CN108318397B - Nuclear magnetic resonance analysis method and device for nano self-assembly intermediate pore structure - Google Patents
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Abstract
The invention provides a nuclear magnetic resonance analysis method and device for a pore structure of a nano self-assembly intermediate. The analysis method of the invention comprises the following steps: obtaining nuclear magnetic resonance transverse relaxation time T of nano self-assembly intermediate2A spectrum; acquiring nitrogen adsorption pore size distribution and mercury intrusion pore size distribution of a nano self-assembly material, wherein the nano self-assembly material is formed by roasting a nano self-assembly intermediate; performing double-C value error analysis on the nitrogen adsorption pore size distribution and the mercury intrusion pore size distribution and a preset nuclear magnetic resonance pore size distribution respectively to obtain a conversion coefficient C; and obtaining the nuclear magnetic resonance aperture distribution of the nano self-assembly intermediate according to the conversion coefficient C. The analysis method and the device can characterize the pore structure of the nano self-assembly intermediate without an actual pore structure.
Description
Technical Field
The invention relates to a pore structure analysis method, in particular to a nuclear magnetic resonance analysis method and a nuclear magnetic resonance analysis device for a pore structure of a nano self-assembly intermediate.
Background
Specific surface area and pore size distribution are conventional parameters for characterizing the pore structure of catalytic materials. The specific surface area is the total surface area of a unit mass of a substance, and is one of important characteristics of powder materials, particularly ultrafine powder and nano powder materials, and the finer the particles of the powder, the larger the specific surface area, the stronger the surface effects such as surface activity, surface adsorption capacity, catalytic capacity and the like. The pore size distribution is the percentage of the pore sizes of the various stages present in the material, calculated by number or volume, and the pores can be divided into three categories by size, namely: micropores with the aperture of less than 2nm, mesopores with the aperture of 2-50nm and macropores with the aperture of more than 50nm, and the aperture distribution has close relation with the catalytic performance of the catalytic material. Currently, nitrogen adsorption and mercury porosimetry are commonly used to characterize the pore structure of catalytic materials.
The nitrogen adsorption method is a conventional method for determining the specific surface area and pore size distribution of a material, can effectively and reliably characterize the surface and interface characteristics of the material, and has been widely applied to the technical fields of electronics, electricity, machinery, construction, biology, medicine, ocean, and the like. The principle of the nitrogen adsorption method is as follows: at the temperature of liquid nitrogen, the adsorption of nitrogen on the surface of the adsorbent is pure physical adsorption, and when the temperature returns to room temperature, the adsorbed nitrogen is completely desorbed; assuming that the nitrogen gas adsorbed on the surface of the adsorbent is exactly one molecular layer, the specific surface area of the adsorbent can be determined if the cross-sectional area of each nitrogen molecule is known.
The adsorption apparatus is used for measuring nitrogen adsorption capacity and mainly comprises a static nitrogen adsorption apparatus and a dynamic nitrogen adsorption apparatus. The static volume method is that a known amount of gas is introduced into a sample tube which is automatically and constantly at the adsorption temperature, the gas is adsorbed on the surface of a sample, and the gas pressure in a fixed space is continuously reduced until the adsorption balance is reached; the specific surface area and pore structure performance of the adsorbent can be calculated from the amount adsorbed at equilibrium pressure (i.e., the difference between the amount of supplied gas and the amount of adsorbed gas remaining in the gas phase). When a nitrogen adsorption method is used for measuring a material, the material to be measured must have actual porosity to adsorb nitrogen, so that the method cannot be applied to measurement of the material without a pore structure.
The mercury intrusion method is a conventional method for researching the microscopic pore structure of a material, and mercury is injected into pore media such as a nano material or rock, so that a mercury capillary pressure curve is obtained and a mercury withdrawal curve is obtained in the mercury withdrawal process, and a series of parameters capable of reflecting pore throat size, pore throat sorting, pore throat connectivity and seepage capacity can be obtained. When the mercury intrusion method is used for measuring the material, the material to be measured also has to have actual porosity to enable liquid mercury to enter the pore channels, so that the method can not be applied to the measurement of the material without the pore channel structure.
