CN108948368A - Method for rapidly preparing nickel-based metal organic framework material - Google Patents
Method for rapidly preparing nickel-based metal organic framework material Download PDFInfo
- Publication number
- CN108948368A CN108948368A CN201810818736.8A CN201810818736A CN108948368A CN 108948368 A CN108948368 A CN 108948368A CN 201810818736 A CN201810818736 A CN 201810818736A CN 108948368 A CN108948368 A CN 108948368A
- Authority
- CN
- China
- Prior art keywords
- based metal
- ball
- metal organic
- organic framework
- nickel based
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for rapidly preparing a nickel-based metal organic framework material, which comprises the steps of adding nickel acetate tetrahydrate and trimesic acid into a reaction container, adding a ball milling ball and water, sealing the reaction container, carrying out ball milling at 25 Hz-50 Hz, cleaning and drying an obtained product, and thus obtaining the nickel-based metal organic framework material. The method is green, environment-friendly and efficient, the required product can be obtained within 1 minute at the fastest speed, the obtained product has better capacitance performance, and the high capacitance of 640F/g can be shown under the current density of 1A/g.
Description
Technical field
The invention belongs to metal-organic framework material preparation fields, are related to one kind and quickly prepare nickel based metal organic frame material
A kind of method of material, and in particular to Ni3(BTC)212H2The quick preparation of O.
Background technique
Metal-organic framework materials (MOFs) cause strong concern due to its attractive structural property, in gas
Body storage, separation, catalysis and sensing etc. have potential application.Recently, MOFs is tunable due to its significant surface area
Aperture, controllable microcellular structure and the special construction with potential pseudo-capacitance redox center have proved to be useful
Electrochemical energy storage and one of the candidate target for being considered as most promising electrode material.Wherein, Ni-based MOFs, especially
Ni3(BTC)2·12H2O (BTC=1,3,5- benzenetricarboxylic acids) has obtained more and more concerns, is not only proved to super capacitor
Device has strong application prospect, but also can have specific structure unique metal oxide and carbon material template/it is preceding
Body.For example, the group of Kong proves the Ni of hydrothermal synthesis3(BTC)2·12H2O has the high specific capacitance of 726F/g.Wang etc. will
Ni-MOF is as presoma, and by calcining precursor preparation mesopore metal oxide in air, prepared NiO is scanned in height
There is high capacitance conservation rate, and due to its spy with excellent cycle life stability with bimodal size distribution under rate
Different meso pore characteristics.Chen etc. uses Ni3(BTC)2·12H2O is the large-scale multi-walled carbon nanotube of precursor synthesis.However, Ni-
The synthesis process of MOFs usually requires volume of solvent, high temperature and long reaction time.For example, Wang etc. is stainless in Telflon liner
Ni has been synthesized in steel autoclave3(BTC)2·12H2O, and heated for 24 hours at 200 DEG C, Du et al. has synthesized Ni-BTC MOF, interior
In lining teflon autoclave, and 150 DEG C being heated in DMF and is kept for 12 hours, the group of Kong is in DMF with 105 DEG C
Lower temperature prepare Ni-MOF, but take more time (for up to 2 days).Although Jin etc. is described at room temperature short
Ni is synthesized in time3(BTC)2·12H2The simple solution phase method of O, but organic linking must preparatory deprotonation, it is also necessary to make
With a large amount of organic solvents.Hence it is highly desirable to which a kind of simple, green, quick and energy-efficient method (does not both need high temperature, not yet
Need a large amount of solvents) prepare Ni-based MOF.
Mechanochemistry, i.e., the chemical synthesis realized or maintained by mechanical force, was once incorporated by replacing for conventional MOF synthesis
Generation.Although the Mechano-chemical Synthesizing of MOFs can be avoided the bulk solvent being usually used in solution synthesis, high temperature and/or corrosivity examination
Agent, still, Pichon and James have studied different nickel salts and H under mechanochemistry condition of no solvent3It is anti-between BTC
It answers, does not succeed.
