CN115193416B - Preparation method and application of rapid high-selectivity gold extraction adsorbent of bionic magnetotactic bacteria - Google Patents

Preparation method and application of rapid high-selectivity gold extraction adsorbent of bionic magnetotactic bacteria Download PDF

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CN115193416B
CN115193416B CN202210529976.2A CN202210529976A CN115193416B CN 115193416 B CN115193416 B CN 115193416B CN 202210529976 A CN202210529976 A CN 202210529976A CN 115193416 B CN115193416 B CN 115193416B
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CN115193416A (en
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李�浩
潘阳
张玉婷
潘建明
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Jiangsu University
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    • 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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28009—Magnetic properties
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    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • C22B11/042—Recovery of noble metals from waste materials
    • C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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    • Y02P10/20—Recycling

Abstract

The invention belongs to the technical field of preparation of adsorption separation functional materials, and relates to preparation and application of a rapid high-selectivity gold extraction adsorbent for bionic magnetotactic bacteria. The invention prepares the magnetic core nano chain of the bionic magnetotactic bacteria by utilizing magnetic induction assembly and hydrolytic condensation of a silicon precursor, utilizes a silane coupling agent to modify double bonds on the surface of the magnetic core nano chain, and adopts a distillation precipitation technology core in the later stage, prepares the composite adsorbent with controllable monomer load by precisely controlling the amount of a distilled solvent, and is used for rapid selective enrichment and recovery of gold in electronic waste liquid. Meanwhile, allyl thiourea is selected as a functional monomer based on the Pirson soft and hard acid alkali theory and the coordination principle, so that the gold ion high-selectivity adsorption separation is realized. The adsorbent prepared by the invention has the advantages of novel structure, controllable size, simple preparation process, low cost, high mass transfer efficiency, large adsorption capacity, easy recovery and stable regeneration performance.

Description

Preparation method and application of rapid high-selectivity gold extraction adsorbent of bionic magnetotactic bacteria
Technical Field
The invention belongs to the technical field of preparation of adsorption separation functional materials, and relates to a preparation method and application of a rapid high-selectivity gold extraction adsorbent for bionic magnetotactic bacteria.
Background
Gold is one of the earliest metals found and has unique physicochemical properties in addition to its original monetary function and its present ornamental value. Gold is now widely used in the high-tech fields of catalysis, electronics and electricity, communications, aerospace, chemical engineering, and medical industry. In recent years, along with the rapid increase of gold demands, the exploitation scale of gold ores is continuously enlarged, a great amount of waste of resources and extreme expansion of wastes are inevitably caused, and serious environmental pollution is brought to harm human health. It is counted that each ton of waste mobile phones without batteries contains more than 270 g of gold, which is far higher than the first grade gold concentrate with the gold content of not less than 100 g per ton. Therefore, the establishment of a green and efficient gold-extracting new method with independent intellectual property rights has important significance.
Currently, technologies for recovering gold from aqueous solutions include adsorption, chemical precipitation, solvent extraction, ion exchange, and the like. Among them, the adsorption method is considered to be a promising adsorption method because of its advantages of simple operation, high cost effectiveness, environmental friendliness, strong capacity, and the like, and has received a great deal of attention in recent years. The micro-nano material has the characteristics of large specific surface area, small size effect, rich adsorption sites and the like, and is widely applied to the field of adsorption separation. Some common nanomaterials such as molecular sieves, carbon nanotubes, metal-organic framework materials, etc. face lengthy post-treatment processes such as centrifugation or filtration that require instrumentation and a lot of time and energy, and conventional adsorbents still require additional mechanical agitation, etc. during the adsorption separation process to increase mass transfer efficiency. Therefore, the design and development of the novel nano adsorbent which is easy to recycle and self-agitate has important significance in the aspects of improving mass transfer efficiency and accelerating adsorption rate.
The magnetic ferroferric oxide serving as a magnetically responsive material has good biocompatibility, stability and low cytotoxicity, and is widely applied to the fields of biology, medicine, materials and the like at present. Inspired by magnetotactic bacteria which can stir or move under the action of an external magnetic field, the magnetic nano particles are directionally assembled into one-dimensional nano chains under the induction action of the external magnetic field. The magnetic anisotropy can enable the adsorbent to be self-stirred or moved, accelerate the mixing process, improve the mass transfer efficiency in the adsorption process, and effectively solve the problem that the adsorbent is difficult to recycle. In addition, since the magnetic component is exposed to the outside, it is easily oxidized or corroded by the environment, and the surface functional group is small, and it is difficult to design functionally. Therefore, through the design of the core-shell structure, the silicon layer is coated on the surface of the core-shell structure by utilizing the hydrolytic condensation of the silicon precursor, so that the directional design of the material function can be realized, and the magnetic core can be absolutely protected from the corrosion of strong acid and alkali environments.
