CN112268918A - Material adsorbed gas in-situ analysis device based on solid nuclear magnetic resonance spectrometer - Google Patents
Material adsorbed gas in-situ analysis device based on solid nuclear magnetic resonance spectrometer Download PDFInfo
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- CN112268918A CN112268918A CN202010663725.4A CN202010663725A CN112268918A CN 112268918 A CN112268918 A CN 112268918A CN 202010663725 A CN202010663725 A CN 202010663725A CN 112268918 A CN112268918 A CN 112268918A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
- G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
- G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
- G01N24/088—Assessment or manipulation of a chemical or biochemical reaction, e.g. verification whether a chemical reaction occurred or whether a ligand binds to a receptor in drug screening or assessing reaction kinetics
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
Abstract
The invention relates to the field of instrument preparation, in particular to a material adsorbed gas in-situ analysis device based on a solid nuclear magnetic resonance spectrometer, which can be used for simultaneously carrying out in-situ analysis research on the adsorption state and the adsorption quantity of gas in the process of adsorbing gas by a material. Based on a solid nuclear magnetic resonance spectrometer, the research device comprises a material sample processing system and an in-situ solid nuclear magnetic testing system. This device uses parallel sample treater in batches, can carry out simultaneous processing and the absorption of multiple material simultaneously, improves the availability factor of instrument. As an intermittent in-situ device, the device has strong expansibility, can be used for the experimental study of the capture of different gases of the absorption material and the study of the gas adsorption state of the catalytic material.
Description
Technical Field
The invention relates to the field of instrument preparation, in particular to a material adsorbed gas in-situ analysis device based on a solid nuclear magnetic resonance spectrometer.
Background
Most of samples measured by the widely used nuclear magnetic resonance spectrometer are liquid, and many properties of substances cannot be observed in the liquid state, so that the solid nuclear magnetic technology is produced. Common solid-state nuclear magnetic techniques mainly utilize magic angle spinning and cross-polarization to enhance resolution and sensitivity of solid samples.
The main display in static solid-state nmr spectroscopy is the information of chemical shift anisotropy, dipole spin coupling and quadrupole interactions, which tend to exhibit broad line spectra. If more attention is paid to chemical shift and J-coupling in the study, the purpose of line narrowing can be achieved by filling the sample into the rotor and rotating the rotor at high speed in the magic angle direction. This is because the time-averaged hamiltonian amounts of the above-mentioned effects all contain a factor (1-3cos2 θ), and therefore, if the sample is rotated at θ of 54.7 ° (i.e., in the diagonal direction of the cube), the above-mentioned strong chemical shift anisotropy, dipole spin coupling, and quadrupole interaction are averaged, while other relatively weak interactions become major factors, and thus it is advantageous to obtain a high-resolution solid nuclear magnetic resonance spectrum.
Although the 13C, 15N and other systems effectively suppress the interaction of homonuclear dipoles through the magic angle rotation technology, the gyromagnetic ratio of the nuclei is small, the natural abundance ratio is low, and the sensitivity of the whole experimental process is very low if an experimental method for directly detecting the nuclei is adopted. In order to further improve the experimental sensitivity of these nuclei, cross-polarization techniques have been developed. By this technique, the magnetization vector of the 1H nucleus can be transferred to a heteronucleus such as 13C or 15N, thereby improving the sensitivity of the experiment.
The solid nuclear magnetic resonance spectrometer has wide application field, and is used for representing the skeleton structure, the crosslinking degree and other local structures of a high molecular polymer in the research of the high molecular polymer so as to explain the relationship between the structural properties of the high molecular polymer; in the research of battery materials, the device is used for tracking and detecting the structural change of the battery materials in the charge and discharge process; used for distinguishing the polymorphic states of different active pharmaceutical ingredients in the field of biological pharmacy; in the field of biological macromolecules, complex structures, kinetic analysis and the like of insoluble biological samples are researched.