Recently, there are also the relevant reports of the fast synthesis method of MOF.For example, Duan et al. is by using organic amine
As supermolecular module (Organic amine template), the classifying porous ZIF-8 material of rapid synthesis in 1 minute at room temperature, but still
Need a large amount of organic solvents (methanol) and additive (organic amine).Jin etc. at room temperature the short time (5min) pass through it is simple molten
Liquid phase method has synthesized Ni3(BTC)2·12H2O, but organic linking must shift to an earlier date deprotonation, and use organic solvent.Huang
F is synthesized in 100s using water assisted milling etc. reporting4- UiO-66, however, source metal must be that previously prepared zirconium oxygen is pre-
The cluster of assembling.In spite of these development, it should be understood that the rapid synthesis without using a large amount of solvents or any previously prepared technology
The method of Ni-MOF there is no.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, particular in existing Ni-based MOFs method
Existing time-consuming, need to use a large amount of solvents or needs the problems such as reacting in advance, proposes a kind of method by water assisted milling
The method for quickly preparing nickel based metal organic framework materials (Ni-MOF), this method is green, environmentally friendly, efficient, most fast only 1 point of needs
Required product can be obtained in clock, and products obtained therefrom has preferable capacitive property, shows height under the current density of 1A/g
Up to the high capacitance of 640F/g.
In order to solve the above technical problems, the present invention uses following technical scheme.
A method of quickly preparing nickel based metal organic framework materials, comprising the following steps:
Four hydration nickel acetates and trimesic acid are added in the reaction vessel as reactant, and ball milling ball and water is added,
Reaction vessel is sealed, ball milling is carried out at 25Hz~50Hz, it is organic to obtain nickel based metal after products therefrom is cleaned and dry
Frame material, as Ni3(BTC)2·12H2O。
Above-mentioned quickly prepares in the method for nickel based metal organic framework materials, it is preferred that the matter of the water and reactant
Amount is than being 0.01~0.8: 1.
It is above-mentioned quickly to prepare in the method for nickel based metal organic framework materials, it is preferred that the four hydration nickel acetate with
The ratio between amount of substance of trimesic acid is 0.2~5: 1 namely 1: 5~5: 1.
Above-mentioned quickly prepares in the method for nickel based metal organic framework materials, it is preferred that the ball milling ball and reactant
Mass ratio be 10~20: 1.
It is above-mentioned quickly to prepare in the method for nickel based metal organic framework materials, it is preferred that the diameter of the ball milling ball is
3mm~15mm, the granule number of the ball milling ball are 2~8.
Above-mentioned quickly prepares in the method for nickel based metal organic framework materials, it is preferred that the reaction vessel includes Ma
Nao tank or zirconium oxide tank；The ball milling ball includes agate ball or zirconium ball.
It is above-mentioned quickly to prepare in the method for nickel based metal organic framework materials, it is preferred that the time of the ball milling is
1min~180min.
Above-mentioned quickly prepares in the method for nickel based metal organic framework materials, it is preferred that the cleaning is using ethyl alcohol
It is respectively washed 2 times~4 times with water.
Above-mentioned quickly prepares in the method for nickel based metal organic framework materials, it is preferred that the temperature of the drying is 30
DEG C~120 DEG C, time of the drying is 2h~for 24 hours.
Compared with the prior art, the advantages of the present invention are as follows:
(1) present invention is very quick, most fast only to need 1 minute, product can be obtained, very efficiently.
(2) present invention is not needed using organic solvent, it is only necessary to and very small amount of water is used, can be completed reaction, green,
Environmental protection.
(3) method proposed by the present invention does not need to carry out any preparatory response, can carry out after raw material is mixed.
Detailed description of the invention
Fig. 1 is Ni in embodiment 13(BTC)2·12H2The infrared spectrogram of O.
Fig. 2 is Ni in embodiment 13(BTC)2·12H2The XRD diagram of O.
Fig. 3 is Ni in embodiment 13(BTC)2·12H2(left figure is 20,000 times of amplification to the SEM photograph of O, and right figure is amplification 60,000
Times).
