CN115684239A - Metal fullerene electron spin probe and application thereof in measuring gas adsorption performance of porous material - Google Patents

Metal fullerene electron spin probe and application thereof in measuring gas adsorption performance of porous material Download PDF

Info

Publication number
CN115684239A
CN115684239A CN202110875660.4A CN202110875660A CN115684239A CN 115684239 A CN115684239 A CN 115684239A CN 202110875660 A CN202110875660 A CN 202110875660A CN 115684239 A CN115684239 A CN 115684239A
Authority
CN
China
Prior art keywords
electron spin
porous material
spin probe
metallofullerene
metal fullerene
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.)
Pending
Application number
CN202110875660.4A
Other languages
Chinese (zh)
Inventor
王太山
张捷
王春儒
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.)
Institute of Chemistry CAS
Original Assignee
Institute of Chemistry CAS
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 Institute of Chemistry CAS filed Critical Institute of Chemistry CAS
Priority to CN202110875660.4A priority Critical patent/CN115684239A/en
Priority to PCT/CN2022/099889 priority patent/WO2023005506A1/en
Publication of CN115684239A publication Critical patent/CN115684239A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/02Separation 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N24/00Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
    • G01N24/10Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using electron paramagnetic resonance

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Polymers & Plastics (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

The invention relates to a metal fullerene electron spin probe and application thereof in measuring gas adsorption capacity of a porous material. The metal fullerene electron spin probe is obtained by adsorbing metal fullerene containing electron spin into a pore channel of a porous material; the metal fullerene containing electron spin is selected from Sc 3 C 2 @C 80 And/or Y 2 @C 79 And N is added. The invention uses the metal fullerene electron spin probe to sense the adsorption capacity of the porous material to the gas, and can realize in-situ gas sensing and measurement. The metal fullerene electron spin probe can realize online, real-time and nondestructive detection of target gas on an electron paramagnetic resonance spectrometer.

