CN114425365A - Preparation method of defect-rich Mn-Co metal oxide catalyst - Google Patents
Preparation method of defect-rich Mn-Co metal oxide catalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
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- 238000000034 method Methods 0.000 claims abstract description 19
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- 239000002243 precursor Substances 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- 238000000498 ball milling Methods 0.000 claims description 27
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- 239000011572 manganese Substances 0.000 claims description 17
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 16
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 14
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- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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Abstract
The invention discloses a preparation method of a defect-rich Mn-Co metal oxide catalyst, which comprises the following steps: synthesizing a Mn/Co bimetal MOFs precursor with coordination defects under the condition of high-energy ball milling, and then preparing a Mn-Co metal oxide with rich defects by calcining; the characteristics of inhibiting the agglomeration of metal ions by using MOFs as a catalyst precursor, and mechanochemistryThe idea of constructing material defects by a method is that a Mn/Co bimetal MOFs precursor prepared by high-energy ball milling is calcined in air to form a defect-rich Mn-Co metal oxide catalyst, the MOFs with a large number of coordination defects has a special structure with short-range order and long-range disorder, the metal ion dispersibility is met, crystal grains are refined, the feasibility is provided for preparing the defect-rich Mn-Co metal oxide, and the maximum specific surface area of the prepared catalyst can reach 85.8m2The proportion of surface defect oxygen is about 60% of the oxygen species.
Description
Technical Field
The invention relates to the field of inorganic nano catalytic materials, in particular to a preparation method of a defect-rich Mn-Co metal oxide catalyst.
Background
Volatile Organic Compounds (VOCs) have become one of the major components of air pollutants and pose serious risks to the ecological environment and human health. In view of energy saving and environmental friendliness, the development of low-temperature oxidation light alkane catalysts and processes is one of the research hotspots of industrial catalysis. The commercial application of the noble metal catalyst is limited due to high price of the noble metal catalyst, and in the metal oxide catalyst, Mn-Co oxide with a spinel structure is one of the most effective active species for activating and cracking C-C bonds and C-H bonds, and has great application potential in the aspect of catalytic elimination of VOCs. However, different preparation methods and post-synthesis modification all affect the specific surface area, morphology, defect density and the like of the catalyst, and further determine the activity of the catalyst. In recent years, defect engineering theory has been successfully applied in the field of catalysis. Such as heat treatment to control grain size, etching, atom doping, high energy ball milling and other methods, improve the performance of the catalyst by constructing defects. Recent studies have found that the amorphous disordered structure exposes a large number of active sites to the surface, and even expands the reaction to the inside of the catalyst volume, greatly improving the catalytic activity. Therefore, increasing the defect density per unit area of the catalyst has become a new breakthrough for improving the catalytic performance. The catalyst synthesized by mechanochemical method is gradually valued for its simple process, capability of preparing amorphous or nano-grade particles, and benefit for manufacturing defects and pore structures. However, the small-sized particles having high surface energy inevitably undergo a hard agglomeration phenomenon during the heat treatment, which is disadvantageous to the exposure of active sites.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a defect-rich Mn-Co metal oxide catalyst, which is implemented by calcining a Mn/Co bimetallic MOFs precursor prepared by high-energy ball milling in air to form the defect-rich Mn-Co metal oxide catalyst, based on the characteristics that MOFs is used as a catalyst precursor to inhibit the agglomeration of metal ions and the idea of constructing material defects by a mechanochemical method.