The specific surface area, morphology and structure of the adsorbent and the surface monomer loading determine the adsorption performance of the adsorbent. The traditional polymerization method has the defects of irregular shape, poor dispersity, complex operation and long reaction time.
When grafting of thermally responsive polymers or their various copolymers onto different matrix materials is involved, the choice of polymerization technique becomes critical, and both the chosen polymerization process and quantitative grafting have a significant impact on the properties of the modified polymer grafted particles. The distillation precipitation polymerization method is an emerging technology combining relatively simple precipitation polymerization and free radical polymerization reaction, can be well combined with various materials, realizes the control of the loading amount of monomers by precisely controlling the amount of distilled solvent, and can prepare the high-crosslinking monodisperse material with easily controlled size.
In the recovery process of noble metal gold, other interference ions such as Ni (II), cr (III), co (II), zn (II), al (II), cu (II) and the like exist, so that the selection of functional monomers with specific selectivity to gold fittings for preparing gold adsorbents is an important problem.
Disclosure of Invention
In order to solve the problems that gold adsorbents are not easy to collect, the adsorption rate is low and the like in the prior art, the invention provides a preparation method of a rapid high-selectivity gold extraction adsorbent (MCSR-ATU) of bionic magnetotactic bacteria, and the rapid high-selectivity gold extraction adsorbent is used for rapid selective gold enrichment in electronic waste liquid.
Firstly, synthesizing ferroferric oxide nano particles with the particle size of about 150nm by a hydrothermal method, then using ethanol as a solvent, catalyzing tetraethyl orthosilicate (TEOS) by ammonia water to carry out hydrolytic condensation to form a compact silicon dioxide layer, and constructing a magnetotactic bacteria-like structure nano chain based on magnetic induction assembly. And then the surface of the compact silicon layer is modified by 3- (methacryloyloxy) propyl trimethoxysilane (MPS). Finally, a functional monomer Allylthiourea (ATU) and carbon-carbon double bonds on the surface of a silicon layer are copolymerized and modified to the surface of the material by a distillation precipitation polymerization method, and the amount of the distilled solvent is precisely controlled to obtain a series of magnetic core-shell type stirring chain adsorbents with different monomer loading amounts, and a series of researches on the gold adsorption performance of the magnetic core-shell type stirring chain adsorbents are carried out.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of a rapid high-selectivity gold extraction adsorbent of bionic magnetotactic bacteria comprises the following steps:
(1) Magnetic base material ferroferric oxide nanoparticles (Fe 3 O 4 NPs) are prepared
Ferric trichloride hexahydrate (FeCl) 3 ·6H 2 O) into ethylene glycol, followed by sequential addition of sodium citrate (Na 3 Cit) and sodium acetate (NaAc), after mixing well, sonicated until an orange-yellow clear solution is formed. Transferring the mixture into a hydrothermal reaction kettle, reacting at a certain temperature for a period of time, naturally cooling to room temperature, centrifuging, washing with deionized water and ethanol for several times to remove residual reagent, and collecting solid (Fe 3 O 4 NPs) were placed in a vacuum oven and dried for use.
(2) Preparation of bionic magnetotactic bacterial Structure (MCSR)
Proper amount of Fe prepared in the step (1) 3 O 4 NPs are placed in a three-neck flask, then a proper amount of absolute ethyl alcohol is added, after ultrasonic dispersion, the mixture is placed in a water bath with a certain temperature, a proper amount of ammonia water is added, mechanical stirring is carried out for a certain period of time at a certain rotating speed, then the rotating speed is reduced to a certain value, a proper amount of tetraethyl orthosilicate (TEOS) is added for reacting for a period of time, the mixture is placed right above a bar magnet with a certain central magnetic field strength and stagnates for a period of time, then the mixture is slowly placed in a stationary place for standing for a period of time, then the mixture is separated by the magnet, residual reagent is removed by washing with deionized water and ethanol for a plurality of times, and the obtained solid (MCSR) is placed in a vacuum oven for drying for standby.