The nano self-assembly technology is characterized in that molecules are spontaneously assembled to form one or more molecular aggregates or structural units of a polymer which have a certain structure, are stable and are spontaneously associated by non-covalent bonds through ionic bonds, hydrogen bonds, weak directional bonds or acting forces such as van der waals force and the like. The required nano structure can be obtained by repeatedly organizing and arranging the materials, and the method is further applied to the preparation and reaction for constructing the ordered structure nano mesoporous material, and the prepared nano self-assembly material has the characteristics of thermodynamic stability, structural determination, special performance and the like. In the process of constructing the structural unit, the size, the shape and the structure of the pore canal of the nano material can be accurately regulated and controlled by utilizing the organic template. The nano self-assembly intermediate is an intermediate product of the nano self-assembly material before roasting, and the pore channel of the nano self-assembly intermediate is filled with the organic template and the adhesive, so that the nano self-assembly intermediate does not have an actual pore channel structure, and the pore structure of the nano self-assembly intermediate cannot be measured by a conventional method.
Disclosure of Invention
The invention provides a nuclear magnetic resonance analysis method and device for a pore structure of a nano self-assembly intermediate, which can characterize the pore structure of the nano self-assembly intermediate without a pore channel structure.
The invention provides a nuclear magnetic resonance analysis method for a pore structure of a nano self-assembly intermediate, which comprises the following steps:
obtaining nuclear magnetic resonance transverse relaxation time T of nano self-assembly intermediate2A spectrum;
acquiring nitrogen adsorption pore size distribution and mercury intrusion pore size distribution of a nano self-assembly material, wherein the nano self-assembly material is formed by roasting a nano self-assembly intermediate;
performing double-C value error analysis on the nitrogen adsorption pore size distribution and the mercury intrusion pore size distribution and a preset nuclear magnetic resonance pore size distribution respectively to obtain a conversion coefficient C;
and obtaining the nuclear magnetic resonance aperture distribution of the nano self-assembly intermediate according to the conversion coefficient C.
The nano self-assembly material refers to a nano material prepared by a nano self-assembly technology; it can be understood that the nano self-assembly material has a pore structure, so that the nitrogen adsorption pore size distribution and the mercury intrusion pore size distribution of the material can be measured by a nitrogen adsorption method and a mercury intrusion method respectively.
The inventionThe nano self-assembly intermediate is an intermediate product of the nano self-assembly material before roasting; it can be understood that the pore channels of the nano self-assembly intermediate are filled with the organic template and the binder, so that the nano self-assembly intermediate does not have an actual pore channel structure, and therefore, the nitrogen adsorption method and the mercury intrusion method cannot be applied. The invention carries out nuclear magnetic resonance transverse relaxation time T on the nano self-assembly intermediate2Measuring to obtain the nuclear magnetic resonance transverse relaxation time T of the nano self-assembly intermediate2A spectrum; then combining the experimental data of nitrogen adsorption aperture distribution and mercury intrusion aperture distribution of the nano self-assembly material to carry out nuclear magnetic resonance transverse relaxation time T on the nano self-assembly intermediate2The spectrum is calibrated by a double C value error analysis method, so that the potential pore structure of the nano self-assembly intermediate is obtained.
In the invention, the nitrogen adsorption pore size distribution and the mercury intrusion pore size distribution of the nano self-assembly material are respectively compared with the preset nuclear magnetic resonance pore size distribution so as to carry out double-C value error analysis; wherein the preset nuclear magnetic resonance aperture distribution refers to the preset conversion coefficient C and the nuclear magnetic resonance transverse relaxation time T2Nuclear magnetic resonance pore size distribution obtained by spectroscopy (obtained by the following formula 2); after a plurality of preset conversion coefficients C are designed in advance, a plurality of preset nuclear magnetic resonance aperture distributions can be obtained, and the nitrogen adsorption aperture distribution and the mercury intrusion aperture distribution are subjected to double-C value error analysis respectively with the plurality of preset nuclear magnetic resonance aperture distributions, so that the C value corresponding to the minimum error position is the actual conversion coefficient C.