Fig. 4 is Ni in embodiment 13(BTC)2·12H2The nitrogen adsorption desorption curve of O.
Fig. 5 is Ni in embodiment 13(BTC)2·12H2Constant current charge-discharge curve of O under the conditions of 1A/g.
Fig. 6 is Ni in embodiment 23(BTC)2·12H2The infrared spectrogram of O.
Fig. 7 is Ni in embodiment 23(BTC)2·12H2The XRD diagram of O.
Fig. 8 is Ni in embodiment 23(BTC)2·12H2(left figure is 20,000 times of amplification to the SEM photograph of O, and right figure is amplification 60,000
Times).
Fig. 9 is Ni in embodiment 23(BTC)2·12H2The nitrogen adsorption desorption curve of O.
Specific embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
Material employed in following embodiment and instrument are commercially available.
A kind of method for quickly preparing nickel based metal organic framework materials of the invention, comprising the following steps:
Four hydration nickel acetates are added with the ratio that the ratio between amount of substance is 0.2~5: 1 (1: 5~5: 1) in the reaction vessel
With trimesic acid as reactant, the ball milling ball of 2~8 3mm~15mm is added, guarantee ball milling ball and the matter of reactant is added
Amount adds water than being 10~20: 1.After reaction vessel is sealed, be put into ball mill, at 25~50Hz ball milling 1~
180min scrapes product, and with dry 2h at ethyl alcohol and washing 2~4 times, 30 DEG C~120 DEG C~for 24 hours, it is organic to obtain nickel based metal
Frame material, i.e. green solid powder are Ni3(BTC)2·12H2O。
In above-mentioned preparation method, the preferable deionized water of water, the mass ratio of the amount of deionized water and reactant is 0.01~
0.8∶1。
In above-mentioned preparation method, reaction vessel is preferably agate pot or zirconium oxide tank, and corresponding ball milling ball is agate ball
Or zirconium ball.
Embodiment 1:
A kind of method for quickly preparing nickel based metal organic framework materials of the invention, comprising the following steps:
Four hydration nickel acetates and trimesic acid are added with the ratio that the ratio between amount of substance is 2: 3 in the agate pot of 80mL
The agate ball (4.5g) of 3 10mm is added in (total amount 0.45g), guarantees agate ball and the mass ratio of reactant is added to be 10: 1, then
0.2mL deionized water is added.It after agate pot is sealed, is put into ball mill, the ball milling 180min at 40Hz scrapes product, first
It is cleaned 2 times with ethyl alcohol, dry 8h is then washed with water at 2 times, 60 DEG C, obtaining green solid powder is Ni3(BTC)2·12H2O,
Nickel based metal organic framework materials are obtained.
Characterize data is as shown in Figure 1,2,3, 4.Product is located at 1680-1700cm in Fig. 1-1The characteristic peak base of-COOH at place
This disappearance, in 1040-1646cm-1The appearance for locating the characteristic peak of BTC indicates the progress of reaction and the generation of novel substance.In Fig. 2
Positioned at the features such as 10.99,14.63,15.24,17.66,17.94,18.92,19.32,22.11,27.37,28.88,29.65 °
Brilliant peak corresponds respectively to Ni3(BTC)2·12H2O 200,001, -111,220,310, -3-11 (111), 400,330, -202, -
112, the peak of the crystal faces such as 002.Compare Ni3(BTC)2·12H2The sample peak of O finds that the position at peak fits like a glove.Fig. 3 shows ball
The product that mill method closes out shows a kind of scrappy small bulk, and maximum block is about 2 microns, the smallest about 500 to receive
Rice.Fig. 4 shows by adsorption/desorption curve it is found that being to belong to II type adsorption/desorption isothermal curve, P/P0There is rising when < 0.1 therefore
It is mesoporous with the presence of rising between 0.1-0.7 there are micropore in material, there is rising between 0.7-1 so there is macropore, BET specific surface
Product is about 10m2/g.Fig. 5 is Ni in the present embodiment3(BTC)2·12H2Perseverance of O under the conditions of 1A/g in 6M NaOH solution
Current charging and discharging curve calculates available, specific capacitance 640F/g according to discharge curve.