The preparation method of the defect-rich Mn-Co metal oxide catalyst comprises the following steps: synthesizing a Mn/Co bimetal MOFs precursor with coordination defects under the condition of high-energy ball milling, and then preparing a Mn-Co metal oxide with rich defects by calcining;
further, the method comprises the following steps:
a. mixing 1,3, 5-benzene tricarboxylic acid, nitrate containing cobalt and manganese, formic acid and N, N-dimethylformamide, then carrying out conversion removal treatment, and then carrying out ball milling treatment;
b. after ball milling treatment, centrifugally cleaning and filtering, drying the obtained solid powder to obtain mauve solid powder MC-BTC, and then calcining in a muffle furnace to obtain a target Mn-Co metal oxide catalyst;
further, in step a, the nitrate containing cobalt and manganese is Mn (NO)3)2·4H2O and Co (NO)3)2·6H2O, in molar ratio Mn (NO)3)2·4H2O：Co(NO3)2·6H2O＝1:4～4:1；
Further, in the step a, 1,3, 5-benzene tricarboxylic acid and nitrate containing cobalt and manganese are mixed and placed in a ball milling tank, formic acid is dissolved in N, N-dimethylformamide and added into the ball milling tank, and finally triethylamine is added;
further, in the step b, after ball milling treatment, centrifuging and cleaning the product by using N, N-dimethylformamide and absolute ethyl alcohol, and filtering, wherein the ball milling time is 25-35 min;
6. the method of preparing a defect rich Mn-Co metal oxide catalyst as claimed in claim 5, wherein: in the step b, the drying temperature is 50-70 ℃, and the drying time is 1.5-2.5 hours;
further, in the step b, the calcining atmosphere is air, the calcining temperature is 500 ℃, the temperature rise rate of the muffle furnace is 4 ℃/min, and the heat preservation time is 1-3 hours.
The invention also discloses a defect-rich Mn-Co metal oxide catalyst prepared by the preparation method of the defect-rich Mn-Co metal oxide catalyst.
The invention has the beneficial effects that: the invention discloses a preparation method of a defect-rich Mn-Co metal oxide catalyst, which is characterized in that the MOFs is used as a catalyst precursor to inhibit the agglomeration of metal ions and the thinking of constructing material defects by a mechanochemical method is utilized, a Mn/Co bimetal MOFs precursor prepared by high-energy ball milling is adopted and calcined in the air to form the defect-rich Mn-Co metal oxide catalyst, the MOFs with a large number of coordination defects has a special structure with short-range order and long-range disorder, the metal ion dispersibility is met, crystal grains are refined, the feasibility is provided for preparing the defect-rich Mn-Co metal oxide, and the maximum specific surface area of the prepared catalyst can reach 85.8m2The proportion of surface defect oxygen is about 60% of the oxygen species.
Drawings
The invention is further described below with reference to the following figures and examples:
FIG. 1 is an X-ray diffraction (XRD) spectrum of a sample of the Mn-Co metal oxide produced, wherein curve A, B, C, D, E corresponds to the XRD spectrum of the samples of example 1, example 2, example 3, example 4 and example 5, respectively;
FIG. 2 is a graph showing the activity of defect rich Mn-Co metal oxide samples prepared for catalytic oxidation of C3H8, wherein A, B, C, D, E corresponds to the activity curves of the samples of example 1, example 2, example 3, example 4 and example 5, respectively;
FIG. 3 is an SEM picture of a sample of a defect-rich Mn-Co metal oxide produced, which is a picture of sample C of example 3;
FIG. 4 is an XPS plot of Mn-Co metal oxide samples.
Detailed Description
Example one
0.1g of Mn (NO) was taken3)2·4H2O，0.47g Co(NO3)2·6H2O, 0.420g of 1,3, 5-benzenetricarboxylic acid are mixed and placed in a ball mill pot. mu.L of formic acid was dissolved in 1mL of N, N-dimethylformamide, the solution was transferred to a ball mill pot and mixed with the solid powder to obtain a suspension, and 420. mu.L of triethylamine was added for deprotonation. And screwing the ball milling tank, and fixing the ball milling tank in a clamping groove of the vibration type high-energy ball mill, wherein the ball milling reaction time is 30 min. Centrifuging and cleaning the product by using N, N-dimethylformamide and absolute ethyl alcohol, filtering, drying the rest solid powder in a drying box at 60 ℃ for 2 hours, and calcining in a muffle furnace to obtain the target Mn-Co metal oxide catalyst (A), wherein the BET specific surface area of a sample is 62.8m2·g-1. The calcining atmosphere is air, the calcining temperature is 400 ℃, the temperature rising rate of a muffle furnace is 4 ℃/min, and the heat preservation time is 2 hours.