Description

Metal fullerene electron spin probe and application thereof in measuring gas adsorption performance of porous material
Technical Field
The invention belongs to the field of porous materials and fullerene composite materials, and particularly relates to a metal fullerene electron spin probe and application thereof in measuring gas adsorption performance of porous materials.
Background
In recent years, porous materials constructed with organic frameworks represented by metal organic framework compounds (MOFs) and Covalent Organic Frameworks (COFs) have been widely used in many fields, for example, they have been widely studied and exhibited excellent properties in fields of storage and separation of gases, heterogeneous phase, energy storage materials, photovoltaics, sensing, and drug delivery. In particular, these porous materials exhibit unique advantages in gas storage, gas sensing, and the like. For example, the organic porous material can well adsorb energy gases such as hydrogen, methane, acetylene and the like, and has good application prospects in gas storage and energy utilization. The gas adsorption method is one of the most important methods for characterizing the adsorption capacity and adsorption process of the porous material, however, the method needs a large amount of samples. The organic porous material can also be used for gas sensing, and can specifically sense certain gas by using the change of absorbance and fluorescence after the gas is adsorbed, so as to further analyze the adsorption capacity of the gas, however, the method cannot realize in-situ detection in the pore canal. In gas adsorption measurements, there is still a need to explore other techniques that enable precise measurements in situ.
The embedded metal fullerene is used as a novel carbon nano material, has excellent electron spin characteristics and paramagnetic properties, has wide application prospects in the fields of quantum technology, magnetic materials, magnetic sensing, precision measurement and the like, and becomes an important functional material in the fields of current physics, chemistry, materials and the like. The electron spin characteristic of the metal fullerene comes from a single electron on the metal fullerene orbit, the electron spin has high stability due to the protection of the carbon cage, the spin state of the electron spin has sensitive sensing capability to the external environment, and the change of the environment can be observed through an Electron Paramagnetic Resonance (EPR) signal. However, the electron spin of metallofullerene is still to be explored in the gas sensing and measurement.
Since metallofullerene has a nano size, its molecular diameter is about 1 nm. Such dimensions and their aromatic carbon cages allow access to the channels of the organic based porous material. For metallofullerenes with electron spin, the environment of the channel will greatly affect the paramagnetic resonance signal of the spin. Such as the size of the pore channel, the deformation of the framework molecules, the filling of the solvent, etc., all affect the relaxation process of the spins, thereby changing the EPR signal of the spins. Therefore, exploring the perception of spin on gas fill in channels would have great feasibility and practical significance. If the detection can realize detection of gas types, detection of gas adsorption capacity, detection of a gas adsorption process and the like, the application of electron spin of metal fullerene can be greatly promoted.
Disclosure of Invention
In order to solve the problems, the invention provides a metal fullerene electron spin probe and application thereof in measuring gas adsorption performance of a porous material.
The invention provides a metal fullerene electron spin probe, which is obtained by adsorbing metal fullerene containing electron spin into a pore channel of a porous material.
According to an embodiment of the invention, the metallofullerene containing electron spin is selected from Sc 3 C 2 @C 80 And/or Y 2 @C 79 And N is added. Preferably, sc 3 C 2 @C 80 Sc of which the electron spin is located in the carbon cage 3 C 2 On clusters, spins are coupled to three Sc. Exemplarily, sc 3 C 2 @C 80 The electron spin of (2) generates 22 EPR hyperfine splitting spectral lines, and the shapes and the intensities of the spectral lines of the EPR spectral lines are equal to those of Sc 3 C 2 @C 80 Is concerned with the surrounding environment.
Preferably, Y 2 @C 79 Electron spin of N Y within the carbon cage 2 On clusters, spins are coupled with 2 ys. Exemplarily, Y 2 @C 79 The electron spin of N generates 3 EPR hyperfine splitting spectral lines, and the shapes and the intensities of the spectral lines of the EPR spectral lines are equal to Y 2 @C 79 N is related to the surrounding environment.