(3) Preparation of gold-extracting adsorbent (MCSR-ATU) of bionic magnetotactic bacteria
1) Placing a proper amount of the MCSR prepared in the step (2) into a round bottom flask, adding a proper amount of absolute ethyl alcohol and deionized water, sequentially adding a proper amount of ammonia water and 3- (methacryloyloxy) propyl trimethoxy silane (MPS) under the condition of stirring at a certain temperature after ultrasonic dispersion, reacting for a period of time, naturally cooling to room temperature, separating by a magnet, washing with deionized water and ethanol for several times to remove residual reagents, and drying the obtained solid (MCSR-MPS) in a vacuum oven for later use.
2) Dispersing the product MCSR-MPS obtained in the step 1) in a proper amount of acetonitrile, sequentially adding a proper amount of Allylthiourea (ATU), N' -Methylene Bisacrylamide (MBA) and Azodiisobutyronitrile (AIBN) after ultrasonic dispersion, placing the mixture in an oil bath with a certain initial temperature to start distillation precipitation polymerization reaction, steaming out a certain amount of acetonitrile within a certain time, naturally cooling to room temperature, separating by a magnet, washing with deionized water and ethanol for several times to remove residual reagents, and placing the obtained solid (MCSR-ATU) in a vacuum oven for drying for standby.
Preferably, in step (1), the FeCl 3 ·6H 2 O, glycol and Na 3 The dosage ratio of Cit to NaAc is 1.6-4.8g:50-150mL:0.6-1.8g:2.8-8.4g, the reaction temperature is 180-220 ℃ and the reaction time is 9-12h.
Preferably, in step (2), the Fe 3 O 4 The NPs dosage is 25-75mg, the proper amount of absolute ethyl alcohol dosage is 30-90mL, the reaction temperature is 25-35 ℃, the dosage of ammonia water is 1.7-4.8mL, the initial mechanical stirring rotation speed is 600-900rpm, the reaction time is 15-25min, the rotation speed after reduction is 200-400rpm, the TEOS dosage is 0.15-0.5mL, the reaction time is 10-20min, the magnetic field intensity of the bar magnet center is about 7.6mT, the dead time is 80-150s, and the standing reaction time is 8-15h.
Preferably, in step (3), 1), the ratio of MCSR, MPS and aqueous ammonia is 50mg:0.2mL:1.5mL, the dosage ratio of absolute ethanol to deionized water is 40mL:10mL, the reaction temperature is 60-80 ℃, the stirring rotation speed is 600-800rpm, and the reaction time is 22-26h.
Preferably, in step (3), 2), the amount of MCSR-MPS, acetonitrile, ATU, MBA and AIBN is 50mg:40mL:125-135mg:50mg:6mg.
Preferably, in step (3), 2), the distillation precipitation polymerization reaction time is 25-35min, the initial oil bath temperature of the distillation precipitation polymerization reaction is 105-115 ℃, and the oil bath temperature after the distillation precipitation polymerization reaction is 125-135 ℃.
The fast high-selectivity gold extraction adsorbent of the bionic magnetotactic bacteria is used for adsorbing and extracting gold ions in a solution.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares the gold-extracting adsorbent of the bionic magnetotactic bacteria with high selectivity and rapid mass transfer efficiency based on the magnetic induction assembly and distillation precipitation polymerization technology. (1) The chain structure of the MCSR-ATU has magnetic anisotropy, can realize rapid enrichment of gold ions by self-stirring under the action of an external magnetic field, strengthen the mass transfer efficiency of adsorption separation, reach 74.67% of the maximum adsorption capacity within 1min, reach adsorption balance within 30min, and reach 217.97mg g of maximum adsorption capacity -1 The method comprises the steps of carrying out a first treatment on the surface of the (2) The separation of the MCSR-ATU from the solution can be easily realized only by a magnet, and time and labor consuming operations such as centrifugation are not needed. (3) The MCSR-ATU has high selective adsorption performance on gold ions in a sample solution with coexisting multiple interference ions, and the adsorption performance is not obviously reduced after four times of circulation, so that the rapid selective enrichment of gold ions can be realized, and the MCSR-ATU can be used for enriching gold in electronic waste liquid.
Drawings
FIG. 1 is a schematic diagram of the preparation flow of a bionic magnetotactic bacteria structure (MCSR-ATU) in example 1.
FIG. 2 is an SEM and TEM image of the material of example 1 at each stage, wherein a and b are SEM and TEM images of the magnetotactic bacteria structure (MCSR) simulated in step (2), respectively; c. d is SEM and TEM images of gold-extracted adsorbent (MCSR-ATU) of the bionic magnetotactic bacteria of step (3).
FIG. 3 is an infrared spectrum of the product of step (2) in example 1, the product of step (3) in MCSR-MPS and the product of step (3) in MCSR-ATU.
FIG. 4 is a graphical representation of the results of the amount of acetonitrile distilled and the amount adsorbed in example 4.
