CN113307245A - Preparation method of porous carbon photothermal material with specific morphology and multi-fractal structure - Google Patents
Preparation method of porous carbon photothermal material with specific morphology and multi-fractal structure Download PDFInfo
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Abstract
The invention relates to a preparation method of a porous carbon photothermal material with a specific morphology and a multi-fractal structure, and belongs to the technical field of seawater desalination. The method comprises the following steps: preparing metal organic framework materials MOFs to be tested; II, secondly: performing thermogravimetry-mass spectrometry combined test and in-situ infrared test on MOFs; thirdly, the method comprises the following steps: recording mass spectrum information of gas byproducts during MOFs pyrolysis; fourthly, the method comprises the following steps: analyzing the change of functional groups in the MOFs pyrolysis process according to the in-situ infrared test result of the MOFs; fifthly: confirming the pyrolysis mechanism of the MOFs according to the mass spectrum information and the functional group information; sixthly, the method comprises the following steps: carrying out a designable carbonization experiment on the MOFs according to a pyrolysis mechanism; seventhly, the method comprises the following steps: and carrying out photo-thermal performance test and seawater desalination experiment on the carbonized products of the MOFs. According to the invention, through in-situ research on the MOFs pyrolysis mechanism, a carbonized product with an expected morphology can be designed and synthesized, and finally, the porous carbon material with excellent photo-thermal property can be prepared.
Description
Technical Field
The invention relates to a preparation method of a porous carbon photothermal material with a specific morphology and a multi-fractal structure and application of the porous carbon photothermal material in photothermal conversion, and belongs to the field of seawater desalination.
Background
The use of natural water and energy is a fundamental factor closely related to human life, economic and social development and social progress. A large number of seawater desalination techniques are currently on the market, such as the seawater freezing method, the electrodialysis method, the distillation method, the reverse osmosis method, and the ammonium carbonate ion exchange method. However, the efficiency of the freezing method of seawater is very low, and the cost of the electrodialysis method and the ion exchange method is very high, so that the method cannot provide a long-term effective solution for seawater desalination. Therefore, scientists have made many contributions in the sustainable utilization of green clean drinking water resources and the research of green clean production technology.
Among these, the solar-powered clean water evaporation system driven by solar cells, which utilizes solar energy as a renewable energy source, is a promising solution that can effectively provide a solution to the shortage of clean water while minimizing the environmental hazard. However, the efficiency of light-to-heat conversion is greatly reduced due to poor absorption of solar energy by the material and heat loss to the surrounding environment due to conventional bulk water heating of the volumetric system, thereby hindering practical applications thereof.
Among all photothermal materials, carbon-based materials, such as amorphous carbon, carbon black, graphite, and the like, have a good ability to absorb broadband light in the visible and infrared ranges due to their unique optical conversion ability of the pi band. Taking amorphous carbon as an example, due to the close pi-electron level spacing within the material, mixed sp is formed2And sp3The carbon atoms of the bonds have a very good broadband light absorption capacity. Meanwhile, the test research on the photo-thermal conversion performance of the carbon material finds that the porous and layered structure can improve the light absorption rate of the material. This is because the porous and layered structure, the phase transformation increases the interaction length of light with a substance, thereby increasing the absorption rate of light. Meanwhile, the low specific heat capacity of the carbon material is another great advantage of the carbon material as a photothermal conversion material.
In the synthesis and preparation process of the carbon material taking MOFs as precursors, various porous carbon materials can be obtained by adjusting the central metal, carbon source molecules and carbonization process conditions. However, the product obtained lacks a certain design and purpose.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a porous carbon photothermal material with a specific morphology and a multi-fractal structure, wherein a precursor of the porous carbon photothermal material is a cluster-based metal organic framework material.
