Phenazine-based electrochemical electrode material and preparation method and application thereof

Abstract

The invention discloses a phenazine-based electrochemical electrode material as well as a preparation method and application thereof. The phenazine-based electrochemical electrode material is an organic small molecule material or an organic polymer which contains nitrogen, has a conjugated structure and can be subjected to electrochemical oxidation-reduction reaction. The phenazine-based electrochemical electrode material disclosed by the invention can be applied to selective separation and extraction of ions, can be used for selective extraction and separation of target ions in a multi-ion complex solution, and can be used for extracting valuable element ions step by step at high performance; the extraction method has the advantages of high ion extraction capacity, low cost, simple process and high element separation and extraction efficiency, is environment-friendly, can realize efficient development and comprehensive utilization in the fields of salt lake resources, marine resources, industrial sewage and wastewater recycling, seawater desalination and the like, and has a better industrialization prospect.

Description

Technical Field

[0001] The present invention belongs to the field of electrochemical selective separation and extraction of aqueous ions, and in particular relates to a phenazine-based electrochemical electrode material and a preparation method and application thereof. Background Art

[0002] With the rapid development of my country's manufacturing industry, the rapid increase in demand for various valuable metals has become one of the important constraints on the development of my country's manufacturing industry. However, traditional channels and methods for extracting valuable metal resources are limited by the problems of insufficient solid mineral resources, high extraction costs, and environmental damage. They can no longer meet current needs. Therefore, finding more efficient, green, and low-cost extraction methods and resource channels for valuable metal resources has become an urgent problem to be solved. Liquid ore resources contain rich and diverse inorganic valuable metal resources, which can effectively solve the problem of insufficient existing valuable metal resources. For example, seawater is rich in low-grade valuable metal ions, and salt lake brine liquid ore contains rich potassium ore, lithium ore, and scattered elements. Industrial waste liquid, as a "recyclable mine", contains a large amount of Al 3+ 、Mn 2+ 、Co 2+ 、Ni 2+ Heavy metal ions such as ions are released. The rise of the new energy industry has led to the generation of numerous waste lithium batteries, resulting in a significant amount of waste lithium battery leachate. Reusing these liquid mineral resources for valuable metals not only addresses the shortage of valuable metals and enables resource reuse, but also allows for wastewater treatment, contributing to ecological protection.

[0003] Ion selective extraction refers to the process of selectively extracting or removing specific ions from a solution using specific materials or technologies, such as ion exchange resins and membrane separation technology. Since liquid mineral resources, such as industrial wastewater and brine, contain complex and diverse metal ion compositions and different grades, it is very difficult to achieve selective extraction of target ions, especially when the solution contains competing ions. For example, salt lake brine usually contains Li+ with similar hydrated ion radius. + and Mg 2+ , its separation is more difficult, such as Li + 、Au 2+ Cr 6+ , Pb 2+ 、Al 3+ 、Mn 2+ 、Co 2+ 、Ni 2+ It is very difficult to perform targeted separation in complex situations such as multi-ion separation.

[0004] In recent years, electrochemical ion extraction has attracted widespread attention due to its time-saving, low environmental impact and high efficiency. In particular, electrochemical technology does not require chemical additives and does not have the by-products found in traditional extraction technologies. It is very environmentally friendly and has low power consumption. It is particularly suitable for the selective extraction of target ions from liquid mineral resources. However, the currently available electrochemical extraction electrode materials can only perform targeted extraction of single ions and cannot cope with the selective extraction and separation of targets in complex multi-ion solutions. At the same time, the stability of the ion selective extraction process is also affected by many factors, such as temperature, pH value, solution composition, etc., which can lead to unstable extraction effects. Therefore, how to solve the low ion adsorption capacity and poor selectivity of materials in the existing technology and perform green and recyclable selective extraction and separation of target high-value ions is a problem that needs to be solved urgently. Summary of the Invention

[0005] The main purpose of the present invention is to provide a phenazine-based electrochemical electrode material and its preparation method and application, so as to overcome the problems of low ion adsorption capacity and poor selectivity of the materials in the prior art.

[0006] To achieve the aforementioned object of the invention, the technical solutions adopted by the present invention include:

[0007] One aspect of the present invention provides a use of a phenazine-based electrochemical electrode material in the selective separation and extraction of ions; the molecular structure of the phenazine-based electrochemical electrode material is as shown in at least any one of formulas (A) to (C):

[0008]

[0009] Among them, the M group includes at least any one of the elements O and S; the R1 group includes at least any one of hydrogen, alkyl chain, and aromatic ring; the R4 group includes any one of hydrogen, halogen, amino, hydroxyl, amine, halogen aromatic ring, amino aromatic ring, amine aromatic ring, and hydroxyl aromatic ring, or a combination of two or more thereof, and at least one of the R4 groups is not hydrogen; the value range of n1 is 0 to 3, and the value range of n2 is 500 to 5000.

[0010] One aspect of the present invention provides a phenazine-based electrochemical electrode material, the molecular structure of which is shown in at least any one of Formulas (D) to (F):

[0011]

[0012] Among them, the M group includes at least any one of the elements O and S; the R1 group includes at least any one of hydrogen, alkyl chain, and aromatic ring; the R4 group includes any one of hydrogen, halogen, amino, hydroxyl, amine, halogen aromatic ring, amino aromatic ring, amine aromatic ring, and hydroxyl aromatic ring, or a combination of two or more thereof, and at least one of the R4 groups is not hydrogen, the value range of n1 is 0 to 3, and the value range of n2 is 500 to 5000.

