CN110668504A - Mesoporous Fe3O4Granules and process for their preparation - Google Patents
Mesoporous Fe3O4Granules and process for their preparation Download PDFInfo
- Publication number
- CN110668504A CN110668504A CN201910911067.3A CN201910911067A CN110668504A CN 110668504 A CN110668504 A CN 110668504A CN 201910911067 A CN201910911067 A CN 201910911067A CN 110668504 A CN110668504 A CN 110668504A
- Authority
- CN
- China
- Prior art keywords
- mesoporous
- particles
- mil
- preparation
- drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000013179 MIL-101(Fe) Substances 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 36
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 239000008187 granular material Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 25
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 2
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000013255 MILs Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000013177 MIL-101 Substances 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000013260 porous coordination network Substances 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide (Fe3O4)
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/39—
-
- B01J35/647—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/41—Particle morphology extending in three dimensions octahedron-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The invention discloses mesoporous Fe3O4The preparation method of the particles comprises the steps of preparing MIL-101(Fe) octahedrons by using Fe ions as coordination centers by adopting a hydrothermal reaction method and an air oxidation method, centrifuging, washing and drying the MIL-101(Fe) octahedrons as matrix materials, standing the mixture at room temperature for oxidation reaction, and calcining the mixture at 400-500 ℃ in a nitrogen environment to prepare the mesoporous Fe3O4Octahedral particle, simple preparation process, no toxicity and no pollution, and the prepared mesoporous Fe3O4The octahedral particles have good dispersibility and controllable components; the obtained mesoporous Fe3O4The particle material has good application prospect in the field of photocatalysis.
Description
Technical Field
The invention relates to Fe3O4The technical field of new materials, in particular to mesoporous Fe3O4Granules and a process for their preparation.
Background
MOFs (Metal-Organic Frameworks) is a short term for Metal-Organic framework complexes, and is a porous crystal material with a periodic multidimensional network structure generated by hybridization of Metal ions and Organic ligands through a self-assembly process. The following types are mainly classified: reticular metal and organic framework materials (IRMOFs for short), zeolite-like imidazole framework materials (ZIFs for short), Laval tin framework materials (MILs for short) and porous framework materials (PCNs) for short. As a new member of a novel porous crystal material family, the material has a plurality of unique and excellent properties, such as extremely high specific surface area, excellent crystallinity, regular pore channel structure, high controllability of pore size and the like.
The MIL-101(Fe) material takes Fe ions as a coordination center, is simple in preparation process, clean, nontoxic and pollution-free, belongs to a novel porous material, and has all the advantages of MOFs materials, so that the MIL-101(Fe) material is widely applied.
The research of the applicant finds that the existing method for preparing the MIL-101(Fe) material is complex, and the prepared MIL-101(Fe) material has poor dispersibility, so that the application of the MIL-101(Fe) material in photocatalysis is not facilitated.
Disclosure of Invention
In view of the above, the present invention is to provide a mesoporous Fe3O4The particles and the preparation method thereof are used for overcoming the defects of complex preparation method and poor dispersibility in the prior art.
Based on the purpose, the invention provides mesoporous Fe3O4A process for the preparation of particles comprising the steps of,
(1) MIL-101(Fe) octahedron preparation, terephthalic acid and FeCl3·6H2Adding O into a dimethylformamide solution, carrying out ultrasonic vibration treatment on the mixed solution, then carrying out hydrothermal reaction, and sequentially centrifuging, washing and drying the reaction product to obtain MIL-101 (Fe);
(2) mesoporous Fe3O4Preparing particles, namely washing the MIL-101(Fe) prepared in the step (1) with absolute ethyl alcohol solution and distilled water alternately for a plurality of times, drying, and then carrying out room temperature washingPlacing for 70-110 days, and finally calcining at 400-500 ℃ in a nitrogen environment to obtain mesoporous Fe3O4And (3) granules.
Optionally, the mesoporous Fe3O4The particles are octahedral.