In the invention, a plurality of mixed ligands MOFs with different coordination bond strengths are selected as research objects. Because the difference of bond strength exists inside the material, the pyrolysis sequence inside the MOFs material also has sequence difference in the pyrolysis process, and then the whole pyrolysis process of the MOFs material can be controlled. Finally, the performance of the MOF-based porous carbon material as a photothermal conversion material is investigated, and the relationship between photothermal efficiency and the pore structure of the carbon material is studied.
The porous carbon material with the multi-fractal structure can prolong the acting distance between light and the carbon material due to the developed pore structure and the complicated pore types, so that the absorbance of the carbon material and the photothermal conversion efficiency can be improved.
In order to prepare the porous carbon photothermal material with the multi-fractal structure by using the cluster-based metal organic framework material as a precursor, the technical scheme adopted by the invention comprises the following specific steps:
selecting proper MOFs as precursors, researching the pyrolysis mechanism of the MOFs crystal by utilizing various modern test methods, and determining the pyrolysis sequence of internal chemical bonds of various MOFs precursors. Therefore, the porous carbon photothermal material with the multi-fractal structure is obtained by designing the temperature rise process.
In order to achieve the above object, the technical solution of the present invention includes the steps of,
the method comprises the following steps: according to the required MOFs crystal, three types of MOFs precursors, i.e., cluster-based MOFs (including, but not limited to, ZIF series, MOF-5 series, etc.), rod-stacked MOFs (including, but not limited to, M-terephthalic acid- (L-lactic acid) -based MOFs, M ═ Zn, Fe, Co, Ni, etc.), and sheet-stacked MOFs (M-P-L-based MOFs, M ═ Zn, Fe, Co, Ni, etc., P ═ terephthalic acid, 4 '-biphenyldicarboxylic acid, fumaric acid, etc., L ═ isonicotinic acid, triethylenediamine, 4' -bipyridine, etc.), are selected from a large number of literatures. And performing characterization test on the MOFs crystal.
Further, in the first step, all MOFs are synthesized and prepared by a hydrothermal method;
step two: and carrying out thermogravimetric mass spectrometry combined test and in-situ infrared test on the prepared MOFs product, and recording and analyzing gas byproduct information and functional group change in the pyrolysis process in real time.
Further, in the second step: mass spectrometry was performed in full scan mode, with a mass number scan ranging from 1 to 200. Screening mass spectrum information to obtain mass numbers with obviously changed ion intensity;
further, in the second step: the thermogravimetric-mass spectrometry combined test and the in-situ infrared test are both carried out on N2Carried out in the atmosphere;
further, comparing the thermogravimetric mass spectrometry data obtained in the second step with an NIST database, confirming ligand molecules corresponding to the gas by-products, and simultaneously confirming the pyrolysis temperature of the ligand molecules;
and further, summarizing and summarizing the change information of the functional groups obtained from the in-situ infrared spectrogram obtained in the second step, and determining the change temperature of the characteristic functional groups belonging to the ligand molecules.
Step three: and designing a heating process according to the conclusion of the second step, so that the chemical bonds of all levels of structures inside the MOFs are selectively broken, and the precursor is subjected to directional pyrolysis to obtain the porous carbon photothermal material with a specific morphology and a multi-fractal structure.
Further, the carbonization treatment temperature in the third step is 500-;
further, the temperature rise mode in the carbonization treatment in the third step is one of direct temperature rise or temperature rise rate of 5-25 ℃/min;
further, the gas atmosphere in the pretreatment and carbonization treatment in the third step is N2And (4) environment.