FIG. 5 is the product Fe in step (1) of example 1 3 O 4 Hysteresis loop test analysis plot of NPs and final product MNSR-MPS of step (3) 2).
Fig. 6 is a pH result display of example 5.
FIG. 7 is a graphical representation of the results of adsorption kinetics experiments in example 6.
FIG. 8 is a graphical representation of the results of equilibrium adsorption experiments in example 7.
FIG. 9 is a graph showing the results of experiments on the regeneration performance of the MCSR-ATU of example 8.
FIG. 10 is a graph showing the competitive adsorption performance of the MCSR-ATU of example 9 on gold ions in the presence of various ions.
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto.
FIG. 1 is a schematic diagram of the preparation flow of a bionic magnetotactic bacteria structure (MCSR-ATU) in example 1.
Example 1:
(1) Magnetic base material ferroferric oxide nanoparticles (Fe 3 O 4 NPs) are prepared
3.2g of ferric trichloride hexahydrate (FeCl) 3 ·6H 2 O) was added to 100mL of ethylene glycol followed by the sequential addition of 1.2g sodium citrate (Na 3 Cit) and 5.6g sodium acetate (NaAc), after mixing well, sonicated for 1h until an orange-yellow clear solution was formed. Transferring the mixture into a hydrothermal reaction kettle, reacting at 200deg.C for 10 hr, naturally cooling to room temperature, centrifuging, washing with deionized water and ethanol for several times to remove residual reagent, and collecting solid (Fe 3 O 4 NPs) were placed in a vacuum oven and dried for use.
(2) Preparation of magnetotactic bacterial Structure (MCSR)
50mg of Fe prepared in step (1) 3 O 4 NPs are placed in a 100mL three-neck flask, 60mL of absolute ethyl alcohol is added, after ultrasonic dispersion, the three-neck flask is placed in a water bath at 30 ℃, 3.4mL of ammonia water is added, mechanical stirring is performed at 700rpm for 20min, then the speed is reduced to 300rpm, 0.3mL of tetraethyl orthosilicate (TEOS) is added to react for 15min, the three-neck flask is placed right above a bar magnet with the central magnetic field strength of about 7.6mT and stagnated for 100s, then the three-neck flask is slowly placed in a stationary place for 12h, then the three-neck flask is separated by the magnet, residual reagent is removed by washing with deionized water and ethanol for several times, and the obtained solid (MCSR) is placed in a vacuum oven for drying for standby.
(3) Preparation of magnetotactic bacterium gold adsorbent (MCSR-ATU)
1) 100mg of the MCSR prepared in the step (2) is placed in a 100mL round bottom flask, 40mL of absolute ethyl alcohol and 10mL of deionized water are added, 1.5mL of ammonia water and 0.2mL of 3- (methacryloyloxy) propyl trimethoxysilane (MPS) are sequentially added under the condition of 800rpm at 70 ℃ after ultrasonic dispersion, reaction is carried out for 24 hours, after natural cooling to room temperature, the reaction product is separated by a magnet, residual reagents are removed by washing with deionized water and ethanol for several times, and the obtained solid (MCSR-MPS) is placed in a vacuum oven for drying for standby.
2) 50mg of the product MCSR-MPS obtained in 1) is dispersed in 40mL of acetonitrile by ultrasonic, 130mg of Allylthiourea (ATU), 50mg of N, N' -Methylenebisacrylamide (MBA) and 6mg of Azobisisobutyronitrile (AIBN) are sequentially added, the ultrasonic dispersion is carried out again and placed in an oil bath with an initial temperature of 115 ℃ to start distillation precipitation polymerization, the temperature of the oil bath is gradually increased to 130 ℃ and the amount of acetonitrile is distilled off to 25mL in 30min, the mixture is naturally cooled to room temperature and separated by a magnet, residual reagent is removed by washing with deionized water and ethanol for several times, and the obtained solid (MCSR-ATU) is placed in a vacuum oven to be dried for standby.
FIG. 2 SEM and TEM images of the materials of example 1 at various stages, wherein a and b are SEM and TEM images of the magnetotactic bacterial structure (MCSR) simulated in step (2), respectively, and the chain structure and the thickness of the silicon layer can be clearly seen; c. d is SEM and TEM images of the gold-extracted adsorbent (MCSR-ATU) of the bionic magnetotactic bacteria of step (3), and the monomer polymer layer can be clearly seen.
FIG. 3 is an infrared spectrum of the product of step (2) in example 1, the product of step (3) MCSR-MPS and the product of step (3) 2) MCSR-ATU, showing the successful modification of MPS and the successful grafting of the monomer ATU by the change of functional groups.