Example two
0.2g of Mn (NO) was taken3)2·4H2O，0.35g Co(NO3)2·6H2O, 0.420g of 1,3, 5-benzenetricarboxylic acid are mixed and placed in a ball mill pot. mu.L of formic acid was dissolved in 1mL of N, N-dimethylformamide, the solution was transferred to a ball mill pot and mixed with the solid powder to obtain a suspension, and 420. mu.L of triethylamine was added for deprotonation. And screwing the ball milling tank, and fixing the ball milling tank in a clamping groove of the vibration type high-energy ball mill, wherein the ball milling reaction time is 30 min. Centrifuging and cleaning the product by using N, N-dimethylformamide and absolute ethyl alcohol, filtering, drying the rest solid powder in a drying box at 60 ℃ for 2 hours, and calcining in a muffle furnace to obtain the target Mn-Co metal oxide catalyst (B), wherein the BET specific surface area of a sample is 72.3m2·g-1. The calcining atmosphere is air, the calcining temperature is 400 ℃, the temperature rising rate of a muffle furnace is 4 ℃/min, and the heat preservation time is 2 hours.
EXAMPLE III
0.3g of Mn (NO) was taken3)2·4H2O，0.23g Co(NO3)2·6H2O, 0.420g of 1,3, 5-benzenetricarboxylic acid are mixed and placed in a ball mill pot. mu.L of formic acid was dissolved in 1mL of N, N-dimethylformamide, the solution was transferred to a ball mill pot and mixed with the solid powder to obtain a suspension, and 420. mu.L of triethylamine was added for deprotonation. And screwing the ball milling tank, and fixing the ball milling tank in a clamping groove of the vibration type high-energy ball mill, wherein the ball milling reaction time is 30 min. Centrifuging and cleaning the product by using N, N-dimethylformamide and absolute ethyl alcohol, filtering, drying the rest solid powder in a drying box at 60 ℃ for 2 hours, and calcining in a muffle furnace to obtain the target Mn-Co metal oxide catalyst (C), wherein the BET specific surface area of a sample is 85.8m2·g-1. The calcining atmosphere is air, the calcining temperature is 400 ℃, the temperature rising rate of a muffle furnace is 4 ℃/min, and the heat preservation time is 2 hours.
Example four
0.4g of Mn (NO) was taken3)2·4H2O，0.12g Co(NO3)2·6H2O, 0.420g of 1,3, 5-benzenetricarboxylic acid are mixed and placed in a ball mill pot. mu.L of formic acid was dissolved in 1mL of N, N-dimethylformamide, the solution was transferred to a ball mill and mixed with the solid powder to give a suspension, and 420. mu.L of triethylamine was added for deprotonation. And screwing the ball milling tank, and fixing the ball milling tank in a clamping groove of the vibration type high-energy ball mill, wherein the ball milling reaction time is 30 min. Centrifuging and cleaning the product by using N, N-dimethylformamide and absolute ethyl alcohol, filtering, drying the rest solid powder in a drying box at 60 ℃ for 2 hours, and calcining in a muffle furnace to obtain the target Mn-Co metal oxide catalyst (D), wherein the BET specific surface area of the sample is 76.3m2·g-1. The calcining atmosphere is air, the calcining temperature is 400 ℃, the temperature rising rate of a muffle furnace is 4 ℃/min, and the heat preservation time is 2 hours.
Comparative experiment
0.3g of Mn (NO) was taken3)2·4H2O，0.23g Co(NO3)2·6H2O, 0.08g NaOH solids were mixed and placed in a ball mill jar. Screwing the ball milling tank to fix the ball milling tank in the clamping groove of the vibrating high-energy ball mill, and performing ball milling reactionThe time interval is 30 min. Centrifugally cleaning the product with absolute ethyl alcohol, filtering, drying the rest solid powder in a drying oven at 60 ℃ for 2 hours, calcining in a muffle furnace to obtain the target Mn-Co metal oxide catalyst (E), wherein the BET specific surface area of the sample is 60.6m2·g-1. The calcining atmosphere is air, the calcining temperature is 400 ℃, the temperature rising rate of a muffle furnace is 4 ℃/min, and the heat preservation time is 2 hours.
Test example 1:
XRD tests were performed on A, B, C, D and E samples of each example, and the results are shown in FIG. 1, wherein the phase structure of A, B, C, D, E sample is Co3O4-Mn3O4The composite oxide, sample a, exhibited a higher crystallinity, while sample B exhibited a lower crystallinity, reflecting that the catalyst grains were finer.
