CN112058236A - Preparation of ferrocenyl metal-organic framework microspheres and application of ferrocenyl metal-organic framework microspheres in gold recovery - Google Patents
Preparation of ferrocenyl metal-organic framework microspheres and application of ferrocenyl metal-organic framework microspheres in gold recovery Download PDFInfo
- Publication number
- CN112058236A CN112058236A CN202010905467.6A CN202010905467A CN112058236A CN 112058236 A CN112058236 A CN 112058236A CN 202010905467 A CN202010905467 A CN 202010905467A CN 112058236 A CN112058236 A CN 112058236A
- Authority
- CN
- China
- Prior art keywords
- organic framework
- metal
- gold
- ions
- ferrocenyl
- 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
Images
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention discloses a preparation method of ferrocenyl metal-organic framework microspheres and application of gold recovery. Using cobalt nitrate Co (NO)3)2And 1, 1' -ferrocene dicarboxylic acid are respectively used as a metal node and a ligand, polyvinylpyrrolidone is used as a surfactant, and the microsphere material is prepared by a solvothermal method. The product results as a high efficiencyThe adsorbent is applied to selective adsorption reduction of gold ions in wastewater containing various metal ions, and has better recovery efficiency in wastewater with different concentrations of gold ions and other metal ions, the recovery efficiency of gold can reach 1800mg/g, and the selectivity exceeds 99%.
Description
Technical Field
The invention belongs to the technical field of resource recovery, and relates to a metal organic framework material and application thereof, in particular to preparation and application of a ferrocenyl metal organic framework (FMOF-Co).
Background
Gold is an extremely important precious metal resource, and has remarkable significance in the aspects of material processing and strategic storage, while the acquisition of gold resources still mainly depends on mineral collection and output, as the gold-rich ore is gradually exploited to be exhausted, the gold content of the ore in the existing ore is continuously reduced, the exploitation and processing cost of high-purity gold is continuously increased, and the gold needs to be acquired from other ways to meet the requirement of the gold resources in various fields. Gold has good ductility and electrical conductivity, and is widely applied to various precision instrument elements, but the recovery of gold from waste elements after the service life of the elements is over still has a small challenge. The recovery means widely adopted at present is gradual reduction after acid washing, metal substances after preliminary separation are dissolved by using strong acid such as aqua regia in advance to obtain acid liquor containing different metal ions, while in the composition of various elements, the content of copper and nickel is far higher than that of gold, and the content of other metals is dozens to hundreds of times of that of gold, so that when a reducing agent is added to gradually reduce non-active metals, the dosage of the reducing agent and the reduction condition need to be strictly regulated, otherwise, a large amount of base metals can be introduced, and the purity of the finally collected gold is insufficient. Therefore, in the large-scale gold recovery industry, there is a very urgent need for a material having strong selective adsorption or reduction of gold ions in acidic wastewater.
As a porous material which is widely concerned in recent years, the metal organic framework has higher specific surface area and porosity, better stability and a structure which is easy to modify and adjust, and has stronger application prospect in the fields of catalysis, separation, energy and biology. By selecting different metal nodes and organic ligands and adjusting preparation conditions, the surface of the metal organic framework can have different charges, and in acid solution containing different metal ions, the gold ions are replaced by [ Au (Cl) ]4]-The negative ions exist in the form of negative ions, and other metals exist in the form of positive ions, so that the surface of the metal organic framework is provided with positive charges, and the efficient selective adsorption of gold ions can be realizedAnd (4) attaching. Meanwhile, the ligand of the metal organic framework can also use molecules with reducibility, such as ferrocene and derivatives thereof, and the divalent iron ions can be used as a reducing agent to realize in-situ reduction of gold ions adsorbed on the surface of the metal organic framework, and finally obtain a gold simple substance.
Disclosure of Invention
To solve the problems of the background art, the present invention is made by using cobalt nitrate (Co (NO)3)2And 1, 1' -ferrocene dicarboxylic acid (FDC) is used as a metal node and a ligand, a series of ferrocenyl metal organic framework microspheres (FMOF-Co) are prepared under the action of a surfactant polyvinylpyrrolidone (PVP), and the selective adsorption and reduction of gold ions in acid liquor containing different metal ions are realized by utilizing the electropositivity and the reducibility of ferrous iron in the ferrocene ligand.