FIG. 5 is the product Fe in step (1) of example 1 3 O 4 Hysteresis loop test analysis of NPs and MNSR-MPS as final product of step (3) 2), it can be seen that both the material before and after modification has stronger paramagnetic properties (maximum magnetization before modification: 66.54emu g -1 After modification: 18.31emu g -1 ) It was confirmed that it can be driven by an externally applied magnetic fieldAnd magnetic separation.
Example 2:
(1) Magnetic base material ferroferric oxide nanoparticles (Fe 3 O 4 NPs) are prepared
1.6g of ferric trichloride hexahydrate (FeCl) 3 ·6H 2 O) was added to 50mL of ethylene glycol followed by the sequential addition of 0.6g sodium citrate (Na 3 Cit) and 2.8g sodium acetate (NaAc), after mixing well, sonicated for 1h until an orange-yellow clear solution was formed. Transferring the mixture into a hydrothermal reaction kettle, reacting at 200deg.C for 12 hr, naturally cooling to room temperature, centrifuging, washing with deionized water and ethanol for several times to remove residual reagent, and collecting solid (Fe 3 O 4 NPs) were placed in a vacuum oven and dried for use.
(2) Preparation of magnetotactic bacterial Structure (MCSR)
40mg of Fe prepared in step (1) 3 O 4 NPs are placed in a 100mL three-neck flask, 50mL of absolute ethyl alcohol is added, after ultrasonic dispersion, the three-neck flask is placed in a water bath at 25 ℃, 2.8mL of ammonia water is added, mechanical stirring is carried out for 25min at 600rpm, then the speed is reduced to 200rpm, 0.25mL of tetraethyl orthosilicate (TEOS) is added for reaction for 15min, the three-neck flask is placed right above a bar magnet with the central magnetic field strength of about 7.6mT and stagnated for 90s, then the three-neck flask is slowly placed in a stationary place for standing for 15h, then the three-neck flask is separated by the magnet, residual reagent is removed by washing with deionized water and ethanol for several times, and the obtained solid (MCSR) is placed in a vacuum oven for drying for standby.
(3) Preparation of gold-extracting adsorbent (MCSR-ATU) of bionic magnetotactic bacteria
1) 50mg of the MCSR prepared in the step (2) is placed in a 100mL round bottom flask, 40mL of absolute ethyl alcohol and 10mL of deionized water are added, 1.5mL of ammonia water and 0.2mL of 3- (methacryloyloxy) propyl trimethoxysilane (MPS) are sequentially added at the temperature of 60 ℃ and the speed of 600rpm after ultrasonic dispersion, reaction is carried out for 20 hours, after natural cooling to room temperature, the reaction product is separated by a magnet, residual reagents are removed by washing with deionized water and ethanol for several times, and the obtained solid (MCSR-MPS) is placed in a vacuum oven for drying for standby.
2) 50mg of the product MCSR-MPS obtained in 1) is dispersed in 40mL of acetonitrile by ultrasonic, 125mg of Allylthiourea (ATU), 50mg of N, N' -Methylenebisacrylamide (MBA) and 6mg of Azobisisobutyronitrile (AIBN) are sequentially added, the ultrasonic dispersion is carried out again, the distillation precipitation polymerization is started in an oil bath with an initial temperature of 110 ℃, the temperature of the oil bath is gradually increased to 128 ℃ and the amount of acetonitrile is distilled off to 30mL in 25min, the mixture is naturally cooled to room temperature, the mixture is separated by a magnet, residual reagent is removed by washing with deionized water and ethanol for several times, and the obtained solid (MCSR-ATU) is dried in a vacuum oven for standby.
Example 3:
(1) Magnetic base material ferroferric oxide nanoparticles (Fe 3 O 4 NPs) are prepared
0.65g of ferric trichloride hexahydrate (FeCl) 3 ·6H 2 O) was added to 50mL of ethylene glycol followed by the sequential addition of 0.3g sodium citrate (Na 3 Cit) and 1.4g sodium acetate (NaAc), after mixing well, sonicated for 1h until an orange-yellow clear solution was formed. Transferring the mixture into a hydrothermal reaction kettle, reacting at 220 ℃ for 10 hours, naturally cooling to room temperature, centrifuging, washing with deionized water and ethanol for several times to remove residual reagent, and obtaining solid (Fe 3 O 4 NPs) were placed in a vacuum oven and dried for use.