According to the embodiment of the invention, the diameter of the pore channel of the porous material is more than 0.8 nanometer, and the diameter of the pore channel is less than 5 nanometer, preferably, the diameter of the pore channel is less than 3 nanometer, and the size of the pore channel can ensure that the metal fullerene enters and is uniformly distributed in the pore channel of the porous material.
According to an embodiment of the invention, the porous material is selected from a metal organic framework compound (MOF) and/or a covalent organic framework Compound (COF).
Preferably, the metal-organic framework compound is selected from metal-organic framework compounds constructed by taking organic carboxylic acid as an organic ligand and metal ions as nodes. Preferably, the metal ions are selected from diamagnetic metal ions such as Zn, mg, zr and the like.
Preferably, the metal organic framework compound is selected from at least one of MOF-177, MOF-180, MOF-200 and the like.
Preferably, the covalent organic framework compound is a high molecular material prepared by co-condensing an organic substance containing benzaldehyde and an organic substance containing aniline.
Preferably, the covalent organic backbone Compound (COF) is selected from at least one of Py-COF, py-TT-COF, and the like. Wherein, py-COF is a two-dimensional pyrenylimine COF (Py-COF) constructed by connecting two benzaldehydes and two anilino groups in a single pyrene nucleus molecule in opposite angles; the Py-Py-COF and Py-TT-COF are covalent organic framework compound materials which are synthesized by taking aldehyde pyrene and aminopyrene as organic ligands and having amide bonds and have a two-dimensional pore channel structure.
According to an embodiment of the invention, the porous material has a complete crystal structure. Preferably, the porous material is obtained by the following preparation method: the porous material is prepared by a preparation method commonly used in the technical field, and crystals with complete crystal forms are selected by matching an optical microscope with a single crystal X-ray diffractometer. Preferably, the crystal size of the porous material is greater than 0.5 mm in any dimension.
The inventor finds that the porous material with the complete crystal structure has a more regular pore channel structure, and is beneficial to the adsorption of metal fullerene.
The invention also provides a preparation method of the metal fullerene electron spin probe, which comprises the following steps: and adsorbing the metal fullerene containing electron spin into the pore channels of the porous material.
Preferably, the organic porous material may be prepared by a solvothermal method, a microwave method, or the like.
According to an embodiment of the present invention, the method for preparing the electron spin probe includes: firstly, preparing a porous material, soaking the porous material in a metal fullerene solution, and adsorbing the metal fullerene to obtain the metal fullerene electron spin probe.
According to an embodiment of the present invention, the solvent is selected from organic solvents capable of dissolving the metallofullerene and incapable of dissolving the porous material. Preferably, the solvent is toluene.
According to an embodiment of the present invention, the concentration of the metallofullerene solution may be 1 × 10 -5 -10 -4 mol/L。
According to an embodiment of the invention, the soaking adsorption is carried out for a period of 1 to 7 days, preferably 3 days.
According to the embodiment of the invention, the electron spin probe is flushed by using the solvent, so that the measurement sensitivity of spin signals to gas adsorption performance is improved. The washing is not particularly limited, and the metal fullerene on the surface of the electronic self-selecting probe can be washed away, so that the metal fullerene is ensured to be positioned in the pore canal.
According to an embodiment of the present invention, another method of preparing the electron spin probe includes: the metal fullerene is added into precursor mother liquor for preparing the porous material, and the metal fullerene electron spin probe with high filling rate of the metal fullerene is obtained by embedding the metal fullerene while the porous material is constructed by cocrystallization.
According to an embodiment of the invention, the metallofullerene electron spin probe has a complete crystal structure. In the invention, the metal fullerene electron spin probe is obtained by selecting an optical microscope and matching with a single crystal X-ray diffractometer. Preferably, the metallofullerene electron spin probe is greater than 0.5 millimeters in either dimension in crystal size.