The solid nuclear magnetic spectrum technology is one of the important characterization means for catalytic research and material adsorption process research, and is mainly used for the research of catalyst acidity and active sitesSynthesis and structural property characterization, and in-situ tracking in the catalytic reaction process. Wherein the acidity of the solid acid catalyst (
Acid and Lewis acid) and active site research, a solid nuclear magnetic spectrum probe molecular technology is used for distinguishing the types of the acid according to chemical shift; by testing 1H MAS NMR, hydroxyl groups on the surface of the catalytic material were obtained, and the structural information was analyzed. A common solid nuclear magnetic spectrum probe molecule trimethyl phosphorus TMP is used for testing 31P MAS of the acid catalytic material at different temperatures, and the acid strength is detected, wherein the acid strength is-2 to-6 ppm at the B acid position, and is-27 to-58 ppm at the L acid position. In addition, the solid nuclear magnetic spectrum probe molecule is deuterated pyridine, and the detection result shows that the acid B is strong or weak, the chemical shift on non-acidic proton is 2-10ppm, and the chemical shift on acidic proton is 12-20 ppm. Chemical shift of hydrogen bond pyridine is 10ppm, and chemical shift of pyridine ion is 14-20 ppm. The catalytic material is characterized by solid nuclear magnetism, the adsorption treatment process of probe molecules and the catalyst is complicated, the time is long, batch treatment cannot be realized, and potential safety hazards exist. Before carrying out solid nuclear magnetic test, the sample needs to be subjected to adsorption and desorption treatment at different temperatures, and probe molecules are fixed on the catalytic material in a chemical adsorption mode through an adsorption and desorption device. The solid nuclear magnetic in-situ research device used in the market at present is a commercialized device of Bruker company, is expensive, can only be used for researching the gas adsorption state of a material, and cannot be used for simultaneously researching the adsorption quantity and the adsorption state. The device is low in price, and can realize simultaneous in-situ research on gas adsorption quantity and adsorption state by different materials. The material adsorbed gas in-situ analysis device based on the solid nuclear magnetic resonance spectrometer needs to embed the ampoule into the rotor when preparing a solid nuclear magnetic sample. The diameters of the rotors equipped in the laboratory of the existing solid nuclear magnetic spectrometer are mostly two types: 4mm (3 mm internal diameter) and 7mm (5.6 mm internal diameter), which are extremely demanding in terms of ampoule external diameter size, requiring just an inset. This design limits the rotor to only operate at lower rotational speeds and many interactions cannot be eliminated. If the rotating speed of the rotor exceeds 5000Hz/s, the size of the ampoule has slight deviation, the rotor is easy to break, thereby causing the damage of the stator and having higher maintenance cost.Therefore, it is extremely important to design and prepare ampoules that are perfectly matched to the rotor size.
Disclosure of Invention
Technical problem to be solved
The designed batch parallel sample processor is internally provided with n (n is 1,2,3 … n) holes, so that batch processing is realized. Greatly improves the working efficiency, can be used for parallel sample testing, or selects different materials to finish the pretreatment process and the adsorption process at one time.
A 7mm probe and rotor were selected to increase the test sample size. The rotor is large, and the sample amount that can adorn is many to reduce sampling time, increase the SNR, improve spectrogram resolution.
The internal diameter of the 7mm rotor is 5.6mm, the size of the ampoule is required to be slightly smaller than 5.6mm, the size is too large, the rotor cannot be embedded, the size is too small, the rotor cannot stably rotate in the probe, even the rotor and the stator are broken, and the maintenance cost is very high. When the parallel adsorption processor is designed, a large-size ampoule is selected, and the sample is weighed and filled in the glove box, so that the operation safety is greatly improved.
(II) technical scheme
In order to achieve the technical problem, the invention provides the following technical scheme: a material adsorbed gas in-situ analysis device based on a solid nuclear magnetic resonance spectrometer is developed, and in-situ analysis research on the adsorption state and the adsorption quantity of gas in the process of adsorbing gas by a material can be carried out simultaneously. The apparatus comprises a material sample handling system and an in situ solid nuclear magnetic testing system. The sample processing system comprises a batch parallel sample processor, a heating control device and a vacuum control system, wherein the number of built-in holes of the parallel sample processor is more than or equal to 1.