(2) Preparation of bionic magnetotactic bacterial Structure (MCSR)
25mg of Fe prepared in step (1) 3 O 4 NPs are placed in a 100mL three-neck flask, 30mL of absolute ethyl alcohol is added, after ultrasonic dispersion, the three-neck flask is placed in a water bath at 35 ℃, 1.7mL of ammonia water is added, the three-neck flask is mechanically stirred at 800rpm for 15min, then the three-neck flask is reduced to 400rpm, 0.2mL of tetraethyl orthosilicate (TEOS) is added for reaction for 10min, the three-neck flask is placed right above a bar magnet with the central magnetic field strength of about 7.6mT and stagnated for 120s, then the three-neck flask is slowly placed in a stationary place for standing for 10h, then the three-neck flask is separated by the magnet, residual reagent is removed by washing with deionized water and ethanol for several times, and the obtained solid (MCSR) is placed in a vacuum oven for drying for standby.
(3) Preparation of gold-extracting adsorbent (MCSR-ATU) for bionic magnetotactic bacteria
1) 50mg of the MCSR prepared in the step (2) is placed in a 100mL round bottom flask, 40mL of absolute ethyl alcohol and 10mL of deionized water are added, 1.5mL of ammonia water and 0.2mL of 3- (methacryloyloxy) propyl trimethoxysilane (MPS) are sequentially added under the condition of 700rpm at 80 ℃ after ultrasonic dispersion, reaction is carried out for 26 hours, after natural cooling to room temperature, the reaction product is separated by a magnet, residual reagents are removed by washing with deionized water and ethanol for several times, and the obtained solid (MCSR-MPS) is placed in a vacuum oven for drying for standby.
2) 50mg of the product MCSR-MPS obtained in 1) is dispersed in 40mL of acetonitrile by ultrasonic, 135mg of Allylthiourea (ATU), 50mg of N, N' -Methylenebisacrylamide (MBA) and 6mg of Azobisisobutyronitrile (AIBN) are sequentially added, the ultrasonic dispersion is carried out again and placed in an oil bath with an initial temperature of 105 ℃ to start distillation precipitation polymerization, the temperature of the oil bath is gradually raised to 125 ℃ and the amount of acetonitrile is distilled off to 15mL within 20min, the mixture is naturally cooled to room temperature and separated by a magnet, residual reagent is removed by washing with deionized water and ethanol for several times, and the obtained solid (MCSR-ATU) is placed in a vacuum oven to be dried for standby.
Example 4: influence of the Loading amount of the functional monomer on the gold ion adsorption capacity
(1) 50mg of the product MCSR-MPS obtained in 1) in example 1 (3) was accurately weighed and dispersed in 40mL of acetonitrile by ultrasonic, then 130mg of Allylthiourea (ATU), 50mg of N, N' -Methylenebisacrylamide (MBA) and 6mg of Azobisisobutyronitrile (AIBN) were sequentially added, the mixture was again subjected to ultrasonic dispersion and placed in an oil bath with an initial temperature of 110 ℃ to begin distillation precipitation polymerization, different amounts of acetonitrile (5, 10, 15, 20, 25, 30 mL) were distilled off respectively in 30min after gradually increasing the temperature of the oil bath to 130 ℃, naturally cooled to room temperature and separated by a magnet, residual reagents were removed by washing with deionized water and ethanol several times, and the obtained adsorbent (MCSR-ATU) with six different monomer loadings was placed in a vacuum oven to be dried for later use.
(2) And (3) accurately weighing six adsorbents with different monomer loadings, namely MCSR-ATU, prepared in the step (1), respectively adding the adsorbents into 4mL of gold ion solution with pH=3 and concentration of 150mg/L, placing the gold ion solution on a magnetic stirrer at 20 ℃, keeping the temperature at 1000rpm for 1h, separating by a magnet, collecting the solution, detecting the concentration of residual gold ions in a sample solution through an inductively coupled plasma emission spectrometer (ICP) after the solution is subjected to film passing, and performing three groups of parallel experiments.
FIG. 4 is a graph showing the results of the amount of acetonitrile distilled off and the adsorption amount in example 4, and it can be seen that the adsorption amount was maximum when 25mL of acetonitrile was distilled off.
Example 5: influence of the pH of the sample solution on the gold ion adsorption capacity
6 parts of 4mg of the MCSR-ATU prepared under the conditions described in example 1 were accurately weighed, added into 4mL of gold ion solutions with pH values of 1,2,3,4,5 and 6 and concentrations of 150mg/L respectively, placed on a magnetic stirrer at 20 ℃ and kept at 1000rpm for 1 hour, then subjected to magnet separation, and after the solution was collected and passed through a membrane, the concentration of the remaining gold ions was detected by an inductively coupled plasma emission spectrometer (ICP), and three groups of experiments were performed in parallel.
