CN113913867B - Application of polybenzimidazole quaternary ammonium salt anion exchange membrane in electrocatalytic reduction of CO 2 In (1) - Google Patents
Application of polybenzimidazole quaternary ammonium salt anion exchange membrane in electrocatalytic reduction of CO 2 In (1) Download PDFInfo
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Abstract
The invention disclosesOpening a polybenzimidazole quaternary ammonium salt anion exchange membrane for the electrocatalytic reduction of CO 2 The use of (1); polybenzimidazole quat anion exchange membranes as electrocatalytic CO reduction 2 Diaphragm of middle H type electrolytic cell. Adding electrolyte into H-type electrolytic cell for 50-70 mL min ‑1 Introducing CO into the electrolyte at a flow rate 2 To discharge oxygen from the electrolyte to make the electrolyte reach CO 2 A saturated state; taking a silver foil with a microporous structure formed on the surface as a working electrode, taking Ag/AgCl as a reference electrode, and taking a platinum sheet as a counter electrode; 15-25 mL min ‑1 Continuously introducing CO into the electrolyte at a speed of 2 Then applying a voltage to promote CO 2 A reduction reaction occurs at the surface of the working electrode. The anion exchange membrane of the invention adopts the novel polybenzimidazole quaternary ammonium salt anion exchange membrane, which can improve the ionic conductivity of the anion exchange membrane and the Faraday effect of CO.
Description
Technical Field
The invention belongs to the field of electrocatalytic reduction of CO 2 Electrolytic cellThe field of anion exchange membranes, and relates to a polybenzimidazole quaternary ammonium salt anion exchange membrane for the electrocatalytic reduction of CO 2 The use of (1).
Background
CO continues to grow with the global population and economy 2 The emission is increasing day by day, and the pollution to the atmosphere is sharply increased. CO 2 2 Is considered to be one of the main factors causing global warming, in CO 2 Under the influence of greenhouse gases, the greenhouse effect is more and more severe, the global temperature rises, and the extreme weather emerges endlessly. Reducing atmospheric CO for maintaining natural environment for human survival 2 The content of greenhouse gases is urgent, and therefore, a new technology for converting or sealing the greenhouse gases is urgently needed. In recent years, various methods for converting CO into CO have been studied 2 Converting into products with high added values such as CO, methanol or dimethyl ether and the like to realize CO 2 Economy and recyclability. Suppression of atmospheric CO at present 2 The method for increasing the content mainly comprises the following steps: biochemical method-Green plants through photosynthesis, CO 2 Converting into organic matter; photocatalysis-under the action of illumination, electrons escape from the surface of a photocatalyst, so that cavities are formed on the surface of the catalyst and are CO 2 Reduction provides a binding site; electrocatalysis-by electrolysis, CO 2 The reduction reaction is carried out at the cathode of the electrolytic cell to obtain a series of CO 2 The reduction product can control CO by adjusting cathode catalytic material and reduction potential 2 Species of products of electroreduction.
Electrocatalytic reduction of CO 2 Is an efficient and environment-friendly technology because it can convert CO into CO 2 And converted into a product with high added value. In addition, CO is introduced 2 The conversion into products such as CO, methanol and methane is of great significance for the efficient utilization of carbon sources. Electrocatalytic reduction of CO 2 Not only can solve CO 2 The problem of emission can also be used to high value the peak power generated by new renewable energy sources (such as solar energy, tidal energy, wind energy, etc.). Electrocatalytic reduction of CO in H-type electrolytic cell as current stage 2 The main flow device mainly comprises an electrolytic cell body, an electrode clamp, a reference electrode, a working electrode and an ion exchange membraneCatalysts, and the like.
The ion exchange membrane is mainly divided into an anion exchange membrane and a cation exchange membrane, and the invention reports a novel anion exchange membrane. The anion exchange membrane is composed of three parts: a polymer backbone (i.e., a polymeric matrix) with specific groups, positively charged reactive groups, and anions freely movable on the reactive groups. Application to electrocatalytic reduction of CO 2 The function of the anion exchange membrane of (a) includes the following aspects: (1) Transfer of OH - Thereby reducing the cathode H + Concentration, inhibiting hydrogen evolution reaction at cathode, and improving the electrocatalytic reduction of CO 2 The Faraday efficiency is reduced, and the influence on a cathode catalyst is reduced; (2) The cathode and the anode are separated, electrolytic products of the two electrodes are prevented from being mixed, and a product with high uniformity is obtained. An ideal anion exchange membrane should have excellent ion conductivity, high mechanical strength, low swelling capacity and excellent chemical stability.
