CN109880112B - In-situ oriented arrangement one-dimensional structure ZIF-67 and preparation method thereof - Google Patents
In-situ oriented arrangement one-dimensional structure ZIF-67 and preparation method thereof Download PDFInfo
- Publication number
- CN109880112B CN109880112B CN201910105466.0A CN201910105466A CN109880112B CN 109880112 B CN109880112 B CN 109880112B CN 201910105466 A CN201910105466 A CN 201910105466A CN 109880112 B CN109880112 B CN 109880112B
- Authority
- CN
- China
- Prior art keywords
- carbon paper
- solution
- dimensional structure
- inner container
- water
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The invention discloses an in-situ oriented arrangement one-dimensional structure ZIF-67 and a preparation method thereof. The preparation method comprises the steps of soaking carbon paper in an aqueous solution of cobalt salt, urea and ammonium fluoride, and obtaining nanowires Co (OH) F with regular arrangement in a one-dimensional structure through a hydrothermal reaction; and then annealing at high temperature to obtain CoO with a one-dimensional structure, and then placing the CoO in a 2-methylimidazole solution to react with 2-methylimidazole to obtain the ZIF-67 which is directionally arranged on the one-dimensional nanowire in situ. The method disclosed by the invention is mild in condition and low in cost, and the in-situ oriented arrangement one-dimensional structure ZIF-67 can be obtained.
Description
Technical Field
The invention relates to a preparation method of a one-dimensional structure ZIF-67, in particular to an in-situ oriented arrangement one-dimensional structure ZIF-67 and a preparation method thereof.
Background
MOFs are short for Metal organic Framework compounds (English name Metal organic Framework). The material is a crystalline porous material with a periodic network structure formed by connecting an inorganic metal center (metal ion or metal cluster) and a bridged organic ligand through self-assembly. MOFs are an organic-inorganic hybrid material, also called coordination polymer, which is different from inorganic porous materials and common organic complexes, and combines the rigidity of inorganic materials and the flexibility of organic materials. The method has great development potential and attractive development prospect in the aspect of modern material research.
ZIF, a zeolitic imidazolate framework material, is a porous crystalline material in which organic imidazolate crosslinks to transition metals to form a tetrahedral framework. ZIF-67 (2-methylimidazolium cobalt) is a typical MOFs porous crystalline material, in which 2-methylimidazolium crosslinks are connected with cobalt, a transition metal, to form a tetrahedral framework. The metal ions are positioned at the top angle of the tetrahedron, the N atom is positioned in the middle of the tetrahedron, and the tetrahedron structural unit formed by the metal ions and the N atom is connected with adjacent metal or organic ligand to form the H-dimensional framework structure material. It has high thermal and chemical stability in an aqueous medium. ZIF-67 has unique photoelectric properties and is widely used for adsorbing and separating gases such as carbon dioxide, methane and the like. The special performance of the novel nano-scale directional arrangement structure enables ZIF-67 to be applied in wider fields.
Currently, the following methods exist for the synthesis of ZIF-67:
1. solvothermal process. Dispersing graphene oxide (0.20g) in water (0.20L) by ultrasonic wave and stirring for two hours, and dispersing Fe (NO)3)3·9H2O (18.870g) and PVP (0.15g) were added dropwise to the above dispersion, and the resulting mixture was stirred at room temperature for four hours, after which a solution of hexamethylenetetramine (4.900g) dissolved in water (30ml) was added dropwise. After stirring for 0.5 hour, a slowly dissolving glucose solution (4.250g in 10ml water) was added. After that, the mixture was stirred for 0.5 hour, and then placed in a polytetrafluoroethylene-lined autoclave (0.5 liter) and kept at 180 ℃ for one day. When the reaction kettle was cooled to the appropriate temperature, the solution was collected by centrifugation to give a brown solid, which was washed with water (3X 5ml) and dried at 85 deg.C (120 min). The dried brown solid was ground and then treated at 550 deg.C (temperature rate of 10 deg.C. min)-1) And annealed for 60 minutes in a nitrogen atmosphere. The black powder obtained after high temperature annealing was named FCG (3.80 g). The resultant FCG (3.80g) was immersed in hydrochloric acid (6M, 30ml) and stirred overnight at room temperature to remove Fe deposited3O4The particles were then collected by repeated centrifugation. (6000 rpm, 2 minutes) with water followed by lyophilization for 36 hours, the resulting powder is denoted C @ rGO. The C @ rGO powder is respectively prepared at 550, 650 and 750 ℃ (the temperature rise rate is 5 ℃ C. min)-1) Annealing for 60 minutes under nitrogen, cooling to room temperature and naming them as C @ rGO-550, C @ rGO-650, and C @ rGO-750[ Liu YY, Wang S, Xing CC, Du H, et al].ACS Omega,2016,1,491-497.]Although the method has simple equipment, the method is sensitive to synthesis conditions and has the defects of influencing the performance of the self-assembled layer and the like.
