CN112517076A - Fe-MOFs @ CNTs composite material and preparation method thereof - Google Patents
Fe-MOFs @ CNTs composite material and preparation method thereof Download PDFInfo
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- CN112517076A CN112517076A CN202011430729.4A CN202011430729A CN112517076A CN 112517076 A CN112517076 A CN 112517076A CN 202011430729 A CN202011430729 A CN 202011430729A CN 112517076 A CN112517076 A CN 112517076A
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 45
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000004020 conductor Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000013384 organic framework Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000013082 iron-based metal-organic framework Substances 0.000 description 16
- 230000005540 biological transmission Effects 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 230000020477 pH reduction Effects 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001903 differential pulse voltammetry Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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Abstract
The invention discloses a preparation method of a Fe-MOFs @ CNTs composite material. The method adopts a water bath synthesis method, takes ferric trichloride as a metal ligand raw material, takes terephthalic acid as an organic framework, adds an acidified carbon nano tube, and performs hydrothermal reaction in a DMF solution after mixing to prepare the Fe-MOFs @ CNTs composite material. The Fe-MOFs @ CNTs composite material prepared by the invention has a three-dimensional regular tetrahedron coating structure, has a porous structure of a metal organic framework and excellent electrical properties of a carbon nano tube, and has a good application prospect in the aspects of conductive materials such as electrochemical sensors, batteries and the like.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a Fe-MOFs @ CNTs composite material and a preparation method thereof.
Background
As a novel classical crystalline porous material with adjustable pore diameter, a Metal Organic Framework (MOFs) mainly comprises a metal center and a functional organic ligand, has a high specific surface area, uniform pore distribution and a changeable structure, attracts people's wide attention, and has a good application prospect in the fields of catalysis, adsorption purification and electrochemistry. However, the MOFs materials are affected by their charge storage singleness, their electrochemical properties are limited, and their low water solubility also affects their applications requiring electrochemistry. Thus, MOFs are combined with other materials to increase their water solubility and electrical conductivity.
At present, three types of composite materials are mainly synthesized for improving the performance of MOFs materials, one type is metal and MOFs, the conductivity of the composite materials is better and the composite materials are mainly used as batteries or special adsorption materials, but the cost is relatively improved in consideration of the addition of various metals; the second type is the synthesis of various MOFs, the synthesized material is mainly applied to various adsorption, and the water solubility and the conductivity of the material are not obviously improved; and finally, synthesizing a carbon material and MOFs, wherein the related synthesis at present mainly comprises the step of further carbonizing the composite material, although the conductivity of the composite material can be obviously improved, the water solubility is not greatly influenced by carbonization, and the operation is relatively complex.
Disclosure of Invention
The invention aims to provide a Fe-MOFs @ CNTs composite material with a simple preparation method and good conductivity and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows:
the preparation method of the Fe-MOFs @ CNTs composite material comprises the following steps:
uniformly dispersing the acidified carbon nano tube in N, N-Dimethylformamide (DMF), adding ferric chloride and terephthalic acid, stirring until the mixture is uniformly mixed, continuously stirring at normal temperature to fully react, then placing at 110 ℃ for hydrothermal reaction for 16-20 h, after the reaction is finished, centrifugally washing, and drying at 60 +/-5 ℃ in vacuum to obtain the Fe-MOFs @ CNTs composite material.
The preparation of the acidified carbon nano tube adopts a method conventionally used in the field, and specifically comprises the following steps: uniformly dispersing the carbon nano tube in a mixed acid solution consisting of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1, carrying out reflux reaction at 80 +/-5 ℃ for 3-6 h, cooling to room temperature after the reaction is finished, separating to obtain a solid phase, washing, and drying at 60 +/-5 ℃ to obtain the acidified carbon nano tube.
The mixed acid solution consisting of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1 is adopted to carry out acidification treatment on the carbon nano tube, and the acidification effect of the carbon nano tube under the condition is superior to that of a single acid solution.
