CN114507786A - Method for assisting dissociation, concentration and in-situ monitoring of low-concentration rare and precious rare earth elements of supercapacitor by using quantum dots - Google Patents

Method for assisting dissociation, concentration and in-situ monitoring of low-concentration rare and precious rare earth elements of supercapacitor by using quantum dots Download PDF

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CN114507786A
CN114507786A CN202111657453.8A CN202111657453A CN114507786A CN 114507786 A CN114507786 A CN 114507786A CN 202111657453 A CN202111657453 A CN 202111657453A CN 114507786 A CN114507786 A CN 114507786A
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rare earth
rare
quantum dots
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super capacitor
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CN114507786B (en
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曹晏
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Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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    • 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
    • C22B59/00—Obtaining rare earth metals
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6402—Atomic fluorescence; Laser induced fluorescence
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a method for assisting dissociation and concentration of a supercapacitor and in-situ monitoring of low-concentration rare and precious rare earth elements by using quantum dots. The method comprises the following steps: putting mineral solid waste raw materials into a super capacitor, wherein the super capacitor comprises a cathode, an anode, an electrolyte and a mixed solution of quantum dots, when a stage capacitor is charged, an acidic water environment is generated, rare and noble rare earth element ions on the surface of the mineral solid waste raw materials are promoted to carry out ion exchange dissociation, the rare and noble rare earth element ions are transferred into the mixed solution to be combined with the quantum dots to form a quantum dot-rare and noble rare earth element aggregate, and the aggregate moves to the surface of the cathode to be further enriched under the action of an electric field of the super capacitor; when the super capacitor is operated reversely, the aggregate is separated from the surface of the cathode, and the aggregate separated from the cathode naturally settles in a solution environment, so that the rare and noble elements of the rare earth are concentrated. The invention constructs the working mechanism of the quantum dot auxiliary supercapacitor for rare earth and precious element ion migration, adsorption, enrichment and fluorescence emission.

Description

Method for assisting dissociation, concentration and in-situ monitoring of low-concentration rare and precious rare earth elements of supercapacitor by using quantum dots
Technical Field
The invention relates to the technical field of environmental protection and mining and metallurgy, in particular to a method for assisting dissociation and concentration of a supercapacitor and monitoring low-concentration rare and precious rare earth elements in situ by using quantum dots.
Background
The symbiotic companion of mineral products is the main reason of complex solid waste components, wherein rare and rare precious elements or technical key elements which have great significance to national economic development of China, particularly high technical fields, such as rare earth, lithium, cobalt, copper, gallium, germanium, indium and other nonferrous metal varieties, are not lacked, but the low concentration occurrence enables the mineral products to be abandoned by the existing mining and metallurgy process, so that high-value resources are lost along with the mining and metallurgy solid waste. Among them, rare earth elements are the general name of seventeen elements including lanthanide series, scandium and yttrium, and the development of many new industries is supported because of the reputation of 'industrial vitamins' obtained by the unique light, electricity and magnetism of the rare earth elements. Wherein, the rare earth accounting for 60 percent of the total consumption amount and 91 percent of the total value is used for permanent magnet materials (praseodymium, neodymium, terbium, dysprosium, holmium and the like) and catalysts (lanthanum, cerium, yttrium and the like); in other aspects, the material can also be used for laser, fluorescence, color display (terbium, europium and the like), ultrahigh temperature and giant magnetostrictive alloy (praseodymium, terbium, dysprosium, scandium and the like), batteries, sensing materials and the like.