In the present invention, the actual conversion coefficient C is obtained by the following formula 1,
equation 1:
wherein:
as an error, VN2Is nitrogen adsorption pore diameter, VHgIs mercury intrusion pore diameter, VT2For presetting the nuclear magnetic resonance aperture, omega(xi)Is weight, n is error number;
when x is less than or equal to 15nm, a is 1, b is 0 (namely, when the aperture is less than or equal to 15nm, the nitrogen adsorption aperture distribution is selected to be compared with the preset nuclear magnetic resonance aperture distribution); when x is larger than 15nm, a is 0, b is 1 (namely, when the aperture is larger than 15nm, the aperture distribution of mercury porosimetry is selected to be compared with the aperture distribution of the preset nuclear magnetic resonance);
in formula 1, the C value corresponding to the minimum position is the conversion coefficient C.
The nitrogen adsorption method can only represent the aperture below 100nm, but can not accurately measure macropores; meanwhile, the mercury intrusion method can represent macropores due to the pressure limit of liquid mercury, and micropores cannot be accurately measured; the method of the invention is implemented by the nuclear magnetic resonance transverse relaxation time T of the nano self-assembly intermediate2And the spectrum is subjected to double-C value error analysis, so that the potential pore characteristics of the nano self-assembly intermediate can be accurately obtained.
Further, after the conversion coefficient C is determined, the nuclear magnetic resonance pore size distribution of the nano self-assembly intermediate can be obtained by the following formula 2,
formula 2: L ═ CT2
Wherein L is nuclear magnetic resonance aperture distribution, C is conversion coefficient, and T is2Transverse relaxation time T for nuclear magnetic resonance2Spectra.
That is, the NMR transverse relaxation time T of the nano self-assembly intermediate can be determined by the formula 22The spectra were converted to nuclear magnetic resonance pore size distribution.
The derivation of equation 2 is as follows:
nuclear magnetic resonance transverse relaxation time T of nano self-assembled intermediate2The spectra include bulk relaxation, surface relaxation and diffusion relaxation, see equation 4 below:
equation 4:
wherein:
T2Bthe bulk relaxation time of water is usually 2-3 s, which is far greater than T2Thus 1/T2B≈0；
ρ2Is T2Surface relaxation rate (unit: mum · ms)-1) S/V is the ratio of pore surface area to fluid volume; d is expansionCoefficient of dispersion (unit: mum)2·ms-1) γ is a gyromagnetic ratio (unit: rad (s Gs)-1) G is the magnetic field gradient (unit: gs cm-1)，TEIs the echo spacing.
Since the magnetic field is uniform and the pore size is small (nano-pore size), the bulk and diffusion relaxations are negligible, resulting in the following equation 5:
equation 5:
from the pore geometry factor Fs 2, the following equation 6 is further derived:
equation 6: L ═ 2r ═ 4 ρ2T2＝CT2
Wherein L is nuclear magnetic resonance aperture distribution, C is conversion coefficient, and T is2Transverse relaxation time T for nuclear magnetic resonance2Spectra.
Further, the analysis method of the present invention further comprises:
obtaining the total porosity of the nano self-assembly material;
transverse relaxation time T of NMR according to total porosity2And (5) graduating the spectrum to obtain the nuclear magnetic resonance interval porosity of the nano self-assembly intermediate.
Wherein the total porosity can be measured by mercury porosimetry, volumetric method, nuclear magnetic resonance method and other conventional methods. Preferably, the total porosity is measured by a mercury intrusion method, and the mercury intrusion method can accurately measure the total porosity of the nano self-assembly material.