2. Seed crystal method. Copper nitrate (2.9g) was dissolved in ice water (25ml), and trimesic acid (1.68g) was dissolved in 25ml of ethanol. Mixing the two solutions. The reaction was then sealed in a thick-walled teflon jar for secondary reactions. The mixture was placed in an oven at 110 ℃ for 24 hours. The precipitate was filtered and the resulting blue crystals were washed 3 times with ethanol, then 3 times with water and allowed to air dry for 3 days. The yield of copper obtained by the reaction is 75 percent. The crystal is in low vacuum (10)-1Torr) and 180 ℃ overnight. Notably, re-exposure to ambient atmosphere can cause hydrates to form at the openings [ Houk R J T, Jacobs B W, El Gabaly F, et al silver cluster formation, dynamics, and chemistry in metal-organic frameworks [ J].Nano Lett.,2009,9:3413-3418.]. The method separates the nucleation and growth processes of the crystal, and can better control the growth of the crystal and the microstructure of the film.
3. Microwave method. A DMF solution of 0.12M zinc nitrate and 0.025M terephthalic acid was prepared by sonicating the precursor for 15 minutes, and then dividing the main batch into 3.5mL aliquots for MOF-5 growth experiments at different surfactant concentrations. Subsequently, F-127 was added to the vial in an amount ranging from 0.05 to 0.4 g, followed by alternate sonication for 15 minutes, to give a colorless and transparent liquid. The sealed samples were then heated at a preset temperature of 95 ℃ using an MRC dry bath incubator. DRMS formation was detected within the first minute of the reaction. The DRMS density per volume was determined according to the surfactant concentration. After 3 hours, the DRM used for further experiments was extracted using a sintered glass filter (n.1) and then redispersed in fresh DMF [ Falcaro P, Hill a J, Nairn K M, et al. a new method to position and functional metal-organic frame crystals [ J ]. nat. command, 2011,2 ]. The method has the advantages of fast crystallization under the condition of microwave and solvent-thermal secondary growth, saving preparation time and having smaller crystal particles.
However, the research focus has been on ZIF-67 powder, which was synthesized by Yagli group for the first time, but this synthesis process is long, has a high temperature, and most importantly, is easy to collapse after the guest molecule is removed [ Banner jeee R, Phan A, Wang B, et al2capture[J].Science,2008,319(5865):939-943.]. Then, the Lotsch group synthesizes the mesoporous ZIFs material [ Junggeburth S C, Schwinghammer K, Virdi K S, et al. aware structured mesoporous structures ] by using a surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) as a template for the first time [ J].Chemistry-A European Journal,2012,18(7):2143-52.]. However, under the condition of introducing an external template, the synthesis process causes the ZIFs materials to agglomerate and collapse when being pyrolyzed at high temperature.
The above methods have some disadvantages, such as difficult control of product size, morphology, etc. The self-template sacrificial method can achieve the purpose of conveniently regulating and controlling the size and the shape of particles by using the self-template sacrificial method as a template, so that the self-template sacrificial liquid is increasingly regarded as important for preparing the orderly-arranged ZIF-67 material. At present, the research on preparing the one-dimensional structure ZIF-67 by a self-template sacrificial method is few. The preparation of the in-situ oriented arrangement one-dimensional structure ZIF-67 is not reported in related documents.
Disclosure of Invention
The invention aims to provide a one-dimensional structure ZIF-67 which is mild in condition, controllable in morphology and directionally arranged in situ and a preparation method thereof.