[0013] Another aspect of the present invention provides a method for preparing the phenazine-based electrochemical electrode material, comprising: subjecting a first mixed system comprising a phenazine-based small molecule monomer, a first ligand monomer, a catalyst, and an organic solvent to a first reaction in a protective atmosphere to obtain the phenazine-based electrochemical electrode material;

[0014] Alternatively, a second mixed system comprising a phenazine-based small molecule monomer, a second ligand monomer, a catalyst, and an organic solvent undergoes a second reaction to generate a phenazine-based precursor material, and the phenazine-based precursor material and a third ligand monomer undergo a third reaction under a protective atmosphere to obtain the phenazine-based electrochemical electrode material.

[0015] Another aspect of the present invention also provides a method for selectively separating and extracting ions, comprising:

[0016] Using the phenazine-based electrochemical electrode material as a cathode;

[0017] The electrochemical reaction system including an anode, a cathode and an electrolyte is electrified, and different voltages are applied to the cathode to perform step-by-step ion extraction to obtain a phenazine-based composite material coordinated with different metal ions; wherein the voltage difference is controlled within 1V.

[0018] Compared with the prior art, the present invention has at least the following beneficial effects:

[0019] (1) The phenazine-based electrochemical electrode material of the present invention can cope with the selective extraction and separation of target ions in multi-ion complex solutions, can extract valuable element ions in a step-by-step and high-performance manner, and can achieve the selective extraction of liquid mineral resources based on green electrochemical ion extraction technology, which is expected to promote the development and utilization of liquid mineral resources.

[0020] (2) The method of the present invention for selectively separating and extracting ions using phenazine-based electrochemical electrode materials has the advantages of high ion extraction capacity, low cost, simple process, and high element separation and extraction efficiency. It is also environmentally friendly and can achieve efficient development and comprehensive utilization of salt lake resources, marine resources, industrial wastewater resource utilization, seawater desalination and other fields, and has good industrialization prospects. DETAILED DESCRIPTION

[0021] In view of the above problems existing in the prior art, the inventors of the present invention have conducted extensive and in-depth research and provide a phenazine-based electrochemical electrode material and a preparation method and application thereof.

[0022] The technical solution, its implementation process and principles are further explained below.

[0023] As one aspect of the technical solution of the present invention, a phenazine-based electrochemical electrode material is provided for use in selectively separating and extracting ions; the molecular structure of the phenazine-based electrochemical electrode material is as shown in at least one of formulas (A) to (C):

[0024]

[0025]

[0026] Among them, the M group includes at least any one of the elements O and S; the R1 group includes at least any one of hydrogen, alkyl chain, and aromatic ring; the R4 group includes any one of hydrogen, halogen, amino, hydroxyl, amine, halogen aromatic ring, amino aromatic ring, amine aromatic ring, and hydroxyl aromatic ring, or a combination of two or more thereof, and at least one of the R4 groups is not hydrogen, the value range of n1 is 0 to 3, and the value range of n2 is 500 to 5000.

[0027] In some embodiments, the application includes the use of phenazine-based electrochemical electrode materials for selectively separating and extracting valuable metal ions in aqueous solution phases.

[0028] In some preferred embodiments, the aqueous solution phase includes at least any one of liquid ore solution, waste battery leachate, salt lake brine, non-ferrous metal production industrial wastewater, etc., but is not limited thereto.

[0029] In some preferred embodiments, the valuable metal ions include Li + 、Au 2+ Cr 6+ , Pb 2+ 、Al 3+ 、Mn 2+ 、Co 2+ 、Ni 2+ At least any one of the above, but not limited to these.

[0030] As one aspect of the technical solution of the present invention, a phenazine-based electrochemical electrode material is provided, wherein the molecular structure thereof is at least one of the following formulas (D) to (F):

[0031]

[0032]

[0033] The M group includes at least one of O and S; the R1 group includes at least one of hydrogen, an alkyl chain, and an aromatic ring; the R4 group includes any one of hydrogen, a halogen, an amino group, a hydroxyl group, an amine group, a halogen aromatic ring, an amino aromatic ring, an amine aromatic ring, and a hydroxyl aromatic ring, or a combination of two or more thereof, at least one of the R4 groups is not hydrogen; the value of n1 ranges from 0 to 3, and the value of n2 ranges from 500 to 5000. The phenazine-based electrochemical electrode material of the present invention is an organic small molecule material or organic polymer containing nitrogen, having a conjugated structure, and capable of undergoing electrochemical redox reactions.

[0034] As one aspect of the technical solution of the present invention, the preparation method of the phenazine-based electrochemical electrode material provided therein comprises: causing a first mixed system including a phenazine-based small molecule monomer, a first ligand monomer, a catalyst, and an organic solvent to undergo a first reaction in a protective atmosphere to obtain the phenazine-based electrochemical electrode material;

[0035] Alternatively, a second mixed system comprising a phenazine-based small molecule monomer, a second ligand monomer, a catalyst, and an organic solvent undergoes a second reaction to generate a phenazine-based precursor material, and the phenazine-based precursor material and a third ligand monomer undergo a third reaction under a protective atmosphere to obtain the phenazine-based electrochemical electrode material.

[0036] In some embodiments, the temperature of the first reaction is 25-200° C., and the time is 5-12 hours.

[0037] In some embodiments, the mass ratio of the phenazine-based small molecule monomer, the first ligand monomer, the catalyst, and the organic solvent in the first mixed system is 1:1-2:0.01-0.05:2-10.

[0038] In some embodiments, the temperature of the second reaction is 25-200° C., and the time is 5-12 hours.

[0039] In some embodiments, the mass ratio of the phenazine-based small molecule monomer, the second ligand monomer, the catalyst and the organic solvent in the second mixed system is 1:1-2:0.01-0.05:2-10.

[0040] In some embodiments, the temperature of the second reaction is 25-200° C., and the time is 5-12 hours.