Further, the analysis method of the present invention may further include:
and obtaining the surface relaxation rate of the nano self-assembly intermediate according to the conversion coefficient C.
Specifically, the surface relaxation rate of the nano self-assembled intermediate can be obtained by the following formula 3,
equation 3: rho2＝C/4
Wherein: rho2C is the surface relaxation rate and C is the conversion coefficient.
In the invention, the nuclear magnetic resonance transverse relaxation time T of the nano self-assembly intermediate can be obtained in a conventional mode2A spectrum; for example, the CPMG pulse sequence can be used for carrying out the nuclear magnetic resonance transverse relaxation time T on the nano self-assembly intermediate2Measuring to obtain the nuclear magnetic resonance transverse relaxation time T of the nano self-assembly intermediate2Spectra.
The invention also provides a nuclear magnetic resonance analysis device of the nano self-assembly intermediate pore structure, which comprises a nuclear magnetic resonance instrument, a nitrogen adsorption experimental device, a mercury-pressing experimental device and a data processor,
the nuclear magnetic resonance apparatus can obtain the nuclear magnetic resonance transverse relaxation time T of the nano self-assembly intermediate2The spectrum of the light beam is measured,
the nitrogen adsorption experimental device can obtain the nitrogen adsorption aperture distribution of the nano self-assembly material,
the mercury intrusion experimental device can obtain the mercury intrusion aperture distribution of the nano self-assembly material,
the data processor is respectively electrically connected with the nuclear magnetic resonance instrument, the nitrogen adsorption experiment device and the mercury intrusion experiment device, and the data processor can respectively carry out double-C-value error analysis on the nitrogen adsorption pore size distribution and the mercury intrusion pore size distribution with the preset nuclear magnetic resonance pore size distribution.
In the invention, the nuclear magnetic resonance apparatus, the nitrogen adsorption experimental device and the mercury intrusion experimental device can be conventional equipment in the field.
Further, the mercury intrusion experimental device can also acquire the total porosity of the nano self-assembly material, and the data processor can perform transverse relaxation time T on the nuclear magnetic resonance according to the total porosity2And (4) carrying out spectrum calibration to obtain the nuclear magnetic resonance interval porosity of the nano self-assembly intermediate.
The implementation of the invention has at least the following advantages:
1. the method can measure the nano material without actual pore channels, and can quickly and accurately measure the T of the nano material2Distribution, measurement time averaged within five minutes per sample, phaseCompared with a nitrogen adsorption method and a mercury pressing method which take too long time, the method saves labor and time cost.
2. The method of the invention is used for the nuclear magnetic resonance transverse relaxation time T of the nano self-assembly intermediate2And performing double-C value error analysis on the spectrum, and comparing the nitrogen adsorption pore size distribution and mercury intrusion pore size distribution of the nano self-assembly material with the preset nuclear magnetic resonance pore size distribution respectively, so that the potential pore characteristics of the nano self-assembly intermediate can be obtained more accurately.
3. The method of the invention is nontoxic, healthy and environment-friendly; the device has simple structure and convenient and quick operation, can quickly, accurately and comprehensively obtain the potential pore characteristics of the nano self-assembly intermediate by utilizing the method and the device, and provides guidance and monitoring functions for the roasted nano self-assembly material.
Drawings
FIG. 1 shows the NMR transverse relaxation time T2 spectrum, interval porosity and cumulative porosity of the nano self-assembled intermediate of example 1 and example 2;
FIG. 2 is the surface relaxation rate of the nano self-assembled intermediate of example 1;
FIG. 3 is the surface relaxation rate of the nano self-assembled intermediate of example 2;
FIG. 4 is the nuclear magnetic resonance pore size distribution of the nano self-assembled intermediates of examples 1 and 2;
fig. 5 is a schematic structural diagram of an embodiment of a nuclear magnetic resonance analysis apparatus for a pore structure of a nano self-assembled intermediate.