The preparation method of the in-situ oriented arrangement one-dimensional structure ZIF-67 comprises the following steps:
1) dissolving cobalt salt, urea and ammonium fluoride in water, controlling the concentrations of the cobalt salt, the urea and the ammonium fluoride in the obtained solution to be 4mol/L, 5mol/L and 0.2mol/L respectively, and uniformly mixing to obtain a solution a; placing carbon paper in an inner container of a hydrothermal reaction kettle, ensuring that one end of the carbon paper is in contact with the bottom end face of the inner container and the included angle formed by the carbon paper and the bottom end face of the inner container is controlled to be 30-60 degrees, then adding the solution a into the inner container, aging, reacting at a constant temperature of 100-120 ℃, cooling, taking out, scraping the surface with deep color on the carbon paper, washing with water, and drying to obtain carbon paper with regularly arranged nano linear Co (OH) F on the surface;
2) calcining the obtained carbon paper with regularly arranged nano linear Co (OH) F on the surface at 500-600 ℃ under the atmosphere protection condition, cooling, taking out, washing with water, and drying to obtain carbon paper with CoO attached to the surface;
3) placing the carbon paper with the CoO attached to the surface in a 2-methylimidazole solution, and soaking for more than or equal to 1h without heating to obtain the in-situ oriented arrangement one-dimensional structure ZIF-67; wherein the solvent of the 2-methylimidazole solution is a composition of water and more than one of methanol, ethanol, isopropanol and propanol.
In step 1) of the above method, the cobalt salt may specifically be Co (NO)3)2·6H2O、CoCl2·6H2O or CoSO4·7H2O; the filling degree of the solution a in the liner can control whether the obtained Co (OH) F is in a one-dimensional structure, and according to the test of the applicant, the preferable filling degree is 70-90%; the aging time is the same as that of the prior art, and is usually more than or equal to 10min, preferably 20-30 min; the reaction time is preferably controlled to be 8 to 14 hours. In the step, the carbon paper is treated by the conventional pretreatment process (such as concentrated nitric acid ultrasound, water washing, acetone ultrasound, water washing, ethanol ultrasound and water washing). The size of the carbon paper can be cut according to needs, and is generally cut into a specification of 2.35cm × 1cm (length × width). Considering from the angle of fully utilizing reaction equipment to improve efficiency, 2 or even more carbon papers can be placed in the same inner container, and at the moment, it needs to be ensured that one end of each carbon paper can be in contact with the bottom end face of the inner container, and included angles formed by each carbon paper and the bottom end face of the inner container are 30-60 degrees, and meanwhile, orthographic projections of the carbon papers are perpendicular to each other.
In step 2) of the above process, the calcination is usually carried out in N2Or other inert gases (such as argon) are used for protection, and the calcination time is preferably controlled to be 1-3 h.
In step 3) of the above method, in the composition of the solvent of the 2-methylimidazole solution, the volume ratio of water therein is 50%, and when two or more kinds of alcohols are selected, the total volume thereof accounts for 50% of the solvent. The concentration of the 2-methylimidazole solution is 100-200 g/L, and preferably 150-200 g/L. The carbon paper with the CoO attached to the surface is soaked in 2-methylimidazole for 5-10 hours preferably, and the soaking is preferably carried out at the temperature of 20-25 ℃.
In the method, the hydrothermal reaction kettle is a hydrothermal reaction kettle which is conventionally used in the hydrothermal reaction in the prior art, and the inner container of the hydrothermal reaction kettle is preferably a polytetrafluoroethylene inner container.
The invention also comprises the in-situ oriented arrangement one-dimensional structure ZIF-67 prepared by the method.
Compared with the prior art, the invention is characterized in that:
1. the CoOHF is formed in the solution, and the molar ratio of cobalt salt, urea and ammonium fluoride is determined and the filling rate of the liner solution is adjusted, so that the CoOHF with a one-dimensional structure is obtained.
2. The morphology and size of the resulting CoO product are controlled by calcination under atmospheric conditions.
3. The method is carried out under the condition of no heating, the reaction condition is mild and easy to control, no energy consumption is needed, the cost is low, and the industrialization is easy.
4. The self-template sacrificial method can be popularized and applied to the preparation of functional materials.
Drawings
FIG. 1 is an SEM image of CoOHF prepared in example 1 of the present invention;
FIG. 2 is an SEM image of CoOHF prepared in example 2 of the present invention;
FIG. 3 is an SEM image of CoOHF prepared in example 3 of the present invention;
FIG. 4 shows Co obtained in example 4 of the present invention3O4SEM picture of (1);
FIG. 5 is an SEM photograph of a one-dimensional structure ZIF-67 obtained in example 5 of the present invention;
FIG. 6 is an XRD pattern of one-dimensional structure ZIF-67 prepared in example 5 of the present invention.