[0041] In some embodiments, the mass ratio of the phenazine-based precursor material to the third ligand monomer is 1:1 to 1:2.

[0042] In some embodiments, the temperature of the third reaction is 25-200° C., and the time is 5-12 hours.

[0043] In some embodiments, the molecular structure of the phenazine-based small molecule monomer is as shown in at least any one of formula (G) to formula (H):

[0044]

[0045] Among them, the M group includes at least any one of O and S elements; the R1 group includes at least any one of hydrogen, alkyl chain, and aromatic ring; the R2 group includes any one of hydrogen, halogen, amino, hydroxyl, and amine, or a combination of two or more thereof, and at least one of the R2 groups is not hydrogen.

[0046] In some embodiments, the molecular structure of the first ligand monomer is as shown in formula (I):

[0047]

[0048] The R3 group includes any one or a combination of two or more of halogen, amino, and hydroxyl groups, and the number of halogen, amino, and hydroxyl functional groups in the first ligand monomer is at least 4.

[0049] In some embodiments, the molecular structure of the second ligand monomer is as shown in formula (J):

[0050]

[0051] The R3 group includes any one or a combination of two or more of halogen, amino, and hydroxyl groups, and the number of halogen, amino, and hydroxyl functional groups in the second ligand monomer is at least 4.

[0052] In some embodiments, the structural formula of the third ligand monomer is the same as that of the second ligand monomer, wherein the R3 group includes any one or a combination of two or more of hydrogen, halogen, amino, and hydroxyl, and at least one of the R3 groups is not hydrogen. At the same time, the R3 group in the third ligand monomer is different from the R3 group in the second ligand monomer.

[0053] In some embodiments, the molecular structure of the phenazine-based precursor material is shown in Formula (K):

[0054]

[0055] The R5 group includes any one of amine, sulfur, and oxygen, or a combination of two or more.

[0056] In some embodiments, the organic solvent includes at least any one of N-methylpyrrolidone, N,N-dimethylformamide, acetic acid, toluene, o-xylene or tetrahydrofuran, but is not limited thereto.

[0057] In some embodiments, the protective atmosphere includes at least any one of nitrogen or argon, but is not limited thereto.

[0058] In some embodiments, the catalyst comprises a palladium-based catalyst, but is not limited thereto.

[0059] In the present invention, there are generally two preparation ideas for preparing the phenazine-based electrochemical electrode material:

[0060] (1) Phenazine monomers and ligand monomers can generate final products under the action of catalysts, which are small molecule phenazine-based electrochemical electrode materials.

[0061] (2) The phenazine-based monomer and the ligand monomer first generate a precursor under the action of a catalyst, and then the corresponding precursor reacts with the ligand monomer to generate the final product, which is a polymer-type phenazine-based electrochemical electrode material.

[0062] Taking the generation of small molecule phenazine-based electrochemical electrode materials containing amines as an example, the preparation process of the small molecule phenazine-based electrochemical electrode materials corresponding to idea (1) is as follows:

[0063]

[0064] A phenazine-based small molecule monomer having four 1R2 groups and a first ligand monomer having four R3 groups, under the conditions of a molar ratio of 1:1 and the presence of a catalyst and a corresponding solvent, the groups 1R2 and R3 react through nucleophilic reaction to generate a phenazine-based small molecule material containing amine, wherein the groups R22 and 3R3 do not participate in the reaction.

[0065] In the preparation process of the small molecule phenazine-based electrochemical electrode material corresponding to idea (1), due to the different types of R2 and R3 groups, the electron donating and electron withdrawing abilities and steric hindrance of each group are different. However, both R2 and R3 groups will eventually be reacted and have no effect on the final product.

[0066] Taking the generation of polymer-type phenazine-based electrochemical electrode materials containing amines as an example, the preparation process of the polymer-type phenazine-based electrochemical electrode materials corresponding to idea (2) is as follows:

[0067]

[0068] The structural characteristics of the phenazine-based small molecule monomer are that it has four R2 groups, namely two R22 groups on the left and two R21 groups on the right. The R22 and R21 groups are each any one of the R2 groups defined above, namely hydrogen, halogen, amino, hydroxyl, and amine, but they are different R2 groups. There are two types of ligand monomers, namely the second ligand monomer and the third ligand monomer. The second ligand monomer has four R3 groups, namely two R32 groups and two R31 groups. The R32 and R31 groups are each any one of the R3 groups defined above, namely halogen, amino, and hydroxyl, but they are different R3 groups. The third ligand monomer has four R3 groups, namely two R33 groups and two R34 groups. The R33 and R34 groups are each any one of the R3 groups defined above, namely halogen, amino, hydroxyl, and hydrogen, but they are different R3 groups. Furthermore, the R33 group and the R34 group in the third ligand monomer are also different from the R32 group and the R31 group in the second ligand monomer.

[0069] In the first step of the reaction of idea (2), the molar ratio of the phenazine-based small molecule monomer and the second ligand monomer is 1:1. Based on the R21 group and the R31 group, a nucleophilic reaction is performed under the conditions of a catalyst, a solvent, a protective atmosphere, and heating to generate a phenazine-based precursor material. The phenazine-based precursor material has two R22 groups and two R32 groups. The phenazine-based precursor is reacted with the third ligand monomer at a molar ratio of 1:1. Based on the R22 group, the R82 group, the R33 group, and the R34 group, R22 reacts with one of R34 or R33. The polymer reacts through the reaction of the R22 and R32 groups with R33 and R34 respectively to achieve chain growth. The R2 and R3 groups are eventually reacted to generate a polymer-type phenazine-based electrochemical electrode material containing amines.