The technical scheme adopted by the invention is as follows:
a ferrocenyl metal-organic framework microsphere comprises:
using cobalt nitrate Co (NO)3)2And 1, 1' -ferrocene dicarboxylic acid (FDC) are respectively used as a metal node and a ligand, polyvinylpyrrolidone (PVP) is used as a surfactant, and the microsphere material FMOF-Co is prepared by a solvothermal method.
The structural formula of the microsphere material is [ Co ]2(FDC)(OH)2]n(ii) a Wherein, is composed of Co2(FDC)(OH)2Asymmetric units are formed, each asymmetric unit comprising two cobalt ions, one FDC ligand and one hydroxyl ligand.
The microsphere material is macroscopically spherical, and the diameter of the whole microsphere is adjusted between 500-1000 nm by changing the reaction condition.
The material is monoclinic system, C2/M space group and has the volume of
(ii) a The length, width and height of the unit cell are respectively
Three angles of the unit cell90.00 degrees, 97.52 degrees and 90.00 degrees.
The preparation method of the ferrocenyl metal-organic framework microsphere comprises the following steps:
cobalt nitrate Co (NO)3)2And dissolving 1,1 '-ferrocene dicarboxylic acid in a solvent, adding a surfactant, wherein the molar ratio of cobalt nitrate to 1, 1' -ferrocene dicarboxylic acid to the surfactant is 1:1:10-30, carrying out closed reaction at the temperature of 125-150 ℃ for 12 hours, and after the reaction is finished, sequentially cooling, washing and drying to obtain the microsphere material.
The surfactant and the solvent are PVP and N, N-dimethylformamide respectively, and the molecular weight of the surfactant PVP is 58000 Mw.
The method specifically comprises the following steps:
(a) dissolving cobalt nitrate and FDC in N, N-dimethylformamide solution, adding PVP, and performing ultrasound at normal temperature for 30 minutes;
(b) transferring the solution into a polytetrafluoroethylene reaction tank, sealing, placing in an electric heating forced air drying oven, heating to 125 ℃ or 150 ℃ at the speed of 5 ℃/min, and reacting at constant temperature for 12 hours;
(c) after the reaction is finished, cooling to 25 ℃, centrifuging for 30 minutes at 3000r.p.m, taking the centrifuged yellow brown precipitate, washing the precipitate with N, N-dimethylformamide for three times, then washing the precipitate with deionized water for two times, and freeze-drying to obtain the ferrocenyl metal-organic framework microsphere.
In specific implementation, the cobalt nitrate and the FDC are used in the same amount, and the amount ratio of the cobalt nitrate to the solvent is 0.6 mmol/ml.
And thirdly, the application of the ferrocenyl metal-organic framework microspheres has the selective adsorption and reduction effects on gold ions in a solution containing the gold ions. And selective adsorption reduction of gold ions in a solution containing a plurality of metal ions.
Taking a solution to be detected, adjusting the pH value to 3-7, adding the microsphere material into the solution to be detected to enable the concentration of the microsphere material to be 0.05-0.5 mg/ml, continuously stirring for 8 hours at 30 ℃, realizing adsorption reduction of more than 95% of gold ions in the solution, and then carrying out centrifugal separation to obtain the gold-ferrocenyl metal organic framework microsphere mixed precipitate, wherein the adsorption capacity of the gold-ferrocenyl metal organic framework microsphere mixed precipitate on the gold ions is obviously higher than that of other ions.
In the reaction solution tested in the examples, the concentration of gold ion was 100ppm, the concentration of nickel ion was 100-.
The FMOF-Co in the invention can realize high-efficiency selective adsorption and partial reduction of gold ions, and in a single gold ion solution, when the pH value is 5, the adsorption and reduction capacity of the material to gold can reach 1950mg/g, and in other pH ranges of 3-7, the adsorption capacity to gold is 1300-1700 mg/g.
In the mixed solution containing different metal ions, when the concentrations of copper ions, nickel ions and gold ions are all 100ppm, the selective adsorption reduction of gold exceeding 95% can be realized, and the adsorption of copper ions and nickel ions is almost not carried out (< 2%). In the simulated acid liquid containing different metal ions, when the ion concentrations of gold ions, nickel ions and copper ions are respectively 100ppm, 3500ppm and 20000ppm, the adsorption reduction of more than 85% of gold ions can be realized, and the adsorption of copper ions and nickel ions is less than 3%, thus proving the selective adsorption reduction effect of the material on gold ions.
The invention adjusts the shape and the yield of the microsphere material by adjusting the addition amount of PVP (polyvinylpyrrolidone) and the reaction temperature of 125-150 ℃.