The inventor finds that the metal fullerene electron spin probe crystal with a better crystal form has a more regular pore channel structure, is more favorable for gas adsorption, and is finally favorable for measuring the gas adsorption performance by using a spin signal.
According to an embodiment of the present invention, in the metallofullerene electron spin probe, the content of the metallofullerene in the porous material is 0.01 to 0.1mol/10mg, for example, 0.06mol/10mg.
According to the embodiment of the invention, the metal fullerene electron spin probe needs to be subjected to vacuum drying to remove the solvent in the pore channel, so that the measurement sensitivity of the spin signal on the gas adsorption performance is improved.
The invention also provides application of the metal fullerene electron spin probe in-situ measurement of gas adsorption capacity of the porous material.
The invention also provides a method for in-situ measurement of gas adsorption capacity of the porous material by using the metal fullerene electron spin probe, which comprises the following steps: and preparing the metal fullerene electron spin probe, filling gas, detecting an Electron Paramagnetic Resonance (EPR) signal of electron spin of the metal fullerene by using an EPR spectrometer, and detecting the gas adsorption capacity of the porous material in situ. Preferably, the metallofullerene has a different EPR signal under different gas conditions.
According to an embodiment of the present invention, the crystal size of the metalfullerene electron spin probe is greater than 0.5 millimeters in either dimension.
The dosage of the metal fullerene electron spin probe in the method is not particularly limited, as long as the EPR signal can be measured. Illustratively, the amount of the metallofullerene electron spin probe is 1mg.
According to the embodiment of the invention, the metal fullerene electron spin probe is placed in a closed atmosphere before being filled with gas. Preferably, the metal fullerene electron spin probe is subjected to vacuum degassing before being filled with gas, so that impurities such as air in the pore channels of the porous material are removed. Preferably, the degree of vacuum of the closed atmosphere is less than 0.1Pa. Preferably, the evacuation time is between 10 and 60 minutes, preferably 30 minutes.
According to an embodiment of the invention, after vacuum degassing, the closed atmosphere is filled with gas to equilibrium.
Preferably, the pressure of the closed atmosphere is maintained at 0.05 to 0.2MPa, preferably 0.1MPa, after the gas is introduced.
Preferably, the aeration equilibration time is between 10 and 60 minutes, preferably 30 minutes.
According to an embodiment of the present invention, the gas is selected from at least one of nitrogen, carbon dioxide, methane, hydrogen, carbon monoxide, acetylene, nitrogen dioxide, ethylene, ethane, propane, propyne, butyne, natural gas, liquefied petroleum gas, biogas, coal gas, and the like.
The inventor finds that an electron paramagnetic resonance spectrometer is used for detecting EPR signals of electron spin of metal fullerene, and the influence of interaction of the metal fullerene and adsorbed gas in a pore channel on the EPR signals is used for analyzing the adsorption capacity of the porous material on the gas. In principle, the more the adsorbed gas molecules, the less the space in the pore channel is, the motion of the metal fullerene is limited, and the motion limitation reduces the relaxation time of the spin, thereby reducing the EPR signal intensity of the spin. Therefore, the adsorption capacity of the porous material to gas can be judged according to the spin EPR signal intensity. According to the method for in-situ measurement of the gas adsorption capacity of the porous material by using the metal fullerene electron spin probe, the adsorption capacity of the porous material to different gases can be rapidly evaluated according to the metal fullerene EPR signal strength.
The invention also provides the application of the metal fullerene electron spin probe in an electron paramagnetic resonance spectrometer.
The invention has the beneficial effects that:
1) The method screens a proper porous material represented by a metal organic framework compound (MOF) and a Covalent Organic Framework (COF), adsorbs metal fullerene containing electron spin to pore channels of the porous material, injects gas into the composite porous material, further detects an Electron Paramagnetic Resonance (EPR) signal of the electron spin of the metal fullerene by using an EPR spectrometer, and analyzes the adsorption capacity of the porous material on the gas according to the change of the EPR signal under the condition of filling different gases by using the influence of the interaction of the metal fullerene and the surrounding environment on the EPR signal.