Description of reference numerals:
1: a nuclear magnetic resonance apparatus; 2: a nitrogen adsorption experimental device; 3: mercury intrusion experimental facility; 4: a data processor.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The materials of the embodiments of the invention are as follows:
nano self-assembly intermediates NSAI-1 and NSAI-2: from the institute of petrochemical engineering, Dalian of petrochemical Co., Ltd., China;
nano self-assembly materials S-1 and S-2: from Dalian petrochemical research institute of petrochemical company, China petrochemical company Limited.
Example 1
In this example, the pore structure of the nano self-assembly intermediate NSAI-1 was analyzed; wherein, the nano self-assembly material S-1 is formed by roasting the nano self-assembly intermediate NSAI-1, and the analysis method comprises the following steps:
1. obtaining nuclear magnetic resonance transverse relaxation time T of nano self-assembly intermediate NSAI-12Spectrum
Performing nuclear magnetic resonance transverse relaxation time T on nano self-assembly intermediate NSAI-1 by using CPMG pulse sequence2Measuring to obtain the nuclear magnetic resonance transverse relaxation time T of the nano self-assembly intermediate NSAI-12The spectra, results are shown in FIG. 1.
2. Obtaining nitrogen adsorption pore size distribution of nano self-assembly material S-1
And (3) performing a nitrogen adsorption test on the nano self-assembly material S-1 by adopting a conventional method to obtain the nitrogen adsorption pore size distribution of the nano self-assembly material S-1.
3. Obtaining the mercury intrusion aperture distribution and the mercury intrusion total porosity of the nano self-assembly material S-1
And (3) carrying out mercury intrusion test on the nano self-assembly material S-1 by adopting a conventional method to respectively obtain mercury intrusion pore size distribution and mercury intrusion total porosity of the nano self-assembly material S-1.
4. Obtaining nuclear magnetic resonance interval porosity of nano self-assembly intermediate NSAI-1
According to the obtained total porosity of mercury intrusion on the nuclear magnetic resonance transverse relaxation time T of the nano self-assembly intermediate NSAI-12The spectrum is scaled to obtain the nuclear magnetic resonance interval porosity sum of the nano self-assembly intermediate NSAI-1The porosity was accumulated and the results are shown in figure 1.
FIG. 1 shows the nuclear magnetic resonance interval porosity T of the nano self-assembly intermediate NSAI-12Spectra and cumulative spectra.
5. Obtaining the conversion coefficient C and the surface relaxation rate of a nano self-assembly intermediate NSAI-1
Performing double-C value error analysis on the nitrogen adsorption pore size distribution and the mercury intrusion pore size distribution and a plurality of preset nuclear magnetic resonance pore size distributions;
the conversion coefficient C is obtained by the following formula 1,
equation 1:
wherein: as an error, VN2Is nitrogen adsorption pore diameter, VHgIs mercury intrusion pore diameter, VT2For presetting the nuclear magnetic resonance aperture, omega(xi)Is weight, n is error number; when x is less than or equal to 15nm, a is 1, and b is 0; at x>At 15nm, a is 0 and b is 1; the conversion coefficient C is the value of C corresponding to the minimum position.
In addition, the surface relaxation rate of the nano self-assembly intermediate NSAI-1 is obtained through the following formula 3;
equation 3: rho2＝C/4
Wherein: rho2C is the surface relaxation rate and C is the conversion coefficient.
The results are shown in FIG. 2; from FIG. 2, the conversion coefficients C of the small hole and the large hole can be obtained by double C value error analysis1And C2。
6. Obtaining nuclear magnetic resonance aperture distribution of nano self-assembly intermediate NSAI-1
Obtaining the nuclear magnetic resonance aperture distribution of the nano self-assembly intermediate NSAI-1 through the following formula 2;
formula 2: L ═ CT2
Wherein L is nuclear magnetic resonance aperture distribution, C is conversion coefficient, and T is2Transverse relaxation time T for nuclear magnetic resonance2Spectra.