Preferably, the concentration of the carbon nanotubes in the mixed acid solution of the carbon nanotubes is 25 mg/mL. Under the condition, the carbon nano tube is more thoroughly acidified, and the conductivity of the carbon nano tube is not influenced.
The invention adopts the reflux reaction temperature of 80 +/-5 ℃ and the reflux time of 3-6 h, ensures the acidification effect and does not influence the basic tubular shape of the reactor.
The invention dries the acidified carbon nano-tube in vacuum at 60 + -5 deg.C to remove the water in the carbon nano-tube, so as to ensure the proportion of the composite material.
Preferably, the mass ratio of the carbon nanotubes to the ferric chloride to the terephthalic acid is 1:20:8, the sizes of the prepared Fe-MOFs are more uniform, and the distribution of the carbon nanotubes is more uniform.
According to the invention, the hydrothermal reaction temperature is 110 ℃, the heating reaction time is 16-20 h, and under the conditions of the temperature and the time, the samples are favorably and fully contacted, the reaction rate is improved, and the generation of byproducts is reduced.
In the invention, the ethanol solution is adopted to wash the sample, and substances which do not participate in the reaction are removed, so that the purity of the sample is ensured.
The invention adopts vacuum drying at 60 +/-5 ℃, better removes the moisture in the composite material and is beneficial to the consistency and performance stability of the sample as the electrode material.
Compared with the prior art, the invention has the following advantages:
the carbon nano tube has good conductivity, and after the MOFs and the carbon nano tube are combined to form the Fe-MOFs @ CNTs composite material, the solubility of the material can be effectively improved, and the electrochemical performance of the material is further improved. Compared with single Fe-MOFs, the Fe-MOFs @ CNTs composite material prepared by the invention is not easily influenced by air, has more stable morphological characteristics, has the advantage of the porosity of a metal organic framework, has excellent electrical property of a carbon nano tube, and is an electrochemical material with good application prospect.
Drawings
FIG. 1 is a transmission electron microscope image of Fe-MOFs prepared by the present invention.
FIG. 2 is a transmission electron micrograph of the acidified carbon nanotubes prepared according to the present invention.
FIG. 3 is a transmission electron microscope image of the Fe-MOFs @ CNTs composite material prepared by the present invention.
FIG. 4 is an X-ray diffraction pattern of the Fe-MOFs @ CNTs composite material prepared by the present invention.
FIG. 5 is a cyclic voltammetry curve of the Fe-MOFs @ CNTs composite material prepared by the present invention as a conductive material.
FIG. 6 is a differential pulse voltammetry curve diagram of the Fe-MOFs @ CNTs composite material prepared by the invention as a conductive material.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1
(1) Preparing acidified carbon nanotubes:
0.1g of carbon nanotubes is weighed into a 50mL round-bottom flask, 3mL of concentrated sulfuric acid (98 wt%) solution and 1mL of concentrated nitric acid (70 wt%) solution are added in sequence, and the solution is subjected to ultrasonic treatment for about 2 hours to uniformly disperse the carbon nanotubes in the solution. And (3) refluxing for 3-6 h under the condition of an oil bath at the temperature of 80 +/-5 ℃, cooling to room temperature after refluxing is finished, washing a solid phase to be neutral by using distilled water, performing suction filtration to obtain a sample, and drying in an oven at the temperature of 60 +/-5 ℃ to obtain the acidified carbon nanotube. The carbon nano tube acidified by the method has excellent acidification effect, and the appearance and the performance of the carbon nano tube are not influenced.