Specifically, for example, when the reaction temperature is 125 ℃ and the amount of PVP is 5 times the molar equivalent of cobalt nitrate, the particle size of the obtained ferrocenyl metal-organic framework microsphere is about 800nm, and when the amount of PVP is 10 times the molar equivalent of cobalt nitrate, the particle size of the obtained ferrocenyl metal-organic framework microsphere is about 1000nm, and the increase in the amount of PVP can slightly reduce the particle size of the obtained microsphere.
When the consumption of PVP is 10 times of the molar equivalent of cobalt nitrate, the particle size of the prepared ferrocenyl metal-organic framework microsphere is about 1000nm at the reaction temperature of 125 ℃, the particle size of the prepared ferrocenyl metal-organic framework microsphere is about 500nm at the reaction temperature of 150 ℃, the microsphere with smaller particle size can be obtained by increasing the reaction temperature, and the regulation and control of the shape and the size of the microsphere are realized.
The invention has the beneficial effects that:
the microsphere material provided by the invention can be prepared by a simple dissolution thermal method, and the appearance and yield of the product are controlled by changing the addition amount of the surface active agent PVP and the reaction temperature condition. The prepared microsphere has good yield and stability, and is suitable for mass production, preparation and storage.
The ferrocenyl metal-organic framework microsphere material has stronger selective adsorption effect on gold ions in an acidic aqueous solution, and the maximum adsorption capacity can reach 1950mg/g (pH is 5) in a single gold ion solution through calculation. In the mixed solution containing other metal ions such as copper ions and nickel ions, the selective adsorption of more than 85% of gold ions can be realized, and the adsorption rate of other metal ions is less than 3%.
In conclusion, the ferrocenyl metal-organic framework microsphere material FMOF-Co provided by the invention is used as an efficient adsorbent for selective adsorption and reduction of gold ions in wastewater containing multiple metal ions, and shows good recovery efficiency in wastewater with different gold ions and other metal ion concentrations, the recovery efficiency of gold can reach 1800mg/g, and the selectivity exceeds 99%.
Drawings
FIG. 1 is a scanning electron microscope image of ferrocenyl metal-organic framework microspheres prepared by the invention.
FIG. 2 is a scanning electron microscope image of the material prepared by the present invention after gold ion adsorption reduction.
Detailed Description
The present invention is described in more detail by the following examples, but the present invention is not limited thereto, and those skilled in the art can make various modifications and improvements without departing from the principle of the present invention, and these modifications and improvements are also considered to be within the scope of the present invention. Those not described in detail in this specification are within the skill of the art.
Example 1:
349mg of cobalt nitrate and 327mg of 1, 1' -ferrocenedicarboxylic acid are weighed in a polytetrafluoroethylene tank, 20 ml of N, N-dimethylformamide solution and 1330mg of PVP are added, and ultrasonic dispersion is carried out for 30 minutes to ensure that the cobalt nitrate and the PVP are completely dissolved. Then, the polytetrafluoroethylene tank containing the solution is sealed in a stainless steel reaction kettle, placed in an electric heating forced air drying oven, heated to 125 ℃ within 20 minutes, and then reacted for 12 hours at constant temperature.
After the reaction is finished, cooling the reaction solution to room temperature, centrifuging the reaction solution at 3000r.p.m for 30 minutes, taking the centrifuged tawny precipitate, washing the tawny precipitate for three times by using an N, N-dimethylformamide solution, then washing the tawny precipitate for two times by using deionized water, and freeze-drying the washed precipitate for 5 days to obtain the dry powder of the ferrocenyl metal-organic framework microsphere. The morphology of the material can be observed by a scanning electron microscope, as shown in fig. 1.
Test procedure 1 of example 1:
10 ml of an aqueous solution of gold ions at a concentration of 100ppm was prepared in a round-bottomed flask, the pH of the solution was adjusted to 5 using potassium hydroxide/hydrochloric acid, and the solution was dispersed uniformly by sonication for 5 minutes. Meanwhile, ferrocenyl metal organic framework microsphere suspension with the concentration of 1 mg/ml is prepared, after the suspension is evenly dispersed by ultrasonic treatment for 20 minutes, 0.5 ml of MOF dispersion liquid is taken by using a liquid transfer gun, added into the prepared gold ion solution, and magnetically stirred in a water bath at the temperature of 30 ℃ for 8 hours at the rotating speed of 400 r.p.m. And after the reaction is finished, centrifuging the reaction solution at the rotating speed of 3000r.p.m for 30 minutes, separating and precipitating, sampling the supernatant, performing ICP (inductively coupled plasma) test to obtain the concentration of the residual gold ions in the supernatant, and calculating to obtain the adsorption reduction capacity of the FMOF-Co to the gold ions.