2) The electron spin probe of the metal fullerene can measure the adsorption capacity of the porous material to gas, and the metal fullerene is also in the pore channel, so that in-situ gas sensing and measurement can be realized. The in-situ measurement of the pore canal can not be realized by the traditional gas adsorption measurement method.
3) The electron spin of the metal fullerene is very sensitive, and the adsorption capacity of the porous material to different gases can be measured by using a crystal with the size of 1 millimeter (about 0.5 mg), while the traditional gas adsorption measurement method needs more than 100mg of samples. Therefore, the method for measuring the gas adsorption capacity of the porous material by the metal fullerene electron spin probe is superior to the traditional gas adsorption measurement method in dosage, and can be used for quickly evaluating the adsorption capacity of the porous material to different gases.
4) The method utilizes an electron paramagnetic resonance spectrometer to detect the EPR signal of electron spin of the metal fullerene, and judges the adsorption capacity of the porous material to the gas according to the EPR signal strength. The more gas molecules adsorbed, the less space in the pore channel, and the restricted motion of the metal fullerene will reduce the relaxation time of the spin, resulting in a lower EPR signal intensity for the spin.
The electron spin probe can realize online, real-time and nondestructive detection on an electron paramagnetic resonance spectrometer, and can monitor the concentration change of target gas in real time and online.
Drawings
FIG. 1 is a schematic diagram of a metallofullerene electron spin probe obtained in example 1 of the present invention after being charged with N 2 And CO 2 The EPR after the comparison is shown.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
3.1mg of 1,3,6, 8-tetrakis (4-formaldehyde-phenyl) pyrene (Py (CHO) 4 ) With 3.5mg of 1,3,6, 8-tetra- (p-aminophenyl) -pyrene (Py (CHO) 4 ) Placing the mixture into a reaction kettle,333. Mu.L of mesitylene, 167. Mu.L of benzyl alcohol and 50. Mu.L of 6M acetic acid were added, the reaction temperature was set at 120 ℃ and the reaction time was 3 days. After cooling to room temperature, the precipitate was filtered and washed 3 times with acetonitrile solvent. After standing for a while, the immersion-washing with the toluene solvent was continued 3 times, and this was repeated several times to replace the solvent in the solid pores with toluene. Selecting and weighing 10mg of air-dried Py-COF and placing in 2mL of Sc 3 C 2 @C 80 Toluene solution (concentration 3.0X 10) - 5 mol/L) to allow it to sufficiently adsorb Sc 3 C 2 @C 80 . Taking out the solid and vacuum drying to obtain
Figure BDA0003190170940000071
The composite material is the metal fullerene electron spin probe of the embodiment. Get the
Figure BDA0003190170940000072
1mg of the composite material is placed in a paramagnetic tube, and a rubber stopper is tightly covered. Inserting a needle from the rubber plug port, vacuumizing and degassing for 30min, and injecting N 2 Equilibration at one atmosphere for 30min, followed by N fill 2 The composite material of (a) was tested in an electron paramagnetic resonance spectrometer to obtain a corresponding EPR spectrum, as shown in sample 1 in figure 1. Then, the composite material is vacuumized and degassed for 30min, and CO is injected 2 And (3) balancing for 30min at one atmospheric pressure, and testing the EPR spectrum in an electron paramagnetic resonance spectrometer to obtain a corresponding EPR spectrum, as shown in a sample 2 in the figure 1.
From FIG. 1, it can be seen that N is adsorbed 2 The signal intensity is higher, and CO is adsorbed 2 The EPR signal strength is low. Description of porous Material to CO 2 The adsorption capacity of the adsorbent is higher, and the EPR result is consistent with the result obtained by the traditional adsorption measurement technology of a static capacity method, which needs 100mg of a sample. Indicating that the amount of the reaction solution can be decreased by a small amount
Figure BDA0003190170940000081
EPR testing of composites to distinguish well between N in the external environment 2 And CO 2
The exemplary embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement and the like made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (10)