(2) Preparing Fe-MOFs @ CNTs composite material:
0.0497g of the acidified carbon nano tube prepared in the step (1) is weighed and evenly dispersed in 5ml of DMF solution, and ultrasonic treatment is carried out for about 30min to form a solution A. 0.9933g of FeCl were weighed into another beaker3.6H2O and 0.4153g of terephthalic acid (H)2BDC) are dissolved under vigorous stirringAdding the solution A into 25mL of N, N-Dimethylformamide (DMF) solution, stirring, transferring into a 50mL polytetrafluoroethylene reaction kettle, heating at 110 ℃ for reaction for 18h, cooling to room temperature, washing with ethanol for more than 3 times, and drying in an oven at 60 ℃ overnight to obtain the dried Fe-MOFs @ CNTs composite material. The Fe-MOFs @ CNTs composite material synthesized according to the feeding proportion is uniform in shape distribution and excellent in conductivity.
(3) Preparing a material modified electrode:
firstly, pretreating a glassy carbon electrode: polishing the electrode on 0.05 μm alumina slurry for 5min, washing the electrode with distilled water, performing ultrasonic treatment in ethanol solution for about 30s, repeating the ultrasonic treatment process, and washing with distilled water. And drying the surface of the electrode by using nitrogen after the end. Dispersing 1mg/mL Fe-MOFs @ CNTs composite material solution uniformly, taking 7 mu L solution, dripping the solution on the center position of a clean electrode, naturally drying the solution, and adding 5.0mM Fe (CN)6]3-/4-The properties were measured in electrolytic solutions.
FIG. 1 is a transmission electron microscope image of Fe-MOFs prepared by the method of the present invention. Therefore, the prepared Fe-MOFs material is a regular tetrahedron, and has a moderate size and a diameter of about 700 nm.
FIG. 2 is a transmission electron microscope image of the acidified carbon nanotube prepared by the method of the present invention. As can be seen, the prepared acidified carbon nanotube has little shape change and obvious tubular shape.
FIG. 3 is a transmission electron microscope image of the Fe-MOFs @ CNTs composite material prepared by the method of the invention, the diameter of the prepared composite material is about 700nm, and the composite material presents a composite structure formed by a carbon nano tube and an Fe-MOFs regular tetrahedron structure.
FIG. 4 is an X-ray diffraction pattern of the Fe-MOFs @ CNTs composite material prepared by the method of the present invention, showing specific peaks of Fe-MOFs and amorphous peaks of carbon nanotubes.
FIG. 5 shows the Fe-MOFs @ CNTs composite material prepared by the present invention as a conductive material at 5.0mM [ Fe (CN)6]3-/4-Compared with Fe-MOFs and carbon nanotubes, the peak current of the Fe-MOFs @ CNTs composite material is obviously increased in a cyclic voltammetry curve diagram in an electrolytic solution.
FIG. 6 shows the Fe-MOFs @ CNTs composite material prepared by the present invention as a conductive material at 5.0mM [ Fe (CN)6]3-/4-The peak position of a differential pulse voltammetry curve chart in an electrolytic solution is about 0.19V, and the peak value of the pure Fe-MOFs material is obviously lower than that of the CNTs material and the composite material.
In conclusion, the Fe-MOFs @ CNTs composite material has good conductivity and cycle stability. The invention mainly utilizes the excellent electrochemical property of the carbon nano tube, and not only does not have great influence on the electrochemical performance and the overall appearance of the carbon nano tube through simple acid treatment reaction, but also improves the water-soluble dispersibility of the carbon nano tube. The composite material obtained by combining the acidified carbon nanotube with the Fe-MOFs regular tetrahedron structure has uniform appearance, the appearance of the acidified carbon nanotube and the Fe-MOFs regular tetrahedron structure is not influenced after combination, meanwhile, the water solubility of the Fe-MOFs material is improved, and the electrochemical performance and the stability of the Fe-MOFs material are obviously improved. The composite material keeps the porous advantage of the Fe-MOFs material, simultaneously has good water solubility and conductivity of the acidified carbon nanotube, and the stability of the composite material at normal temperature is obviously superior to the stability of the pure Fe-MOFs material. The Fe-MOFs @ CNTs composite material prepared by the invention is used for electrode materials, the electrochemical performance of the composite material is obviously improved compared with that of a pure Fe-MOFs material, and the composite material has good conductivity.