Test example 2:
c on fixed bed reactor System for A, B, C, D and E samples in each example3H8Evaluation test of catalytic oxidation activity of (3). 0.9g of quartz sand mixed with 50mg of catalyst was taken and placed in a quartz tube reactor, on both sides of which were quartz sand and quartz wool. The total flow rate of the reaction gas was 100mL min-1(1mL min-1C3H8、89mL min-1N2、10mL min-1O2) The mass space velocity is 120000ml g-1h-1. The reaction temperature is controlled by a thermocouple, the temperature measuring device can detect the temperature of the fixed bed in time, and the heating rate is 10 ℃ min-1(ii) a Gas chromatography is adopted to detect C after mixed gas passes through catalyst on line3H8The concentration of (c).
Test example 3:
the sample C of example 3 was subjected to Scanning Electron Microscope (SEM) testing, and the result is shown in fig. 3, which is a 30000-fold magnified SEM image of the sample. As can be seen, the obtained catalyst has a porous flocculent morphology.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (8)
1. A preparation method of a defect-rich Mn-Co metal oxide catalyst is characterized by comprising the following steps: the method comprises the following steps: synthesizing a Mn/Co bimetal MOFs precursor with coordination defects under the condition of high-energy ball milling, and then preparing the Mn-Co metal oxide with rich defects by calcining.
2. The method of preparing a defect rich Mn-Co metal oxide catalyst as claimed in claim 1, wherein: the method comprises the following steps:
a. mixing 1,3, 5-benzene tricarboxylic acid, nitrate containing cobalt and manganese, formic acid and N, N-dimethylformamide, then carrying out conversion removal treatment, and then carrying out ball milling treatment;
b. and after ball milling treatment, centrifugally cleaning and filtering, drying the obtained solid powder to obtain mauve solid powder MC-BTC, and then calcining in a muffle furnace to obtain the target Mn-Co metal oxide catalyst.
3. The method of preparing a defect rich Mn-Co metal oxide catalyst as claimed in claim 2, wherein: in step a, the nitrate containing cobalt and manganese is Mn (NO)3)2·4H2O and Co (NO)3)2·6H2O, in molar ratio Mn (NO)3)2·4H2O：Co(NO3)2·6H2O＝1:4～4:1。
4. The method of preparing a defect rich Mn-Co metal oxide catalyst as claimed in claim 3, wherein: in the step a, 1,3, 5-benzenetricarboxylic acid and nitrate containing cobalt and manganese are mixed and placed in a ball milling tank, formic acid is dissolved in N, N-dimethylformamide and added into a 50mL ball milling tank, and finally triethylamine is added.
5. The method of preparing a defect rich Mn-Co metal oxide catalyst as claimed in claim 4, wherein: in the step b, after ball milling treatment, the product is centrifugally cleaned by N, N-dimethylformamide and absolute ethyl alcohol, and then is filtered, wherein the ball milling time is 25-35 min.
6. The method of preparing a defect rich Mn-Co metal oxide catalyst as claimed in claim 5, wherein: in the step b, the drying temperature is 50-70 ℃, and the drying time is 1.5-2.5 hours.
7. The method of preparing a defect rich Mn-Co metal oxide catalyst of claim 6, wherein: in the step b, the calcining atmosphere is air, the calcining temperature is 500 ℃, the temperature rising rate of the muffle furnace is 4 ℃/min, and the heat preservation time is 1-3 hours.