The imidazole group has excellent stability in an alkaline environment, and can improve the chemical and mechanical stability of a membrane material. The invention takes polybenzimidazole containing imidazole groups as a main chain, and aims to improve the stability and the mechanical property of an anion exchange membrane. However, the OH groups of pure polybenzimidazole - The conductivity is not ideal. Therefore, in order to improve the conductivity of the polybenzimidazole, pure polybenzimidazole needs to be modified, and specific groups (such as quaternary ammonium groups, imidazolium ions and the like) capable of transmitting OH < - > are increased. Based on the method, the imidazole group of the polybenzimidazole is utilized to carry out ring-opening grafting reaction, and the quaternary ammonium group is grafted to the main chain, so that the electro-catalytic reduction of CO in the polybenzimidazole is effectively improved 2 The application performance of (1).
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the purpose of the invention, a polybenzimidazole quaternary anion exchange membrane for the electrocatalytic reduction of CO is provided 2 The use of (1).
Preferably, the polybenzimidazole quaternary ammonium salt anion exchange membrane has a structural formula:
preferably, the polybenzimidazole quaternary anion exchange membrane is used for electrocatalytic reduction of CO 2 Diaphragm of middle H type electrolytic cell.
Preferably, the electrolyte is added into an H-type electrolytic cell and is added for 50-70 mL min -1 Introducing CO into the electrolyte at a flow rate 2 To discharge oxygen from the electrolyte to make the electrolyte reach CO 2 A saturated state; taking a silver foil with a microporous structure formed on the surface as a working electrode, taking Ag/AgCl as a reference electrode, and taking a platinum sheet as a counter electrode; 15-25 mL min -1 Continuously introducing CO into the electrolyte at a speed of 2 Then applying a voltage to promote CO 2 A reduction reaction occurs at the surface of the working electrode.
Preferably, the process for forming the microporous structure on the surface of the silver foil comprises the following steps: silver foil with the thickness of 0.5mm is used as a cathode catalytic material, the constant-voltage electrolysis function of a CHI660E type electrochemical workstation is used, the surface of the silver foil is oxidized for 3min under the condition of 2.6V, and then is reduced for 3min under the condition of-2.6V, so that a microporous structure is formed on the surface of the silver foil.
Preferably, the working electrode is formed by forming a microporous structure on the surface of the silver foil and then clamping the silver foil by a glassy carbon electrode clamp.
Preferably, the electrolyte is 0.1mol L -1 KHCO of 3 And (3) solution.
Preferably, the thickness of the polybenzimidazole quaternary anion exchange membrane is 10 to 50 μm.
Preferably, the polybenzimidazole quaternary ammonium salt anion exchange membrane is soaked by deionized water, sandwiched between rubber gaskets, and mounted in the middle of an H-shaped electrolytic cell as a diaphragm.
The invention at least comprises the following beneficial effects: the anion exchange membrane of the invention adopts the novel polybenzimidazole quaternary ammonium salt anion exchange membrane, which can improve the ionic conductivity of the anion exchange membrane and the Faraday effect of CO.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is a schematic diagram of the synthesis of a polybenzimidazole quat anion exchange membrane according to the present invention;
FIG. 2 is an infrared image of a polybenzimidazole quat anion exchange membrane of the present invention;
FIG. 3 is a graph of the CO Faraday efficiencies of polybenzimidazole quat anion exchange membranes of examples 1-3 of the present invention and of a polybenzimidazole membrane of comparative example 1;
FIG. 4 is a graph of the CO Faraday efficiency of polybenzimidazole quat anion exchange membranes of examples 2 and 4 of the present invention;
FIG. 5 is a plot of the CO current density of polybenzimidazole quat anion exchange membranes of examples 1-3 of the present invention and of the polybenzimidazole membrane of comparative example 1;