Detailed Description
The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.
The carbon paper used in the following examples was carbon paper treated as follows: cutting the carbon paper into a specification of 2.35cm multiplied by 1cm (length multiplied by width), placing the cut carbon paper in a beaker, adding concentrated nitric acid for immersion, carrying out ultrasonic treatment for 30min, and washing with deionized water; then adding acetone for immersion, performing ultrasonic treatment for 15min, and washing with deionized water; then adding ethanol for immersion, performing ultrasonic treatment for 15min, and washing with deionized water; adding deionized water, immersing, performing ultrasonic treatment for 15min, and washing with deionized water; finally, the paper is placed in an oven at 60 ℃ and dried for 10min, and the carbon paper which can be directly applied to the following examples is obtained.
Example 1
Weighing raw Co (NO)3)2·6H2O (4mmol), Urea (Urea, 5mmol), NH4F (6mmol) is put into a 50mL beaker, 20mL of deionized water is added, and the mixture is stirred for 10 minutes on a constant-temperature magnetic stirrer to obtain a solution a; inserting a piece of carbon paper into the polytetrafluoroethylene inner carrier transversely and obliquely, and then inserting a piece of carbon paper in the same way, wherein one end of each piece of carbon paper is in contact with the bottom end face of the inner container, the included angle formed by each piece of carbon paper and the bottom end face of the inner container is 30 degrees, and the orthographic projections of the two pieces of carbon paper are perpendicular to each other; measuring 18mL of solution a, adding the solution a into a polytetrafluoroethylene inner container (at the moment, the filling degree of the solution a is 72%), standing and aging for 30min, placing the inner container into a hydrothermal reaction kettle, sealing, transferring the reaction kettle into an oven, heating to 120 ℃ for constant-temperature reaction for 12h, cooling to room temperature, taking out, slightly scraping one side with dark color (namely one side with thicker thickness) by using a knife, repeatedly washing by using deionized water, and drying to obtain the CoOHF, wherein the SEM image of the obtained CoOHF is shown in figure 1. As can be seen from fig. 1, the obtained CoOHF was nanosheet-shaped, and it was found that no nano-wire-shaped structure of CoOHF was obtained under these conditions.
Example 2
Weighing raw Co (NO)3)2·6H2O(4mmol)、Urea(10mmol)、NH4F (6mmol) is put into a 50mL beaker, 20mL deionized water is added, and the mixture is stirred for 10 minutes on a constant temperature magnetic stirrer to obtain a solution a; inserting a piece of carbon paper into the polytetrafluoroethylene inner carrier transversely and obliquely, and then inserting a piece of carbon paper in the same way, wherein one end of each piece of carbon paper is in contact with the bottom end face of the inner container, the included angle formed by each piece of carbon paper and the bottom end face of the inner container is 30 degrees, and the orthographic projections of the two pieces of carbon paper are perpendicular to each other; measuring 18mL of solution a, adding the solution a into a polytetrafluoroethylene inner container (the filling degree of the solution a is 72 percent at the moment), standing and aging for 30min, placing the inner container into a hydrothermal reaction kettle, sealing, transferring the reaction kettle into an oven, heating to 120 ℃, reacting at a constant temperature for 12h, cooling to room temperature, taking out, slightly scraping one side with dark color (namely one side with thicker thickness) by using a knife, repeatedly washing by using deionized water, and drying to obtain the polytetrafluoroethylene inner containerThe SEM image of CoOHF is shown in FIG. 2. As can be seen from fig. 2, the resulting CoOHF is a nano-hexagon. Comparing FIGS. 1 and 2, urea and NH were observed4The change of F content affects the structure of CoOHF, and further affects the product morphology.