Optionally, in the step (1), the molar concentration of the terephthalic acid in the dimethylformamide solution is 0.07-0.08 mol/L.
Optionally, FeCl is used in the step (1)3·6H2The molar concentration of O in the dimethylformamide solution is 0.15-0.16 mol/L.
Optionally, in the ultrasonic vibration treatment in the step (1), the ultrasonic treatment is performed on the mixed solution at 25 ℃ and room temperature for 15-30 min, and the frequency of the ultrasonic wave is 90 Hz.
Optionally, the temperature of the hydrothermal reaction in the step (1) is 110-130 ℃, and the reaction time is 18-24 hours.
Optionally, the specific operations of centrifuging, washing and drying are as follows: repeatedly washing with absolute ethyl alcohol and distilled water, centrifuging, fully operating for 3-4 times, and finally drying at 60 ℃ for 8-10 hours.
As can be seen from the above, the present invention provides a mesoporous Fe3O4The particles are prepared by a hydrothermal reaction method and an air oxidation method, and Fe ions are used as coordination centers to prepare mesoporous Fe3O4The octahedral particle material has simple preparation process, is clean, non-toxic and pollution-free, is one kind of MOFs material, belongs to novel porous material, has all the advantages of MOFs material, and may be used widely3O4The octahedral particles have good dispersibility and controllable components; the obtained mesoporous Fe3O4The particle material has good application prospect in the field of photocatalysis.
Drawings
FIG. 1 example of the present invention MIL-101(Fe) and mesoporous Fe3O4Particle XRD pattern;
FIG. 2 is an SEM image of MIL-101(Fe) according to an embodiment of the present invention;
FIG. 3 Fe prepared in example 2 of the present invention3O4Particle SEM image;
FIG. 4 Fe prepared in example 3 of the present invention3O4Particle SEM image;
FIG. 5 is a mesoporous Fe prepared in example 4 of the present invention3O4SEM comparison of particles with MIL-101 (Fe); (ii) a
FIG. 6 is a mesoporous Fe prepared in example 4 of the present invention3O4The particles were mixed with MIL-101(Fe), TiO2Photocurrent test contrast plots.
Detailed Description
In the following description of the embodiments, the detailed description of the present invention, such as the manufacturing processes and the operation and use methods, will be further described in detail to help those skilled in the art to more fully, accurately and deeply understand the inventive concept and technical solutions of the present invention.
MIL-101 is one of the most classical representatives of MILs series, has some characteristics which are not possessed by other MOFs materials, and not only has a mesoporous structure, but also has microporous pipelines (the diameter is less than 2nm and is microporous, and the diameter is 2-50 nm and is mesoporous), so that the material has larger pore volume and specific surface area, can stably exist in air, and is resistant to high temperature.
In order to solve the problem that the MIL-101(Fe) material prepared in the prior art has poor dispersibility and influences the application of the material in the field of photocatalysis, the invention provides mesoporous Fe3O4A process for the preparation of particles comprising the steps of,
(1) MIL-101(Fe) octahedron preparation, terephthalic acid and FeCl3·6H2Adding O into a dimethylformamide solution, carrying out ultrasonic vibration treatment on the mixed solution, then carrying out hydrothermal reaction, and sequentially centrifuging, washing and drying the reaction product to obtain MIL-101 (Fe);
(2) mesoporous Fe3O4Preparing particles, namely washing the MIL-101(Fe) prepared in the step (1) with an absolute ethyl alcohol solution and distilled water alternately for a plurality of times, drying, then placing at room temperature for 70-110 d, and finally calcining at 400-500 ℃ in a nitrogen environment to obtain mesoporous Fe3O4And (3) granules.
The method comprises the steps of preparing MIL-101(Fe) octahedrons by using a hydrothermal method, taking the MIL-101(Fe) octahedrons as a matrix material, centrifuging, washing, drying, standing at room temperature for oxidation reaction, and calcining at 400-500 ℃ in a nitrogen environment to obtain the mesoporous Fe3O4Octahedral particles, the process is simple and easy to operate; and the prepared mesoporous Fe3O4The octahedral particles have good dispersibility and controllable components; the obtained mesoporous Fe3O4The particle material has good application prospect in the field of photocatalysis.