FIG. 6 is an electrocatalytic reduction of CO by polybenzimidazole quat anion exchange membrane of example 2 of the present invention 2 Stability graph.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
application of polybenzimidazole quaternary ammonium salt anion exchange membrane in electrocatalytic reduction of CO 2 The structural formula of the polybenzimidazole quaternary ammonium salt anion exchange membrane is as follows:
wherein the thickness of the polybenzimidazole quat anion exchange membraneThe degree is 21 μm; the polybenzimidazole quaternary ammonium salt anion exchange membrane is soaked by deionized water, sandwiched between rubber gaskets, installed in the middle of an H-shaped electrolytic cell as a diaphragm, and 0.1mol L of the polybenzimidazole quaternary ammonium salt anion exchange membrane is added into the H-shaped electrolytic cell -1 KHCO of 3 The solution was used as electrolyte and 60mL min -1 Introducing CO into the electrolyte at a flow rate 2 To discharge oxygen from the electrolyte to make the electrolyte reach CO 2 A saturated state; a glassy carbon electrode of a silver foil with a surface formed with a microporous structure is clamped as a working electrode (wherein, the process of forming the microporous structure on the surface of the silver foil is that the silver foil with the thickness of 0.5mm is used as a cathode catalytic material, the constant voltage electrolysis function of a CHI660E type electrochemical workstation produced by Shanghai Chenghua instruments and Co., ltd is used under the condition of 2.6V, the surface of the silver foil is oxidized for 3min, and then is reduced for 3min under the condition of-2.6V, so that the microporous structure is formed on the surface of the silver foil), ag/AgCl is used as a reference electrode, and a platinum sheet is used as a counter electrode; at a rate of 20mL min -1 Continuously introducing CO into the electrolyte at a speed of 2 Then applying different voltages to promote CO 2 Carrying out reduction reaction on the surface of the working electrode for 1h; the gas product is introduced into a 9790Plus type gas chromatograph manufactured by Fuzhou Fuli instruments Co., ltd for testing to obtain the ppm value of CO in the product; the calculation formula of the Faraday efficiency and the cathode total current density of CO is as follows:
wherein alpha is CO 2 The number of transferred electrons of the CO is 2,n, which is the molar weight (mol) of the CO, F is a Faraday constant (96485 mol/C), and Q is the total coulomb amount (C) transferred by the cathode;
j CO ＝FEco×j total
wherein j is total Is the total current density (mA/cm) of the cathode 2 )，FE CO Faradaic efficiency (%) for CO; jco is the fractional current density of CO.
The preparation method (the synthesis scheme is shown in figure 1) of the novel polybenzimidazole quaternary ammonium salt anion exchange membrane (QABBI-1) in the embodiment comprises the following steps:
step one, weighing 1mmol of polybenzimidazole, placing the polybenzimidazole in a three-neck flask, adding 40mL of dimethyl sulfoxide, and stirring in an oil bath at 80 ℃ until the polybenzimidazole is completely dissolved. Then, adding 1.0mmol of 2, 3-epoxypropyltrimethylammonium chloride, continuously stirring and reacting for 24 hours at 80 ℃ to obtain a brown viscous solution, pouring the brown viscous solution into 200mL of acetone for precipitation, carrying out suction filtration and deionized water washing for 5 times, and carrying out vacuum drying for 48 hours at room temperature to obtain a precursor;
weighing a certain precursor, dissolving the precursor in dimethyl sulfoxide to prepare brown viscous liquid with the mass ratio of 10wt%, pouring the viscous liquid on a dry and clean glass plate for casting to form a film, and then drying for 24 hours at the temperature gradient of 120 ℃ to obtain the novel polybenzimidazole quaternary ammonium salt anion exchange membrane;
step three, soaking the prepared novel polybenzimidazole quaternary ammonium salt anion exchange membrane in ethanol for 24 hours, washing with deionized water, and drying;
step four, putting the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in 1mol L -1 Soaking in KOH solution for 24h to realize the exchange of chloride ions and hydroxide radicals; finally, washing with deionized water and drying.