China gradually forms the only country with the whole industrial chain of rare earth in the world, and occupies the first position in the world all the year around in the aspects of rare earth storage, production, smelting separation, consumption, export total amount and the like. However, rapid depletion has led to a rapid decline in rare earth occupancy in our world-wide proven reserves since 2000. The strategic, limited and non-renewable properties of rare earth resources have prompted China to implement protective rare earth limited production. In view of the important strategic position of rare earth resources influencing future development of the world, China needs to further maintain the leading position of rare earth storage, production and application of the world so as to maintain the strategic consideration of development needs and international supply of China. Due to the associated nature of minerals to a plurality of solid wastes and the fact that tailings contain a large amount of low-concentration rare earth resources, the technical problems to be solved are how to realize rapid secondary rare earth raw material detection general survey (>100 mug/g, ppm), efficient low-occurrence rare earth dissociation extraction and concentration, lower process energy consumption, avoidance of environmental hazards and the like.
The existing related industrialization technology can not avoid adopting acid leaching extraction, has large environment and energy consumption load, requires high existing rare and precious rare earth element raw materials (the concentration of solid waste rare earth elements is more than one hundred times of the order), and causes environmental pollution and ecological destruction to be industrial scaling. Other extraction methods include ionic liquid, ion exchange, solvent extraction, resin extraction, membrane separation and the like, are mostly in research and development states, have different requirements on the chemical state, structure and grade of an extraction object, and need to improve the extraction efficiency, energy efficiency and economy. The rare and precious rare earth elements have the problem of being concentrated due to the fact that the rare and precious rare earth elements are thin and challenging, at present, organic chelates are mainly relied on, and effective substitutes need to be found in consideration of the cost and the environmental influence.
Therefore, the extraction of high-value associated elements from the tailings or mining and metallurgy solid wastes can accelerate the promotion of the mineral and metallurgy industrial chain in China, has great significance for high-value resource supply and solid waste high-value utilization of rare and precious rare earth elements and the like, saves mining steps, and reduces the environmental pollution and ecological damage caused by the stacking of the solid wastes and the tailings related to the mining steps.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for assisting dissociation, concentration and in-situ monitoring of low-concentration rare earth and precious elements by using quantum dots for a supercapacitor, the method provided by the invention constructs an integrated technology of dissociation, concentration and in-situ analysis of the low-concentration rare earth and precious elements, and expands a new mechanism of quantum dot adsorption, electrochemical enhanced fluorescence spectrum analysis and supercapacitor electrolyte regulation; the method develops an integrated framework integration, solves the dissociation, concentration and in-situ analysis and discrimination of rare and precious elements of low-occurrence rare earth, develops a new separation engineering technology, and has innovative technical inspiration for the dissociation-enrichment-detection of all low-occurrence and high-value substances.
The technical scheme adopted by the invention is as follows:
the invention provides a method for assisting dissociation, concentration and in-situ monitoring of rare and precious rare earth elements in a supercapacitor by using quantum dots, which comprises the following steps: crushing mineral solid waste raw materials into powder, and putting the powder into a super capacitor, wherein the super capacitor comprises a cathode, an anode, and a mixed solution of electrolyte and quantum dots, when the super capacitor is charged, the super capacitor generates an acidic water environment to promote low-occurrence rare and precious rare earth element ions adsorbed on the surface of the mineral solid waste raw materials to perform ion exchange dissociation, the rare and precious rare earth element ions are transferred into the mixed solution to be combined with quantum dots to form a quantum dot-rare and precious earth element aggregate, and the aggregate moves to the surface of the cathode to be further enriched under the action of an electric field of the super capacitor; when the super capacitor is operated reversely, the aggregate is separated from the surface of the cathode, the electrode is regenerated, and the aggregate separated from the cathode naturally settles in a solution environment, so that the rare and noble elements of the rare earth are concentrated; according to the optical effect, the electrical effect and the magnetic effect of the quantum dot-rare earth and noble element, the in-situ analysis and discrimination and enrichment capacity of the rare earth and noble element are realized.