Embodiment 2
A kind of method for quickly preparing nickel based metal organic framework materials of the invention, comprising the following steps:
Four hydration nickel acetates and trimesic acid are added with the ratio that the ratio between amount of substance is 2: 3 in the agate pot of 80mL
The agate ball (9.0g) of 6 10mm is added in (total amount 0.45g), guarantees agate ball and the mass ratio of reactant is added to be 20: 1, then
0.1mL deionized water is added.It after agate pot is sealed, is put into ball mill, at 50 hz ball milling 1min, scrapes product, first use
Ethyl alcohol cleans 3 times, dry 8h is then washed with water at 3 times, 60 DEG C, obtaining green solid powder is Ni3(BTC)2·12H2O, i.e.,
Nickel based metal organic framework materials are obtained.
Characterize data is as shown in Fig. 6,7,8,9.Product is located at 1680-1700cm in Fig. 6-1The characteristic peak base of-COOH at place
This disappearance, in 1040-1646cm-1The appearance for locating the characteristic peak of BTC indicates the progress of reaction and the generation of novel substance.In Fig. 7
Positioned at the features such as 10.99,14.63,15.24,17.66,17.94,18.92,19.32,22.11,27.37,28.88,29.65 °
Brilliant peak corresponds respectively to Ni3(BTC)2·12H2O 200,001, -111,220,310, -3-11 (111), 400,330, -202, -
112, the peak of the crystal faces such as 002.Fig. 8 shows the product that ball-milling method closes out, shows a kind of scrappy small bulk, maximum
Block is about 2 microns, about 500 nanometers the smallest.Fig. 9 shows by adsorption/desorption curve it is found that being to belong to II type adsorption/desorption etc.
Warm curve, P/P0There is rising therefore in material there are micropore when < 0.1, it is mesoporous with the presence of rising between 0.1-0.7, between 0.7-1
There is rising so there is macropore, BET specific surface area is about 4.85m2/g。
Comparative example 1:
A method of nickel based metal organic framework materials being prepared, preparation process is substantially the same manner as Example 1, and difference only exists
In: it is added without deionized water in agate pot, even if Ball-milling Time is up to 90min, also generates without product, is distinguished with ethyl alcohol and water
After washing three times, the product after reaction is all washed away.
Comparative example 2:
A method of nickel based metal organic framework materials being prepared, preparation process is substantially the same manner as Example 1, and difference only exists
In: the power of ball milling is 20Hz, the results showed that even if Ball-milling Time is up to 90min, is also generated without product, with water and ethyl alcohol
After washing three times respectively, the product after reaction is all washed away.
The above described is only a preferred embodiment of the present invention, being not intended to limit the present invention in any form.Though
So the present invention is disclosed as above with preferred embodiment, and however, it is not intended to limit the invention.It is any to be familiar with those skilled in the art
Member, in the case where not departing from Spirit Essence of the invention and technical solution, all using in the methods and techniques of the disclosure above
Appearance makes many possible changes and modifications or equivalent example modified to equivalent change to technical solution of the present invention.Therefore,
Anything that does not depart from the technical scheme of the invention are made to the above embodiment any simple according to the technical essence of the invention
Modification, equivalent replacement, equivalence changes and modification, all of which are still within the scope of protection of the technical scheme of the invention.
Claims (9)
1. a kind of method for quickly preparing nickel based metal organic framework materials, comprising the following steps:
Four hydration nickel acetates and trimesic acid are added in the reaction vessel as reactant, are additionally added ball milling ball and water, it will be anti-
It answers container to seal, ball milling is carried out at 25Hz~50Hz and obtains nickel based metal organic frame after products therefrom is cleaned and dry
Material, as Ni3(BTC)2·12H2O。
2. the method according to claim 1 for quickly preparing nickel based metal organic framework materials, which is characterized in that the water
Mass ratio with reactant is 0.01~0.8: 1.