Example 3
Weighing raw Co (NO)3)2·6H2O(4mmol)、Urea(5mmol)、NH4F (2mmol) is put into a 50mL beaker, 20mL of deionized water is added, and the mixture is stirred for 10 minutes on a constant temperature magnetic stirrer to obtain a solution a; inserting a piece of carbon paper into the polytetrafluoroethylene inner carrier transversely and obliquely, and then inserting a piece of carbon paper in the same way, wherein one end of each piece of carbon paper is in contact with the bottom end face of the inner container, the included angle formed by each piece of carbon paper and the bottom end face of the inner container is 30 degrees, and the orthographic projections of the two pieces of carbon paper are perpendicular to each other; measuring 18mL of the solution a, adding the solution a into a polytetrafluoroethylene inner container (at the moment, the filling degree of the solution a is 72%), standing and aging for 30min, placing the inner container into a hydrothermal reaction kettle, sealing, transferring the reaction kettle into an oven, heating to 120 ℃ for constant-temperature reaction for 12h, cooling to room temperature, taking out, slightly scraping one side with dark color (namely one side with thicker thickness) by using a knife, repeatedly washing by using deionized water, and drying to obtain the CoOHF, wherein an SEM image of the obtained CoOHF is shown in figure 3. As shown in FIG. 3, the Co (OH) F obtained in this example is a nanowire-like Co (OH) F with regular arrangement of one-dimensional structures.
Example 4
Placing the carbon paper with regularly arranged nano-wire Co (OH) F on the surface, which is obtained in the embodiment 3, in a clean porcelain boat, then placing in a tube furnace, heating to 600 ℃ in the air atmosphere (the heating rate is 2 ℃/min), calcining at constant temperature and high temperature for 2h, cooling to room temperature, taking out, washing with deionized water, and drying to obtain the calcined carbon paper with CoO attached to the surface; weighing 1.6400g of 2-methylimidazole in a 25mL small beaker, and adding 5mL of deionized water and 5mL of ethanol to obtain a 2-methylimidazole solution; putting the calcined carbon paper with the CoO attached to the surface into a 2-methylimidazole solution, and soaking at room temperature for 10 hours to obtain the nanowire-shaped Co3O4The SEM image is shown in FIG. 4. Under this condition, a one-dimensional ZIF-67 structure was not obtained.
Example 5
Example 4 was repeated except that the calcination was carried out under argon protection.
Fig. 5 shows an SEM image of the final product obtained in this example, and as can be seen from fig. 5, the product obtained in this example is an in-situ oriented one-dimensional structure ZIF-67, and an XRD image thereof is shown in fig. 6.
Example 6
1) Weighing raw material CoCl2·6H2O(4mmol)、Urea(5mmol)、NH4F (2mmol) is put into a 50mL beaker, 20mL of deionized water is added, and the mixture is stirred for 10 minutes on a constant temperature magnetic stirrer to obtain a solution a; inserting a piece of carbon paper into the polytetrafluoroethylene inner carrier transversely and obliquely, and then inserting a piece of carbon paper in the same way, wherein one end of each piece of carbon paper is in contact with the bottom end face of the inner container, the included angle formed by each piece of carbon paper and the bottom end face of the inner container is 60 degrees, and the orthographic projections of the two pieces of carbon paper are perpendicular to each other; measuring 18mL of solution a, adding the solution a into a polytetrafluoroethylene inner container (the filling degree of the solution a is 80 percent at the moment), standing and aging for 90min, placing the inner container into a hydrothermal reaction kettle, sealing, transferring the reaction kettle into an oven, heating to 100 ℃, reacting at a constant temperature for 14h, cooling to room temperature, taking out, slightly scraping one side with dark color (namely one side with thicker thickness) by using a knife, repeatedly washing by using deionized water, and drying to obtain carbon paper with a one-dimensional structure and regularly arranged nano linear Co (OH) F on the surface;
2) calcining the obtained carbon paper with the nano-wire Co (OH) F with the regularly arranged surface one-dimensional structure at 500 ℃ for 3h under the protection of helium, cooling, taking out, washing with water, and drying to obtain carbon paper with CoO attached to the surface;
3) the carbon paper with the CoO attached to the surface was placed in a 2-methylimidazole solution (solvent: water and methanol as 1: 1) is soaked for 8 hours without heating, and the in-situ oriented one-dimensional structure ZIF-67 is obtained.