The catalytic material was placed in a batch parallel sample processor and loaded with 1-n (n-1, 2,3 … n) samples/sample at a time. Connecting device, opening vacuum control system, vacuumizing, less than 10-4Pa, and heating the temperature to a required temperature for material treatment, and then weighing the material mass in a glove box. Finally, the samples are placed in a batch parallel sample processor, and the samples are vacuumized again for next sample treatmentOpening the valve of the gas cylinder or the glass container, and allowing the gas or steam probe molecules to enter the processor to be adsorbed on the surface of the material. And vacuumizing again to remove the unadsorbed gas or steam probe molecules of the catalytic material. And (3) dismantling the processor, transferring the processor into a glove box in a sealed state, filling the sample into an ampoule, sealing the ampoule, installing the ampoule into a nuclear magnetic rotor, and testing and analyzing data by using a nuclear magnetic system.
(III) advantageous effects
Compared with the prior art, the invention provides a material adsorbed gas in-situ analysis device based on a solid nuclear magnetic resonance spectrometer, which has the following beneficial effects:
the device uses batch parallel sample processors to improve the use efficiency of the instrument; the experiment process can realize accurate temperature control, and the temperature range is as follows: room temperature to 500 deg.C, vacuum degree less than 10-4Environment of Pa. And as intermittent in-situ device, the device expansibility is strong, can be used for gas adsorption research of different catalytic materials, and can also be used for experimental research such as absorption material gas capture.
Drawings
The invention relates to a commercialized solid nuclear magnetic spectrometer, which comprises a material sample processing system and an in-situ solid nuclear magnetic testing system, and specifically comprises a batch processor, a glass container, a gas cylinder, a vacuum system, a vacuum control system, a glove box and an ampoule matched with a rotor, so that intermittent in-situ solid nuclear magnetic testing research is realized.
Fig. 1 is an overall view of a material adsorbed gas in-situ analysis device based on a solid-state nuclear magnetic resonance spectrometer according to the present invention.
Fig. 2 is a cross-sectional view of a material adsorbed gas in-situ analysis device based on a solid-state nuclear magnetic resonance spectrometer according to the present invention.
FIG. 3 shows the adsorption of CO by MOF material at different temperatures2Front and back hydrogen spectrum change diagrams.
FIG. 4 shows the adsorption of CO by MOF material at different temperatures2Front and back aluminum spectrum change diagrams.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Referring to the attached drawings 1-2 of the specification, the device comprises a material sample processing system and an in-situ solid nuclear magnetic testing system, and specifically comprises a batch processor, a glass container, a gas cylinder, a vacuum system, a vacuum control system, a glove box and an ampoule matched with a rotor, so that intermittent in-situ solid nuclear magnetic testing research is realized. Putting the catalyst/absorbing material into a batch parallel sample processor, filling 1-n (n is 1,2,3 … n) samples at a time, connecting the device, opening a vacuum control system, vacuumizing to less than 10%-4Pa, and heating the temperature to a required temperature for material treatment, and then weighing the material mass in a glove box. And finally, placing the sample in a batch parallel sample processor, vacuumizing again to process the sample, opening a valve of a gas cylinder or a glass container, and allowing gas or steam probe molecules to enter the processor to be adsorbed on the surface of the material. And vacuumizing again to remove the gas or steam probe molecules which are not adsorbed by the catalytic material. Disconnecting the processor from the gas circuit, transferring the processor into a glove box in a sealed state, filling a sample into an ampoule, packaging the sample, installing the sample into a nuclear magnetic rotor, and placing the rotor into a nuclear magnetic system for testing and analyzing data.
In summary, based on the solid nuclear magnetic spectrometer, the device includes a material sample processing system and an in-situ solid nuclear magnetic testing system, and can simultaneously perform in-situ solid nuclear magnetic testing research on the adsorption state and the adsorption amount of the material in the adsorption process. This device uses parallel sample treater in batches, improves the availability factor of instrument, can realize accurate temperature control, temperature range: room temperature to 500 ℃; vacuum degree: < 10-4Environment of Pa. And the device has strong expandability. As an intermittent in-situ device, the device,the method can be used for the research of the adsorption state of the catalytic material and the experimental research of gas trapping of the absorbing material and the like.