The results are shown in FIG. 4; the conversion factor C which can be obtained by calculation from FIG. 41And C2Obtaining quantitative T2Pore size distribution of T2The spectrum is converted from time units to length units.
Example 2
In this example, the pore structure of the nano self-assembly intermediate NSAI-2 was analyzed; wherein, the nano self-assembly material S-2 is formed by roasting the nano self-assembly intermediate NSAI-2, and the analysis method comprises the following steps:
1. obtaining nuclear magnetic resonance transverse relaxation time T of nano self-assembly intermediate NSAI-22Spectrum
Performing nuclear magnetic resonance transverse relaxation time T on nano self-assembly intermediate NSAI-2 by using CPMG pulse sequence2Measuring to obtain the nuclear magnetic resonance transverse relaxation time T of the nano self-assembly intermediate NSAI-22The spectra, results are shown in FIG. 1.
2. Obtaining nitrogen adsorption pore size distribution of nano self-assembly material S-2
And (3) performing a nitrogen adsorption test on the nano self-assembly material S-2 by adopting a conventional method to obtain the nitrogen adsorption pore size distribution of the nano self-assembly material S-2.
3. Obtaining the mercury intrusion aperture distribution and mercury intrusion total porosity of the nano self-assembly material S-2
And (3) carrying out mercury intrusion test on the nano self-assembly material S-2 by adopting a conventional method to respectively obtain mercury intrusion pore size distribution and mercury intrusion total porosity of the nano self-assembly material S-2.
4. Obtaining nuclear magnetic resonance interval porosity of nano self-assembly intermediate NSAI-2
According to the obtained total porosity of mercury intrusion on the nuclear magnetic resonance transverse relaxation time T of the nano self-assembly intermediate NSAI-22The spectrum is scaled to obtain the nuclear magnetic resonance interval porosity and the accumulated porosity of the nano self-assembly intermediate NSAI-2, and the result is shown in figure 1.
FIG. 1 shows the nuclear magnetic resonance interval porosity T of the nano self-assembly intermediate NSAI-22Spectra and cumulative spectra.
5. Obtaining the conversion coefficient C and the surface relaxation rate of a nano self-assembly intermediate NSAI-2
Performing double-C value error analysis on the nitrogen adsorption pore size distribution and the mercury intrusion pore size distribution and a plurality of preset nuclear magnetic resonance pore size distributions;
the conversion coefficient C is obtained by the following formula 1,
equation 1:
wherein: as an error, VN2Is nitrogen adsorption pore diameter, VHgIs mercury intrusion pore diameter, VT2For presetting the nuclear magnetic resonance aperture, omega(xi)Is weight, n is error number; when x is less than or equal to 15nm, a is 1, and b is 0; at x>At 15nm, a is 0 and b is 1; the conversion coefficient C is the value of C corresponding to the minimum position.
In addition, the surface relaxation rate of the nano self-assembly intermediate NSAI-2 is obtained through the following formula 3;
equation 3: rho2＝C/4
Wherein: rho2C is the surface relaxation rate and C is the conversion coefficient.
The results are shown in FIG. 3; from FIG. 3, the conversion coefficients C of the small hole and the large hole can be obtained by double C value error analysis1And C2。
6. Obtaining nuclear magnetic resonance aperture distribution of nano self-assembly intermediate NSAI-2
Obtaining the nuclear magnetic resonance aperture distribution of the nano self-assembly intermediate NSAI-2 through the following formula 2;
formula 2: L ═ CT2
Wherein L is nuclear magnetic resonance aperture distribution, C is conversion coefficient, and T is2Transverse relaxation time T for nuclear magnetic resonance2Spectra.
The results are shown in FIG. 4; the conversion factor C which can be obtained by calculation from FIG. 41And C2Obtaining quantitative T2Pore size distribution of T2The spectrum is converted from time units to length units.