FIG. 6 is a pH display of example 5, showing that the adsorption of the MCSR-ATU is maximum to 147.28mg in an environment of pH 3 -1 。
Example 6: influence of time on gold ion adsorption Capacity
8 parts of 4mg of the MCSR-ATU prepared under the conditions described in example 1 were accurately weighed, added to 4mL of gold ion solution with a concentration of 150mg/L and a pH value of 3, placed on a magnetic stirrer at 20 ℃ and kept at 1,5, 10, 20, 30, 46, 60 and 120min respectively, separated by a magnet after the solution was collected and the concentration of the remaining gold ions was detected by an inductively coupled plasma emission spectrometer (ICP) after the solution was subjected to film coating, and three groups of experiments were performed in parallel.
Fig. 7 shows the adsorption kinetics experiment result of example 6, and can show that the MCSR-ATU can realize rapid enrichment of gold ions under the action of an external magnetic field, and can reach 74.67% of the maximum adsorption capacity within 1min and reach adsorption equilibrium within 30 min.
Example 7: influence of initial gold ion concentration in sample on adsorption Capacity
Accurately weighing 7 parts of 4mg of the MCSR-ATU prepared under the conditions described in example 1, respectively adding into 4mL of gold ion solution (pH=3) with the concentration of 50, 100, 150, 200, 300, 400 and 500mg/L in sequence, placing on a magnetic stirrer at 20 ℃, keeping at 1000rpm for 1 hour, separating by a magnet, and collecting an adsorption liquid; the operations at 30℃and 40℃are the same as those at 20 ℃. After film coating, the concentration of the residual gold ions was detected by inductively coupled plasma emission spectrometry (ICP), and three groups of experiments were performed in parallel.
FIG. 8 is a graph showing the equilibrium adsorption test results of example 7, showing that the adsorption capacity of the MCSR-ATU gradually increases with increasing initial concentration of gold ions, up to 217.97mg g -1 And the fitting result of the adsorption data is more in line with the Langmuir model.
Example 8: investigation of the regeneration Properties of the adsorbent
Accurately weighing 4mg of the MCSR-ATU prepared under the condition of the example 1, adding 4mL of gold ion solution with the concentration of 150mg/L and the pH value of 3, placing on a magnetic stirrer at 20 ℃, keeping for 1h at 1000rpm, separating by a magnet, washing the solution by deionized water, adding 4mL of eluent consisting of 1mol/L thiourea and 0.1mol/L hydrochloric acid, continuously placing on the magnetic stirrer, keeping for 1h at 1000rpm, separating by the magnet, washing the solution by deionized water, performing four cycles in total, detecting by an inductively coupled plasma emission spectrometer (ICP) after the adsorption solution and the desorption solution pass through a membrane, and performing three groups of parallel experiments.
FIG. 9 shows the regeneration performance test results of the MCSR-ATU in example 8, and shows that the adsorption performance of the MCSR-ATU is not obviously reduced after 4 cycles, and the MCSR-ATU has better stability and durability.
Example 9: influence of multiple interfering ions in a sample on gold ion selective adsorption performance
4mg of the MCSR-ATU prepared under the conditions described in example 1 was accurately weighed, 4mL of simulated electron waste liquid (pH=3) containing Au (III), al (III), co (II), cr (III), cu (II), mn (II), na (I), ni (II) and Zn (II) was added, the mixture was placed on a magnetic stirrer at 25 ℃ and kept at 1000rpm for 1 hour, then the mixture was separated by a magnet, the adsorption liquid was collected, and after passing through the membrane, the concentration of each remaining ion was detected by an inductively coupled plasma emission spectrometer (ICP), and three groups of experiments were made in parallel.
FIG. 10 is a graph showing the competitive adsorption performance of the MCSR-ATU of example 9 on gold ions in the presence of various ions, resulting inIndicating that the adsorption amount of gold ions by the MCSR-ATU (49.877 mg g -1 The adsorption rate is 99.76 percent), which is obviously higher than other ions, thus showing that the gold ion has high selectivity.