[0070] The preparation process of the phenazine-based electrochemical electrode material containing a halogen, amino, or hydroxyl group-containing phenazine-based small molecule monomer and a second ligand monomer to generate a polymer type is the same as the preparation process of the above idea (2).

[0071] In some more specific embodiments, the method for preparing the phenazine-based electrochemical electrode material specifically includes:

[0072] Based on the number of halogen, amino, or hydroxyl functional groups contained, a phenazine-based small molecule monomer, a first ligand monomer, a catalyst, and an organic solvent are adjusted in a mass ratio of 1:1-2:0.01-0.05:2-10 to form a first mixed system, and a first reaction is carried out at a temperature of 25-200° C. for 5-12 hours to synthesize the target phenazine-based electrochemical electrode material;

[0073] Alternatively, based on the number of halogen, amino, or hydroxyl functional groups contained, a phenazine-based small molecule monomer, a second ligand monomer, a catalyst, and an organic solvent are prepared in a mass ratio of 1:1-2:0.01-0.05:2-10 to form a second mixed system, and a second reaction is carried out at a temperature of 25-200°C for 5-12 hours to generate a phenazine-based precursor material. The phenazine-based precursor material and the third ligand monomer are subjected to a third reaction at a temperature of 25-200°C for 5-12 hours under a protective atmosphere to obtain the phenazine-based electrochemical electrode material.

[0074] As one aspect of the technical solution of the present invention, a method for selectively separating and extracting ions is also provided, comprising:

[0075] Using the phenazine-based electrochemical electrode material as a cathode;

[0076] The electrochemical reaction system including an anode, a cathode and an electrolyte is electrified, and different voltages are applied to the cathode to perform step-by-step ion extraction to obtain a phenazine-based composite material coordinated with different metal ions; wherein the voltage difference is controlled within 1V.

[0077] The voltage-step method refers to the application of different voltage values ​​to the phenazine electrode for different ion types in a mixed ion solution, enabling the extraction of one ion at a time. For example, when the mixed solution contains Al, Mn, Ni, Co, and Li ions, applying a voltage of -0.4V can extract Al ions, applying a voltage of -0.5V can extract Mn ions, applying a voltage of around -0.6V can extract Ni ions, applying a voltage of -0.7V can extract Co ions, and applying a voltage of -0.8V can extract Li ions. As the applied potential gradually decreases, each ion can be extracted step by step.

[0078] In some embodiments, the voltage range includes -1.5 to 1.5V.

[0079] In some embodiments, the anode includes at least any one of a carbon material or a p-type organic material, and the p-type organic material includes polyaniline.

[0080] In some embodiments, the electrolyte includes at least any one of liquid ore solution, waste battery leachate, salt lake brine, and non-ferrous metal production industrial wastewater.

[0081] In some embodiments, the ions include Li + 、Au 2+ Cr 6+ , Pb 2+ 、Al 3+ 、Mn2+ 、Co 2+ 、Ni 2+ At least any one of .

[0082] In some embodiments, during the ion extraction process, the adsorption sites of different metal ions are from high to low: Au 2 + 、Al 豇 Cr 6+ 、Mn 2+ 、Co 2+ 、Ni 2+ 、Li + , Pb 2+ .

[0083] Through the selective separation and extraction of ions, the phenazine-based electrochemical electrode material of the present invention has a lithium extraction capacity greater than 55 mg / g in salt lake brine and a lithium / sodium selective distribution coefficient greater than 45.

[0084] The phenazine-based electrochemical electrode material has a capacity of extracting chromium from chromium-containing wastewater greater than 400 mg / g.

[0085] The phenazine-based electrochemical electrode material has a lead extraction capacity greater than 1600 mg / g in lead-containing wastewater.

[0086] The phenazine-based electrochemical electrode material has a gold extraction capacity of greater than 1050 mg / g in gold-containing wastewater.

[0087] The phenazine-based electrochemical electrode material has a capacity of extracting aluminum from aluminum-containing wastewater greater than 260 mg / g.

[0088] The phenazine-based electrochemical electrode material has a capacity of extracting manganese from manganese-containing wastewater greater than 560 mg / g.

[0089] The phenazine-based electrochemical electrode material has a capacity of extracting cobalt from cobalt-containing wastewater greater than 250 mg / g.

[0090] The phenazine-based electrochemical electrode material has a capacity of extracting nickel from nickel-containing wastewater greater than 550 mg / g.

[0091] In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiment. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. Those skilled in the art will make modifications or equivalent substitutions based on understanding the technical solution of the present invention, without departing from the spirit and scope of the technical solution of the present invention, and all should be encompassed within the protection scope of the present invention.

[0092] Where specific experimental procedures or conditions are not specified in the examples, the experiments were carried out according to conventional experimental procedures or conditions described in literature in the field. Reagents or instruments used without manufacturer specified are commercially available. Commercially available options for other raw materials and instruments not mentioned are conventional and do not relate to the core technical means of the present invention.

[0093] Example 1

[0094] 5,10-Dihydrodichlorodiaminephenazine and hydroxybromobenzene were weighed in a molar ratio of 1:2, added to 100 mL of tetrahydrofuran and 0.03 g of trisdibenzylideneacetone dipalladium. The reaction was carried out at 50°C for 12 hours to synthesize the target phenazine-based electrochemical electrode material. The pure phenazine-based electrochemical electrode material was obtained through acetone washing and Soxhlet extraction. The yield was approximately 75%.

[0095] The specific operating steps of the method for selectively separating and extracting ions are as follows: applying voltage to the prepared phenazine-based electrochemical material, and gradually reducing the voltage from the open circuit voltage by 200mV each time until the voltage drops to -1.5V.