1. A metal fullerene electron spin probe is characterized in that the electron spin probe is obtained by adsorbing metal fullerene containing electron spin into a pore channel of a porous material; the metal fullerene containing electron spin is selected from Sc 3 C 2 @C 80 And/or Y 2 @C 79 N;
The diameter of the pore channel of the porous material is larger than 0.8 nanometer, the diameter of the pore channel is smaller than 5 nanometers, and the size of the pore channel can ensure that the metal fullerene enters and is uniformly distributed in the pore channel of the porous material.
2. Metallofullerene electron spin probe according to claim 1, characterized in that Sc 3 C 2 @C 80 Sc in which electron spin of (2) is located in a carbon cage 3 C 2 On clusters, spins are coupled to three Sc.
Preferably, Y 2 @C 79 Electron spin of N Y within the carbon cage 2 On the cluster, spins are coupled with 2Y.
Preferably, the pore diameter is less than 3 nanometers.
3. Metallofullerene electron spin probe according to claim 1 or 2, characterized in that the porous material is selected from metal organic framework compounds (MOF) and/or covalent organic framework Compounds (COF).
Preferably, the metal-organic framework compound is selected from metal-organic framework compounds constructed by taking organic carboxylic acid as an organic ligand and taking metal ions as nodes. Preferably, the metal ions are selected from diamagnetic metal ions such as Zn, mg, zr and the like.
Preferably, the metal organic framework compound is selected from at least one of MOF-177, MOF-180, MOF-200 and the like.
Preferably, the covalent organic framework compound is a high molecular material prepared by co-condensing an organic matter containing benzaldehyde and an organic matter containing aniline.
Preferably, the covalent organic backbone Compound (COF) is selected from at least one of Py-COF, py-TT-COF, and the like. The two-dimensional pyrenylimine COF (Py-COF) is constructed by connecting two benzaldehydes and two anilino groups in opposite angles in a single pyrene nucleus molecule; the Py-Py-COF and Py-TT-COF are covalent organic framework compound materials which are synthesized by taking aldehyde pyrene and aminopyrene as organic ligands and having amide bonds and have a two-dimensional pore channel structure.
4. A metallofullerene electron spin probe according to any one of claims 1-3, characterised in that the porous material has a complete crystal structure.
Preferably, the porous material is obtained by the following preparation method: the porous material is subjected to optical microscopy and a single crystal X-ray diffractometer to select crystals with complete crystal forms. Preferably, the crystal size of the porous material is greater than 0.5 mm in either dimension.
5. A method of fabricating a metallofullerene electron spin probe as claimed in any one of claims 1-4, characterized in that the method of fabricating comprises: and adsorbing the metal fullerene containing the electron spin into the pore channels of the porous material.
Preferably, the organic porous material may be prepared by a solvothermal method, a microwave method, or the like.
Preferably, the preparation method of the electron spin probe comprises the following steps: firstly, preparing a porous material, soaking the porous material in a metal fullerene solution, and adsorbing metal fullerene to obtain the metal fullerene electron spin probe.
Preferably, the solvent is selected from organic solvents capable of dissolving the metallofullerene and incapable of dissolving the porous material. Preferably, the solvent is toluene.
Preferably, the concentration of the metallofullerene solution is1×10 -5 -10 -4 mol/L。
Preferably, the soaking adsorption time is 1-7 days, preferably 3 days.
Preferably, the electron spin probe is flushed with the solvent, so that the measurement sensitivity of spin signals to gas adsorption performance is improved.
6. The method of manufacturing the electron spin probe according to claim 5, wherein the other method of manufacturing the electron spin probe comprises: the metal fullerene is added into precursor mother liquor for preparing the porous material, and the metal fullerene electron spin probe with high filling rate of the metal fullerene is obtained by embedding the metal fullerene while the porous material is constructed by cocrystallization.
Preferably, the metallofullerene electron spin probe has a complete crystal structure. Preferably, the metallofullerene electron spin probe is obtained by selecting the metallofullerene electron spin probe in an optical microscope in cooperation with a single crystal X-ray diffractometer. Preferably, the metallofullerene electron spin probe is larger than 0.5 mm in either dimension in crystal size.
Preferably, in the metallofullerene electron spin probe, the content of the metallofullerene in the porous material is 0.01-0.1mol/10mg, for example, 0.06mol/10mg.
Preferably, the metal fullerene electron spin probe needs to be subjected to vacuum drying to remove the solvent in the pore channel, so that the measurement sensitivity of the spin signal to the gas adsorption performance is improved.
7. Use of a metallofullerene electron spin probe according to any one of claims 1-4 for in situ measurement of the gas adsorption capacity of the porous material.
8. A method of in situ measurement of gas adsorption capacity of a porous material using a metallofullerene electron spin probe according to any one of claims 1-4, characterised in that the method comprises: and preparing the metal fullerene electron spin probe, filling gas, detecting an Electron Paramagnetic Resonance (EPR) signal of electron spin of the metal fullerene by using an EPR spectrometer, and detecting the gas adsorption capacity of the porous material in situ.
Preferably, the metallofullerene has a different EPR signal under different gas conditions.
Preferably, the crystal size of the metallofullerene electron spin probe is greater than 0.5 millimeters in either dimension.
Illustratively, the amount of the metallofullerene electron spin probe is 1mg.
9. The method of claim 8, wherein the metalfullerene electron spin probe is placed in a closed atmosphere prior to filling with gas. Preferably, the metal fullerene electron spin probe is subjected to vacuum degassing before being filled with gas, so that impurities such as air in the pore channels of the porous material are removed. Preferably, the degree of vacuum of the closed atmosphere is less than 0.1Pa. Preferably, the evacuation time is between 10 and 60 minutes, preferably 30 minutes.
Preferably, after vacuum degassing, the closed atmosphere is filled with gas to equilibrium.
Preferably, the pressure of the closed atmosphere is maintained at 0.05 to 0.2MPa, preferably 0.1MPa, after the gas is introduced.
Preferably, the aeration equilibration time is between 10 and 60 minutes, preferably 30 minutes.
Preferably, the gas is selected from at least one of nitrogen, carbon dioxide, methane, hydrogen, carbon monoxide, acetylene, nitrogen dioxide, ethylene, ethane, propane, propyne, butyne, natural gas, liquefied petroleum gas, biogas, coal gas, and the like.
10. Use of a metallofullerene electron spin probe according to any one of claims 1 to 4 in an electron paramagnetic resonance spectrometer.
CN202110875660.4A 2021-07-30 2021-07-30 Metal fullerene electron spin probe and application thereof in measuring gas adsorption performance of porous material Pending CN115684239A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202110875660.4A CN115684239A (en) 2021-07-30 2021-07-30 Metal fullerene electron spin probe and application thereof in measuring gas adsorption performance of porous material
PCT/CN2022/099889 WO2023005506A1 (en) 2021-07-30 2022-06-20 Metal fullerene electron spin probe and application thereof in measuring gas adsorption capacity of porous material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110875660.4A CN115684239A (en) 2021-07-30 2021-07-30 Metal fullerene electron spin probe and application thereof in measuring gas adsorption performance of porous material