The maximum adsorption capacity obtained under the conditions of this experimental example was about 1950 mg/g. Scanning electron microscope images of gold-FMOF-Co in the isolated precipitates are shown in fig. 2.
Test procedure 2 of example 1:
100 ml of aqueous solution with the gold ion concentration of 100ppm, the nickel ion concentration of 3500ppm and the copper ion concentration of 20000ppm is prepared in a round-bottom flask, the pH value of the solution is adjusted to 3 by using potassium hydroxide/hydrochloric acid, and the solution is uniformly dispersed by ultrasonic treatment for 5 minutes. Meanwhile, ferrocenyl metal organic framework microsphere suspension with the concentration of 1 mg/ml is prepared, after the suspension is evenly dispersed by ultrasonic treatment for 20 minutes, 5 ml of MOF dispersion liquid is absorbed by a liquid transfer gun, added into the prepared gold ion solution, and magnetically stirred in a water bath at the temperature of 30 ℃ for 2 hours at the rotating speed of 4000 r.p.m. After the reaction is finished, the reaction solution is centrifuged for 30 minutes at the rotating speed of 3000r.p.m, the precipitate is separated, the supernatant is sampled and subjected to ICP test, and the adsorption capacity and selectivity of FMOF-Co to the triple ions can be calculated according to the concentration of each ion remained in the supernatant.
The adsorption rates for gold, nickel and copper ions calculated in this experimental example were 85.0%, 2.9% and 2.5%, respectively.
Example 2
And collecting the gold/FMOF-Co precipitate obtained after adsorption, pyrolyzing the gold/FMOF-Co precipitate in the air at 800 ℃ for 2 hours to obtain a gold/iron oxide/cobalt oxide mixture, washing the gold/iron oxide/cobalt oxide mixture by using a nitric acid/aqueous acid solution with a volume ratio of 1:1, and centrifuging the washed gold/aqueous acid solution again to obtain a gold simple substance with higher purity, wherein the purity of the finally recovered gold is about 95% and the recovery rate is about 60% through tests.
Claims (9)
1. A ferrocenyl metal-organic framework microsphere is characterized in that: using cobalt nitrate Co (NO)3)2And 1, 1' -ferrocene dicarboxylic acid (FDC) are respectively used as a metal node and a ligand, polyvinylpyrrolidone (PVP) is used as a surfactant, and the microsphere material is prepared by a solvothermal method.
2. A ferrocenyl metal-organic framework microsphere according to claim 1, wherein:
the structural formula of the microsphere material is [ Co ]2(FDC)(OH)2]n(ii) a Wherein, is composed of Co2(FDC)(OH)2Asymmetric units are formed, each asymmetric unit comprising two cobalt ions, one FDC ligand and one hydroxyl ligand.
3. A ferrocenyl metal-organic framework microsphere according to claim 1, wherein:
the materialThe material is monoclinic system, C2/M space group and the volume is
The length, width and height of the unit cell are respectively
The three included angles of the unit cell are respectively 90.00 degrees, 97.52 degrees and 90.00 degrees.
4. A process for the preparation of ferrocenyl metal-organic framework microspheres as defined in any one of claims 1 to 3, comprising the steps of: cobalt nitrate Co (NO)3)2And dissolving 1,1 '-ferrocene dicarboxylic acid in a solvent, adding a surfactant, wherein the molar ratio of cobalt nitrate to 1, 1' -ferrocene dicarboxylic acid to the surfactant is 1:1:10-30, carrying out closed reaction at the temperature of 125-150 ℃ for 12 hours, and after the reaction is finished, sequentially cooling, washing and drying to obtain the microsphere material.
5. The method for preparing ferrocenyl metal-organic framework microspheres according to claim 4, wherein: the surfactant and the solvent are PVP and N, N-dimethylformamide respectively, and the molecular weight of the surfactant PVP is 58000 Mw.