[0096] The preparation process of the phenazine-based electrochemical electrode material of Example 1 is as follows:

[0097]

[0098] The phenazine-based electrochemical electrode material prepared in this Example 1 has four CN and C═N functional groups, and has a lithium extraction capacity of greater than 60 mg / g in salt lake brine, and a lithium / sodium selective distribution coefficient of greater than 80; a chromium extraction capacity of greater than 400 mg / g in chromium-containing wastewater; a lead extraction capacity of greater than 1750 mg / g in lead-containing wastewater; a gold extraction capacity of greater than 1185 mg / g in gold-containing wastewater; an aluminum extraction capacity of greater than 300 mg / g in aluminum-containing industrial wastewater; a manganese extraction capacity of greater than 600 mg / g in manganese-containing wastewater; a cobalt extraction capacity of greater than 290 mg / g in cobalt-containing wastewater; and a nickel extraction capacity of greater than 580 mg / g in nickel-containing wastewater.

[0099] When the solution is a mixed solution containing Al ions, Ni ions, Li ions, and Co ions, selective extraction of ions is achieved by applying a step-by-step voltage. For example, applying a voltage of -0.4V can achieve the extraction of Al ions, applying a voltage of -0.6V can achieve the extraction of Ni ions, applying a voltage of -0.7V can achieve the extraction of Co ions, and applying a voltage of -0.8V can achieve the extraction of Li ions.

[0100] Example 2

[0101] Dibromodiamino-5,10-dihydrophenazine and dibromodihydroxybenzene were added to a three-necked flask in a stoichiometric ratio of 1:1. Palladium acetate was used as a catalyst, and toluene was added. The mixture was reacted at 100°C for 12 hours to obtain a phenazine-based precursor material. 1.0 mmol of the phenazine-based precursor material and 10 mL of anhydrous toluene were placed in a pressure tube to completely dissolve the precursor. The mixture was thoroughly purged with nitrogen for 30 minutes and then stirred at 65°C for 12 hours. After cooling to room temperature, the mixture was filtered, washed with 20 mL of ethyl acetate, and purified to obtain the pure phenazine-based electrochemical electrode material. The yield was approximately 80%.

[0102] The preparation process of the phenazine-based electrochemical electrode material of Example 2 is as follows:

[0103]

[0104] The phenazine-based electrochemical electrode material prepared in this Example 2 has 6 CN and C═N functional groups, and its lithium extraction capacity in salt lake brine is higher than 55 mg / g, and its lithium / sodium selective distribution coefficient is higher than 76; its chromium extraction capacity in chromium-containing wastewater is higher than 420 mg / g; its lead extraction capacity in lead-containing wastewater is higher than 1700 mg / g; its gold extraction capacity in gold-containing wastewater is higher than 1060 mg / g; its aluminum extraction capacity in aluminum-containing industrial wastewater is higher than 290 mg / g; its manganese extraction capacity in manganese-containing wastewater is higher than 590 mg / g; its cobalt extraction capacity in cobalt-containing wastewater is higher than 260 mg / g; and its nickel extraction capacity in nickel-containing wastewater is greater than 570 mg / g.

[0105] When the solution contains a mixed solution of Al ions, Mn ions, Co ions, and Li ions, selective extraction of ions is achieved by applying a step-by-step voltage. For example, applying a voltage of -0.4V can extract Al ions, applying a voltage of -0.5V can extract Mn ions, applying a voltage of -0.7V can extract Co ions, and applying a voltage of -0.8V can extract Li ions.

[0106] Example 3

[0107] The operation steps of this example are the same as those of Example 1, except that the first reaction temperature is 100° C., the reaction time is 12 h, and the yield is about 73%.

[0108] The phenazine-based electrochemical electrode material prepared in this embodiment has a lithium extraction capacity of higher than 58 mg / g in salt lake brine, and a lithium / sodium selective distribution coefficient of higher than 72; a chromium extraction capacity of higher than 409 mg / g in chromium-containing wastewater; a lead extraction capacity of higher than 1730 mg / g in lead-containing wastewater; a gold extraction capacity of higher than 1190 mg / g in gold-containing wastewater; an aluminum extraction capacity of higher than 276 mg / g in aluminum-containing industrial wastewater; a manganese extraction capacity of higher than 564 mg / g in manganese-containing wastewater; a cobalt extraction capacity of higher than 270 mg / g in cobalt-containing wastewater; and a nickel extraction capacity of greater than 573 mg / g in nickel-containing wastewater.

[0109] When the solution is a mixed solution containing Al ions, Ni ions, Li ions, and Co ions, selective extraction of ions is achieved by applying a step-by-step voltage. For example, applying a voltage of -0.4V can achieve the extraction of Al ions, applying a voltage of -0.6V can achieve the extraction of Ni ions, applying a voltage of -0.7V can achieve the extraction of Co ions, and applying a voltage of -0.8V can achieve the extraction of Li ions.

[0110] Example 4

[0111] The operation steps of this example are the same as those of Example 2, except that the second reaction temperature is 120°C and the reaction time is 12 hours, and the third reaction temperature is 70°C and the reaction time is 12 hours. The yield is about 80%.

[0112] The phenazine-based electrochemical electrode material prepared in this embodiment has a lithium extraction capacity of higher than 72 mg / g in salt lake brine, and a lithium / sodium selective distribution coefficient of higher than 80; a chromium extraction capacity of higher than 419 mg / g in chromium-containing wastewater; a lead extraction capacity of higher than 1760 mg / g in lead-containing wastewater; a gold extraction capacity of higher than 1190 mg / g in gold-containing wastewater; an aluminum extraction capacity of higher than 286 mg / g in aluminum-containing industrial wastewater; a manganese extraction capacity of higher than 584 mg / g in manganese-containing wastewater; a cobalt extraction capacity of higher than 280 mg / g in cobalt-containing wastewater; and a nickel extraction capacity of greater than 584 mg / g in nickel-containing wastewater.