The invention has the following positive effects:
the invention provides a preparation method for various porous carbon photothermal materials with multi-fractal structures, which takes proper MOFs materials as precursors, utilizes a modern analysis and test method to research and determine the pyrolysis mechanism of the materials and designs the materials. Selecting organic ligands and metal salts as raw materials, and obtaining MOFs structures with different appearances by adopting solvothermal reaction. By controlling the solvothermal reaction conditions, the types of metal salts and the types of carbon source molecules, the obtained MOFs can show different self-assembly modes due to different ligands and different coordination effects among different metal ions, wherein the MOFs comprise the described cluster-based MOFs material, the rod-shaped stacked MOFs and the sheet-layer stacked MOFs. As various chemical bonds with different strengths exist in different MOFs in the pyrolysis process, the pyrolysis sequences of the MOFs are different, the pyrolysis process can be determined by thermogravimetric tests, thermogravimetric mass spectrometry, in-situ infrared analysis and other methods, and various porous carbon materials with multi-fractal structures are designed and prepared. And the prepared carbon material shows excellent performance in the field of seawater desalination when being used as a photo-thermal conversion material.
Drawings
FIG. 1 is a scanning electron microscope photograph of MOFs crystalline zinc-terephthalic acid- (l-lactic acid) (ZBl) prepared in inventive example 1.
FIG. 2 is a diagram of the preparation of N of MOFs crystal ZBl in inventive example 12Adsorption and desorption curves and pore size distribution curves.
FIG. 3 is a TG-MS curve of MOFs crystal ZBl prepared in inventive example 1.
FIG. 4 is a spectrum of an in-situ infrared test of MOFs crystal ZBl prepared in inventive example 1.
FIG. 5 is a scanning electron microscope image of a carbonized product obtained at 900 ℃ after pretreatment of MOFs crystals ZBl prepared in inventive example 1.
FIG. 6 is a test curve of photothermal properties of the carbonized product of inventive example 1.
Fig. 7 is a seawater desalination test curve of the carbonized product of the embodiment 1 of the invention.
Detailed description of the preferred embodiment
The present invention will be described in detail below with reference to the drawings and examples, but the present invention is not limited to the following examples.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to better illustrate the invention, the following examples are given by way of further illustration.
Example 1
The embodiment provides a preparation method of a porous carbon photothermal material with a specific morphology and a multi-fractal structure and application of the porous carbon photothermal material in photothermal conversion, and the preparation method comprises the following steps:
the method comprises the following steps: rod-shaped stacked MOFs (zinc-terephthalic acid- (l-lactic acid) (ZBl) are prepared by a hydrothermal method, and the specific preparation process is the prior art and does not need to be described any more.
The material was characterized by the Scanning Electron Microscope (SEM) N2 adsorption/desorption curve test (BET), which is shown in FIGS. 1 and 2, respectively, wherein the BET data is a specific surface area of 47.63m2Per g, pore volume 0.06cm3(ii) in terms of/g. As can be seen from characterization tests, the MOFs serving as metal-organic framework materials are successfully obtained.
Step two: and carrying out thermogravimetric mass spectrometry combined test and in-situ infrared test on the prepared MOFs product, and recording and analyzing gas byproduct information and functional group change in the pyrolysis process in real time. Specifically, the thermogravimetric mass spectrometry and in-situ infrared testing performed on ZBl in this example were performed at 25-800 ℃ in a test atmosphere of N2。
When the thermogravimetric-mass spectrometry is used for testing, the test is carried out in a full scanning mode, and the scanning range of mass number is 1-200;
during in-situ infrared testing, information is collected once every 10 ℃;
the results are shown in FIGS. 3 and 4, respectively;
and D, comparing the thermogravimetric mass spectrometry data obtained in the step two with an NIST database, confirming the ligand molecules corresponding to the gas by-products, and simultaneously confirming the pyrolysis temperature of the ligand molecules. The results are shown in table 1:
TABLE 1 thermogravimetric mass spectrometry data of 1 ZBl
Step three: designing a heating process to ensure that chemical bonds of all levels of structures inside the MOFs are selectively broken, and performing directional pyrolysis on the precursor to obtain the porous carbon photothermal material with a specific morphology and a multi-fractal structure. The morphology is shown in fig. 5. FIG. 6 shows the photo-thermal performance test using the carbonized product as the photo-thermal material, the test light source is 808nm infrared laser, and the power of the light source is 0.64 w. The material can be found to reach the maximum temperature of 122 ℃ in 3 minutes under the irradiation of a light source, and the photothermal conversion efficiency is as high as 58.3%. Fig. 7 is a seawater desalination experimental test performed by using a carbonized product as a photo-thermal material, and a test result shows that the seawater desalination efficiency of the material is 73.4%.
