN113680325A (en) 2021-08-09 2021-08-09 Preparation method and application of diamine-modified MOF/GO alkene composite adsorbent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110906210.7A CN113680325A (en) 2021-08-09 2021-08-09 Preparation method and application of diamine-modified MOF/GO alkene composite adsorbent

Publications (1)

Publication Number Publication Date
CN113680325A true CN113680325A (en) 2021-11-23

Family

ID=78579158

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110906210.7A Withdrawn CN113680325A (en) 2021-08-09 2021-08-09 Preparation method and application of diamine-modified MOF/GO alkene composite adsorbent

Country Status (1)

Country Link
CN (1) CN113680325A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115591524A (en) * 2022-10-20 2023-01-13 合肥工业大学（Cn） GO functionalized UiO-66-NH 2 Preparation and application methods of

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115591524A (en) * 2022-10-20 2023-01-13 合肥工业大学（Cn） GO functionalized UiO-66-NH 2 Preparation and application methods of

Similar Documents

Publication Publication Date Title
Feng et al. Hydrothermal stable ZIF-67 nanosheets via morphology regulation strategy to construct mixed-matrix membrane for gas separation
CN110496604B (en) Cobalt-nickel bimetallic organic framework carbon dioxide adsorption material and preparation method and application thereof
CN111266089B (en) Metal organic framework composite material and preparation method and application thereof
CN108339522B (en) Amino acid @ Cu-BTC composite adsorbent and preparation method thereof
CN108751189B (en) Preparation and application of aluminum-based MOF (metal organic framework) porous carbon material with high specific surface area
CN105233802B (en) One kind doping arginic copper base metal organic framework materials of L and preparation method thereof
He et al. One-step fabrication of PEI-modified GO particles for CO 2 capture
CN109293467A (en) A kind of method of adsorbing separation propylene, propine, propane and allene
Eshraghi et al. Dative post synthetic methods on SBUs of MWCNT@ MOFs hybrid composite and its effect on CO2 uptake properties
Li et al. High dispersion of polyethyleneimine within mesoporous UiO-66s through pore size engineering for selective CO2 capture
CN113683784A (en) Preparation method and application of carbon dioxide adsorbing material with metal organic framework
CN108329484A (en) Double ligand metal organic framework materials of a kind of iron-based of Preferential adsorption ethane and the preparation method and application thereof
Ding et al. Novel and versatile PEI modified ZIF-8 hollow nanotubes to construct CO2 facilitated transport pathway in MMMs
CN112827470A (en) Selective air water-absorbing MOFs material with high stability and preparation method thereof
Gaikwad et al. Bimetallic UTSA-16 (Zn, X; X= Mg, Mn, Cu) metal organic framework developed by a microwave method with improved CO2 capture performances
CN113332959A (en) Novel aluminum-based water-absorbing MOFs material with high stability, preparation method thereof and air water collection application
CN113680325A (en) Preparation method and application of diamine-modified MOF/GO alkene composite adsorbent
CN114849651A (en) Activated carbon packaged carboxylic acid metal organic framework composite material, preparation thereof and gas adsorption separation application
CN114146688B (en) Preparation method and application of water-resistant MOFs (metal-organic frameworks) based material
Du et al. Pebax mixed matrix membrane with bimetallic CeZr-MOFs to enhance CO2 separation
Qian et al. High-performance ZIF-302 mixed-matrix membranes for efficient CO2 capture
CN113600135A (en) Three-dimensional porous graphene aerogel material and preparation method and application thereof
CN108772038A (en) The adsorbent and its preparation method and application of lead ion in a kind of removing water
CN115558120B (en) Metal organic framework material for trace BTEX adsorption and preparation method thereof
CN112940269A (en) Copper-based metal organic framework material Cu-IPA for separating ethane and methane, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20211123

WW01 Invention patent application withdrawn after publication