Example 3
As shown in FIG. 5, the nuclear magnetic resonance analysis device of the nano self-assembly intermediate pore structure comprises a nuclear magnetic resonance instrument 1, a nitrogen adsorption experimental device 2, a mercury intrusion experimental device 3 and a data processor4; wherein the nuclear magnetic resonance apparatus 1 can obtain the nuclear magnetic resonance transverse relaxation time T of the nano self-assembly intermediate2The spectrum, nitrogen adsorption experimental apparatus 2 can acquire the nitrogen adsorption aperture distribution of nanometer self-assembled material, and mercury intrusion experimental apparatus 3 can acquire the mercury intrusion aperture distribution of nanometer self-assembled material, and data processor 4 is connected with nuclear magnetic resonance appearance 1, nitrogen adsorption experimental apparatus 2 and mercury intrusion experimental apparatus 3 electricity respectively, and data processor 4 can carry out two C value error analysis with nitrogen adsorption aperture distribution and mercury intrusion aperture distribution respectively with predetermineeing nuclear magnetic resonance aperture distribution.
Further, the mercury intrusion experimental device 3 can also obtain the total porosity of the nano self-assembly material, and the data processor 4 can also obtain the nuclear magnetic resonance transverse relaxation time T according to the total porosity2The spectrum is scaled to obtain the nuclear magnetic resonance interval porosity of the nano self-assembled intermediate.
The device can be used for analyzing the pore structure of the nano self-assembly intermediate, and specifically comprises the following steps:
obtaining NMR transverse relaxation time T of nano self-assembly intermediate by NMR 12Spectrum, meanwhile, nitrogen adsorption aperture distribution of the nano self-assembly material is obtained through a nitrogen adsorption experimental device 2, and mercury intrusion aperture distribution and total porosity of the nano self-assembly material are obtained through a mercury intrusion experimental device 3; the data obtained by each device is then transmitted to the data processor 4 for data processing.
The data processor 4 respectively performs double-C value error analysis on the nitrogen adsorption pore size distribution and the mercury intrusion pore size distribution and a preset nuclear magnetic resonance pore size distribution to obtain a conversion coefficient C; meanwhile, according to the conversion coefficient C, the surface relaxation rate and the nuclear magnetic resonance aperture distribution of the nano self-assembly intermediate are obtained. Furthermore, the data processor 4 is also capable of determining the NMR transverse relaxation time T from the total porosity2And (4) graduating the spectrum, thereby obtaining the nuclear magnetic resonance interval porosity of the nano self-assembly intermediate.
The method and the device can quickly and accurately measure the nano self-assembly intermediate without actual pore channels and other materials, and the nuclear magnetic resonance transverse relaxation of the nano self-assembly intermediate is realizedTime T2And performing double C value error analysis on the spectrum, and comparing the nitrogen adsorption pore size distribution and mercury intrusion pore size distribution of the nano self-assembly material with the preset nuclear magnetic resonance pore size distribution respectively, so that the potential pore characteristics of the nano self-assembly intermediate can be obtained more accurately, and a guiding and monitoring effect is provided for the roasted nano self-assembly material.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A nuclear magnetic resonance analysis method for a pore structure of a nano self-assembly intermediate is characterized by comprising the following steps:
obtaining nuclear magnetic resonance transverse relaxation time T of nano self-assembly intermediate2A spectrum;
acquiring nitrogen adsorption pore size distribution and mercury intrusion pore size distribution of a nano self-assembly material, wherein the nano self-assembly material is formed by roasting a nano self-assembly intermediate;
performing double-C value error analysis on the nitrogen adsorption pore size distribution and the mercury intrusion pore size distribution and a preset nuclear magnetic resonance pore size distribution respectively to obtain a conversion coefficient C;
obtaining the nuclear magnetic resonance aperture distribution of the nano self-assembly intermediate according to the conversion coefficient C, wherein the conversion coefficient C is obtained by the following formula 1,
equation 1:
wherein:
as an error, VN2Is nitrogen adsorption pore diameter, VHgIs mercury intrusion pore diameter, VT2For presetting the nuclear magnetic resonance aperture, omega(xi)Is weight, n is error number;
when x is less than or equal to 15nm, a is 1, and b is 0; a is 0 and b is 1 when x >15 nm;
the conversion coefficient C is the value of C corresponding to the minimum position.