Claims (9)

1. A preparation method of a rapid high-selectivity gold extraction adsorbent of bionic magnetotactic bacteria is characterized by comprising the following steps:
(1) Magnetic base material ferroferric oxide nano particle Fe 3 O 4 Preparation of NPs
Ferric trichloride hexahydrate FeCl 3 ·6H 2 O is added into glycol, and then sodium citrate Na is added in turn 3 Mixing Cit and sodium acetate NaAc, performing ultrasonic treatment until orange transparent solution is formed, transferring the mixture into a hydrothermal reaction kettle, reacting for a period of time at a certain temperature, naturally cooling to room temperature, centrifuging, washing with deionized water and ethanol for several times to remove residual reagent, and obtaining solid Fe 3 O 4 Drying NPs in a vacuum oven for standby;
(2) Preparation of bionic magnetotactic bacteria structure MCSR
Proper amount of Fe prepared in the step (1) 3 O 4 NPs are placed in a three-neck flask, then a proper amount of absolute ethyl alcohol is added, after ultrasonic dispersion, the mixture is placed in a water bath with a certain temperature, a proper amount of ammonia water is added, mechanical stirring is carried out for a certain period of time at a certain rotating speed, then the rotating speed is reduced to a certain value, a proper amount of tetraethyl orthosilicate TEOS is added for reacting for a period of time, the mixture is placed right above a bar magnet with a certain central magnetic field strength and is stopped for a period of time, then the mixture is slowly placed in a stationary place for standing for a period of time, then the mixture is separated by the magnet, residual reagent is removed by washing with deionized water and ethanol for a plurality of times, and the obtained solid MCSR is placed in a vacuum oven for drying for standby;
(3) Preparation of gold-extracting adsorbent MCSR-ATU of bionic magnetotactic bacteria
1) Placing a proper amount of the MCSR prepared in the step (2) into a round bottom flask, then adding a proper amount of absolute ethyl alcohol and deionized water, sequentially adding a proper amount of ammonia water and 3- (methacryloyloxy) propyl trimethoxy silane (MPS) under the condition of stirring at a certain temperature after ultrasonic dispersion, reacting for a period of time, naturally cooling to room temperature, separating by a magnet, washing with deionized water and ethanol for several times to remove residual reagents, and placing the obtained solid MCSR-MPS into a vacuum oven for drying for later use;
2) Dispersing the product MCSR-MPS obtained in the step 1) in a proper amount of acetonitrile by ultrasonic, sequentially adding a proper amount of allylthiourea ATU, N' -methylene bisacrylamide MBA and azobisisobutyronitrile AIBN, carrying out ultrasonic dispersion, placing in an oil bath with a certain initial temperature to start distillation precipitation polymerization reaction, evaporating a certain amount of acetonitrile within a certain time, naturally cooling to room temperature, separating by a magnet, washing with deionized water and ethanol for a plurality of times to remove residual reagents, and placing the obtained solid MCSR-ATU in a vacuum oven for drying for standby.
2. The method for preparing the rapid high-selectivity gold-extracting adsorbent of the bionic magnetotactic bacteria according to claim 1, wherein in the step (3), the dosage ratio of the MCSR, the MPS and the ammonia water is 50mg:0.2mL:1.5mL.
3. The method for preparing the rapid high-selectivity gold-extracting adsorbent of the bionic magnetotactic bacteria according to claim 1, wherein in the step (3), the dosage ratio of the absolute ethyl alcohol to the deionized water is 40mL:10mL.
4. The method for preparing a rapid high-selectivity gold-extracting adsorbent of a bionic magnetotactic bacterium according to claim 1, wherein in the step (3), the reaction temperature is 60-80 ℃, the stirring speed is 600-800rpm, and the reaction time is 22-26h.
5. The method for preparing a rapid high selectivity gold extraction adsorbent of a bionic magnetotactic bacterium according to claim 1, wherein the amount ratio of MCSR-MPS, acetonitrile, ATU, MBA and AIBN in 2) in step (3) is 50mg:40mL:125-135mg:50mg:6mg.
6. The method for preparing a rapid high-selectivity gold-extracting adsorbent of a bionic magnetotactic bacterium according to claim 1, wherein in the step (3) 2), the distillation precipitation polymerization reaction time is 25-35min.
7. The method for preparing a rapid highly selective gold adsorbent by using a bionic magnetotactic bacterium according to claim 1, wherein the initial oil bath temperature of the distillative precipitation polymerization reaction in the step (3) 2) is 105-115 ℃.
8. The method for preparing a rapid high-selectivity gold-extracting adsorbent of a bionic magnetotactic bacterium according to claim 1, wherein in the step (3) 2), the oil bath temperature after the distillation precipitation polymerization reaction is 125-135 ℃.
9. Use of a fast high selectivity gold extraction adsorbent of a biomimetic magnetotactic bacterium prepared by the preparation method of any one of claims 1 to 8 for adsorption extraction of gold ions in solution.
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