6. The method for preparing ferrocenyl metal-organic framework microspheres according to claim 5, wherein the method specifically comprises the following steps:
(a) dissolving cobalt nitrate and FDC in N, N-dimethylformamide solution, adding PVP, and performing ultrasound at normal temperature for 30 minutes;
(b) transferring the solution into a polytetrafluoroethylene reaction tank, sealing, placing in an electric heating forced air drying oven, heating to 125 ℃ or 150 ℃ at the speed of 5 ℃/min, and reacting at constant temperature for 12 hours;
(c) after the reaction is finished, cooling to 25 ℃, centrifuging for 30 minutes at 3000r.p.m, taking the centrifuged yellow brown precipitate, washing the precipitate with N, N-dimethylformamide for three times, then washing the precipitate with deionized water for two times, and freeze-drying to obtain the ferrocenyl metal-organic framework microsphere.
7. Use of ferrocenyl metal-organic framework microspheres according to any one of claims 1 to 2, characterized by selective adsorption reduction of gold ions in a gold ion-containing solution.
8. The use of ferrocenyl metal-organic framework microspheres according to claim 7, wherein the selective adsorption reduction of gold ions is performed in a solution containing a plurality of metal ions.
9. The method of use of claim 7, wherein:
taking a solution to be detected, adjusting the pH value to 3-7, adding the microsphere material into the solution to be detected to enable the concentration of the microsphere material to be 0.05-0.5 mg/ml, continuously stirring for 8 hours at 30 ℃, realizing adsorption reduction of more than 95% of gold ions in the solution, and then carrying out centrifugal separation to obtain the mixed precipitate of the gold-ferrocenyl metal organic framework microspheres.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010905467.6A CN112058236B (en) | 2020-09-01 | 2020-09-01 | Preparation of ferrocenyl metal-organic framework microspheres and application of ferrocenyl metal-organic framework microspheres in gold recovery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010905467.6A CN112058236B (en) | 2020-09-01 | 2020-09-01 | Preparation of ferrocenyl metal-organic framework microspheres and application of ferrocenyl metal-organic framework microspheres in gold recovery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112058236A true CN112058236A (en) | 2020-12-11 |
| CN112058236B CN112058236B (en) | 2021-09-03 |
Family
ID=73664817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010905467.6A Active CN112058236B (en) | 2020-09-01 | 2020-09-01 | Preparation of ferrocenyl metal-organic framework microspheres and application of ferrocenyl metal-organic framework microspheres in gold recovery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112058236B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113368240A (en) * | 2021-06-13 | 2021-09-10 | 重庆医科大学 | Ferrocenyl metal-organic framework nanoparticle and preparation method thereof |
| CN114573825A (en) * | 2022-01-21 | 2022-06-03 | 浙江大学 | Ligand-exchanged hollow MIL-101 metal organic framework material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435813A (en) * | 2013-08-25 | 2013-12-11 | 浙江大学 | Coordination polymer microsphere and preparation method thereof and purpose thereof for hydrogen storage |
| CN104892518A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院大连化学物理研究所 | Preparation method and application of porous nano metal organic framework material |
| WO2019038645A1 (en) * | 2017-08-21 | 2019-02-28 | Ecole Polytechnique Federale De Lausanne (Epfl) | New composites for extraction of metal or contaminating chemical species |
| CN110483800A (en) * | 2019-09-07 | 2019-11-22 | 湖南理工学院 | A kind of preparation and its application of the metal-organic framework material containing S |
| CN110605098A (en) * | 2019-09-30 | 2019-12-24 | 江南大学 | Non-reversible covalent organic framework for efficiently and selectively recovering gold and preparation method thereof |
| CN111013659A (en) * | 2018-10-10 | 2020-04-17 | 中国科学院兰州化学物理研究所苏州研究院 | Graphene-doped cobalt-based metal organic framework composite material, and preparation method and application thereof |
| CN111234248A (en) * | 2020-01-20 | 2020-06-05 | 安徽师范大学 | Method for synthesizing size-adjustable metal complex microspheres from Schiff base and metal complex microspheres |
-
2020
- 2020-09-01 CN CN202010905467.6A patent/CN112058236B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435813A (en) * | 2013-08-25 | 2013-12-11 | 浙江大学 | Coordination polymer microsphere and preparation method thereof and purpose thereof for hydrogen storage |
| CN104892518A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院大连化学物理研究所 | Preparation method and application of porous nano metal organic framework material |