The quantum dot can be an excellent candidate material, has the advantages of nanoscale, controllable scale, low toxicity, easy synthesis and good dispersion in water, and can generate the rare earth and precious element adsorption and enrichment functions similar to a chelating agent by virtue of rich functional groups such as carbonyl, hydroxyl and the like on the surface, and is easy to agglomerate and separate to form rare earth enrichment and concentration; meanwhile, the quantum fluorescence characteristics of the quantum dots and the rare and noble rare earth elements enable the quantum dots and the rare and noble rare earth elements to be combined to generate excellent rare and noble rare earth element detection performance. The invention relates to a quantum chemistry, electrochemistry and optical spectrum analysis coupling cooperative mechanism for rare earth element set detection, which is used for constructing a supercapacitor framework technology integrating dissociation, concentration and in-situ analysis and discrimination of low-concentration rare earth, meets various application requirements of in-situ on-line detection of low-concentration rare earth elements, high-efficiency cleaning and low-energy consumption enrichment of low-concentration rare earth and the like, has higher economic and application values, and has innovative technical inspiration for dissociation-enrichment-detection of all low-concentration and high-value substances.
Preferably, the method specifically comprises the following steps:
(1) putting mineral solid waste raw materials into a super capacitor, and when the super capacitor is charged, increasing the concentration of hydrogen ions in electrolyte to improve the acidity of the electrolyte to form an acidic water environment; the rare-earth and precious element ions with low occurrence, which are adsorbed on the surface of the mineral solid waste raw material, are subjected to ion exchange dissociation, hydrogen ions are neutralized, and the rare-earth and precious element ions subjected to ion exchange dissociation enter an electrolyte solution to become free rare-earth and precious element ions; the quantum dots existing in the electrolyte of the super capacitor are combined with rare earth and precious element ions to form a quantum dot-rare earth and precious element aggregate, so that the dissociated rare earth and precious element ions are captured by the quantum dots and complete primary enrichment, and the aggregate moves to the surface of the cathode under the action of an electric field of the super capacitor to complete further enrichment of rare earth and precious elements;
(2) reversely operating the super capacitor to separate the aggregate from the surface of the cathode and regenerate the electrode; the quantum dot-rare earth and precious element aggregate separated from the cathode naturally settles in the electrolyte solution environment to complete a cycle of operation;
(3) according to the optical effect, the electrical effect and the magnetic effect of the quantum dot-rare earth and precious element, the in-situ analysis and discrimination of the rare earth and precious element and the dynamics and the enrichment capacity of the rare earth and precious element ion enrichment process are realized, and the in-situ acid dissociation, concentration and monitoring of the integrated low-concentration rare earth and precious element are realized.
The carbon point-rare earth and precious element aggregate separated from the cathode can be accelerated to settle in the electrolyte solution environment by adding a settling agent, and the settling agent can be any substance which can enable the pH value of the electrolyte solution to be 5-12, such as strong base, weak base and strong acid and weak base salt, and the like.
The optical effect comprises the combined use of detection means such as fluorescence spectrum, absorption spectrum, infrared spectrum, Raman spectrum, X-ray energy spectrum and the like; the electrical effect includes electrochemical spectrum, electrochemical impedance, electrochemical power generation and the like, and the magnetic effect includes magnetoresistance effect, magnetoluminescence and the like.
Due to the optical effect, the electrical effect and the magnetic effect of the quantum dot-rare earth and precious element, the system can also realize in-situ analysis and discrimination of rare earth and real-time tracking of rare earth ion enrichment process dynamics and enrichment capacity, finally realize in-situ acid dissociation, concentration and detection of the integrated low-concentration rare earth and precious element, and get rid of the dependence on a heavy ICP-MS offline detection technology.
Preferably, the solid waste raw material for mineral production in step (1) comprises coal-based solid waste and waste tailings, the coal-based solid waste is selected from one of fly ash, coal slurry and coal gangue, the waste tailings are selected from one of iron ore slag, phosphate rock, red mud and composite associated slag, and the content of rare and precious elements in the solid waste raw material for mineral production is 10-50000 mu g/g.
Preferably, the super capacitor is formed by immersing a cathode and an anode in a mixed solution of electrolyte and quantum dots, the proportion of the quantum dots to the electrolyte is that 1-1000 mg of the quantum dots are added in each gram of the electrolyte, and the anode and the cathode are made of metal oxide, metal sulfide, metal nitride or a compound of the metal oxide, the metal sulfide and the metal nitride; the pH value of the electrolyte solution is 0-7. The electrolyte is organic acid, inorganic acid, organic salt or inorganic salt.