Specifically, the mesoporous Fe provided in embodiment 1 of the present invention3O4A process for the preparation of a granulate comprising mixing 0.14g of terephthalic acid and 0.5g of FeCl3·6H2Adding O into 12mL of dimethylformamide, performing ultrasonic vibration treatment at 25 ℃ and room temperature at the frequency of 90Hz for 15min, pouring the treated solution into a reaction kettle, and performing hydrothermal reaction at 120 ℃ for 24 h. Then cooling the reaction liquid to room temperature, repeatedly washing with absolute ethyl alcohol and distilled water, then centrifuging, repeating the operation for 3-4 times, and finally placing the centrifugate in a 60 ℃ oven for 10 hours to obtain MIL-101(Fe) octahedral powder; then exposing MIL-101(Fe) octahedral powder in the air, keeping the temperature at 25 ℃ and the room temperature, standing for 90 days, and finally calcining the placed sample at 400-500 ℃ in a nitrogen environment to obtain the mesoporous Fe3O4And (3) granules.
The product was analyzed by X-ray light diffraction (XRD) and Scanning Electron Microscopy (SEM), respectively. FIG. 1 is XRD patterns of the product of example 1 before and after compounding, which are XRD pattern of MIL-101(Fe) and Fe3O4XRD pattern of (a). The results show that the product of example 1 contains Fe3O4And is Fe3O4The diffraction peak of (A) is sharper, indicating that Fe is grown on the surface3O4The particles crystallized well.
FIG. 2(a) (b) SEM image of MIL-101(Fe) obtained during the preparation of example 1, where it can be seen that the MIL-101(Fe) octahedral structure is intact; FIG. 2(c) (d) shows mesoporous Fe of the product of example 13O4SEM image of octahedral particle, wherein octahedral morphology can be seen, and a layer of Fe grows on MIL-101(Fe) octahedron3O4Crystal particles.
Similarly, the mesoporous Fe provided in embodiment 2 of the present invention3O4A process for the preparation of a granulate comprising mixing 0.2g of terephthalic acid and 0.66g of FeCl3·6H2Adding O into 15mL of dimethylformamide, performing ultrasonic vibration treatment at 25 ℃ and room temperature at the frequency of 90Hz for 30min, pouring the treated solution into a reaction kettle, and performing hydrothermal reaction at 110 ℃ for 18 h. Then cooling the reaction liquid to room temperature, repeatedly washing with absolute ethyl alcohol and distilled water, then centrifuging, repeating the operation for 3-4 times, and finally placing the centrifugate in a 60 ℃ oven for 10 hours to obtain MIL-101(Fe) octahedral powder; then exposing MIL-101(Fe) octahedral powder in the air, keeping the temperature at 25 ℃ and the room temperature, standing for 90 days, and finally calcining the placed sample at 400-500 ℃ in a nitrogen environment to obtain the mesoporous Fe3O4And (3) granules.
The SEM spectrum of the product of example 2 of the invention is shown in FIG. 3, from which it can be seen that a layer of Fe has grown on the surface of the MIL-101(Fe) octahedron3O4And (4) crystals.
The mesoporous Fe provided by the embodiment 3 of the invention3O4A process for the preparation of a granulate comprising mixing 0.14g of terephthalic acid and 0.5g of FeCl3·6H2Adding O into 15mL of dimethylformamide, performing ultrasonic vibration treatment at 25 ℃ and room temperature at the frequency of 90Hz for 15min, pouring the treated solution into a reaction kettle, and performing hydrothermal reaction at 110 ℃ for 18 h. Then cooling the reaction liquid to room temperature, repeatedly washing with absolute ethyl alcohol and distilled water, then centrifuging, repeating the operation for 3-4 times, and finally placing the centrifugate in a 60 ℃ oven for 10 hours to obtain MIL-101(Fe) octahedral powder; then exposing MIL-101(Fe) octahedral powder in the air, keeping the temperature at 25 ℃ and the room temperature, standing for 90 days, and finally calcining the placed sample at 400-500 ℃ in a nitrogen environment to obtain the mesoporous Fe3O4And (3) granules.