The pyrolysis mechanism determined in this example is: in the range of 30-100 ℃, guest water molecules in the MOFs crystal escape; in the range of 100-300 ℃, the lactic acid molecule is pyrolyzed; in the temperature range of 300 ℃ and 550 ℃, part of hydrocarbon positive ions, benzene ring ions and N, N-Dimethylformamide (DMF) escape. The product after pretreatment at 300 ℃ is carbonized to obtain the appearance of dissociation along a zinc- (l-lactic acid) rod-shaped structure.
Claims (6)
1. A preparation method of a porous carbon photothermal material with a specific morphology and a multi-fractal structure is characterized by comprising the following steps:
step one, according to the existing reports, selecting and preparing MOFs with specific structures and compositions as precursors;
researching a pyrolysis mechanism of the MOFs crystal by using a modern test characterization method, and determining a pyrolysis sequence for maintaining chemical bonds of each level of structures in the MOFs;
and step three, designing a heating program to ensure that chemical bonds of all levels of structures inside the MOFs are selectively broken, and performing directional pyrolysis on the precursor to obtain the porous carbon photothermal material with a specific morphology and a multi-fractal structure.
2. The method for selecting appropriate MOFs precursors according to claim 1, step one, characterized in that: as required, three types of MOFs precursors, including cluster-based MOFs (including, but not limited to, ZIF series, MOF-5 series, etc.), rod-stacked MOFs (including, but not limited to, M-terephthalic acid- (L-lactic acid) -based MOFs, M ═ Zn, Fe, Co, Ni, etc.), and sheet-stacked MOFs (M-P-L-based MOFs, M ═ Zn, Fe, Co, Ni, etc., P ═ terephthalic acid, 4 '-biphenyldicarboxylic acid, fumaric acid, etc., L ═ isonicotinic acid, triethylenediamine, 4' -bipyridine, etc.), are selected from reported documents.
3. The modern testing method as claimed in claim 1, wherein the step two comprises in-situ infrared diffuse reflection, thermogravimetry-mass spectrometry, X-ray diffraction, X-ray small-angle scattering, and electron scanning microscopy.
4. The method according to claim 1, wherein said determining the pyrolysis order for maintaining the chemical bonds of each level of structure within the MOFs in step two mainly determines the temperature range for maintaining the pyrolysis of the chemical bonds of each level of structure within the MOFs.
5. The design ramp program of claim 1, wherein: the heating process is one of direct heating or constant heating at 5-25 ℃/min, wherein the direct heating refers to directly placing the precursor in an inert environment which is heated to the specified temperature.
6. When the material is used as a photo-thermal conversion material, the photo-thermal conversion efficiency is higher than 40%, and the seawater evaporation efficiency is higher than 60% under the irradiation of sunlight.
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| CN117535045A (en) * | 2023-07-12 | 2024-02-09 | 中国热带农业科学院分析测试中心 | Zn-MOF@Au NPS/DNA aptamer fluorescent probe for trace thiamethoxam detection and preparation method thereof |
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| CN117535045A (en) * | 2023-07-12 | 2024-02-09 | 中国热带农业科学院分析测试中心 | Zn-MOF@Au NPS/DNA aptamer fluorescent probe for trace thiamethoxam detection and preparation method thereof |
| CN117535045B (en) * | 2023-07-12 | 2024-05-31 | 中国热带农业科学院分析测试中心 | Zn-MOF@Au NPS/DNA aptamer fluorescent probe for trace thiamethoxam detection and preparation method thereof |
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