Preferably, the anode material is a metal oxide or a metal sulfide, and the metal is at least one selected from iron, manganese, cobalt, nickel, magnesium, and zinc.
Further preferably, the anode material is selected from FeCo2O4、Ni Co2O4、ZnCo2O4、CoFeO4、Ni2S3And Co2S3One kind of (1). Further preferably, the anode material is a composite metal oxide, i.e., FeCo2O4@MnO2。
Preferably, the quantum dot material is a composite state quantum dot of carbon quantum dots, metal sulfur and metal nitrogen quantum dots and the quantum dots, and the particle size of the quantum dots is 1-50 nm; the carbon quantum dot is an aggregate of oxygen, sulfur, nitrogen and modified metal taking a carbon element as a core.
Further preferably, the carbon quantum dots are folic acid or multi-element nitrogen-phosphorus-sulfur doped semiconductor type carbon quantum dots.
Preferably, the charging energy of the super capacitor is supplied by renewable solar energy.
Preferably, the operating temperature of the supercapacitor is in the range of 5 ℃ to 300 ℃ and the pressure is in the range of 0.01 to 30 MPa.
Compared with the prior art, the invention has the advantages that:
(1) in theory, the invention fuses and applies the relevant theories of material chemistry, electrochemistry, thermodynamics, physical field and separation engineering; the working mechanism of the quantum dot auxiliary supercapacitor for rare earth and precious element ion migration, adsorption, enrichment and fluorescence emission can be constructed in a narrow sense, and the synergistic action mechanism of intermolecular force dissociation and adsorption balance, electric field action charged ion migration, electrochemical electron transfer and fluorescence spectrum fusion can be constructed in a broad sense;
(2) in the technology, the integrated technology of dissociation, concentration and in-situ analysis of rare and precious rare earth elements with low occurrence is constructed, and a new mechanism of quantum dot adsorption, electrochemical enhanced fluorescence spectrum analysis and supercapacitor electrolyte regulation is expanded; the method develops an integrated framework integration, solves the problems of dissociation, concentration and in-situ analysis and discrimination of rare and precious elements of low-occurrence rare earth, develops a new separation engineering technology, and has innovative technical inspiration on the dissociation-enrichment-detection of all low-occurrence and high-value substances;
(3) in application, rare earth and precious elements are taken as an example, the invention shows double application prospects in the fields of analysis detection or detection and separation engineering, such as a novel low-occurrence rare earth in-situ enrichment detection method and a novel low-occurrence rare earth and precious element high-efficiency cleaning low-energy-consumption enrichment technology, wherein the former refers to an instrument framework capable of being formed in a portable or in-situ manner, and the latter refers to a separation engineering technology capable of forming large industry, so that the formation of secondary industry for recovering and enriching low-occurrence rare earth and precious elements and other high-value substances is promoted, the development of in-situ detection means and separation engineering technology paths is promoted, and the integration and high-quality development of related operations of dissociation-enrichment-detection in the solid waste industry is led.