The SEM spectrum of the product of example 3 of the invention is shown in FIG. 4, from which it can be seen that a layer of Fe grows on the surface of the MIL-101(Fe) octahedron3O4Crystals, except without example 1 and practiceExample 2 is obvious. This may be related to the short duration of the ultrasonic oscillation.
The mesoporous Fe provided by the embodiment 4 of the invention3O4The difference between the preparation method of the granules and the example 1 is that: MIL-101(Fe) powder prepared by the conditions of example 1 was placed in an oven at 60 ℃ for 24 h.
Shown in SEM spectrum of FIG. 5 are MIL-101(Fe) (left image) and calcination at 400-500 deg.C in nitrogen atmosphere to obtain mesoporous Fe3O4The particles (right panel) in the case of the aqueous solution, Fe was observed by comparison of the graphs3O4The particles are easily oxidized by air and easily agglomerated, so that Fe with good dispersibility is difficult to obtain3O4Particles, the dispersibility is obviously lower than MIL-101 (Fe).
Photocurrent measurements of the product of example 4 of the invention photocurrent measurements were carried out in a three-electrode cell using an electrochemical analyzer (CHI-760E, shanghai chenghua) as shown in fig. 6. The electrolyte is 0.1M Na2SO4Aqueous solution (pH 7.0). By using TiO2Mesoporous Fe3O4And MIL-101(Fe) photoanode as working electrode; the platinum wire is used as a counter electrode, and the Ag/AgCl electrode is used as a reference electrode. The conductive glass was irradiated with a 300w xenon lamp. The scanning rate of the cyclic voltammetry is 30mV/s, and the current value of the material under the condition of alternate illumination of a light state and a dark state within a certain time is measured by an Amperometric I-t curve, wherein the measurement time is 100s, and the voltage is + 0.4V. The photocurrent test result shows that the photocurrent intensity of the MIL-101(Fe) is basically stable within 6 cycle periods and no attenuation phenomenon occurs when the recorded transient photocurrent values are respectively used as working electrodes under 6 periodical visible light irradiation, which indicates that the MIL-101(Fe) sample has good repeatability.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also features in the above embodiments or in different embodiments may be combined, steps may be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The embodiments of the invention are intended to embrace all such alternatives, modifications and variances that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. Mesoporous Fe3O4A process for the preparation of granules, characterized in that it comprises the following steps,
(1) MIL-101(Fe) octahedron preparation, terephthalic acid and FeCl3·6H2Adding O into a dimethylformamide solution, carrying out ultrasonic vibration treatment on the mixed solution, then carrying out hydrothermal reaction, and sequentially centrifuging, washing and drying the reaction product to obtain MIL-101 (Fe);
(2) mesoporous Fe3O4Preparing particles, namely washing the MIL-101(Fe) prepared in the step (1) with an absolute ethyl alcohol solution and distilled water alternately for a plurality of times, drying, then placing at room temperature for 70-110 d, and finally calcining at 400-500 ℃ in a nitrogen environment to obtain mesoporous Fe3O4And (3) granules.
2. Mesoporous Fe according to claim 13O4A method for producing particles, characterized in that the mesoporous Fe3O4The particles are octahedral.
3. Mesoporous Fe according to claim 13O4The preparation method of the particles is characterized in that in the step (1), the molar concentration of the terephthalic acid in the dimethylformamide solution is 0.07-0.08 mol/L.
4. Mesoporous Fe according to claim 13O4A method for producing particles, wherein FeCl is used in the step (1)3·6H2The molar concentration of O in the dimethylformamide solution is 0.15 to0.16mol/L。
5. Mesoporous Fe according to claim 13O4The preparation method of the particles is characterized in that in the step (1), the ultrasonic vibration treatment is to perform ultrasonic treatment on the mixed solution at 25 ℃ and room temperature for 15-30 min, and the frequency of the ultrasonic waves is 90 Hz.