Example 2:
application of polybenzimidazole quaternary ammonium salt anion exchange membrane in electrocatalytic reduction of CO 2 The structural formula of the polybenzimidazole quaternary ammonium salt anion exchange membrane is as follows:
wherein the thickness of the polybenzimidazole quaternary ammonium salt anion exchange membrane is 21 mu m; the polybenzimidazole quaternary ammonium salt anion exchange membrane is soaked by deionized water, sandwiched between rubber gaskets, installed in the middle of an H-shaped electrolytic cell as a diaphragm, and 0.1mol L of the polybenzimidazole quaternary ammonium salt anion exchange membrane is added into the H-shaped electrolytic cell -1 KHCO of 3 The solution was used as electrolyte and 60mL min -1 Introducing CO into the electrolyte at a flow rate 2 To discharge oxygen from the electrolyte to make electricityThe solution reaches CO 2 A saturated state; a glassy carbon electrode of a silver foil with a micro-pore structure formed on the surface is clamped as a working electrode (wherein, the process of forming the micro-pore structure on the surface of the silver foil is to oxidize the surface of the silver foil for 3min under the condition of 2.6V by using the silver foil with the thickness of 0.5mm as a cathode catalytic material and using the constant voltage electrolysis function of a CHI660E type electrochemical workstation produced by Shanghai Chenhua apparatus Co., ltd., and then reduce the surface of the silver foil for 3min under the condition of-2.6V, so that the micro-pore structure is formed on the surface of the silver foil), ag/AgCl is used as a reference electrode, and a platinum sheet is used as a counter electrode; at 20mL min -1 Continuously introducing CO into the electrolyte at a speed of 2 Then applying different voltages to promote CO 2 Carrying out reduction reaction on the surface of the working electrode for 1h; the gas product is introduced into a 9790Plus type gas chromatograph manufactured by Fuzhou Fuli instruments Co., ltd for testing to obtain the ppm value of CO in the product; the faradaic efficiency of CO and the cathode total current density calculation formula are as follows:
wherein alpha is CO 2 The number of transferred electrons of the CO is 2,n, which is the molar weight (mol) of the CO, F is a Faraday constant (96485 mol/C), and Q is the total coulomb amount (C) transferred by the cathode;
j CO ＝FEco×j total
wherein j is total Is the total current density (mA/cm) of the cathode 2 )，FE CO Faraday efficiency (%) for CO; jco is the fractional current density of CO.
The preparation method of the novel polybenzimidazole quaternary ammonium salt anion exchange membrane (QAPBI-2) in the embodiment comprises the following steps:
step one, weighing 1mmol of polybenzimidazole, placing the polybenzimidazole in a three-neck flask, adding 40mL of dimethyl sulfoxide, and stirring in an oil bath at 80 ℃ until the polybenzimidazole is completely dissolved. Then, 2.0mmol of 2, 3-epoxypropyltrimethylammonium chloride is added, the mixture is continuously stirred and reacted for 24 hours at the temperature of 80 ℃, a brown viscous solution is obtained, the brown viscous solution is poured into 200mL of acetone for precipitation, and after the acetone is filtered and washed for 5 times by deionized water, the mixture is dried for 48 hours in vacuum at room temperature, and a precursor is obtained;
weighing a certain precursor, dissolving the precursor in dimethyl sulfoxide to prepare brown viscous liquid with the mass ratio of 10wt%, pouring the viscous liquid on a dry and clean glass plate for casting to form a film, and then drying for 24 hours at the temperature gradient of 120 ℃ to obtain the novel polybenzimidazole quaternary ammonium salt anion exchange membrane;
and step three, soaking the prepared novel polybenzimidazole quaternary ammonium salt anion exchange membrane in ethanol for 24 hours, washing with deionized water, and drying.
Step four, putting the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in 1mol L -1 Soaking in KOH solution for 24h to realize the exchange of chloride ions and hydroxide radicals; finally, washing with deionized water and drying.