2. The nuclear magnetic resonance analysis method for the pore structure of the nano self-assembled intermediate according to claim 1, wherein the nuclear magnetic resonance pore size distribution of the nano self-assembled intermediate is obtained by the following formula 2,
formula 2: L ═ CT2
Wherein L is nuclear magnetic resonance aperture distribution, C is conversion coefficient, and T is2Transverse relaxation time T for nuclear magnetic resonance2Spectra.
3. The method for nuclear magnetic resonance analysis of the pore structure of the nano self-assembled intermediate according to claim 1 or 2, further comprising:
obtaining the total porosity of the nano self-assembly material;
transverse relaxation time T of NMR according to total porosity2And (5) graduating the spectrum to obtain the nuclear magnetic resonance interval porosity of the nano self-assembly intermediate.
4. The method for nuclear magnetic resonance analysis of the pore structure of a nano self-assembled intermediate according to claim 3, characterized in that the total porosity is measured by mercury intrusion, volumetric or nuclear magnetic resonance.
5. The method for nuclear magnetic resonance analysis of the pore structure of the nano self-assembled intermediate according to claim 1 or 2, further comprising: and obtaining the surface relaxation rate of the nano self-assembly intermediate according to the conversion coefficient C.
6. The NMR analysis method for a pore structure of a nano self-assembled intermediate according to claim 5, wherein the surface relaxation rate of the nano self-assembled intermediate is obtained by the following formula 3,
equation 3: rho2＝C/4
Wherein: rho2C is the surface relaxation rate and C is the conversion coefficient.
7. The method for nuclear magnetic resonance analysis of the pore structure of the nano self-assembled intermediate according to claim 1 or 2, wherein the CPMG pulse sequence is used to perform the nuclear magnetic resonance transverse relaxation time T on the nano self-assembled intermediate2Measuring to obtain the nuclear magnetic resonance transverse relaxation time T of the nano self-assembly intermediate2Spectra.
8. A nuclear magnetic resonance analysis device of a nano self-assembly intermediate pore structure is characterized by comprising a nuclear magnetic resonance instrument, a nitrogen adsorption experimental device, a mercury-pressing experimental device and a data processor,
the nuclear magnetic resonance apparatus can obtain the nuclear magnetic resonance transverse relaxation time T of the nano self-assembly intermediate2The spectrum of the light beam is measured,
the nitrogen adsorption experimental device can obtain the nitrogen adsorption aperture distribution of the nano self-assembly material,
the mercury intrusion experimental device can obtain the mercury intrusion aperture distribution of the nano self-assembly material,
the data processor is respectively electrically connected with the nuclear magnetic resonance instrument, the nitrogen adsorption experimental device and the mercury intrusion experimental device, the data processor can respectively carry out double-C-value error analysis on the nitrogen adsorption pore size distribution and the mercury intrusion pore size distribution and a preset nuclear magnetic resonance pore size distribution to obtain a conversion coefficient C, wherein the conversion coefficient C is obtained through the following formula 1,
equation 1:
wherein:
as an error, VN2Is nitrogen adsorption pore diameter, VHgIs mercury intrusion pore diameter, VT2For presetting the nuclear magnetic resonance aperture, omega(xi)Is weight, n is error number;
when x is less than or equal to 15nm, a is 1, and b is 0; a is 0 and b is 1 when x >15 nm;
the conversion coefficient C is the value of C corresponding to the minimum position.
9. The apparatus according to claim 8, wherein the mercury intrusion experimental device is further capable of obtaining a total porosity of the nano self-assembly material, and the data processor is capable of determining the transverse relaxation time T of the NMR according to the total porosity2And (4) carrying out spectrum calibration to obtain the nuclear magnetic resonance interval porosity of the nano self-assembly intermediate.
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