Publications (1)

Publication Number Publication Date
CN115684239A true CN115684239A (en) 2023-02-03

Family

ID=85060058

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110875660.4A Pending CN115684239A (en) 2021-07-30 2021-07-30 Metal fullerene electron spin probe and application thereof in measuring gas adsorption performance of porous material

Country Status (2)

Country Link
CN (1) CN115684239A (en)
WO (1) WO2023005506A1 (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2010203281B2 (en) * 2009-01-05 2013-06-27 Commonwealth Scientific And Industrial Research Organisation Gas adsorption material
CN105622645B (en) * 2014-11-17 2018-03-23 中国科学院化学研究所 A kind of metal organic framework compound metal fullerene compound and preparation method thereof
JP6477086B2 (en) * 2015-03-19 2019-03-06 株式会社豊田中央研究所 Method for producing porous material
CN106824103B (en) * 2017-03-15 2019-09-13 北京福纳康生物技术有限公司 A kind of fullerene complex and its in removing flue gas free radical application
CN107880279A (en) * 2017-12-15 2018-04-06 遵义医学院 Metal fullerene porous polymer composite and preparation method thereof
CN108676366B (en) * 2018-05-14 2020-11-06 中国科学院化学研究所 Metal fullerene-photoactive MOF (Metal organic framework) compound, preparation method and application thereof, and method for regulating magnetism of metal fullerene molecules

Also Published As

Publication number Publication date
WO2023005506A1 (en) 2023-02-02

Similar Documents

Publication Publication Date Title
Bon et al. Unraveling structure and dynamics in porous frameworks via advanced in situ characterization techniques
Ritschel et al. Hydrogen storage in different carbon nanostructures
Chen et al. Metal–organic framework MIL-53 (Al) as a solid-phase microextraction adsorbent for the determination of 16 polycyclic aromatic hydrocarbons in water samples by gas chromatography–tandem mass spectrometry
Jiao et al. Preparation of a Co-doped hierarchically porous carbon from Co/Zn-ZIF: An efficient adsorbent for the extraction of trizine herbicides from environment water and white gourd samples
Guo et al. In situ fabrication of nitrogen doped graphitic carbon networks coating for high-performance extraction of pyrethroid pesticides
CN114160105B (en) High-selectivity core-shell structure boric acid doped metal-organic framework magnetic adsorbent and preparation method and application thereof
Rzepka et al. Hydrogen storage capacity of catalytically grown carbon nanofibers
Liu et al. Porous carbon derived from a metal–organic framework as an efficient adsorbent for the solid‐phase extraction of phthalate esters
Liu et al. A metal–organic framework-derived nanoporous carbon/iron composite for enrichment of endocrine disrupting compounds from fruit juices and milk samples
Xie et al. In-situ exfoliation of graphitic carbon nitride with metal-organic framework via a sonication-assisted approach for dispersive solid-phase extraction of perfluorinated compounds in drinking water samples
Ji et al. Application of biocharcoal aerogel sorbent for solid‐phase microextraction of polycyclic aromatic hydrocarbons in water samples
Feng et al. Triazine-based covalent porous organic polymer for the online in-tube solid-phase microextraction of polycyclic aromatic hydrocarbons prior to high-performance liquid chromatography-diode array detection
Meng et al. An implanted paramagnetic metallofullerene probe within a metal–organic framework
Zhang et al. Embedded nano spin sensor for in situ probing of gas adsorption inside porous organic frameworks
André et al. Porous materials applied to biomarker sensing in exhaled breath for monitoring and detecting non-invasive pathologies
Liang et al. A hybrid triazine‐imine core‐shell magnetic covalent organic polymer for analysis of pesticides in fruit samples by ultra high performance liquid chromatography with tandem mass spectrometry
Zhang et al. Metal–organic framework based in‐syringe solid‐phase extraction for the on‐site sampling of polycyclic aromatic hydrocarbons from environmental water samples
Guo et al. Eyes of covalent organic frameworks: Cooperation between analytical chemistry and COFs
Li et al. Triazine‐based organic polymers@ SiO2 nanospheres for sensitive solid‐phase microextraction of polycyclic aromatic hydrocarbons
Loussala et al. Carbon nanotubes functionalized mesoporous silica for in‐tube solid‐phase microextraction of polycyclic aromatic hydrocarbons
CN104399353A (en) Methane-carbon dioxide-nitrogen gas or hydrogen gas multi-component separation method and device
CN115684239A (en) Metal fullerene electron spin probe and application thereof in measuring gas adsorption performance of porous material
Wang et al. Triazine‐based covalent organic polymer: A promising coating for solid‐phase microextraction
Zhang et al. Preparation of magnetic zeolitic imidazolate framework-67 composites for the extraction of phthalate esters from environmental water samples
CN111521534A (en) Method for quantitatively characterizing content of open pores in coal

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