Example 3:
application of polybenzimidazole quaternary ammonium salt anion exchange membrane in electrocatalytic reduction of CO 2 The structural formula of the polybenzimidazole quaternary ammonium salt anion exchange membrane is as follows:
wherein the thickness of the polybenzimidazole quaternary ammonium salt anion exchange membrane is 21 mu m; the polybenzimidazole quaternary ammonium salt anion exchange membrane is soaked by deionized water, sandwiched between rubber gaskets, installed in the middle of an H-shaped electrolytic cell as a diaphragm, and 0.1mol L of the polybenzimidazole quaternary ammonium salt anion exchange membrane is added into the H-shaped electrolytic cell -1 KHCO of 3 The solution was used as electrolyte and 60mL min -1 Introducing CO into the electrolyte at a flow rate 2 To discharge oxygen from the electrolyte to make the electrolyte reach CO 2 A saturated state; a glassy carbon electrode holding a silver foil with a micro-pore structure formed on the surface thereof as a working electrode (wherein the micro-pore structure formed on the surface of the silver foil is prepared by oxidizing the surface of the silver foil for 3min under 2.6V by using a silver foil with a thickness of 0.5mm as a cathode catalytic material and using a CHI660E type electrochemical workstation constant voltage electrolysis function produced by Shanghai Chenghua instruments Co., ltd., and then oxidizing the surface of the silver foil under-2.6VReducing for 3min to form a microporous structure on the surface of the silver foil), and taking Ag/AgCl as a reference electrode and a platinum sheet as a counter electrode; at a rate of 20mL min -1 Continuously introducing CO into the electrolyte at a speed of 2 Then applying different voltages to promote CO 2 Carrying out reduction reaction on the surface of the working electrode for 1h; the gas product is introduced into a 9790Plus type gas chromatograph manufactured by Fuzhou Fuli instruments Co., ltd for testing to obtain the ppm value of CO in the product; the faradaic efficiency of CO and the cathode total current density calculation formula are as follows:
wherein alpha is CO 2 The number of transferred electrons of the CO is 2,n, which is the molar weight (mol) of the CO, F is a Faraday constant (96485 mol/C), and Q is the total coulomb amount (C) transferred by the cathode;
j CO ＝FEco×j total
wherein j is total Is the total current density (mA/cm) of the cathode 2 )，FE CO Faradaic efficiency (%) for CO; jco is the fractional current density of CO.
The preparation method of the novel polybenzimidazole quaternary ammonium salt anion exchange membrane (QAPBI-3) in the embodiment comprises the following steps:
step one, weighing 1mmol of polybenzimidazole, placing the polybenzimidazole in a three-neck flask, adding 40mL of dimethyl sulfoxide, and stirring in an oil bath at 80 ℃ until the polybenzimidazole is completely dissolved. Then, adding 3.0mmol of 2, 3-epoxypropyltrimethylammonium chloride, continuously stirring and reacting for 24 hours at 80 ℃ to obtain a brown viscous solution, pouring the brown viscous solution into 200mL of acetone for precipitation, carrying out suction filtration and deionized water washing for 5 times, and carrying out vacuum drying for 48 hours at room temperature to obtain a precursor;
weighing a certain precursor, dissolving the precursor in dimethyl sulfoxide to prepare brown viscous liquid with the mass ratio of 10wt%, pouring the viscous liquid on a dry and clean glass plate for casting to form a film, and then drying for 24 hours at the temperature gradient of 120 ℃ to obtain the novel polybenzimidazole quaternary ammonium salt anion exchange membrane;
and step three, soaking the prepared novel polybenzimidazole quaternary ammonium salt anion exchange membrane in ethanol for 24 hours, washing with deionized water, and drying.
Step four, putting the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in 1mol L -1 Soaking in KOH solution for 24h to realize the exchange of chloride ions and hydroxide radicals; finally, washing with deionized water and drying.
Example 4:
the polybenzimidazole quaternary ammonium salt anion exchange membrane of the embodiment is used for reducing CO in electrocatalysis 2 The procedure of the application in (1) is the same as in example 2.
The preparation method of the novel polybenzimidazole quaternary ammonium salt anion exchange membrane (QAPBI-4) in the embodiment comprises the following steps:
step one, weighing 1mmol of polybenzimidazole, placing the polybenzimidazole in a three-neck flask, adding 40mL of dimethyl sulfoxide, and stirring in an oil bath at 80 ℃ until the polybenzimidazole is completely dissolved. Then, 2.0mmol of 2, 3-epoxypropyltrimethylammonium chloride is added, the mixture is continuously stirred and reacted for 24 hours at the temperature of 80 ℃, a brown viscous solution is obtained, the brown viscous solution is poured into 200mL of acetone for precipitation, and after the acetone is filtered and washed for 5 times by deionized water, the mixture is dried for 48 hours in vacuum at room temperature, and a precursor is obtained;
weighing a certain precursor, dissolving the precursor in dimethyl sulfoxide to prepare brown viscous liquid with the mass ratio of 10wt%, pouring the viscous liquid on a dry and clean glass plate for casting to form a film, and then drying for 24 hours at the temperature gradient condition of 120 ℃ to obtain the novel polybenzimidazole quaternary ammonium salt anion exchange membrane;
and step three, soaking the prepared novel polybenzimidazole quaternary ammonium salt anion exchange membrane in ethanol for 24 hours, washing with deionized water, and drying.