| WO2019038645A1 (en) * | 2017-08-21 | 2019-02-28 | Ecole Polytechnique Federale De Lausanne (Epfl) | New composites for extraction of metal or contaminating chemical species |
| CN111013659A (en) * | 2018-10-10 | 2020-04-17 | 中国科学院兰州化学物理研究所苏州研究院 | Graphene-doped cobalt-based metal organic framework composite material, and preparation method and application thereof |
| CN110483800A (en) * | 2019-09-07 | 2019-11-22 | 湖南理工学院 | A kind of preparation and its application of the metal-organic framework material containing S |
| CN110605098A (en) * | 2019-09-30 | 2019-12-24 | 江南大学 | Non-reversible covalent organic framework for efficiently and selectively recovering gold and preparation method thereof |
| CN111234248A (en) * | 2020-01-20 | 2020-06-05 | 安徽师范大学 | Method for synthesizing size-adjustable metal complex microspheres from Schiff base and metal complex microspheres |
Non-Patent Citations (4)
| Title |
|---|
| JIA HUO，ET AL.: "Synthesis, characterization and magnetic properties of hollow microspheres with micro-mesoporous shells assembled from cobalt-based ferrocenyl coordination polymers", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| RUOLI SUN,ET AL.: "Molecular Recognition and Sensing Based on Ferrocene Derivatives and Ferrocene-Based Polymers", 《ORGANOMETALLICS》 * |
| 乔庆东等: "《碳五烯烃的精细化工利用》", 31 January 2015, 沈阳：辽宁科学技术出版社 * |
| 霍甲等: "锰-二茂铁基配位聚合物微球的制备与表征", 《高分子学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113368240A (en) * | 2021-06-13 | 2021-09-10 | 重庆医科大学 | Ferrocenyl metal-organic framework nanoparticle and preparation method thereof |
| CN114573825A (en) * | 2022-01-21 | 2022-06-03 | 浙江大学 | Ligand-exchanged hollow MIL-101 metal organic framework material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112058236B (en) | 2021-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108786812B (en) | Porous carbon/nano bimetal oxide composite photocatalytic material with adsorption and catalysis functions and preparation method thereof | |
| CN112058236B (en) | Preparation of ferrocenyl metal-organic framework microspheres and application of ferrocenyl metal-organic framework microspheres in gold recovery | |
| CN109485085B (en) | A kind of preparation method of hollow octahedra cuprous oxide | |
| CN103193223A (en) | Controllable synthetic method of graphitized carbon spheres with hollow structure | |
| CN105798320A (en) | Method for preparing nanometer copper powder at low temperature | |
| CN104722276B (en) | A kind of melon ring/graphene oxide magnetic composite and preparation method thereof | |
| CN107899592B (en) | Magnetic recyclable flaky NiFe2O4Preparation method and application of/BiOI composite nano material | |
| CN109569548B (en) | Magnetic nano functional material for extracting uranium from seawater and preparation method thereof | |
| CN113368812B (en) | Co3O4Halloysite composite material, preparation method and application | |
| CN113477220A (en) | Noble metal ion adsorption material based on magnetic metal organic framework and preparation method thereof | |
| CN110931806A (en) | Carbon-supported noble metal alloy catalyst, and preparation method and application thereof | |
| CN109755485A (en) | A kind of SnO2/ graphene lithium ion battery cathode material preparation method | |
| CN107694563A (en) | Palladium carbon catalyst and its preparation method and application | |
| CN113275011A (en) | Preparation method of cuprous oxide photocatalyst with flower-ball-shaped multi-stage structure | |
| CN109876774B (en) | Adsorption material for treating dye sewage and preparation method thereof | |
| CN103570072A (en) | Trimanganese tetroxide preparation method and trimanganese tetroxide prepared therethrough | |
| CN105271443B (en) | Method for preparing flaky nano CoO or Co3O4 through assistant microwave heating | |
| CN112169771A (en) | Preparation method of magnetic molasses hydrothermal carbon-based heavy metal adsorbent | |
| CN106699550A (en) | Preparation method of nano Cu-CuBTC type metal organic framework material | |
| CN108183203A (en) | The preparation method of multilevel hierarchy molybdenum carbide/nitrogen-doped carbon complex microsphere electrode material | |
| CN109939740B (en) | Preparation method and application of gold nanoparticle-loaded two-dimensional nanosheet | |
| CN114984926B (en) | Preparation method of high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer | |
| CN108217754A (en) | A kind of Large ratio surface IrO2Preparation method | |
| CN115337964A (en) | Cobalt-iron modified ZIF-8 composite material and preparation method and application thereof | |
| CN105880624B (en) | A kind of method that spherical golden nanometer particle is synthesized using bacitracin as templating self-assembly |
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 |