Example 1
Using MOF material Al-Fum (molecular formula: C)4H2O5Al; BET specific surface area 900m2Per g) as adsorbent, CO2As the adsorbed gas. Al-Fum was added to the ampoules of the batch parallel sample processor and the kettle lid was tightened to form a closed space. Starting a heater, heating to 150 ℃, starting a vacuum pump, vacuumizing for 2h, cooling to room temperature, and weighing 0.0251g of a sample in a glove box. And (3) connecting the absorption kettle with the vacuum device again, vacuumizing, starting an absorption gas steel cylinder for gas absorption when the temperature is raised to 150 ℃, starting timing when the absorption is saturated, and keeping the absorption standing time for 48 hours. And stopping heating after the time reaches 48 hours, and continuing to stand for 15 minutes after the adsorption kettle is naturally cooled to room temperature. And (3) putting the adsorption kettle into a glove box, weighing, increasing the weight by 0%, then carrying out nuclear magnetic sample preparation, and finally carrying out test adsorption state research by using solid nuclear magnetic.
Example 2
Using MOF material Al-Fum (molecular formula: C)4H2O5Al; BET specific surface area 900m2Per g) as adsorbent, CO2As the adsorbed gas. Al-Fum was added to the ampoules of the batch parallel sample processor and the kettle lid was tightened to form a closed space. Starting a heater, heating to 150 ℃, starting a vacuum pump, vacuumizing for 2h, cooling to room temperature, and weighing 0.1502g of sample in a glove box. And (3) connecting the absorption kettle with the vacuum device again, vacuumizing, starting an absorption gas steel cylinder for gas absorption when the temperature is raised to 50 ℃, starting timing when the absorption is saturated, and keeping the absorption standing time for 52 hours. And stopping heating after the time reaches 52 hours, and continuing to stand for 15 minutes after the adsorption kettle is naturally cooled to room temperature. The adsorption kettle is placed in a glove box, the weight is increased by 1.80 percent after the weighing, then nuclear magnetism sample preparation is carried out, finally, the adsorption state research is carried out by solid nuclear magnetism, and the hydrogen spectrum and aluminum spectrum change analysis are shown in figure 3 and figure 4.
Example 3
Using MOF material Al-Fum (molecular formula: C)4H2O5Al; BET specific surface area 900m2Per g) as adsorbent, CO2As the adsorbed gas. Al-Fum was added to the ampoules of the batch parallel sample processor and the kettle lid was tightened to form a closed space. Starting a heater, heating to 150 ℃, starting a vacuum pump, vacuumizing for 2h, cooling to room temperature, and weighing 0.0775g of sample in a glove box. And (4) connecting the absorption kettle with the vacuum device again, starting an absorption gas steel cylinder at room temperature for gas absorption after vacuumizing, starting timing when the absorption is saturated, and keeping the absorption for 72 hours. And after the time reaches 72h, putting the adsorption kettle into a glove box, weighing, increasing the weight by 13.03%, performing nuclear magnetic sample preparation, and finally performing test adsorption state research by using solid nuclear magnetic, wherein hydrogen spectrum change analysis is shown in figure 3.
Example 4
Using MOF material Al-Fum (molecular formula: C)4H2O5Al; BET specific surface area 900m2Per g) as adsorbent, CO2As the adsorbed gas. Al-Fum was added to the ampoules of the batch parallel sample processor and the kettle lid was tightened to form a closed space. Starting a heater, heating to 150 ℃, starting a vacuum pump, vacuumizing for 2h, cooling to room temperature, and weighing the sample in a glove box to be 0.0666 g. And (3) connecting the absorption kettle with the vacuum device again, starting an absorption gas steel cylinder at room temperature for gas absorption after vacuumizing, starting timing when the absorption is saturated, and keeping the absorption standing time for 120 h. And vacuumizing for 20min after the time reaches 120h, putting the adsorption kettle into a glove box, weighing, increasing the weight by 13.16%, performing nuclear magnetism sample preparation, and finally performing test adsorption state research by using solid nuclear magnetism.