Example 7
1) Weighing raw material CoSO4·7H2O(4mmol)、Urea(5mmol)、NH4F (2mmol) is put into a 50mL beaker, 20mL of deionized water is added, and the mixture is stirred for 10 minutes on a constant temperature magnetic stirrer to obtain a solution a; a piece of carbon paper is transversely and obliquely insertedPutting the carbon paper into the polytetrafluoroethylene inner carrier, and inserting a piece of carbon paper in the same way, wherein one end of each piece of carbon paper is in contact with the bottom end face of the inner container, the included angle formed by each piece of carbon paper and the bottom end face of the inner container is 50 degrees, and the orthographic projections of the two pieces of carbon paper are mutually vertical; measuring 18mL of solution a, adding the solution a into a polytetrafluoroethylene inner container (the filling degree of the solution a is 90 percent at the moment), standing and aging for 60min, placing the inner container into a hydrothermal reaction kettle, sealing, transferring the reaction kettle into an oven, heating to 140 ℃, reacting at a constant temperature for 8h, cooling to room temperature, taking out, slightly scraping one side with dark color (namely one side with thicker thickness) by using a knife, repeatedly washing by using deionized water, and drying to obtain carbon paper with regularly arranged nanowire Co (OH) F in a one-dimensional structure on the surface;
2) calcining the obtained carbon paper with the nano-wire Co (OH) F with the regularly arranged surface one-dimensional structure at 550 ℃ for 1h under the protection of helium, cooling, taking out, washing with water, and drying to obtain carbon paper with CoO attached to the surface;
3) the carbon paper with the CoO attached to the surface was placed in a 2-methylimidazole solution (solvent: water and propanol as 1: 1) is soaked for 5 hours without heating, and the in-situ oriented one-dimensional structure ZIF-67 is obtained.
Claims (8)
1. The preparation method of the in-situ oriented arrangement one-dimensional structure ZIF-67 comprises the following steps:
1) dissolving cobalt salt, urea and ammonium fluoride in water, controlling the concentrations of the cobalt salt, the urea and the ammonium fluoride in the obtained solution to be 4mol/L, 5mol/L and 0.2mol/L respectively, and uniformly mixing to obtain a solution a; placing carbon paper in an inner container of a hydrothermal reaction kettle, ensuring that one end of the carbon paper is in contact with the bottom end face of the inner container and the included angle formed by the carbon paper and the bottom end face of the inner container is controlled to be 30-60 degrees, then adding a solution a into the inner container, controlling the filling degree of the solution a in the inner container to be 70-90 percent, performing constant-temperature reaction at 100-120 ℃ after aging, cooling, taking out, scraping the surface with the color depth on the carbon paper, washing with water, and drying to obtain the carbon paper with regularly arranged nano linear Co (OH) F on the surface;
2) calcining the obtained carbon paper with regularly arranged nano linear Co (OH) F on the surface at 500-600 ℃ under the atmosphere protection condition, cooling, taking out, washing with water, and drying to obtain carbon paper with CoO attached to the surface;
3) placing the carbon paper with the CoO attached to the surface in a 2-methylimidazole solution, and soaking for more than or equal to 1h without heating to obtain the in-situ oriented arrangement one-dimensional structure ZIF-67; wherein the solvent of the 2-methylimidazole solution is a composition of water and more than one of methanol, ethanol, isopropanol and propanol.
2. The method of claim 1, wherein: in the step 1), the reaction time is 8-14 h.
3. The method of claim 1, wherein: in the step 1), the cobalt salt is Co (NO)3)2·6H2O、CoCl2·6H2O or CoSO4·7H2O。
4. The method of claim 1, wherein: in the step 2), the calcining time is 1-3 h.
5. The method of claim 1, wherein: in the step 3), soaking for 5-10 hours.
6. The method of claim 1, wherein: in the step 3), the volume ratio of water in the solvent of the 2-methylimidazole solution is 50%.