Claims (5)
- A preparation method of Fe-MOFs @ CNTs composite material is characterized by comprising the following steps:uniformly dispersing the acidified carbon nano tubes in N, N-dimethylformamide, adding ferric chloride and terephthalic acid, stirring until the materials are uniformly mixed, continuously stirring at normal temperature to fully react, then placing the mixture at 110 ℃ for hydrothermal reaction for 16-20 h, after the reaction is finished, centrifugally washing, and drying in vacuum at 60 +/-5 ℃ to obtain the Fe-MOFs @ CNTs composite material.
- 2. The method of claim 1, wherein the acidified carbon nanotubes are prepared by the following steps: uniformly dispersing the carbon nano tube in a mixed acid solution consisting of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1, carrying out reflux reaction at 80 +/-5 ℃ for 3-6 h, cooling to room temperature after the reaction is finished, separating to obtain a solid phase, washing, and drying at 60 +/-5 ℃ to obtain the acidified carbon nano tube.
- 3. The method according to claim 2, wherein the concentration of the carbon nanotubes in the mixed acid solution of carbon nanotubes is 25 mg/mL.
- 4. The method according to claim 1, wherein the mass ratio of the carbon nanotubes to the ferric chloride to the terephthalic acid is 1:20: 8.
- 5. The method according to claim 1, wherein the washing is carried out with an ethanol solution.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113078002A (en) * | 2021-04-10 | 2021-07-06 | 河南工业大学 | Preparation method and application of conductive MOFs/CNTs composite electrode material |
| CN113437279A (en) * | 2021-08-26 | 2021-09-24 | 河南师范大学 | Preparation method of MOFs-coated high-conductivity multi-wall carbon nanotube composite material and application of MOFs-coated high-conductivity multi-wall carbon nanotube composite material in potassium ion battery |
| CN115591584A (en) * | 2022-10-20 | 2023-01-13 | 中科检测技术服务（广州）股份有限公司（Cn） | Iron MOFs/nano carbon material with quick response to fentanyl and preparation method and application thereof |
| WO2024007911A1 (en) * | 2022-07-05 | 2024-01-11 | 中国农业科学院农业资源与农业区划研究所 | Fe-mof/ben@cnts composite conductive material, preparation method therefor, and use thereof |
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2020
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113078002A (en) * | 2021-04-10 | 2021-07-06 | 河南工业大学 | Preparation method and application of conductive MOFs/CNTs composite electrode material |
| CN113437279A (en) * | 2021-08-26 | 2021-09-24 | 河南师范大学 | Preparation method of MOFs-coated high-conductivity multi-wall carbon nanotube composite material and application of MOFs-coated high-conductivity multi-wall carbon nanotube composite material in potassium ion battery |
| CN113437279B (en) * | 2021-08-26 | 2021-11-16 | 河南师范大学 | Preparation method of MOFs-coated high-conductivity multi-wall carbon nanotube composite material and application of MOFs-coated high-conductivity multi-wall carbon nanotube composite material in potassium ion battery |
| WO2024007911A1 (en) * | 2022-07-05 | 2024-01-11 | 中国农业科学院农业资源与农业区划研究所 | Fe-mof/ben@cnts composite conductive material, preparation method therefor, and use thereof |
| CN115591584A (en) * | 2022-10-20 | 2023-01-13 | 中科检测技术服务（广州）股份有限公司（Cn） | Iron MOFs/nano carbon material with quick response to fentanyl and preparation method and application thereof |
| CN115591584B (en) * | 2022-10-20 | 2023-10-31 | 中科检测技术服务(广州)股份有限公司 | Iron MOFs/nano-carbon material with quick response to fentanyl and preparation method and application thereof |
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