6. Mesoporous Fe according to claim 13O4The preparation method of the particles is characterized in that the temperature of hydrothermal reaction in the step (1) is 110-130 ℃, and the reaction time is 18-24 h.
7. Mesoporous Fe according to claim 13O4The preparation method of the particles is characterized by comprising the following specific operations of centrifugation, washing and drying: repeatedly washing with absolute ethyl alcohol and distilled water, centrifuging, fully operating for 3-4 times, and finally drying at 60 ℃ for 8-10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910911067.3A CN110668504A (en) | 2019-09-25 | 2019-09-25 | Mesoporous Fe3O4Granules and process for their preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910911067.3A CN110668504A (en) | 2019-09-25 | 2019-09-25 | Mesoporous Fe3O4Granules and process for their preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110668504A true CN110668504A (en) | 2020-01-10 |
Family
ID=69079411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910911067.3A Pending CN110668504A (en) | 2019-09-25 | 2019-09-25 | Mesoporous Fe3O4Granules and process for their preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110668504A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111208287A (en) * | 2020-01-16 | 2020-05-29 | 长沙理工大学 | Construction method of magnetic resonance sensor |
| CN112570029A (en) * | 2020-12-17 | 2021-03-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of aluminum ion doped modified iron oxide catalyst with metal organic framework structure |
| CN112569950A (en) * | 2020-12-17 | 2021-03-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of magnetic ferroferric oxide-zinc oxide composite photocatalyst with octahedral structure, product and application thereof |
| CN115770619A (en) * | 2022-11-08 | 2023-03-10 | 安徽信息工程学院 | MOF in-situ conversion Fe 2 O 3 Nanorods and porous Fe 2 O 3 Process for preparing nano composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103521269A (en) * | 2013-11-04 | 2014-01-22 | 北京化工大学 | Metal-organic framework materials with magnetic cores and preparation and application thereof |
| CN107042087A (en) * | 2017-01-19 | 2017-08-15 | 中国石油大学(华东) | A kind of method that Situ Hydrothermal prepares magnetic metal organic framework core-shell material |
| CN109081381A (en) * | 2018-10-11 | 2018-12-25 | 东莞市中航华讯卫星技术有限公司 | Nanoporous negative electrode material Fe3O4Preparation method |
| US20190020028A1 (en) * | 2016-01-14 | 2019-01-17 | Agency For Science, Technology And Research | Free-standing mof-derived hybrid porous carbon nanofiber mats |
| CN109663571A (en) * | 2018-11-22 | 2019-04-23 | 浙江农林大学 | A kind of preparation method of magnetism-metal organic frame MOF material |
-
2019
- 2019-09-25 CN CN201910911067.3A patent/CN110668504A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103521269A (en) * | 2013-11-04 | 2014-01-22 | 北京化工大学 | Metal-organic framework materials with magnetic cores and preparation and application thereof |
| US20190020028A1 (en) * | 2016-01-14 | 2019-01-17 | Agency For Science, Technology And Research | Free-standing mof-derived hybrid porous carbon nanofiber mats |
| CN107042087A (en) * | 2017-01-19 | 2017-08-15 | 中国石油大学(华东) | A kind of method that Situ Hydrothermal prepares magnetic metal organic framework core-shell material |
| CN109081381A (en) * | 2018-10-11 | 2018-12-25 | 东莞市中航华讯卫星技术有限公司 | Nanoporous negative electrode material Fe3O4Preparation method |
| CN109663571A (en) * | 2018-11-22 | 2019-04-23 | 浙江农林大学 | A kind of preparation method of magnetism-metal organic frame MOF material |
Non-Patent Citations (1)
| Title |
|---|
| WENHUI LI ET AL.: ""Magnetic porous Fe3O4/carbon octahedra derived from iron-based metal-organic framework as heterogeneous Fenton-like catalyst"", 《APPLIED SURFACE SCIENCE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111208287A (en) * | 2020-01-16 | 2020-05-29 | 长沙理工大学 | Construction method of magnetic resonance sensor |