8. A defect-rich Mn-Co metal oxide catalyst, characterized by: prepared by the method for preparing a defect-rich Mn-Co metal oxide catalyst according to any one of claims 1 to 7.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103432997A (en) * | 2013-08-30 | 2013-12-11 | 华南理工大学 | Cu-based organic skeleton-graphene oxide composite porous material and preparation method thereof |
| GB201515869D0 (en) * | 2015-09-08 | 2015-10-21 | Johnson Matthey Fuel Cells Ltd | Oxygen reduction reactor catalyst |
| WO2017210874A1 (en) * | 2016-06-08 | 2017-12-14 | Xia, Ling | Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation |
| WO2018103144A1 (en) * | 2016-12-08 | 2018-06-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Manganese-based catalyst for use in treatment of volatile organic compounds, and preparation and application thereof |
| CN109012164A (en) * | 2018-09-04 | 2018-12-18 | 广州华园科技有限公司 | It is a kind of can room temperature decomposing formaldehyde micro/nano fibrous membrane material and its preparation method and application |
| CN110681382A (en) * | 2019-09-18 | 2020-01-14 | 太原理工大学 | MOF-cobalt-based metal oxide catalyst for catalytic oxidation of toluene and preparation method thereof |
| CN110841621A (en) * | 2019-11-28 | 2020-02-28 | 怀化学院 | Preparation method of MOF-5-based photocatalyst |
| CN111013602A (en) * | 2019-12-20 | 2020-04-17 | 广州华园科技有限公司 | Formed Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature and preparation method and application thereof |
| CN111686694A (en) * | 2019-03-15 | 2020-09-22 | 中国石油化工股份有限公司 | Preparation method and application of MIL-101 material |
| WO2020199368A1 (en) * | 2019-04-02 | 2020-10-08 | 中车工业研究院有限公司 | Methods of preparing mof compound and non-precious metal catalyst |
| CN111872600A (en) * | 2020-07-08 | 2020-11-03 | 中国矿业大学 | MOFs carbonized product, preparation method and application in lead-free solder modification |
| CN113559941A (en) * | 2021-08-24 | 2021-10-29 | 大连工业大学 | MOFs material-based metal nanoparticle-loaded catalyst and preparation method and application thereof |
| CN113559936A (en) * | 2021-07-30 | 2021-10-29 | 陕西科技大学 | Defective UiO-66 photocatalytic material and preparation method and application thereof |
-
2022
- 2022-01-29 CN CN202210112488.1A patent/CN114425365B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103432997A (en) * | 2013-08-30 | 2013-12-11 | 华南理工大学 | Cu-based organic skeleton-graphene oxide composite porous material and preparation method thereof |
| GB201515869D0 (en) * | 2015-09-08 | 2015-10-21 | Johnson Matthey Fuel Cells Ltd | Oxygen reduction reactor catalyst |
| US20180294485A1 (en) * | 2015-09-08 | 2018-10-11 | Johnson Matthey Fuel Cells Limited | Oxygen reduction reaction catalyst |
| WO2017210874A1 (en) * | 2016-06-08 | 2017-12-14 | Xia, Ling | Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation |
| WO2018103144A1 (en) * | 2016-12-08 | 2018-06-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Manganese-based catalyst for use in treatment of volatile organic compounds, and preparation and application thereof |
| CN109012164A (en) * | 2018-09-04 | 2018-12-18 | 广州华园科技有限公司 | It is a kind of can room temperature decomposing formaldehyde micro/nano fibrous membrane material and its preparation method and application |
| CN111686694A (en) * | 2019-03-15 | 2020-09-22 | 中国石油化工股份有限公司 | Preparation method and application of MIL-101 material |
| WO2020199368A1 (en) * | 2019-04-02 | 2020-10-08 | 中车工业研究院有限公司 | Methods of preparing mof compound and non-precious metal catalyst |
| CN110681382A (en) * | 2019-09-18 | 2020-01-14 | 太原理工大学 | MOF-cobalt-based metal oxide catalyst for catalytic oxidation of toluene and preparation method thereof |
| CN110841621A (en) * | 2019-11-28 | 2020-02-28 | 怀化学院 | Preparation method of MOF-5-based photocatalyst |
| CN111013602A (en) * | 2019-12-20 | 2020-04-17 | 广州华园科技有限公司 | Formed Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature and preparation method and application thereof |
| CN111872600A (en) * | 2020-07-08 | 2020-11-03 | 中国矿业大学 | MOFs carbonized product, preparation method and application in lead-free solder modification |
| CN113559936A (en) * | 2021-07-30 | 2021-10-29 | 陕西科技大学 | Defective UiO-66 photocatalytic material and preparation method and application thereof |
| CN113559941A (en) * | 2021-08-24 | 2021-10-29 | 大连工业大学 | MOFs material-based metal nanoparticle-loaded catalyst and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| CHUANQIANG LI ET AL.: "Metal-organic framework derived hexagonal layered cobalt oxides with {112} facets and rich oxygen vacancies: High efficiency catalysts for total oxidation of propane", 《ADVANCED POWDER TECHNOLOGY》, pages 1 - 10 * |
| 冷福成: "铟基卟啉MOFs的合成及其光催化产氢过程的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 1, pages 014 - 1346 * |
| 赵慎龙: "MOFs 及其衍生物的制备与电催化性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, no. 1, pages 014 - 154 * |
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