3. the method according to claim 1 for quickly preparing nickel based metal organic framework materials, which is characterized in that described four
Being hydrated the ratio between amount of substance of nickel acetate and trimesic acid is 0.2~5: 1.
4. the method according to claim 1 for quickly preparing nickel based metal organic framework materials, which is characterized in that the ball
The mass ratio of abrading-ball and reactant is 10~20: 1.
5. the method according to claim 4 for quickly preparing nickel based metal organic framework materials, which is characterized in that the ball
The diameter of abrading-ball is 3mm~15mm, and the granule number of the ball milling ball is 2~8.
6. the method according to any one of claims 1 to 5 for quickly preparing nickel based metal organic framework materials, feature
It is, the reaction vessel includes agate pot or zirconium oxide tank；The ball milling ball includes agate ball or zirconium ball.
7. the method according to any one of claims 1 to 5 for quickly preparing nickel based metal organic framework materials, feature
It is, the time of the ball milling is 1min~180min.
8. the method according to any one of claims 1 to 5 for quickly preparing nickel based metal organic framework materials, feature
It is, the cleaning is to be respectively washed 2 times~4 times using ethyl alcohol and water.
9. the method according to any one of claims 1 to 5 for quickly preparing nickel based metal organic framework materials, feature
It is, the temperature of the drying is 30 DEG C~120 DEG C, and the time of the drying is 2h~for 24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810818736.8A CN108948368B (en) | 2018-07-24 | 2018-07-24 | Method for rapidly preparing nickel-based metal organic framework material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810818736.8A CN108948368B (en) | 2018-07-24 | 2018-07-24 | Method for rapidly preparing nickel-based metal organic framework material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108948368A true CN108948368A (en) | 2018-12-07 |
| CN108948368B CN108948368B (en) | 2021-05-07 |
Family
ID=64463464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810818736.8A Active CN108948368B (en) | 2018-07-24 | 2018-07-24 | Method for rapidly preparing nickel-based metal organic framework material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108948368B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372877A (en) * | 2019-07-29 | 2019-10-25 | 南京工业大学 | A kind of method that green prepares metal-organic framework materials |
| CN110790944A (en) * | 2019-11-14 | 2020-02-14 | 中国人民解放军国防科技大学 | Method for preparing zirconium metal organic framework nanotube |
| CN114230806A (en) * | 2022-01-05 | 2022-03-25 | 太原理工大学 | Large-scale preparation method of nickel-based MOF material and application of nickel-based MOF material in separation of ethylene from multi-component gas |
| CN115304779A (en) * | 2022-07-07 | 2022-11-08 | 中国人民解放军国防科技大学 | MIL-101 (Cr) and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007023295A2 (en) * | 2005-08-25 | 2007-03-01 | The Queen's University Of Belfast | Use of grinding in chemical synthesis |
| CN106397491A (en) * | 2016-08-31 | 2017-02-15 | 太原理工大学 | Method for synthesizing Ni-BTC by utilizing additive |
| CN107096569A (en) * | 2017-04-28 | 2017-08-29 | 新疆大学 | A kind of efficient catalytic carbon dioxide and the catalyst of epoxides cycloaddition reaction |
| CN107983385A (en) * | 2017-11-28 | 2018-05-04 | 渤海大学 | A kind of nickel radical magnetic composite materials and its synthetic method and application |
-
2018
- 2018-07-24 CN CN201810818736.8A patent/CN108948368B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007023295A2 (en) * | 2005-08-25 | 2007-03-01 | The Queen's University Of Belfast | Use of grinding in chemical synthesis |
| CN106397491A (en) * | 2016-08-31 | 2017-02-15 | 太原理工大学 | Method for synthesizing Ni-BTC by utilizing additive |
| CN107096569A (en) * | 2017-04-28 | 2017-08-29 | 新疆大学 | A kind of efficient catalytic carbon dioxide and the catalyst of epoxides cycloaddition reaction |