[0113] When the solution contains a mixed solution of Al ions, Mn ions, Co ions, and Li ions, selective extraction of ions is achieved by applying a step-by-step voltage. For example, applying a voltage of -0.4V can extract Al ions, applying a voltage of -0.5V can extract Mn ions, applying a voltage of -0.7V can extract Co ions, and applying a voltage of -0.8V can extract Li ions.

[0114] Example 5

[0115] This example follows the same procedures as Example 2, except that the mass ratio of the phenazine-based small molecule monomer, the second ligand monomer, the catalyst, and the organic solvent is 1:1.5:0.02:10; and the mass ratio of the phenazine-based precursor material to the third ligand monomer is 1:1.5. The yield is approximately 79%.

[0116] The phenazine-based electrochemical electrode material prepared in this embodiment has a lithium extraction capacity of greater than 61 mg / g in salt lake brine, and a lithium / sodium selective distribution coefficient of greater than 73; a chromium extraction capacity of greater than 405 mg / g in chromium-containing wastewater; a lead extraction capacity of greater than 1776 mg / g in lead-containing wastewater; a gold extraction capacity of greater than 1185 mg / g in gold-containing wastewater; an aluminum extraction capacity of greater than 282 mg / g in aluminum-containing industrial wastewater; a manganese extraction capacity of greater than 581 mg / g in manganese-containing wastewater; a cobalt extraction capacity of greater than 285 mg / g in cobalt-containing wastewater; and a nickel extraction capacity of greater than 581 mg / g in nickel-containing wastewater.

[0117] When the solution contains a mixed solution of Al ions, Mn ions, Co ions, and Li ions, selective extraction of ions is achieved by applying a step-by-step voltage. For example, applying a voltage of -0.4V can extract Al ions, applying a voltage of -0.5V can extract Mn ions, applying a voltage of -0.7V can extract Co ions, and applying a voltage of -0.8V can extract Li ions.

[0118] Example 6

[0119] 5,10-Dihydrodichlorodiaminephenoxazine, hydroxybromobenzene, and bromobenzene were weighed at a molar ratio of 1:1.5, added to 100 mL of tetrahydrofuran and 0.03 g of trisdibenzylideneacetone dipalladium. The reaction was carried out at 80°C for 12 hours to synthesize the target phenazine-based electrochemical electrode material. The material was then washed with acetone and purified by Soxhlet extraction. The yield was approximately 70%.

[0120] The preparation process of the phenazine-based electrochemical electrode material of this embodiment is as follows:

[0121]

[0122] The phenazine-based electrochemical electrode material prepared in this embodiment has four CN and C═N functional groups, and has a lithium extraction capacity of greater than 68 mg / g in salt lake brine, and a lithium / sodium selective distribution coefficient of greater than 52; a chromium extraction capacity of greater than 436 mg / g in chromium-containing wastewater; a lead extraction capacity of greater than 1720 mg / g in lead-containing wastewater; a gold extraction capacity of greater than 1153 mg / g in gold-containing wastewater; an aluminum extraction capacity of greater than 264 mg / g in aluminum-containing industrial wastewater; a manganese extraction capacity of greater than 591 mg / g in manganese-containing wastewater; a cobalt extraction capacity of greater than 275 mg / g in cobalt-containing wastewater; and a nickel extraction capacity of greater than 581 mg / g in nickel-containing wastewater.

[0123] When the solution is a mixed solution containing Al ions, Ni ions, Li ions, and Co ions, selective extraction of ions is achieved by applying a step-by-step voltage. For example, applying a voltage of -0.4V can achieve the extraction of Al ions, applying a voltage of -0.6V can achieve the extraction of Ni ions, applying a voltage of -0.7V can achieve the extraction of Co ions, and applying a voltage of -0.8V can achieve the extraction of Li ions.

[0124] Example 7

[0125] 5,10-phenothiazine and bromobenzene were weighed at a molar ratio of 1:1.5, added to 150 mL of tetrahydrofuran and 0.03 g of trisdibenzylideneacetone dipalladium. The reaction was carried out at 100°C for 12 hours to synthesize the target phenazine-based electrochemical electrode material. The material was then washed with acetone and purified by Soxhlet extraction. The yield was approximately 72%.

[0126] The preparation process of the phenazine-based electrochemical electrode material of this embodiment is as follows:

[0127]

[0128] The phenazine-based electrochemical electrode material prepared in this embodiment has four CN and C=N functional groups, and its lithium extraction capacity in salt lake brine is higher than 56 mg / g, and its lithium / sodium selective distribution coefficient is higher than 45; its chromium extraction capacity in chromium-containing wastewater is higher than 435 mg / g; its lead extraction capacity in lead-containing wastewater is higher than 1620 mg / g; its gold extraction capacity in gold-containing wastewater is higher than 1124 mg / g; its aluminum extraction capacity in aluminum-containing industrial wastewater is higher than 282 mg / g; its manganese extraction capacity in manganese-containing wastewater is higher than 589 mg / g; its cobalt extraction capacity in cobalt-containing wastewater is higher than 256 mg / g; and its nickel extraction capacity in nickel-containing wastewater is greater than 559 mg / g.

[0129] When the solution is a mixed solution containing Al ions, Ni ions, Li ions, and Co ions, selective extraction of ions is achieved by applying a step-by-step voltage. For example, applying a voltage of -0.4V can achieve the extraction of Al ions, applying a voltage of -0.6V can achieve the extraction of Ni ions, applying a voltage of -0.7V can achieve the extraction of Co ions, and applying a voltage of -0.8V can achieve the extraction of Li ions.