Drawings
FIG. 1 is a technical route diagram of the invention for assisting dissociation, concentration and in-situ monitoring of low-concentration rare earth by quantum dots in a supercapacitor;
FIG. 2 is a composite metal oxide electrode material preparation in example 1 of the present invention; FIG. 2a is a schematic diagram of a supercapacitor light-emitting diode assembled based on a synthetic composite metal oxide electrode material; FIG. 2b shows the capacitance characteristics of the composite metal oxide; FIG. 2c is a schematic view of a lighting system with more LED light emitters;
FIG. 3 is an electron microscope image of the composite metal oxide electrode material of example 1 of the present invention, wherein FIGS. 3a-d are electron microscope images of the same composite metal oxide electrode material synthesized with different microscopic dimensions (see the figure notation), i.e., different magnifications;
FIG. 4 is a graph showing a distribution of particle diameters of (a) NPS-GQDs in example 1 of the present invention; (b) NPS-GQDs high resolution projection electron micrographs; (c) NPS-GQDsAdding Tb into the solution3+(0-50. mu.M) fluorescence spectrum; (d) fluorescence intensity and Tb3+A linear plot of concentration;
FIG. 5 is a diagram showing a process for producing acidic water by using the supercapacitor according to example 2;
FIG. 6 shows that Eu is added to a carbon quantum dot solution with different concentrations in folic acid raw material (a) in example 33+The subsequent fluorescence spectrogram; (b) fluorescence intensity and Eu3+A linear plot of concentration; (c) 1-1200 mu M Eu3+A current response graph of concentration change, and (d) a corresponding linear fitting graph of (c); (e) a current response plot of the CDs/GCE electrode for Ce (III) ions; (f) is a linear relationship graph of Ce (III) ions and fluorescence intensity.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof. Unless otherwise specified, the reagents and equipment proposed in the present invention are commercially available. Each of the gas or liquid flow paths in the embodiments described below is provided with a valve for controlling the entry or exit of gas or liquid.
Example 1
As shown in fig. 1, the method for dissociation, concentration and in-situ monitoring of rare and precious rare earth elements with low concentration by using quantum dots to assist a supercapacitor comprises the following steps: crushing coal-based solid waste raw materials into powder, putting the powder into a super capacitor, wherein the operating temperature range of the super capacitor is 50-100 ℃, the pressure is 0.5-5MPa, the content of rare and noble elements in the coal-based solid waste raw materials is 10 mu g/g, the super capacitor comprises two electrodes and a mixed solution of electrolyte and quantum dots, the anode material is FeCo2O4@MnO2The cathode material is FeCo2O4@MnO2The electrolyte is 1M sodium phosphate solution, the quantum dots are multi-element nitrogen-phosphorus-sulfur-doped semiconductor type carbon quantum dots (NPS-GQDs), the proportion of the electrolyte to the quantum dots is that 10 mg of quantum dots are added into each gram of electrolyte, when the super capacitor is charged at normal temperature and normal pressure, the super capacitor generates an acidic water environment, low-occurrence rare earth and precious element ions adsorbed on the surface of mineral solid waste raw materials are subjected to ion exchange dissociation, and the rare earth and precious element ions are transferred into mixed solution to be combined with the quantum dots to form the quantum dotsRare earth-rare-noble element aggregates, which move to the surface of the cathode under the action of the supercapacitor electric field for further enrichment (the electrode which can be adsorbed with quantum dots is shown as the cathode in fig. 1); when the super capacitor is operated reversely, the aggregate is separated from the surface of the cathode, the electrode is regenerated, and the aggregate separated from the cathode naturally settles in a solution environment, so that the rare and noble elements of the rare earth are concentrated. The extraction efficiency of rare earth reaches 80 percent, and the enrichment rate is more than 300 times.
The anode and the cathode are made of FeCo2O4The electrode (prepared from 1M of ferric nitrate and cobalt nitrate by a 160-10 h hydrothermal method) shows the maximum electricity storage capacity of 182.8C g-1(39.7W h kg-1), the matching current is 0.5A g-1, the performance is even improved by 21.1% after a life test is carried out for 500 cycles, and research shows that OH-1The mass transfer is a speed control step, and the application of the relevant electrode material in acidic water preparation tests shows that the lowest pH value can reach 3-4. As shown in FIGS. 2 and 3, the prepared supercapacitor made of the iron-based electrode material has good performance, and the electron microscope photo shows that the supercapacitor has a regular and fine nano structure.
According to the optical effect, the electrical effect and the magnetic effect of the quantum dot-rare earth and noble element, the in-situ analysis and discrimination and enrichment capacity of the rare earth and noble element are realized.
Synthesizing anthracite into C with molecular structure40H15N3O7S2P2The preparation method of the multi-element nitrogen-phosphorus-sulfur doped semiconductor type carbon quantum dots (NPS-GQDs) is disclosed in the Applied Surface Science 445(2018) 519-526. As shown in fig. 4. The fluorescent material has obvious fluorescent emission, lead ions can enable the fluorescent material to be subjected to fluorescent quenching (the detection limit reaches 0.75 mu M), and the fluorescent material is not interfered by most ions; NPS-GQDs can be used for treating rare earth ions Tb3+Has the antenna sensitization effect and sends out Tb3+Fluorescence spectra of the ions themselves.
Example 2
In this example, the acid water was prepared by using the supercapacitor of example 1, and as shown in FIG. 5, three electrode materials CoFeO4、 Ni2S3And Co2S3The pH value can be reduced to 4-5 by changing in neutral electrolyte solutionThe super capacitor provided by the invention enables the solution to be in an acidic water environment, and is beneficial to extraction of rare and precious rare earth elements in mineral solid waste raw materials.
Example 3
The same as example 1, except that: the carbon quantum dots are folic acid.
FIG. 6 shows that Eu is added to a carbon quantum dot solution with different concentrations in folic acid raw material (a) in example 33+The subsequent fluorescence spectrogram; (b) fluorescence intensity and Eu3+A linear plot of concentration; (c) 1-1200 mu M Eu3+A current response graph of concentration change, and (d) a corresponding linear fitting graph of (c); (e) a current response plot of the CDs/GCE electrode for Ce (III) ions; (f) is a linear relationship graph of Ce (III) ions and fluorescence intensity.
The carbon quantum dots taking folic acid as a carbon source-a plurality of fluorescence mechanisms (fluorescence quenching, antenna sensitization fluorescence, spectral line red shift effect and the like) of rare earth successfully establish an indirect method (carbon quantum dot fluorescence quenching) and a direct method (transferring absorption energy to generate rare earth characteristic fluorescence) rare earth element detection method by utilizing the carbon quantum dots, and can detect typical light, medium and heavy rare earth ions such as Ce, Eu, Tb and the like in a wider linear range (0-50 mu M) and a lower detection limit (0.3 mu M); it is further found that the electrochemical scanning of the electrode loaded with the carbon quantum dot generates voltage response peaks to typical light and medium rare earth ions such as Ce and Eu, the linear detection range (Ce: 1-100 mu M, Eu: 1-1200 mu M) is widened under the lower detection limit (Ce: 0.72 mu M and Eu: 0.68 mu M), and the stable working life of the electrode exceeds 5 months; in the research, physical and chemical information of the carbon points is represented by a transmission electron microscope, an X-ray diffractometer, a Fourier infrared transform spectrum, an X-ray photoelectron spectrometer, a cyclic voltammetry, electrochemical impedance and the like. Meanwhile, a plasma fluorescence enhancement mechanism of the quantum dots is also researched.
The total extraction efficiency of the rare earth is 80 percent.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims (10)

1. A method for utilizing quantum dots to assist dissociation, concentration and in-situ monitoring of low-concentration rare-earth and precious elements of a super capacitor is characterized by comprising the following steps: the mineral solid waste raw materials are crushed and then placed into a super capacitor, the super capacitor comprises a cathode, an anode, electrolyte and a mixed solution of quantum dots, when the super capacitor is charged, the super capacitor generates an acidic water environment to promote low occurrence rare earth and precious element ions adsorbed on the surface of the mineral solid waste raw materials to carry out ion exchange dissociation, the rare earth and precious element ions are transferred into the mixed solution to be combined with quantum dots to form a quantum dot-rare earth and precious element aggregate, and the aggregate moves to the surface of the cathode to be further enriched under the action of an electric field of the super capacitor; when the super capacitor is operated reversely, the aggregate is separated from the surface of the cathode, the electrode is regenerated, and the aggregate separated from the cathode naturally settles in a solution environment, so that the rare and noble elements of the rare earth are concentrated; according to the optical effect, the electrical effect and the magnetic effect of the quantum dot-rare earth and noble element, the in-situ analysis and discrimination and enrichment capacity of the rare earth and noble element are realized.