It is to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The material adsorbed gas in-situ analysis device based on the solid nuclear magnetic resonance spectrometer is characterized in that the device can simultaneously carry out in-situ analysis research on the adsorption state and the adsorption quantity of gas in the process of adsorbing gas by a material based on the solid nuclear magnetic resonance spectrometer. The set of devices includes a material sample handling system and an in situ solid nuclear magnetic testing system. The sample processing system comprises a batch parallel sample processor, a heating control device and a vacuum control system, wherein the number of built-in holes of the parallel sample processor is more than or equal to 1.
2. The apparatus for in-situ analysis of adsorbed gas on material by a solid-state nuclear magnetic resonance spectrometer as claimed in claim 1, wherein said batch parallel adsorption processor sample-containing apparatus is an ampoule.
3. The device for in-situ analysis of adsorbed gas in material based on solid nuclear magnetic resonance spectrometer as claimed in claim 1, wherein said heating device has a temperature-controlled heating function between room temperature and 500 ℃.
4. The apparatus according to claim 1, wherein the vacuum control system comprises a gas inlet and a gas outlet.
5. The in-situ analysis device for the adsorbed gas of the material based on the solid-state nuclear magnetic resonance spectrometer as claimed in claim 1, wherein the vacuum pumping device of the vacuum control system is at least one of a vacuum oil pump, a molecular pump, an isolation pump and an ion pump.
6. The solid-state nmr spectrometer-based material adsorbed gas in-situ analysis device of claim 2, wherein the ampoule is adapted for use with an in-situ solid-state nmr measurement system.
7. The device for in-situ analysis of catalytic material adsorption based on solid-state nuclear magnetic resonance spectrometer of claim 1, wherein the vacuum control system is used for evacuating the sample and then introducing gas for adsorption.
8. The device for in-situ analysis of catalytic material adsorption based on solid-state nuclear magnetic resonance spectrometer of claim 7, wherein the gas used for adsorption is CO2、NH3、H2S、SO2、O2And H2At least one of them.
9. The apparatus for in-situ analysis of adsorbed gas in solid-state nmr spectrometer-based material according to claim 1, wherein the sample weighing before and after adsorption is performed in a glove box.
10. The device for in-situ analysis of catalytic material adsorption based on solid-state nuclear magnetic resonance spectrometer as claimed in claim 1, can be used for the study of gas adsorption state and gas adsorption amount of catalytic material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6466814B1 (en) * | 1998-01-05 | 2002-10-15 | Amersham Health As | Method of magnetic resonance investigation |
| CN101634651A (en) * | 2008-07-25 | 2010-01-27 | 中国科学院大连化学物理研究所 | Multiphase catalytic reaction device for testing in situ solid-state nuclear magnetic resonance |
| CN104237283A (en) * | 2014-09-26 | 2014-12-24 | 清华大学 | Method and system for detecting adsorption capacity of solid sample to hydrogen-atom-containing gas |
| CN110961034A (en) * | 2018-09-28 | 2020-04-07 | 中国科学院大连化学物理研究所 | Reactor for solid nuclear magnetic resonance spectrum research under high-temperature high-pressure chemical reaction in-situ reaction condition |
-
2020
- 2020-07-10 CN CN202010663725.4A patent/CN112268918A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6466814B1 (en) * | 1998-01-05 | 2002-10-15 | Amersham Health As | Method of magnetic resonance investigation |
| CN101634651A (en) * | 2008-07-25 | 2010-01-27 | 中国科学院大连化学物理研究所 | Multiphase catalytic reaction device for testing in situ solid-state nuclear magnetic resonance |
| CN104237283A (en) * | 2014-09-26 | 2014-12-24 | 清华大学 | Method and system for detecting adsorption capacity of solid sample to hydrogen-atom-containing gas |
| CN110961034A (en) * | 2018-09-28 | 2020-04-07 | 中国科学院大连化学物理研究所 | Reactor for solid nuclear magnetic resonance spectrum research under high-temperature high-pressure chemical reaction in-situ reaction condition |
Non-Patent Citations (2)
| Title |
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| 张毓凡 等: "《有机化学实验》", 31 December 1999 * |
| 齐国栋: "锌负载ZSM-5分子筛上催化活性中心与反应机理的固体核磁共振研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
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