| CN107983385A (en) * | 2017-11-28 | 2018-05-04 | 渤海大学 | A kind of nickel radical magnetic composite materials and its synthetic method and application |
Non-Patent Citations (2)
| Title |
|---|
| DENGCHAO WANG等: ""Preparation of mesoporous NiO with a bimodal pore size distribution and application in electrochemical capacitors"", 《ELECTROCHIMICA ACTA》 * |
| SHUAIQI ZHAO等: ""Removal of Congo red dye from aqueous solution with nickel-based metalorganic framework/graphene oxide composites prepared by ultrasonic wave-assisted ball milling"", 《ULTRASONICS - SONOCHEMISTRY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372877A (en) * | 2019-07-29 | 2019-10-25 | 南京工业大学 | A kind of method that green prepares metal-organic framework materials |
| CN110790944A (en) * | 2019-11-14 | 2020-02-14 | 中国人民解放军国防科技大学 | Method for preparing zirconium metal organic framework nanotube |
| CN114230806A (en) * | 2022-01-05 | 2022-03-25 | 太原理工大学 | Large-scale preparation method of nickel-based MOF material and application of nickel-based MOF material in separation of ethylene from multi-component gas |
| CN115304779A (en) * | 2022-07-07 | 2022-11-08 | 中国人民解放军国防科技大学 | MIL-101 (Cr) and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108948368B (en) | 2021-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108948368A (en) | Method for rapidly preparing nickel-based metal organic framework material | |
| Yang et al. | Synthesis of metal–organic framework MIL-101 in TMAOH-Cr (NO3) 3-H2BDC-H2O and its hydrogen-storage behavior | |
| CN107312181B (en) | Method for rapidly preparing Cu-BTC | |
| CN102992308A (en) | Graphene with high specific capacitance and preparation method thereof | |
| CN106450349A (en) | Preparation method of iron-nickel hydrotalcite structure nanosheet for oxygen evolution reaction | |
| CN111514895A (en) | Preparation method and application of transition bimetallic catalyst | |
| CN110467182A (en) | A kind of multi-stage porous carbon sill and its preparation method and application based on reaction template | |
| CN112670096B (en) | Alkali metal salt nano material and preparation method and application thereof | |
| CN109569609A (en) | A kind of preparation method of novel nickel-base composite material | |
| CN107673412A (en) | A kind of porous Co3O4 nanometer material and its preparation method and application | |
| CN109516507A (en) | A kind of preparation method of porous cobaltosic oxide nano piece | |
| CN109192526A (en) | A kind of porous carbon/metal oxide sandwich and its preparation method and application | |
| CN102267718A (en) | Synthesis method of tin dioxide nanometer material | |
| CN106698365A (en) | Preparation method and application of hollow porous transition metal chalcogenide nanosheets | |
| CN107446138B (en) | A kind of method and application preparing MIL-100 (Fe) using floride-free auxiliary agent sodium carbonate | |
| CN109671574B (en) | MnCo2O4Nano-spherical particles, preparation method thereof and application thereof in super capacitor | |
| CN108440767A (en) | It is a kind of that nanometer Au is combined to the new method for preparing Au@MOF composite materials with porous MOF | |
| CN113617334B (en) | Preparation method of metal organic framework material | |
| CN110078137A (en) | Vulcanize nickel electrode material and the preparation method and application thereof | |
| CN110729132A (en) | Application of metaborate column supported alpha-phase nickel hydroxide material in supercapacitor | |
| CN108314084B (en) | Preparation method of metal phase molybdenum disulfide nanospheres | |
| CN106699550A (en) | Preparation method of nano Cu-CuBTC type metal organic framework material | |
| CN105375017A (en) | Molybdenum diselenide/titanium dioxide composite material and preparation method and application therefor | |
| CN108910948A (en) | A kind of niobic acid tin nanometer sheet and preparation method thereof | |
| CN106219603B (en) | A kind of nanotube and its preparation method and application of titanium dioxide nanoplate composition |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |