CN113214235A - Thienyl and selenophenyl viologen derivatives, and synthetic method and application thereof - Google Patents

Thienyl and selenophenyl viologen derivatives, and synthetic method and application thereof Download PDF

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CN113214235A
CN113214235A CN202110316770.7A CN202110316770A CN113214235A CN 113214235 A CN113214235 A CN 113214235A CN 202110316770 A CN202110316770 A CN 202110316770A CN 113214235 A CN113214235 A CN 113214235A
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viologen
viologen derivative
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何刚
刘旭
张旭日
张冰洁
张思坤
李国平
杨小东
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Xian Jiaotong University
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Abstract

The invention relates to thienyl and selenophenyl viologen derivatives, a synthesis method and application thereof, wherein an ideal electron acceptor material is obtained by combining viologen compounds with electron donating thiophene groups and selenophen groups, so that the conjugation property and stability of the viologen derivatives are widened, the rapid intramolecular electron transfer is realized, and the viologen derivatives have outstanding dynamic performance; by introducing quaternary ammonium salt, the reduction threshold of the material is greatly reduced, the solubility and the conductivity are improved, multi-electron charging and discharging can be carried out, and the capacity is further improved. Single electron charging and discharging can be carried out by introducing hydroxyl, so that the structural stability is further improved; after the bromide ions of the corresponding viologen derivatives are converted into chloride ions, the electrode material can keep consistent with ions in the electrolyte and balance charges when being applied to a neutral water system organic redox flow battery; the molecular weight is reduced, the solubility is improved, and the influence of bromine ion electricity on electrochemical test can be eliminated.

Description

Thienyl and selenophenyl viologen derivatives, and synthetic method and application thereof
Technical Field
The invention belongs to the technical field of electrode materials of flow batteries, and particularly relates to thienyl and selenophenyl viologen derivatives, and a synthetic method and application thereof.
Background
Energy shortage and environmental problems are two major problems facing human beings at present. The use of clean and efficient energy sources, represented by solar and wind energy, is becoming a trend in the world. However, the strong fluctuation and intermittency of solar energy and wind power generation bring great challenges to the stable output of the traditional power grid, and the efficient storage and transportation of such electric energy becomes a hot issue of current research. However, at present, the existing energy infrastructure based on fossil fuel cannot meet the requirements of social sustainable development, and thus, the improvement of energy supply capacity and energy safety face a serious challenge. To solve these problems and improve the ability of the grid to adapt to the intermittent nature of renewable energy generation, large capacity, large scale energy storage technologies are required. These energy storage devices can provide am, fm, smooth output, and regulated power generation, providing continuity, stability, and controllability of renewable energy power generation, reducing renewable energy challenges. Therefore, high capacity large scale energy storage technology is the key to expanding renewable energy. The electrochemical energy storage has the advantages of longer discharge time and capacity range, no pollution operation, high energy efficiency, low maintenance cost, no space-time limitation and the like, and can meet the requirements of power grids of different scales.
Traditional energy storage devices, such as secondary batteries of lithium ion batteries, super capacitors and the like, cannot be applied in large scale due to the limitation of the cost of raw materials and the like. Active substances of redox flow batteries (RFBs for short) are separately filled in a liquid storage tank in the form of aqueous solution, have the characteristics of high capacity and high power, and are regarded as one of the most important technologies for large-scale power grid energy storage. At present, the raw materials of the all-vanadium redox flow battery and the zinc-bromine redox flow battery are expensive, the electrolyte has corrosivity and toxic and side effects, the energy density is difficult to further improve, potential dangers exist, and the large-scale use of the redox flow battery is greatly limited. Therefore, a flow battery with high power, large capacity, low cost and high safety is urgently needed.
In recent years, aqueous organic redox flow batteries (abbreviated as AORFBs) have attracted much attention worldwide, and their positive and negative electrode materials are composed of organic molecules rich in earth, such as C, H, O, N, S, etc., and are various in types, cheap and easily available; the electrolyte is a cheap sodium chloride/potassium chloride aqueous solution, is not easy to volatilize, has no corrosivity and good safety performance; the electrochemical performance of the material can be adjusted by molecular engineering.
At present, viologen derivatives, anthraquinone molecules, ferrocene, TEMPO compounds and oxazine compounds are widely used in the research of water-based organic redox flow batteries, wherein the ferrocene and TEMPO compounds are very excellent positive electrode materials, and have good stability and high solubility; quinone molecules and oxazine compounds are mainly used in harsh acidic and alkaline environments and are used as cathode materials, the electrolyte has strong corrosivity, and system components such as a liquid storage tank, a flow channel and the like which are matched with the electrolyte have corresponding corrosion resistance, so that the potential cost of the system is increased; the viologen derivative is widely used as a negative electrode material in a neutral environment, and has the advantages of high safety coefficient, rich molecular structure and low cost. Viologen derivatives are cationic organic molecules with excellent redox properties, commonly referred to as N-alkylated derivatives of 4,4' -bipyridine, which can undergo two-step reversible, one-electron redox by application of a voltage or direct irradiation:
Figure BDA0002987409980000021
the reaction mechanism is shown below, and has obvious color change. Due to the multi-functionality, adjustability, electron-withdrawing ability and faster electron transfer property of the viologen derivative, the viologen derivative has wide application rangeThe viologen derivatives have a potential application prospect, and in the past decades, the viologen derivatives show excellent performance in the fields of electrochromic devices (ECD for short), metal supermolecule assembly, host-guest complexes, solar fuel conversion, photocatalysis and energy storage (such as lithium ion batteries and flow batteries).
Figure BDA0002987409980000022
In a neutral water-based organic redox flow battery, an viologen derivative is generally used as a single-electron storage medium. The result shows that the second electron of the methyl viologen can not be utilized, and the zero-valent compound formed after the second electron is obtained is insoluble in water and forms a dimer. Therefore, only 50% of the theoretical capacity of methyl viologen can be utilized and the energy density of the battery is significantly limited. Aiming at the problem, several ultraviolet derivatives are designed as double-electron storage media by the Liutian dart team of the institute of chemistry and biochemistry of the State university of Utah in the United states, but because the ultraviolet derivatives have low conjugation degree, large energy gap and large potential difference of different electronic structures, two step platforms are generated in the double-electron transfer process of the ultraviolet derivatives in a charging and discharging platform, and battery management is inconvenient.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a thienyl and selenophenyl viologen derivative, a synthesis method and application thereof, solves the problems of low conjugation, low electron transfer rate, low solubility and low capacity of the viologen derivative, effectively improves the application performance of the viologen system in the field of neutral water system organic redox flow batteries, and can further expand the application field of the viologen derivative.
The invention is realized by adopting the following technical scheme:
a thienyl viologen derivative or selenophenyl viologen derivative, the structural formula of which is shown as follows:
Figure BDA0002987409980000031
wherein R ═ C3NPr or C3OH, X ═ Br or Cl, when E ═ S, the viologen derivatives are thienyl viologen derivatives, when E ═ Se, the viologen derivatives are selenophenyl viologen derivatives.
Process for the synthesis of viologen derivatives when R ═ C3NPr, X ═ Br under the protection of inert gas according to the ratio of 1: 5, dissolving the precursor and (3-bromopropyl) trimethyl ammonium bromide in an organic solvent, reacting at 110-120 ℃ for 40-60 hours to obtain a reaction solution, and then separating and drying a product in the reaction solution to obtain the viologen derivative;
when the viologen derivative is a thienyl viologen derivative, the structural formula of the precursor is shown as a formula 1, and when the viologen derivative is a selenophenyl viologen derivative, the structural formula of the precursor is shown as a formula 2;
Figure BDA0002987409980000041
process for the synthesis of viologen derivatives when R ═ C3And when OH and X are Br, under the protection of inert gas, the reaction is carried out according to the ratio of 1: 5, dissolving the precursor and 3-bromo-1-propanol in an organic solvent, reacting at 80-90 ℃ for 65-75 h to obtain a reaction solution, and then separating and drying a product in the reaction solution to obtain the viologen derivative;
when the viologen derivative is a thienyl viologen derivative, the structural formula of the precursor is shown as a formula 1, and when the viologen derivative is a selenophenyl viologen derivative, the structural formula of the precursor is shown as a formula 2;
Figure BDA0002987409980000042
process for the synthesis of viologen derivatives when R ═ C3NPr, X ═ Cl, comprising the following steps:
step 1, under the protection of inert gas, according to the proportion of 1: 5, dissolving the precursor and (3-bromopropyl) trimethyl ammonium bromide in an organic solvent, reacting at 110-120 ℃ for 40-60 hours to obtain a reaction solution, and then separating and drying a product in the reaction solution to obtain an intermediate product A;
when the viologen derivative is a thienyl viologen derivative, the structural formula of the precursor is shown as a formula 1, and when the viologen derivative is a selenophenyl viologen derivative, the structural formula of the precursor is shown as a formula 2;
Figure BDA0002987409980000043
and 2, dissolving the intermediate product A in deionized water, carrying out anion exchange by using chloride ion exchange resin, separating and drying a product in an exchange solution to obtain an intermediate product B, and removing a unilateral product in the intermediate product B to obtain the viologen derivative.
Further, step 2, firstly dissolving the intermediate product B in methanol, then adding tetrahydrofuran, dichloromethane or ethyl acetate for recrystallization, then adding acetonitrile into the obtained precipitate for condensation reflux to obtain reflux liquid, and finally filtering the reflux liquid to obtain a filter cake and drying the filter cake to obtain the viologen derivative.
Further, step 2, filtering the reflux liquid to obtain filtrate, spin-drying to obtain solid A, and then mixing the solid A with the filtrate according to the proportion of 1: 1, dissolving a solid A and (3-bromopropyl) trimethyl ammonium bromide in an organic solvent under a microwave condition, reacting at 120-130 ℃ for 2-3 h to obtain a reaction solution, and then separating and drying a product in the reaction solution to obtain the viologen derivative.
Process for the synthesis of viologen derivatives when R ═ C3When OH and X are Cl, the method comprises the following steps:
step 1, under the protection of inert gas, according to the proportion of 1: 5, dissolving the precursor and 3-bromo-1-propanol in an organic solvent, reacting at 80-90 ℃ for 65-75 h to obtain a reaction solution, and then separating and drying a product in the reaction solution to obtain an intermediate product C;
when the viologen derivative is a thienyl viologen derivative, the structural formula of the precursor is shown as a formula 1, and when the viologen derivative is a selenophenyl viologen derivative, the structural formula of the precursor is shown as a formula 2;
Figure BDA0002987409980000051
and 2, dissolving the intermediate product C in deionized water, carrying out anion exchange by using chloride ion exchange resin, separating and drying a product in an exchange solution to obtain an intermediate product D, and removing a unilateral product in the intermediate product D to obtain the viologen derivative.
Further, step 2, firstly dissolving the intermediate product D in methanol, then adding tetrahydrofuran, dichloromethane or ethyl acetate for recrystallization, then adding acetonitrile into the obtained precipitate for condensation reflux to obtain reflux liquid, and finally filtering the reflux liquid to obtain a filter cake and drying the filter cake to obtain the viologen derivative.
Further, step 2, filtering the reflux liquid to obtain filtrate, spin-drying to obtain solid B, and then mixing the solid B with the filtrate according to the proportion of 1: 1, dissolving the solid B and 3-bromo-1-propanol in an organic solvent under a microwave condition, reacting at 120-130 ℃ for 2-3 h to obtain a reaction solution, and then separating and drying a product in the reaction solution to obtain the viologen derivative.
Application of viologen derivatives in neutral aqueous organic redox flow batteries.
Compared with the prior art, the invention has the following beneficial effects:
the invention relates to an viologen derivative containing quaternary ammonium salt and bromide ions, which is characterized in that an viologen compound is combined with an electron-donating thiophene group and a selenophene group, the thiophene group and the selenophene group are introduced between two pyridine units, so that an ideal electron acceptor material is obtained, the conjugation property and the stability of the viologen derivative are widened, the rapid intramolecular electron transfer is realized, the viologen derivative has outstanding dynamic performance, the reduction threshold of the material is greatly reduced by introducing a polar functional group quaternary ammonium salt, the solubility and the conductivity are improved, meanwhile, multi-electron charging and discharging can be carried out, and the capacity is further improved.
The viologen derivatives containing hydroxyl and bromide ions are prepared by combining viologen compounds with electron donating thiophene groups and selenophene groups, and introducing the thiophene groups and the selenophene groups between two pyridine units, so that an ideal electron acceptor material is obtained, the conjugation property and the stability of the viologen derivatives are widened, the fast intramolecular electron transfer is realized, the viologen derivatives have outstanding dynamic performance, the solubility and the conductivity can be improved by introducing polar functional group hydroxyl, single electron charge and discharge can be carried out, and the structural stability can be further improved due to the existence of H bonds in the structure.
According to the violet salt and chloride ion-containing viologen derivatives, after bromide ions of the corresponding violet salt derivatives are converted into chloride ions, when the electrode material is applied to a neutral water system organic redox flow battery, the bromide ions are consistent with ions in an electrolyte and are chloride ions, the chloride ions have smaller radius and are easy to exchange, and therefore, charges are balanced; the molecular weight is reduced, and the solubility is improved; and the chloride ions have higher oxidation potential (1.40V vs NHE) than the bromide ions, so that the influence of the bromide ions on electrochemical tests can be eliminated.
According to the viologen derivatives containing hydroxyl and chloride ions, after bromide ions of the corresponding viologen derivatives are converted into chloride ions, when the electrode material is applied to a neutral water system organic redox flow battery, the electrode material is consistent with ions in an electrolyte and is all chloride ions, the radius of the chloride ions is smaller, and the chloride ions are easy to exchange, so that charges are balanced; the molecular weight is reduced, and the solubility is improved; and the chloride ions have higher oxidation potential (1.40V vs NHE) than the bromide ions, so that the influence of the bromide ions on electrochemical tests can be eliminated.
According to the synthesis method of the viologen derivative containing the quaternary ammonium salt and the bromide ions, as the nitrogen atom of pyridine in the precursor contains lone pair electrons, the nitrogen atom belongs to alkali, and the bromide reagent (3-bromopropyl) trimethyl ammonium bromide is an electrophilic reagent and belongs to acid, the two reagents can generate the pyridine ions, so that different thienyl viologen derivatives and selenophenyl viologen derivatives can be obtained by designing one-step reaction. Simple operation process and mild reaction condition. The viologen derivative can be used for preparing a high-performance negative electrode material of a flow battery, and has important significance for synthesis and application of thienyl and selenophenyl viologen derivatives with novel structures.
According to the synthesis method of the viologen derivatives containing hydroxyl and bromide ions, as the nitrogen atom of pyridine in the precursor contains lone pair electrons, belonging to alkali, and the bromization reagent 3 bromo-1-propanol is an electrophilic reagent and belonging to acid, the two reagents can generate pyridine ions, so that different thienyl viologen derivatives and selenophenyl viologen derivatives can be obtained by designing one-step reaction. Simple operation process and mild reaction condition. The viologen derivative can be used for preparing a high-performance negative electrode material of a flow battery, and has important significance for synthesis and application of thienyl and selenophenyl viologen derivatives with novel structures.
The invention relates to a synthesis method of viologen derivatives containing quaternary hydroxyl and chloride ions, which comprises the steps of firstly carrying out anion exchange on the viologen derivatives containing quaternary ammonium salt and bromide ions by using chloride ion exchange resin, carrying out ion equivalent exchange because the adsorption effect of the resin on bromide ions is stronger than that of chloride ions, and removing the obtained products to obtain corresponding chloride ion thienyl viologen derivatives and selenophenyl viologen derivatives. The viologen derivative can be used for preparing a high-performance negative electrode material of a flow battery, and has important significance for synthesis and application of thienyl and selenophenyl viologen derivatives with novel structures.
The invention relates to a synthesis method of viologen derivatives containing hydroxyl and chloride ions, which comprises the steps of firstly carrying out anion exchange on the viologen derivatives containing hydroxyl and bromide ions by using chloride ion exchange resin, carrying out ion equivalent exchange because the adsorption effect of the resin on bromide ions is stronger than that of chloride ions, but removing the single-side products to obtain the corresponding chloride ion thienyl viologen derivatives and selenophenyl viologen derivatives. The viologen derivative can be used for preparing a high-performance negative electrode material of a flow battery, and has important significance for synthesis and application of thienyl and selenophenyl viologen derivatives with novel structures.
Drawings
FIG. 1 shows cyclic voltammograms of thienylviologen derivatives A1 ', A2' and FcNCl prepared in example 1 of the present invention.
FIG. 2 is a Linear Sweep Voltammogram (LSV) (rotation speed of 300-2700 rpm) of thienyl violet derivative A1' prepared in example 1 of the present invention.
FIG. 3 is a column Virgilla diagram of limiting current and square root of rotation rate of thienyl violet crystal derivative A1' prepared in example 1 of the present invention.
FIG. 4 is the UV-VIS absorption spectrum of the thienyl violet derivative A1 ', A2' and the precursor A prepared in example 1 of the invention in DMSO solution, with the concentration of 10～5M。
FIG. 5 shows the spectral band gap curves of thienyl viologen derivatives A1 ', A2' and precursor A prepared in example 1 of the present invention.
FIG. 6 shows UV-visible spectra of thienyl violet derivative A1' prepared in example 1 of the present invention in 1M aqueous solution of sodium chloride.
FIG. 7 shows the relationship between the absorbance and concentration at 376nm of thienyl violet compass derivative A1' prepared in example 1 of the present invention (1M aqueous solution of sodium chloride).
FIG. 8 shows UV-visible spectra of thienyl violet derivative A1' prepared in example 1 according to the present invention in pure water.
FIG. 9 shows the relationship between the absorbance at 376nm and the concentration (pure water) of the thienylviologen derivative A1' prepared in example 1 of the present invention.
FIG. 10 is a graph showing the charge/discharge cycle curves of 0.1M thienyl violet derivative A1 '(8 mL)/0.1M FcNCl (18mL) in 1M aqueous solution of sodium chloride (abbreviated as 0.1M A1'/FcNCl system) prepared in example 1 of this invention and its specific charge/discharge capacity in 1M aqueous solution of sodium chlorideAnd a plot of coulombic efficiency versus cycle number, current density of 40mA/cm2。
FIG. 11 shows that the 0.1M A1'/FcNCl system prepared in example 1 of the present invention has a current density of 20 to 90mA/cm2And the relationship graph of the lower charge-discharge specific capacity and the number of circulating turns.
FIG. 12 shows that the 0.1M A1'/FcNCl system prepared in example 1 of the present invention has a current density of 20 to 90mA/cm2Representative charge and discharge curves for time.
FIG. 13 shows that the 0.1M A1'/FcNCl system prepared in example 1 of the present invention has a current density of 20 to 90mA/cm2Average Coulombic Efficiency (CE), Energy Efficiency (EE), and Voltage Efficiency (VE) plots.
FIG. 14 shows the cyclic voltammogram of the 0.1M A1'/FcNCl system prepared in example 1 of the present invention after 300 cycles.
FIG. 15 is a Nyquist plot (sweep rate of 0.1 mV/cm) of the 0.1M A1'/FcNCl system prepared in example 1 of the present invention2)。
FIG. 16 is a schematic diagram of the positive and negative half-cell reactions of the 0.1M A1'/FcNCl system prepared in example 1 of the present invention.
FIG. 17 is a schematic representation of a charge and discharge device of the 0.1M A1'/FcNCl system prepared in example 1 of the present invention.
FIG. 18 is a graph showing the specific charge-discharge capacity and coulombic efficiency of 0.3M thienyl violet essence derivative A1 '(8 mL)/0.3M FcNCl (18mL) (abbreviated as 0.3M A1'/FcNCl system) prepared in example 1 of the present invention in 1M aqueous solution of sodium chloride, and the current density is 40mA/cm2。
FIG. 19 is a graph showing the specific charge-discharge capacity and coulombic efficiency of 0.1M thienyl violet essence derivative A2 '(8 mL)/0.1M FcNCl (12mL) (abbreviated as 0.1M A2'/FcNCl system) prepared in example 1 of the present invention in 1M aqueous solution of sodium chloride, and the current density is 40mA/cm2。
FIG. 20 shows that the 0.1M A2'/FcNCl system prepared in example 1 of the present invention has a current density of 20 to 90mA/cm2And the relationship graph of the lower charge-discharge specific capacity and the number of circulating turns.
FIG. 21 shows the current density of the 0.1M A2'/FcNCl system prepared in example 1 of the present inventionIs 20 to 90mA/cm2Representative charge and discharge curves for time.
FIG. 22 shows that the 0.1M A2'/FcNCl system prepared in example 1 of the present invention has a current density of 20 to 90mA/cm2Average Coulombic Efficiency (CE), Energy Efficiency (EE), and Voltage Efficiency (VE) plots.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
1. The invention relates to a synthetic method of thienyl viologen derivatives, which comprises the following steps:
1) synthesizing a precursor A of a thienyl viologen derivative through a Suzuki coupling reaction;
under the protection atmosphere of argon, 2, 5-dibromothiophene (4.13mmol), 4-pyridine borate (10.33mmol) and tetratriphenylphosphine palladium (0.21mmol) are placed in a pressure-resistant tube, and the molar ratio of the tetratriphenylphosphine palladium to the tetratriphenylphosphine palladium is 1: 2.5: 0.05, methyltrioctylammonium chloride (phase transfer catalyst), 40mL of oxygen-free potassium carbonate solution (2M) and 60mL of freshly distilled toluene (anhydrous oxygen-free toluene as solvent) were added, the volume ratio of potassium carbonate solution to toluene being 2: 3. the mixture is stirred well and heated to react for 3d at 130 ℃.
And (3) post-treatment process: cooling the reaction mixture to room temperature, separating the liquid, taking the organic matter on the upper layer, spin-drying, and adding 25-30 mL of CHCl3Dissolving, filtering a small amount of black unreacted tetratriphenylphosphine palladium catalyst, washing with water for 3 times, removing inorganic salt potassium carbonate, collecting to obtain an organic phase, then adding 5-8 mL of concentrated hydrochloric acid into the organic phase for ionization, allowing brick red precipitate to appear, adding 20-30 mL of water, allowing the precipitate to disappear, separating the liquid, taking an upper-layer aqueous solution, finally slowly dropwise adding a NaOH saturated aqueous solution for acid-base neutralization until the pH value is 8, and thus precipitating a yellow solid, filtering, and vacuum drying to obtain a precursor A.
The reaction equation is as follows:
Figure BDA0002987409980000101
2) ionizing and modifying the precursor;
ionizing the quaternary ammonium salt: under the protection of inert gas, precursor A (4.2mmol), (3-bromopropyl) trimethyl ammonium bromide (21mmol) is transferred into a pressure resistant pipe, and the molar ratio of the precursor A to the (3-bromopropyl) trimethyl ammonium bromide is 1: and 5, adding 100mL of anhydrous and oxygen-free DMF, continuously heating at 110-120 ℃ for 40-60 h to obtain an orange solid, cooling to room temperature, filtering, washing with DMF and acetone sequentially for three times, and drying in vacuum to obtain a product A1. The reaction equation is as follows:
Figure BDA0002987409980000111
hydroxyl group ionization: under the protection of inert gas, the precursor A (2.1mmol) and 3-bromo-1-propanol (10.5mmol) are transferred into a pressure-resistant tube, and the molar ratio of the two is 1: and 5, adding anhydrous and oxygen-free acetonitrile, carrying out condensation reflux at the temperature of 80-90 ℃ for 65-75 h to obtain an orange-red solid, filtering, washing with acetonitrile and diethyl ether for three times in sequence, and carrying out vacuum drying to obtain a product A2. The reaction equation is as follows:
Figure BDA0002987409980000112
3): ion exchange;
the products A1 and A2 in 2) are Br ion compounds
Figure BDA0002987409980000113
The IRA-900 chloride ion exchange resin carries out column type anion exchange on the bromide ion products A1 and A2 to obtain chloride ion products A1 'and A2'. The product contains a small amount of single-side products and can be removed by the following method: according to the difference of the single-side and double-side product solubility, after 10mL of good solvent methanol is used for dissolving, poor solvent THF, DCM or EA is slowly added, and the volume ratio of the good solvent to the poor solvent is 1: (2 to 3) first, tetrahydrofuranRecrystallizing in pyran (THF), Dichloromethane (DCM) or Ethyl Acetate (EA), and further purifying, placing the precipitate obtained after filtration in 100mL acetonitrile, condensing and refluxing for 20-30 h, repeating for 2-3 times to obtain purer thienyl viologen derivatives A1 'or A2'. Obtaining a filtered filter cake, namely the final product. And (3) spin-drying the separated filtrate to obtain a unilateral product, and then performing reaction according to the weight ratio of 1: 1, recovering, adding (3-bromopropyl) trimethyl ammonium bromide or 3 bromo-1-propanol, and repeating the ionization process, wherein the difference is that the reaction is carried out for 2-3 hours at the temperature of 120-130 ℃ by using microwaves.
The reaction equation is as follows:
Figure BDA0002987409980000121
2. the invention relates to a synthetic method of a selenophenyl viologen derivative, which comprises the following steps:
1) synthesizing a precursor B of the thienyl viologen derivative through Suzuki coupling reaction;
under the protection of argon, 2, 5-dibromoselenophene (3.46mmol), 4-pyridine borate (8.66mmol) and tetratriphenylphosphine palladium (0.17mmol) are put into a pressure-resistant tube, and the molar ratio of the three is 1: 2.5: 0.05, methyltrioctylammonium chloride (phase transfer catalyst), 40mL of oxygen-free potassium carbonate solution (2M) and 60mL of freshly distilled toluene are added in a volume ratio of 2: 3. the mixture is stirred well and heated to react for 3d at 130 ℃.
And (3) post-treatment process: cooling the reaction mixture to room temperature, separating the liquid, taking the organic matter on the upper layer, spin-drying, and adding 25-30 mL of CHCl3Dissolving, filtering a small amount of black unreacted tetratriphenylphosphine palladium catalyst, washing with water for 3 times, removing inorganic salt potassium carbonate, collecting to obtain an organic phase, then adding 5-8 mL of concentrated hydrochloric acid into the organic phase for ionization, allowing brick red precipitate to appear, adding 20-30 mL of water, allowing the precipitate to disappear, separating the liquid, taking an upper-layer aqueous solution, finally slowly dropwise adding a NaOH saturated aqueous solution for acid-base neutralization until the pH value is 8, so as to separate out a brown solid, filtering, and vacuum drying to obtain a precursor B.
The reaction equation is as follows:
Figure BDA0002987409980000122
2) ionizing and modifying the precursor;
ionizing the quaternary ammonium salt: under the protection of inert gas, precursor B (3.51mmol), (3-bromopropyl) trimethylammonium bromide (17.53mmol) was transferred into a pressure-resistant tube in a molar ratio of 1: and 5, adding 100mL of anhydrous and oxygen-free DMF, continuously heating at 110-120 ℃ for 40-60 h to obtain a dark red solid, cooling to room temperature, filtering, washing with DMF and acetone sequentially for three times, and drying in vacuum to obtain a product B1. The reaction equation is as follows:
Figure BDA0002987409980000131
hydroxyl group ionization: under the protection of inert gas, the precursor B (1.75mmol) and 3-bromo-1-propanol (10.5mmol) are transferred into a pressure-resistant tube, and the molar ratio of the two is 1: and 5, adding 100mL of anhydrous oxygen-free acetonitrile, carrying out condensation reflux at 80-90 ℃ for 65-75 h to obtain an orange-red solid, filtering, washing with acetonitrile and diethyl ether for three times in sequence, and carrying out vacuum drying to obtain a product B2. The reaction equation is as follows:
Figure BDA0002987409980000132
3): ion exchange;
the products B1 and B2 in 2) are Br ion compounds
Figure BDA0002987409980000133
The IRA-900 chloride ion exchange resin carries out column type anion exchange on the bromide ion products B1 and B2 to obtain chloride ion products B1 'and B2'. The product contains a small amount of single-side products and can be removed by the following method: according to the difference of the single-side and double-side product solubility, after 10mL of good solvent methanol is used for dissolving, poor solvent THF, DCM or EA is slowly added, and the good solvent and the poor solvent are addedThe volume ratio of the agents is 1: (2-3), recrystallizing in Tetrahydrofuran (THF), Dichloromethane (DCM) or Ethyl Acetate (EA), and for further purification, placing the precipitate obtained after filtration in 100mL acetonitrile, condensing and refluxing for 20-30 h, repeating for 2-3 times to obtain the pure selenophenyl-containing viologen derivative B1 'or B2'. Obtaining a filtered filter cake, namely the final product. And (3) spin-drying the separated filtrate to obtain a unilateral product, and then performing reaction according to the weight ratio of 1: 1, recovering, adding (3-bromopropyl) trimethyl ammonium bromide or 3 bromo-1-propanol, and repeating the ionization process, wherein the difference is that the reaction is carried out for 2-3 hours at the temperature of 120-130 ℃ by using microwaves.
Figure BDA0002987409980000141
Example 1:
1. the invention relates to a synthetic method of thienyl viologen derivatives, which comprises the following steps:
1) synthesizing a precursor A of a thienyl viologen derivative through a Suzuki coupling reaction;
a100 mL mouth-branched bottle and a 250mL pressure tube were dried and pumped down for use. 40mL of potassium carbonate solution (2M) was prepared and bubbled for 20 minutes. 1g of 2, 5-dibromothiophene (4.13mmol) and 2.12g of 4-pyridineboronic acid ester (10.33mmol) are taken, and the molar ratio of the two is 1: 2.5, into a 250mL pressure resistant tube prepared in advance, 260mg of tetrakistriphenylphosphine palladium (0.21mmol) was weighed in a glove box as a reaction catalyst. Under an argon atmosphere, 1mL of methyltrioctylammonium chloride (phase transfer catalyst), 40mL of potassium carbonate solution (2M), 60mL of freshly distilled toluene were added. The mixture is stirred well and heated to react for 3d at 130 ℃.
And (3) post-treatment process: cooling the reaction mixture to room temperature, separating, collecting the upper organic layer, spin-drying, and adding CHCl3Dissolving, filtering a small amount of black unreacted tetratriphenylphosphine palladium catalyst, washing with water for 3 times (removing inorganic salt potassium carbonate), collecting to obtain an organic phase, adding concentrated hydrochloric acid into the organic phase for ionization, allowing brick red precipitate to appear, adding 30ml water, allowing the precipitate to disappear, separating, collecting the upper layer aqueous solution, and slowly dropwise adding NaOH saturated aqueous solution(acid-base neutralization) until pH 8, whereby a yellow solid precipitated, filtered and dried in vacuo to yield 0.71g of precursor a in 72% yield. The reaction equation is as follows:
Figure BDA0002987409980000151
2) ionizing and modifying the precursor;
ionizing the quaternary ammonium salt: under the protection of inert gas, 1g of precursor A (4.2mmol), 5.5g of (3-bromopropyl) trimethyl ammonium bromide (21mmol) are transferred into a pressure resistant tube, and the molar ratio of the two is 1: 5, 100mL of anhydrous and oxygen-free DMF was added and heating was continued at 110 ℃ for 2d to give an orange-yellow solid which was cooled to room temperature, filtered, washed three times with DMF and acetone in that order and dried under vacuum to give 2.23g of product A1 in 70% yield. The reaction equation is as follows:
Figure BDA0002987409980000152
hydroxyl group ionization: under the protection of inert gas, 0.5g of precursor A (2.1mmol), 1.5g of 3-bromo-1-propanol (10.5mmol) were transferred into a pressure tube in a molar ratio of 1: 5, 100mL of anhydrous and oxygen-free acetonitrile is added, and the mixture is condensed and refluxed for 3d at 85 ℃ to obtain orange-red solid, filtered, washed with acetonitrile and ether for three times in sequence, and dried in vacuum to obtain 0.8g of product A2 with the yield of 74 percent. The reaction equation is as follows:
Figure BDA0002987409980000153
3): ion exchange;
the products A1 and A2 in 2) are Br ion compounds
Figure BDA0002987409980000154
The IRA-900 chloride exchange resin performs column anion exchange on the bromide product a1, a 2. Prepared 50ml of pretreated
Figure BDA0002987409980000155
IRA-900 chloride ion exchange resin, packed in a column. 1g of product A1(1.32mmol) and 1g of product A2(1.94mmol) are dissolved in 10ml of pure water, and the solution is added into a column and slowly subjected to column separation at a flow rate of less than 10 drops/min. The chloride ion products 760mg A1 'and 820mg A2' were obtained in nearly 100% yield. The product contains a small amount of single-side products and can be removed by the following method: according to the difference of the solubility of single and double side products, firstly using 10mL of good solvent methanol to dissolve, then slowly adding 30mL of the above-mentioned poor solvent, simultaneously stirring, when a small amount of turbidity appears, standing still, when a large amount of precipitate appears, filtering and drying. For further purification, the precipitate obtained after filtration was placed in 100mL acetonitrile, and condensed and refluxed for 1d, and repeated for 2 times, to obtain a more pure thienyl viologen derivative A1 'or A2'. Obtaining a filtered filter cake, namely the final product. And (3) spin-drying the separated filtrate to obtain a unilateral product, and then performing reaction according to the weight ratio of 1: 1, (3-bromopropyl) trimethylammonium bromide or 3-bromo-1-propanol were recovered and the above ionization process was repeated except that the reaction was carried out at microwave 130 ℃ for 2 h. The reaction equation is as follows:
Figure BDA0002987409980000161
2. the invention relates to a synthetic method of a selenophenyl viologen derivative, which comprises the following steps:
1) synthesizing a precursor B of the selenophenyl viologen derivative through Suzuki coupling reaction;
the preparation reaction process comprises the following steps: a100 mL mouth-branched bottle and a 250mL pressure tube were dried and pumped down for use. 40mL of potassium carbonate solution (2M) was prepared and bubbled for 20 minutes. 1g of 2, 5-dibromoselenophene (3.46mmol) and 1.77g of 4-pyridine borate (8.66mmol) are taken, and the molar ratio of the two is 1: 2.5, a 250mL pressure resistant tube prepared in advance was charged, and 200mg of tetrakistriphenylphosphine palladium (0.17mmol) was weighed in a glove box as a reaction catalyst. Under an argon atmosphere, 5 drops of methyltrioctylammonium chloride (phase transfer catalyst), 40ml of potassium carbonate solution (2M), 60ml of freshly distilled toluene were added. The mixture is stirred well and heated to react for 3d at 130 ℃.
And (3) post-treatment process: cooling the reaction mixture to room temperature, separating, collecting the upper organic layer, spin-drying, and adding CHCl3Dissolving, filtering a small amount of black unreacted catalyst, washing for 3 times (removing inorganic salts), collecting an organic phase, then adding concentrated hydrochloric acid into the organic phase (ionizing), generating red brick-shaped precipitate, adding a proper amount of water, removing the precipitate, separating, taking an upper-layer aqueous solution, finally slowly dropwise adding a saturated aqueous solution of NaOH (neutralizing acid and alkali) until the pH value is 8, thereby separating out brown solid, filtering, and drying in vacuum to obtain 1.82g of precursor B with the yield of 65%. The reaction equation is as follows:
Figure BDA0002987409980000171
2) ionizing and modifying the precursor;
ionizing the quaternary ammonium salt: under the protection of inert gas, 1g of precursor B (3.51mmol), 4.58g of (3-bromopropyl) trimethylammonium bromide (17.53mmol) were transferred into a pressure-resistant tube in a molar ratio of 1: 5, 100mL of anhydrous and oxygen-free DMF was added and heating continued at 110 ℃ for 2d to give a dark red solid which was cooled to room temperature, filtered, washed three times with DMF, acetone in that order and dried under vacuum to give 2g of product B1 in 71% yield. The reaction equation is as follows:
Figure BDA0002987409980000172
hydroxyl group ionization: under the protection of inert gas, 0.5g of precursor B (1.75mmol), 1.22g of 3-bromo-1-propanol (10.5mmol) were transferred into a pressure tube in a molar ratio of 1: 5, 100mL of anhydrous and oxygen-free acetonitrile was added, and the mixture was condensed and refluxed at 85 ℃ for 3d to obtain an orange-red solid, which was filtered, washed three times with acetonitrile and ether in this order, and dried under vacuum to obtain 0.72g of product B2 with a yield of 73%. The reaction equation is as follows:
Figure BDA0002987409980000173
3): ion exchange;
the products B1 and B2 in 2) are Br ion compounds
Figure BDA0002987409980000174
The IRA-900 chloride ion exchange resin performs column anion exchange on the bromide ion products B1, B2. Prepared 50ml of pretreated
Figure BDA0002987409980000181
IRA-900 chloride ion exchange resin, packed in a column. 1g of product B1(1.24mmol) and 1g of product B2(1.78mmol) are respectively dissolved in 10ml of pure water, added into a column and slowly subjected to column separation at a flow rate of less than 10 drops/min. The chloride ion products 780mg B1 'and 840mg B2' were obtained with yields approaching 100%. The product contains a small amount of single-side products and can be removed by the following method: according to the difference of the solubility of single and double side products, firstly using 10mL of good solvent methanol to dissolve, then slowly adding 30mL of the above-mentioned poor solvent, simultaneously stirring, when a small amount of turbidity appears, standing still, when a large amount of precipitate appears, filtering and drying. For further purification, the precipitate obtained after filtration is placed in 100mL of acetonitrile, condensed and refluxed for 1d, and repeated for 2 times, so as to obtain the purer selenophenyl-containing puro-derivative B1 'or B2'. Obtaining a filtered filter cake, namely the final product. And (3) spin-drying the separated filtrate to obtain a unilateral product, and then performing reaction according to the weight ratio of 1: 1, (3-bromopropyl) trimethylammonium bromide or 3-bromo-1-propanol were recovered and the above ionization process was repeated except that the reaction was carried out at microwave 130 ℃ for 2 h. The reaction equation is as follows:
Figure BDA0002987409980000182
3. the thienyl and selenophenyl viologen derivatives prepared in the embodiment 1 of the invention are analyzed for physical properties and structures, and the specific hydrogen spectrum data and carbon spectrum data are as follows:
a compound A:1H NMR(400MHz,DMSO)δ8.63(dd,J＝4.6,1.5Hz,2H),7.94(s,1H),7.72(dd,J＝4.6,1.6Hz,2H).13C NMR(101MHz,DMSO)δ151.01(s),142.19(s),140.33(s),128.57(s),119.96(s).
compound a 1:1H NMR(400MHz,D2O)δ8.89(d,J＝5.5Hz,1H),8.40(d,J＝5.5Hz,1H),8.19(s,1H),4.72(t,J＝7.4Hz,1H),3.64–3.48(m,1H),3.20(s,4H),2.64(s,1H).13C NMR(101MHz,D2O)δ148.50,144.53,142.81,133.20,123.85,62.45,57.24,53.15,24.48.HRMS(ESI)m/z:[M-4Br]4+calcd for C26H40N4S 110.0737；found 110.0735.
compound a 1':1H NMR(400MHz,D2O)δ8.88(d,J＝6.5Hz,2H),8.39(d,J＝6.4Hz,2H),8.19(s,1H),4.73–4.69(m,2H),3.59–3.53(m,2H),3.20(s,9H),2.63(s,2H).13C NMR(101MHz,D2O)δ148.50,144.53,142.81,133.20,123.85,62.45,57.24,53.15,24.48.HRMS(ESI)m/z:[M-4Cl]4+calcd for C26H40N4S 110.0737；found 110.0735.
compound a 2:1H NMR(400MHz,D2O)δ8.80(d,J＝6.8Hz,2H),8.28(d,J＝6.8Hz,2H),8.09(s,1H),4.66(t,J＝7.2Hz,2H),3.67(t,J＝5.9Hz,2H),2.27–2.21(m,2H).13C NMR(101MHz,D2O)δ147.85,144.59,142.63,132.86,123.44,123.25,58.36,57.77,32.52.HRMS(ESI)m/z:[M-2Br]2+calcd for C20H24N2O2S 178.0773；found 178.0771.
compound a 2':1H NMR(400MHz,D2O)δ8.83(d,J＝3.9Hz,2H),8.30(s,2H),8.09(s,1H),4.68(s,2H),3.70(s,2H),2.26(s,2H).13C NMR(101MHz,D2O)δ147.67,144.68,142.64,132.96,123.42,58.45,57.85,32.63.HRMS(ESI)m/z:[M-2Cl]2+calcd for C20H24N2O2S 178.0773；found 178.0771.
compound B:1H NMR(400MHz,DMSO)δ8.63(dd,J＝4.6,1.5Hz,2H),7.94(s,1H),7.72(dd,J＝4.6,1.6Hz,2H).13C NMR(101MHz,DMSO)δ151.00,148.46,142.30,130.73,120.40.
compound B1：1H NMR(400MHz,D2O)δ8.87(d,J＝6.2Hz,2H),8.37(s,1H),8.33(d,J＝5.9Hz,2H),4.71(t,J＝7.7Hz,2H),3.60–3.54(m,2H),3.20(s,9H),2.65(d,J＝6.8Hz,2H).13C NMR(101MHz,D2O)δ150.60,149.20,144.46,135.68,124.29,62.49 57.21,53.21,24.49.HRMS(ESI)m/z:[M-4Br]4+calcd for C26H40N4Se122.0599；found 122.0591；
Compound B1':1H NMR(400MHz,D2O)δ8.84(d,J＝6.3Hz,1H),8.30(d,J＝4.6Hz,1H),8.28(s,1H),4.68(t,J＝7.5Hz,1H),3.53(d,J＝8.6Hz,1H),3.17(s,5H),2.61(d,J＝7.2Hz,1H).13C NMR(101MHz,D2O)δ150.52,149.17,144.43,135.65,124.20,62.44,57.17,53.13,24.45.HRMS(ESI)m/z:[M-4Cl]4+calcd for C26H40N4Se122.0599；found 122.0594；
compound B2:1H NMR(400MHz,D2O)δ8.75(d,J＝6.3Hz,2H),8.18(d,J＝4.6Hz,3H),4.61(t,J＝6.8Hz,2H),3.64(t,J＝5.9Hz,2H),2.21(dd,J＝12.3,6.1Hz,2H).13C NMR(101MHz,D2O)δ149.26,148.69,144.24,135.09,123.47,58.04,57.50,32.28.HRMS(ESI)m/z:[M-2Br]2+calcd for C20H24N2O2Se 202.0496；found202.0492；
compound B2':1H NMR(400MHz,D2O)δ8.77(d,J＝6.3Hz,2H),8.26–8.16(m,3H),4.63(t,J＝6.9Hz,2H),3.65(t,J＝5.8Hz,2H),2.26–2.18(m,2H).13C NMR(101MHz,D2O)δ149.26,148.69,144.24,135.09,123.47,58.04,57.50,32.28.HRMS(ESI)m/z:[M-2Cl]2+calcd for C20H24N2O2Se 202.0496；found 202.0492；
it was confirmed that the above process indeed synthesized these compounds.
4. The invention relates to the application of thienyl and selenophenyl viologen derivatives
The thienyl and selenophenyl viologen derivatives prepared in example 1 are used for preparing a flow battery electrode material, and the preparation method can be implemented through the following steps:
the method comprises the following steps: assembling a core clamp; the neutral water system organic redox flow battery used for testing is of a single cell structure, and a positive electrode end plate, a positive electrode insulating plate, a positive electrode conducting plate, a positive electrode flow frame, a positive electrode graphite felt, a positive electrode gasket, an anion exchange membrane, a negative electrode gasket, a negative electrode graphite felt, a negative electrode flow frame, a negative electrode conducting plate, a negative electrode insulating plate and a negative electrode end plate are sequentially fixed by bolts, are connected with an external pipeline, check whether the bolts are loosened, and can be reinforced again if the bolts are loosened. Before the test, the tightness and pressure test should be carried out, 2 liquid storage bottles (with the same volume) and peristaltic pumps are connected on the basis of the clamp, and after 2h circulation, if the liquid leakage condition does not exist, and the liquid volume does not change, the liquid can be reserved for standby.
Step two: preparing an electrode material; a 1M NaCl solution was prepared in a volumetric flask, and a certain amount of each of the products a1 ', a 2', B1 ', B2' and (ferrocenyl methyl) trimethylammonium chloride (abbreviated as FcNCl) was dissolved in each of the NaCl solutions B ═ 8ml and c ═ 18ml, the concentration was 0.1M, the solution was stirred until completely dissolved, argon gas was introduced, and bubbling was carried out for 10 minutes, and the NaCl solutions of the products a1 ', a 2', B1 'and B2' were used as a negative electrode and the NaCl solution of FcNCl was used as a positive electrode, respectively.
It should be noted that c/b is greater than 1 in the single electron test, and is greater than 2 in the double electron test, and so on.
Step three: preparing a neutral water system organic redox flow battery; the prepared jig and solution were placed in a glove box, with the product a1 '(a 2', B1 ', B2') solution as the negative electrode and the FcNCl solution as the positive electrode. And connecting an external power supply, the peristaltic pump and the Xinwei tester, and setting a program to perform charge and discharge tests.
Through the above steps, the two-electron 0.1M A1'/FcNCl system is in the voltage range of 1.8-0.1V, 40mA/cm2At the current density of the capacitor, the capacity of the system reaches 36.5mAh (the specific capacity is 4.56Ah/L, and the theoretical specific capacity is 5.36Ah/L), after 300 cycles, the capacity attenuation is 30.1mAh (the specific capacity is 3.76Ah/L), the total capacity retention rate is 82.5%, the single-cycle capacity retention rate is 99.94%, the total coulombic efficiency is about 99.8%, and the energy efficiency is 65%. The single electron 0.1M A2'/FcNCl system is 1.8-0.1VWithin the voltage range, 40mA/cm2At the current density of the capacitor, the capacity of the system reaches up to 15mAh (the specific capacity is 1.88Ah/L, and the theoretical specific capacity is 2.56Ah/L), after 1200 cycles, the capacity attenuation is 13.5mAh (the specific capacity is 1.69Ah/L), the total capacity retention rate is 90%, the single-cycle capacity retention rate is 99.99%, the total coulombic efficiency is about 99.9%, and the energy efficiency is 61%.
Therefore, the above-mentioned system confirms that thienyl viologen derivatives a1 'and a 2' are excellent negative electrode materials in a neutral water redox flow battery, the thienyl viologen derivative a1 'ionized by the quaternary ammonium salt is pulled close to double redox potential, the double electron transfer is quicker, and the peak current is increased by the thienyl viologen derivative a 2' ionized by the hydroxyl group, so that the battery performance with high capacity and long service life is realized. Se, which is a cognate element of S, also has excellent battery properties.
5. In order to verify the effect of the present invention, relevant experiments on the preparation of electrode materials of a flow battery were performed on the thiophene-based viologen derivatives and selenophene-based viologen derivatives synthesized in example 1, and the test results are shown in fig. 1 to fig. 22.
Referring to FIG. 1, which is a cyclic voltammogram of 4mM of thienyl viologen derivatives A1 ', A2' and 4mM of FcNCl, the scan rate was 0.1V/s, it is clear from the figure that when the potential is converted to a normal hydrogen electrode, the first and second redox potentials of thienyl viologen derivatives A1 'were-0.69V and-0.56V, respectively, the redox potential of thienyl viologen derivatives A2' was-0.56V, and the redox potential of FcNCl was 0.61V. The single-electron cell voltage of the A1 '/FcNCl system was 1.07V, the two-electron cell voltage was 1.3V, and the cell voltage of the A2'/FcNCl system was 1.07V. Compared with an viologen derivative without thiophene bridging, the thiophene viologen derivative A1 'after the quaternary ammonium salt ionization is close to the potential of two redox peaks, so that the potential platform is smaller and the management is easy, and the thiophene viologen derivative A2' after the hydroxyl ionization makes the first redox peak value lower, the second redox peak value higher, the potential difference value is larger, and the single electron action is enhanced.
Referring to fig. 2 and fig. 3, a Linear Sweep Voltammogram (LSV) of the thienyl viologen derivative a 1' obtained by rotating a disk electrode, and a column vickers plot of limiting current versus square root of rotation speed are shown, respectively. The kinetics of the molecule can be studied from the LSV curve, resulting in a diffusion coefficient and an electron transfer constant. Linearly fitting the slope of the curve of fig. 2 to obtain a straight line shown in fig. 3, and combining the slope corresponding to the straight line with the following formula of Levich Plot Slop ═ 0.62nFAC0D2/3v～1/6The diffusion coefficient D of 2.45 × 10 can be obtained～6cm2S; by the following formula psi ═ k0(ΠDnF/RT)～1/2v～1/2When the scan rate is less than or equal to 0.5V/s, Ep is less than 61mV and ψ is 20, so that when V is 0.5V/s, the average electron transfer constant K is obtained0Greater than 0.35cm/s suggests that the molecule has rapid electron transfer.
Referring to fig. 4 and 5, the ultraviolet-visible absorption spectra and the spectral band gaps of thienyl viologen derivatives a1 'and a 2' are shown, respectively. As can be clearly seen from the figure, the compound after the ionization modification generates red shift in the absorption of the visible light region, the absorption peak becomes high, and the optical band gap gradually decreases; the main absorption peaks of the compounds A, A1 'and A2' are 332nm, 376nm and 376nm, the absorption peaks of hydroxyl ionization and quaternary ammonium salt ionization are not obviously changed, but the absorption peaks of the hydroxyl ionization and the quaternary ammonium salt ionization are stronger, the quaternary ammonium salt ionization absorption is higher than that of the hydroxyl ionization, and the optical band gaps of the three compounds are respectively 3.38eV, 3.04eV and 3 eV. The result shows that the conjugation is increased by modifying the thiophene group, the electron-donating capability of the system is increased, and the electron transfer is faster after the modification by ionization.
Referring to fig. 6, fig. 7, fig. 8 and fig. 9, regarding the test of solubility of thienyl viologen derivative a1 ', whether in 1M sodium chloride aqueous solution or in pure water, according to ultraviolet absorption of different concentrations, taking the intensity at 376nm, according to the relationship between concentration and intensity, the solubility of compound a 1' in 1M sodium chloride aqueous solution is 1.2M (64.32Ah/L), and the solubility in pure water is 1.5M (80.4Ah/L), which confirms that our molecule has very good solubility, and the theoretical specific capacity can reach very high value.
See fig. 10 for a two-electron cycle charge-discharge curve plot of the 0.1M A1'/FcNCl system in 1M aqueous sodium chloride solution, where the charge-discharge curves are nearly coincident. When the current density is 40mA/cm2When the cut-off voltage is 1.8V, the battery system shows a relation graph of 300-turn charge-discharge specific capacity and coulombic efficiency and cycle number, the total capacity retention rate is 82.5%, the single-turn capacity retention rate is 99.94%, the total coulombic efficiency is about 99.8%, and the energy efficiency is 65%.
Referring to FIGS. 11, 12 and 13, the 0.1M A1'/FcNCl system described above was used at different current densities (from 20 mA/cm)2To 90mA/cm2) And (4) testing the double-electron multiplying power performance. As the current density increases, fig. 11 shows that the voltage difference between the charge and discharge curves increases gradually, and the curves show a single electron plateau; fig. 12 shows that the specific capacity of the battery gradually decreases due to the increase in ohmic loss; fig. 13 shows that coulombic efficiency was maintained at substantially 99.9%, and voltage efficiency and energy efficiency were continuously decreased.
Referring to fig. 14 and fig. 15, after 300 cycles, impedance test and electrochemical cycle test are respectively performed on the 0.1M A1'/FcNCl system, the internal resistance of the system is increased to 1.15 Ω, and it can be seen from the CV graph that the positive and negative electrode materials have very obvious characteristic peaks in respective voltage ranges, and no opposite peak is found, which confirms that the materials are not cross-contaminated, the ion exchange membrane is good, and charging and discharging can be continuously performed.
Referring to FIG. 16, which is a schematic structural diagram of the positive and negative half-cell reactions of the 0.1M A1 '/FcNCl system, compound A1' can undergo two-electron transfer under pressure, respectively [ (NPr)2DPT]4+/[(NPr)2DPT]3+·And [ (NPr)2DPT]3+·/[(NPr)2DPT]2+Whereas compound FcNCl undergoes only a single electron change.
See fig. 17 for a charge and discharge device display diagram for the 0.1M A1'/FcNCl system. The color of compounds FcNCl and a 1' is orange/orange, respectively, when no voltage is applied; when charged, the color changes to dark red/dark green, respectively; when discharged, the color changes to orange/dark green, respectively; the color of compound a 1' was not restored due to partial radical oxidation.
Referring to fig. 18, which is a graph of the relationship between the specific charge-discharge capacity of two electrons and the coulombic efficiency of the 0.3M sodium chloride aqueous solution of the 0.3M A1'/FcNCl system and the number of cycles, the performance is generally similar to that of the 0.1M concentration system, the battery performance is tested for 100 cycles, the overall capacity retention rate is 93%, the retention rate of one cycle is 99.9%, and the energy efficiency is 61%, which is reduced due to the increase of the concentration and the increase of the internal resistance of the battery.
Referring to FIG. 19, a graph of a one-electron cycle charge and discharge curve in a 1M aqueous sodium chloride solution for a 0.1M A2'/FcNCl system, wherein the charge and discharge curves are nearly coincident. When the current density is 40mA/cm2When the cut-off voltage is 1.8V, the battery system shows a 1200-turn charge-discharge specific capacity and a relation graph of coulombic efficiency and cycle number, the total capacity retention rate is 82.5%, the single-turn capacity retention rate is 99.99%, the total coulombic efficiency is about 99.9%, and the energy efficiency is 65%.
Referring to FIGS. 20, 21 and 22, the 0.1M A2'/FcNCl system described above was used at different current densities (from 20mA/cm2To 90mA/cm2) And (4) testing the single electron multiplying power performance. As the current density increases, fig. 20 shows that the voltage difference between the charge and discharge curves increases gradually, and the curves show a single electron plateau; fig. 21 shows that the specific capacity of the battery gradually decreased due to the increase in ohmic loss; fig. 22 shows that coulombic efficiency was maintained at substantially 99.9%, and voltage efficiency and energy efficiency were continuously decreased.

Claims (10)

1. A thienyl viologen derivative or selenophenyl viologen derivative is characterized in that the structural formula of the viologen derivative is as follows:
Figure FDA0002987409970000011
wherein R ═ C3NPr or C3OH, X ═ Br or Cl, when E ═ S, the viologen derivatives are thienyl viologen derivatives, when E ═ SeThe viologen derivative is selenophenyl viologen derivative.
2. A process for the synthesis of viologen derivatives according to claim 1, wherein when R ═ C3NPr, X ═ Br under the protection of inert gas according to the ratio of 1: 5, dissolving the precursor and (3-bromopropyl) trimethyl ammonium bromide in an organic solvent, reacting at 110-120 ℃ for 40-60 hours to obtain a reaction solution, and then separating and drying a product in the reaction solution to obtain the viologen derivative;
when the viologen derivative is a thienyl viologen derivative, the structural formula of the precursor is shown as a formula 1, and when the viologen derivative is a selenophenyl viologen derivative, the structural formula of the precursor is shown as a formula 2;
Figure FDA0002987409970000012
3. a process for the synthesis of viologen derivatives according to claim 1, wherein when R ═ C3And when OH and X are Br, under the protection of inert gas, the reaction is carried out according to the ratio of 1: 5, dissolving the precursor and 3-bromo-1-propanol in an organic solvent, reacting at 80-90 ℃ for 65-75 h to obtain a reaction solution, and then separating and drying a product in the reaction solution to obtain the viologen derivative;
when the viologen derivative is a thienyl viologen derivative, the structural formula of the precursor is shown as a formula 1, and when the viologen derivative is a selenophenyl viologen derivative, the structural formula of the precursor is shown as a formula 2;
Figure FDA0002987409970000013
4. the method for synthesizing an viologen derivative according to claim 1, wherein R is C3NPr, X ═ Cl, comprising the following steps：
Step 1, under the protection of inert gas, according to the proportion of 1: 5, dissolving the precursor and (3-bromopropyl) trimethyl ammonium bromide in an organic solvent, reacting at 110-120 ℃ for 40-60 hours to obtain a reaction solution, and then separating and drying a product in the reaction solution to obtain an intermediate product A;
when the viologen derivative is a thienyl viologen derivative, the structural formula of the precursor is shown as a formula 1, and when the viologen derivative is a selenophenyl viologen derivative, the structural formula of the precursor is shown as a formula 2;
Figure FDA0002987409970000021
and 2, dissolving the intermediate product A in deionized water, carrying out anion exchange by using chloride ion exchange resin, separating and drying a product in an exchange solution to obtain an intermediate product B, and removing a unilateral product in the intermediate product B to obtain the viologen derivative.
5. The method for synthesizing an viologen derivative according to claim 4, wherein in the step 2, the intermediate product B is dissolved in methanol, then tetrahydrofuran, dichloromethane or ethyl acetate is added for recrystallization, then acetonitrile is added to the obtained precipitate for condensation reflux to obtain a reflux liquid, and finally a filter cake obtained by filtering the reflux liquid is dried to obtain the viologen derivative.
6. The method for synthesizing an viologen derivative according to claim 5, wherein the step 2 comprises the steps of filtering the reflux liquid to obtain a filtrate, spin-drying the filtrate to obtain a solid A, and mixing the solid A with the filtrate according to a ratio of 1: 1, dissolving a solid A and (3-bromopropyl) trimethyl ammonium bromide in an organic solvent under a microwave condition, reacting at 120-130 ℃ for 2-3 h to obtain a reaction solution, and then separating and drying a product in the reaction solution to obtain the viologen derivative.
7. As claimed in claim1 the process for synthesizing an viologen derivative, wherein R is C3When OH and X are Cl, the method comprises the following steps:
step 1, under the protection of inert gas, according to the proportion of 1: 5, dissolving the precursor and 3-bromo-1-propanol in an organic solvent, reacting at 80-90 ℃ for 65-75 h to obtain a reaction solution, and then separating and drying a product in the reaction solution to obtain an intermediate product C;
when the viologen derivative is a thienyl viologen derivative, the structural formula of the precursor is shown as a formula 1, and when the viologen derivative is a selenophenyl viologen derivative, the structural formula of the precursor is shown as a formula 2;
Figure FDA0002987409970000031
and 2, dissolving the intermediate product C in deionized water, carrying out anion exchange by using chloride ion exchange resin, separating and drying a product in an exchange solution to obtain an intermediate product D, and removing a unilateral product in the intermediate product D to obtain the viologen derivative.
8. The method for synthesizing a selenophenyl viologen derivative as claimed in claim 7, wherein in step 2, the intermediate product D is dissolved in methanol, then tetrahydrofuran, dichloromethane or ethyl acetate is added for recrystallization, then acetonitrile is added to the obtained precipitate for condensation reflux to obtain a reflux liquid, and finally the filter cake obtained by filtering the reflux liquid is dried to obtain the viologen derivative.
9. The method for synthesizing a selenophenyl viologen derivative as claimed in claim 8, wherein the step 2 comprises the steps of filtering the reflux liquid to obtain a filtrate, spin-drying the filtrate to obtain a solid B, and mixing the solid B with the filtrate according to a ratio of 1: 1, dissolving the solid B and 3-bromo-1-propanol in an organic solvent under a microwave condition, reacting at 120-130 ℃ for 2-3 h to obtain a reaction solution, and then separating and drying a product in the reaction solution to obtain the viologen derivative.
10. Use of the viologen derivative of claim 1 in a neutral aqueous organic redox flow battery.
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