CN112058236B - 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
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- 239000010931 gold Substances 0.000 title claims abstract description 66
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 63
- 239000004005 microsphere Substances 0.000 title claims abstract description 51
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 41
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title abstract description 30
- 238000011084 recovery Methods 0.000 title abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 7
- -1 gold ions Chemical class 0.000 claims abstract description 40
- 238000001179 sorption measurement Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 22
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 22
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 22
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 17
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- LDSUEKXPKCHROT-UHFFFAOYSA-N cyclopenta-1,3-diene-1-carboxylic acid;iron(2+) Chemical compound [Fe+2].OC(=O)C1=CC=C[CH-]1.OC(=O)C1=CC=C[CH-]1 LDSUEKXPKCHROT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000004729 solvothermal method Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000002244 precipitate Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
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- 238000005485 electric heating Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 5
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 26
- 229910001453 nickel ion Inorganic materials 0.000 description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 7
- 229910001431 copper ion Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
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- 230000002378 acidificating effect Effects 0.000 description 2
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- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 229910001922 gold oxide Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
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- 238000010998 test method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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]
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- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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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 result is used as an efficient adsorbent for selective adsorption reduction of gold ions in wastewater containing various metal ions, the recovery efficiency is better 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, 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 realized. 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)The microsphere material FMOF-Co is prepared by taking polyvinylpyrrolidone (PVP) as a surfactant and adopting a solvothermal method as a metal node and a ligand.
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
The three included angles of the unit cell are respectively 90.00 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 (7)
1. The application of the ferrocenyl metal-organic framework microsphere is characterized in that: selective adsorption and reduction of gold ions in a solution containing the gold ions; the ferrocenyl metal-organic framework microsphere uses cobalt nitrate Co (NO)3)2And 1, 1' -ferrocene dicarboxylic acid 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;
the structural formula of the microsphere material is [ Co ]2(FDC)(OH)2]n(ii) a Wherein, is composed of Co2(FDC)(OH)2And (2) forming asymmetric units, wherein each asymmetric unit comprises two cobalt ions, one FDC ligand and one hydroxyl ligand, and the FDC is 1, 1' -ferrocene dicarboxylic acid.
2. The use of ferrocenyl metal-organic framework microspheres according to claim 1, wherein: the material is monoclinic system, C2/M space group and has the volume of 599.63A 3; the length, width and height of the unit cell are 28.719A, 3.329A and 6.272A respectively, and the three included angles of the unit cell are 90.00 degrees, 97.52 degrees and 90.00 degrees respectively.
3. Use of a ferrocenyl metal-organic framework microsphere according to any one of claims 1-2, wherein the ferrocenyl metal-organic framework microsphere is prepared by: 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.
4. The use of ferrocenyl metal-organic framework microspheres according to claim 3, wherein: the surfactant and the solvent are PVP and N, N-dimethylformamide respectively, and the molecular weight of the surfactant PVP is 58000 MW.
5. The application of the ferrocenyl metal-organic framework microsphere as claimed in claim 4, 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.
6. The use of ferrocenyl metal-organic framework microspheres according to claim 1, wherein the selective adsorption reduction of gold ions is performed in a solution containing a plurality of metal ions.
7. The use of claim 1, 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.
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