| CN112570029A (en) * | 2020-12-17 | 2021-03-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of aluminum ion doped modified iron oxide catalyst with metal organic framework structure |
| CN112569950A (en) * | 2020-12-17 | 2021-03-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of magnetic ferroferric oxide-zinc oxide composite photocatalyst with octahedral structure, product and application thereof |
| CN115770619A (en) * | 2022-11-08 | 2023-03-10 | 安徽信息工程学院 | MOF in-situ conversion Fe 2 O 3 Nanorods and porous Fe 2 O 3 Process for preparing nano composite material |
| CN115770619B (en) * | 2022-11-08 | 2024-03-12 | 安徽信息工程学院 | MOF in-situ conversion Fe 2 O 3 Nanorods and porous Fe 2 O 3 Method for preparing nanocomposite |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110668504A (en) | Mesoporous Fe3O4Granules and process for their preparation | |
| Chen et al. | Hollow Cu–TiO 2/C nanospheres derived from a Ti precursor encapsulated MOF coating for efficient photocatalytic hydrogen evolution | |
| Xian et al. | Enhanced photocatalytic activity of BaTiO3@ g-C3N4 for the degradation of methyl orange under simulated sunlight irradiation | |
| CN108842169B (en) | Metal oxide loaded bismuth vanadate composite material and preparation and application thereof | |
| CN109759110A (en) | A kind of N doping porous carbon loaded titanium dioxide photocatalyst and the preparation method and application thereof | |
| Sudhagar et al. | Enhanced photoelectrocatalytic water splitting at hierarchical Gd3+: TiO2 nanostructures through amplifying light reception and surface states passivation | |
| CN103736480B (en) | A kind of corner star pucherite as catalysis material and preparation method thereof | |
| CN106587134A (en) | Preparation method of noble metal doped flower-like CuO nano material and method for preparing gas-sensitive element from same | |
| Teodorescu-Soare et al. | Growth and characterization of TiO2 nanotube arrays under dynamic anodization. Photocatalytic activity | |
| CN104150536B (en) | There is the MoO of good photoelectric properties 2the preparation method of powder and application | |
| CN110575832A (en) | Preparation method and application of silver-titanium dioxide-nano diamond composite photocatalyst | |
| CN104511280B (en) | A kind of visible light catalyst and preparation method thereof | |
| Liu et al. | Fabrication of novel fibrous BiVO4/CdS heterostructures by electrospinning method for efficient visible light photodegradation | |
| CN105664969B (en) | A kind of titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material and preparation method thereof | |
| CN107824797B (en) | Porous high-specific-surface-area bismuth nanoparticle modified nitrogen-doped carbon nanosheet material and preparation method and application thereof | |
| CN105776311A (en) | Method for preparing copper oxide nano material | |
| CN109012729A (en) | A kind of preparation method of porous nitrogen fluorine codope carbon oxygen reduction catalyst | |
| CN103506104B (en) | Carbon-doped TiO2 visible light-responding catalytic film on glass carrier and preparation method thereof | |
| CN110935441B (en) | Titanium-based composite catalytic net for efficiently degrading formaldehyde and preparation method thereof | |
| CN106145186B (en) | A kind of sheet fluorine oxygen bismuth and its application | |
| CN108298633B (en) | Nano TiO (titanium dioxide)2Process for degrading dye wastewater by using photocatalyst | |
| CN106745279A (en) | A kind of carbon modification MnZn oxygen nano material and its preparation method and application | |
| CN109046439B (en) | Synthesis method of high-doping high-acidity mesoporous silica solid acid catalyst | |
| CN110841686A (en) | Carbon-coated titanium suboxide composite carbon nitride composite material and preparation method and application thereof | |
| GB2618635A (en) | Photocatalytic material for degrading tetracycline in wastewater and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200110 |