[0130] Comparative Example 1

[0131] This comparative example uses commercially available or conventional electrochemical extraction electrode materials for selective extraction and separation in a multi-ion complex solution.

[0132] When commercially available anthraquinone is used as a comparative electrode material, its lithium extraction capacity in salt lake brine is higher than 14 mg / g, and its lithium / sodium selective distribution coefficient is higher than 4; its chromium extraction capacity in chromium-containing wastewater is higher than 257 mg / g; its lead extraction capacity in lead-containing wastewater is higher than 586 mg / g; its gold extraction capacity in gold-containing wastewater is higher than 354 mg / g; its aluminum extraction capacity in aluminum-containing industrial wastewater is higher than 127 mg / g; its manganese extraction capacity in manganese-containing wastewater is higher than 245 mg / g; its cobalt extraction capacity in cobalt-containing wastewater is higher than 138 mg / g; and its nickel extraction capacity in nickel-containing wastewater is greater than 245 mg / g.

[0133] This comparative example cannot perform distributed voltage ion extraction using commercially available or conventional electrochemical extraction electrode materials.

[0134] Comparative Example 2

[0135] The operation steps of this comparative example are the same as those of Example 8, except that the first reaction temperature is 250° C., the reaction time is 5 h, and the yield is about 30%.

[0136] The phenazine-based electrochemical electrode material prepared in this comparative example has a lithium extraction capacity higher than 35 mg / g in salt lake brine, and a lithium / sodium selective distribution coefficient higher than 32; its chromium extraction capacity in chromium-containing wastewater is higher than 346 mg / g; its lead extraction capacity in lead-containing wastewater is higher than 1257 mg / g; its gold extraction capacity in gold-containing wastewater is higher than 967 mg / g; its aluminum extraction capacity in aluminum-containing industrial wastewater is higher than 215 mg / g; its manganese extraction capacity in manganese-containing wastewater is higher than 524 mg / g; its cobalt extraction capacity in cobalt-containing wastewater is higher than 218 mg / g; and its nickel extraction capacity in nickel-containing wastewater is greater than 462 mg / g.

[0137] When the solution is a mixed solution containing Al ions, Ni ions, Li ions, and Co ions, selective ion extraction is achieved by applying a step-by-step voltage. For example, applying a voltage of -0.4V can extract Al ions, applying a voltage of -0.6V can extract Ni ions, applying a voltage of -0.7V can extract Co ions, and applying a voltage of -0.8V can extract Li ions. In this comparative example, the ion extraction effect of using a step-by-step voltage is only 57% of that of Al ions, 64% of that of Ni ions, 58% of that of Co ions, and 32% of that of Li ions in the embodiment.

[0138] Comparative Example 3

[0139] The operation steps of this comparative example are the same as those of Example 1, except that the first reaction temperature is 10° C., the reaction time is 12 h, and the yield is about 8%.

[0140] The phenazine-based electrochemical electrode material prepared in this comparative example has a lithium extraction capacity higher than 12 mg / g in salt lake brine, and a lithium / sodium selective distribution coefficient higher than 8; a chromium extraction capacity higher than 114 mg / g in chromium-containing wastewater; a lead extraction capacity higher than 725 mg / g in lead-containing wastewater; a gold extraction capacity higher than 657 mg / g in gold-containing wastewater; an aluminum extraction capacity higher than 124 mg / g in aluminum-containing industrial wastewater; a manganese extraction capacity higher than 246 mg / g in manganese-containing wastewater; a cobalt extraction capacity higher than 56 mg / g in cobalt-containing wastewater; and a nickel extraction capacity greater than 89 mg / g in nickel-containing wastewater.

[0141] When the solution is a mixed solution containing Al ions, Ni ions, Li ions, and Co ions, selective extraction of ions is achieved by applying a step-by-step voltage, such as applying a -0.4V voltage to achieve extraction of Al ions, applying a -0.6V voltage to achieve extraction of Ni ions, applying a -0.7V voltage to achieve extraction of Co ions, and applying a -0.8V voltage to achieve extraction of Li ions. In this comparative example, a step-by-step voltage is used for ion extraction, and the ion extraction effect is only 12% of Al ions, 24% of Ni ions, 18% of Co ions, and 13% of Li ions in the embodiment. Aspects, embodiments, features, and examples of the present invention should be considered to be illustrative in all aspects and are not intended to limit the present invention. The scope of the present invention is defined only by the claims. Without departing from the spirit and scope of the claimed invention, other embodiments, modifications, and uses will be apparent to those skilled in the art.

[0142] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments using other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0143] Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions, and / or additions may be made and that substantial equivalents may be substituted for the elements of the embodiments without departing from the spirit and scope of the present invention. Additionally, many modifications may be made to adapt specific circumstances or materials to the teachings of the present invention without departing from the scope of the present invention. Therefore, it is not intended herein to limit the present invention to the disclosed specific embodiments for carrying out the present invention, but rather to include all embodiments within the scope of the appended claims. Furthermore, unless specifically stated, any use of the terms first, second, etc. does not indicate any order or importance, but rather uses the terms first, second, etc. to distinguish one element from another.

Claims

1. Use of a phenazine-based electrochemical electrode material in the selective separation and extraction of ions; the molecular structure of the phenazine-based electrochemical electrode material is at least one of the following: in, The M group includes any one of the elements O and S; The R1 group includes at least one of hydrogen, an alkyl chain, and an aromatic ring; The R4 group includes any one or a combination of two or more of hydrogen, halogen, amino, hydroxyl, amine, halogen aromatic ring, amino aromatic ring, amine aromatic ring, and hydroxyl aromatic ring, and at least one of the R4 groups is not hydrogen; The value range of n1 is 0 to 3, and the value range of n2 is 500 to 5000.