7. The method of claim 1, wherein: in the step 3), the concentration of the 2-methylimidazole solution is 100-200 g/L.
8. An in-situ oriented one-dimensional structure ZIF-67 prepared by the method of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910105466.0A CN109880112B (en) | 2019-02-01 | 2019-02-01 | In-situ oriented arrangement one-dimensional structure ZIF-67 and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910105466.0A CN109880112B (en) | 2019-02-01 | 2019-02-01 | In-situ oriented arrangement one-dimensional structure ZIF-67 and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109880112A CN109880112A (en) | 2019-06-14 |
| CN109880112B true CN109880112B (en) | 2021-07-16 |
Family
ID=66927936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910105466.0A Expired - Fee Related CN109880112B (en) | 2019-02-01 | 2019-02-01 | In-situ oriented arrangement one-dimensional structure ZIF-67 and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109880112B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110690434B (en) * | 2019-10-17 | 2021-05-25 | 安徽大学 | beta-MnO2@Co3O4Composite material and preparation method and application thereof |
| CN114160162B (en) * | 2021-12-29 | 2024-01-05 | 天津工业大学 | Au/Co (OH) 2 Layered metal hydroxide hollow structure photocatalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108346522A (en) * | 2018-03-28 | 2018-07-31 | 安徽师范大学 | A kind of cobaltosic oxide hierarchical structure nano-array material, preparation method and applications |
| CN108500292A (en) * | 2018-04-08 | 2018-09-07 | 合肥学院 | A kind of preparation method of chain-like metal Ni nanopowders |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8110173B2 (en) * | 2009-09-05 | 2012-02-07 | Bahari Molla Mahaleh Yaser | Fabrication of NIO nanoparticles and chip-like nanoflakes by solvothermal technique |
-
2019
- 2019-02-01 CN CN201910105466.0A patent/CN109880112B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108346522A (en) * | 2018-03-28 | 2018-07-31 | 安徽师范大学 | A kind of cobaltosic oxide hierarchical structure nano-array material, preparation method and applications |
| CN108500292A (en) * | 2018-04-08 | 2018-09-07 | 合肥学院 | A kind of preparation method of chain-like metal Ni nanopowders |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109880112A (en) | 2019-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109956463B (en) | Carbon nano tube and preparation method thereof | |
| US7485488B2 (en) | Biomimetic approach to low-cost fabrication of complex nanostructures of metal oxides by natural oxidation at low-temperature | |
| Karizi et al. | Ultrasound-assisted synthesis of nano-structured 3D zinc (II) metal–organic polymer: Precursor for the fabrication of ZnO nano-structure | |
| CN107312181B (en) | Method for rapidly preparing Cu-BTC | |
| CN107459029A (en) | A kind of nitrogen/metal atom doped hollow polyhedral nano-sized carbon shell material and preparation method | |
| CN109880112B (en) | In-situ oriented arrangement one-dimensional structure ZIF-67 and preparation method thereof | |
| CN111533124A (en) | Two-dimensional nitrogen-doped nano porous carbon material and preparation method thereof | |
| CN110270333A (en) | A kind of bimetallic organic frame nano flower and its derivative and preparation method and application | |
| CN113121838B (en) | Method for preparing MOF/carbon composite material with assistance of atomic layer deposition, obtained product and application | |
| CN113087016A (en) | Preparation method of rod-shaped bismuth sulfide/reduced graphene oxide composite material | |
| CN111013659A (en) | Graphene-doped cobalt-based metal organic framework composite material, and preparation method and application thereof | |
| CN113501552A (en) | MOFs-derived hollow polyhedrons Co3S4And preparation method and application thereof | |
| Zhang et al. | MOF-5 decorated hierarchical ZnO nanorod arrays and its photoluminescence | |
| CN113292105A (en) | Carbon and nitrogen coated Fe0.4Co0.6S2Preparation method and application of @ NC hollow nano box | |
| CN112063183A (en) | Three-dimensional ordered structure with semiconductor and MOF framework space complementary, and preparation method and application thereof | |
| Seifpanah Sowmehesaraee et al. | The effect of Zn (II) containing metal-organic frameworks on perovskite solar cells | |
| CN103212721B (en) | Method for synthesizing copper nanowire under catalysis of nickel ions | |
| Ding et al. | Ultrathin defective nanosheet subunit ZnIn2S4 hollow nanoflowers for efficient photocatalytic hydrogen evolution | |
| CN113289501B (en) | Preparation method of nano porous carbon ceramic membrane nanofiltration composite membrane | |
| CN110639521A (en) | Preparation method of iron oxide dodecahedral nanocrystal catalyst with exposed high-index surface | |
| Shi et al. | Thermochemical transformation in the single-step synthesis of zeolitic imidazole frameworks under solvent-free conditions | |
| Sowmehsaraee et al. | Incorporating MOF-235 in lead iodide perovskite solar cell and investigating its efficiency and stability | |
| CN114260027A (en) | Method for preparing metal oxide @ metal organic framework core-shell material | |
| CN109487243B (en) | Two-dimensional noble metal material and preparation method thereof | |
| CN111662705A (en) | Method for improving stability of perovskite |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210716 Termination date: 20220201 |