2. The method according to claim 1, characterized in that it comprises in particular the steps of:
(1) putting mineral solid waste raw materials into a super capacitor, and when the super capacitor is charged, increasing the concentration of hydrogen ions in electrolyte to improve the acidity of the electrolyte to form an acidic water environment; the rare-earth and precious element ions with low occurrence, which are adsorbed on the surface of the mineral solid waste raw material, are subjected to ion exchange dissociation, hydrogen ions are neutralized, and the rare-earth and precious element ions subjected to ion exchange dissociation enter an electrolyte solution to become free rare-earth and precious element ions; the quantum dots existing in the electrolyte of the super capacitor are combined with rare earth and precious element ions to form a quantum dot-rare earth and precious element aggregate, so that the dissociated rare earth and precious element ions are captured by the quantum dots and complete primary enrichment, and the aggregate moves to the surface of the cathode under the action of an electric field of the super capacitor to complete further enrichment of rare earth and precious elements;
(2) reversely operating the super capacitor to separate the aggregate from the surface of the cathode and regenerate the electrode; the quantum dot-rare earth and precious element aggregate separated from the cathode naturally settles in the electrolyte solution environment to complete a cycle of operation;
(3) according to the optical effect, the electrical effect and the magnetic effect of the quantum dot-rare earth and precious element, the in-situ analysis and discrimination of the rare earth and precious element and the dynamics and the enrichment capacity of the rare earth and precious element ion enrichment process are realized, and the in-situ acid dissociation, concentration and monitoring of the integrated low-concentration rare earth and precious element are realized.
3. The method according to claim 1 or 2, wherein the mineral solid waste raw material in the step (1) comprises coal-based solid waste and waste tailings, the coal-based solid waste is selected from one of fly ash, coal slurry and coal gangue, the waste tailings is selected from one of iron ore slag, phosphate rock, red mud and composite associated slag, and the content of rare and noble elements in the mineral solid waste raw material is 10-50000 μ g/g.
4. The method as claimed in claim 1 or 2, wherein the supercapacitor is composed of a cathode and an anode immersed in a mixed solution of electrolyte and quantum dots, the proportion of the quantum dots and the electrolyte is 1-1000 mg of quantum dots added in each gram of the electrolyte, and the anode and the cathode are made of metal oxide, metal sulfide, metal nitride or a compound of the metal oxide, the metal sulfide and the metal nitride; the electrolyte is inorganic acid, organic acid, inorganic salt or organic salt, and the pH value of the electrolyte solution is 0-7.
5. The method of claim 4, wherein the anode and cathode materials are metal oxides or metal sulfides, and the metal is at least one selected from the group consisting of iron, manganese, cobalt, nickel, magnesium, and zinc.
6. The method according to claim 4 or 5,characterized in that the anode and cathode materials are selected from FeCo2O4、NiCo2O4、ZnCo2O4、CoFeO4、Ni2S3And Co2S3One kind of (1).
7. The method according to claim 1 or 2, wherein the quantum dot material is selected from carbon quantum dots, metal sulfur and metal nitrogen quantum dots and composite state quantum dots of the quantum dots, and the particle size of the quantum dots is 1-50 nm; the carbon quantum dot is an aggregate of oxygen, sulfur, nitrogen and modified metal taking a carbon element as a core.
8. The method of claim 7, wherein the carbon quantum dots are folic acid or multi-element nitrogen phosphorus sulfur doped semiconductor type carbon quantum dots.
9. A method according to claim 1 or 2, characterized in that the charging energy of the supercapacitor is supplied by renewable solar energy.
10. The method according to claim 1 or 2, wherein the operating temperature of the supercapacitor is in the range of 5 ℃ to 300 ℃ and the pressure is in the range of 0.01 to 30 MPa.
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