2. The use according to claim 1, characterized in that: The applications include the application of phenazine-based electrochemical electrode materials to selectively separate and extract valuable metal ions in aqueous solution phases; Preferably, the aqueous solution phase comprises at least any one of liquid ore solution, waste battery leachate, salt lake brine, and non-ferrous metal production industrial wastewater; Preferably, the valuable metal ions include Li + 、Au 2+ Cr 6+ , Pb 2+ 、Al 3+ 、Mn 2+ 、Co 2+ 、Ni 2+ At least any one of .

3. A phenazine-based electrochemical electrode material, characterized in that: The molecular structure of the phenazine-based electrochemical electrode material is at least one of the following: Wherein, the M group includes any one of O and S elements; The R1 group includes at least one of hydrogen, an alkyl chain, and an aromatic ring; The R4 group includes any one or a combination of two or more of hydrogen, halogen, amino, hydroxyl, amine, halogen aromatic ring, amino aromatic ring, amine aromatic ring, and hydroxyl aromatic ring, and at least one of the R4 groups is not hydrogen; The value range of n1 is 0 to 3, and the value range of n2 is 500 to 5000.

4. The method for preparing the phenazine-based electrochemical electrode material according to claim 3, characterized in that: include: allowing a first mixed system including a phenazine-based small molecule monomer, a first ligand monomer, a catalyst, and an organic solvent to undergo a first reaction in a protective atmosphere to obtain the phenazine-based electrochemical electrode material; Alternatively, a second mixed system comprising a phenazine-based small molecule monomer, a second ligand monomer, a catalyst, and an organic solvent undergoes a second reaction to generate a phenazine-based precursor material, and the phenazine-based precursor material and a third ligand monomer undergo a third reaction under a protective atmosphere to obtain the phenazine-based electrochemical electrode material.

5. The preparation method according to claim 4, characterized in that: The temperature of the first reaction is 25-200°C and the time is 5-12h; And / or, the mass ratio of the phenazine-based small molecule monomer, the first ligand monomer, the catalyst and the organic solvent in the first mixed system is 1:1-2:0.01-0.05:2-10.

6. The preparation method according to claim 4, characterized in that: The temperature of the second reaction is 25-200°C and the time is 5-12h; and / or, the mass ratio of the phenazine-based small molecule monomer, the second ligand monomer, the catalyst, and the organic solvent in the second mixed system is 1:1-2:0.01-0.05:2-10; and / or, the temperature of the second reaction is 25 to 200° C., and the time is 5 to 12 hours; and / or, the mass ratio of the phenazine-based precursor material to the third ligand monomer is 1:1 to 1:2; And / or, the temperature of the third reaction is 25-200° C., and the time is 5-12 hours.

7. The preparation method according to claim 4, characterized in that The molecular structure of the phenazine-based small molecule monomer is at least one of the following: Wherein, the M group includes any one of O and S elements; the R1 group includes at least any one of hydrogen, alkyl chain, and aromatic ring; the R2 group includes any one of hydrogen, halogen, amino, hydroxyl, and amine, or a combination of two or more thereof, and at least one of the R2 groups is not hydrogen; And / or, the molecular structure of the first ligand monomer is as shown in formula (I): wherein R3 includes any one or a combination of two or more of hydrogen, halogen, amino, and hydroxyl groups, at least one of the R3 groups is not hydrogen, and the number of halogen, amino, or hydroxyl functional groups in the first ligand monomer is at least 4; And / or, the molecular structure of the second ligand monomer is as shown in formula (J): Wherein, R3 includes any one or a combination of two or more of halogen, amino, and hydroxyl groups, and the number of halogen, amino, or hydroxyl functional groups in the second ligand monomer is at least 4; and / or, the structural formula of the third ligand monomer is the same as that of the second ligand monomer, wherein the R3 group comprises any one or a combination of two or more of hydrogen, halogen, amino, and hydroxyl, at least one of the R3 groups is not hydrogen, and the R3 group in the third ligand monomer is different from the R3 group in the second ligand monomer; And / or, the molecular structure of the phenazine-based precursor material is shown in formula (K): The R5 group includes any one of amine, sulfur, and oxygen, or a combination of two or more.

8. The preparation method according to claim 4, characterized in that: The organic solvent includes at least any one of N-methylpyrrolidone, N,N-dimethylformamide, acetic acid, toluene, o-xylene or tetrahydrofuran; And / or, the protective atmosphere includes at least any one of nitrogen or argon; And / or, the catalyst comprises a palladium-based catalyst.

9. A method for selectively separating and extracting ions, characterized in that: include: The phenazine-based electrochemical electrode material according to claim 3 is used as a cathode; The electrochemical reaction system including an anode, a cathode and an electrolyte is electrified, and different voltages are applied to the cathode to perform step-by-step ion extraction to obtain a phenazine-based composite material coordinated with different metal ions; wherein the voltage difference is controlled within 1V.

10. The method for selectively separating and extracting ions according to claim 9, characterized in that: The voltage range includes -1.5 to 1.5V; And / or, the anode comprises at least any one of a carbon material or a p-type organic material; Preferably, the p-type organic material includes polyaniline; And / or, the electrolyte includes at least any one of liquid ore solution, waste battery leachate, salt lake brine, and non-ferrous metal production industrial wastewater; And / or, the metal ions include Li + 、Au 2+ Cr 6+ , Pb 2+ 、Al 3+ 、Mn 2+ 、Co 2+ 、Ni 2+ At least one of the following: And / or, during the ion extraction process, the adsorption sites of different metal ions are from high to low: Au 2+ 、Al 3+ Cr 6+ 、Mn 2+ 、Co 2+ 、Ni 2+ 、Li + , Pb 2+ .

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