Step four, putting the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in 1mol L -1 Soaking in KOH solution for 24h to realize the exchange of chloride ions and hydroxide radicals; finally, washing and drying by using deionized water;
and fifthly, placing the novel polybenzimidazole quaternary ammonium salt anion exchange membrane obtained in the fourth step into a treatment cavity of a low-temperature plasma treatment instrument, pumping the system air pressure in the treatment cavity to 3Pa, introducing ammonia gas at a speed of 30L/min for washing, introducing ammonia gas into the treatment cavity again after washing to ensure that the pressure in the cavity of the treatment cavity is constant to 30Pa, turning on a radio frequency power supply of the low-temperature plasma treatment instrument, adjusting the discharge power of the radio frequency power supply, and performing ammonia gas plasma treatment on the surface of the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in the treatment cavity for 3min with the discharge power of 100W.
Comparative example 1:
application of polybenzimidazole membrane in electrocatalytic reduction of CO 2 The use of (1);
the structural formula of the polybenzimidazole membrane is as follows:
wherein the thickness of the polybenzimidazole membrane is 21 μm; the polybenzimidazole membrane is soaked by deionized water, sandwiched between rubber gaskets, installed in the middle of an H-shaped electrolytic cell as a diaphragm, and 0.1mol L of polybenzimidazole is added into the H-shaped electrolytic cell -1 KHCO (m) 3 The solution was used as electrolyte and 60mL min -1 Introducing CO into the electrolyte at a flow rate 2 To discharge oxygen from the electrolyte to make the electrolyte reach CO 2 A saturated state; a glassy carbon electrode of a silver foil with a surface formed with a microporous structure is clamped as a working electrode (wherein, the process of forming the microporous structure on the surface of the silver foil is that the silver foil with the thickness of 0.5mm is used as a cathode catalytic material, the CHI660E type electrochemical workstation constant voltage electrolysis function produced by Shanghai Chenghua instruments and Co., ltd is used for oxidizing the surface of the silver foil for 3min under the condition of 2.6 zxft 8978, and then is reduced for 3min under the condition of-2.6V, so that the microporous structure is formed on the surface of the silver foil), ag/AgCl is used as a reference electrode, and a platinum sheet is used as a counter electrode; at 20 mol L -1 Continuously introducing CO into the electrolyte at a speed of 2 Then applying different voltages to promote CO 2 Carrying out reduction reaction on the surface of the working electrode for 1h; the gas product is introduced into a 9790Plus type gas chromatograph produced by Fuzhou Fuli instruments Co, ltd for testing to obtain CO in the productThe ppm value of (A); the calculation formula of the Faraday efficiency and the cathode total current density of CO is as follows:
wherein alpha is CO 2 The number of transferred electrons of the CO is 2,n, which is the molar weight (mol) of the CO, F is a Faraday constant (96485 mol/C), and Q is the total coulomb amount (C) transferred by the cathode;
j CO ＝FEco×j total
wherein j is total As the total current density (mA/cm) of the cathode 2 )，FE CO Faraday efficiency (%) for CO; jco is the fractional current density of CO.
The method for preparing a polybenzimidazole membrane (PBI) in this example comprises:
weighing 1mmol of polybenzimidazole, placing the polybenzimidazole in a three-necked flask, adding 40mL of dimethyl sulfoxide, stirring in an oil bath at 80 ℃ until the polybenzimidazole is completely dissolved, pouring the polybenzimidazole on a dry and clean glass plate for casting to form a film, and then drying for 24 hours at the temperature gradient of 120 ℃ to obtain a novel polybenzimidazole film; soaking the prepared polybenzimidazole membrane in ethanol for 24 hours, washing with deionized water, and drying; the polybenzimidazole membrane is added to 1mol L -1 Soaking in KOH solution for 24h to realize the exchange of chloride ions and hydroxide radicals; finally, washing with deionized water and drying.
The FITR spectra of the QAPBI-1, QAPBI-2 and QAPBI-3 membranes of examples 1, 2 and 3 of the present invention are shown in FIG. 2 at 3203cm -1 And 3315cm -1 The peak of (A) belongs to-NH 2 The expansion vibration of (2) is at 1603cm -1 And 1437cm -1 Peaks ascribed to stretching vibration of C = N group and in-plane deformation of benzimidazole ring, and the QAPBI membrane after grafting of PBI membrane was 1408cm -1 And 960cm -1 And new peaks appear, wherein the former is classified into the stretching vibration of C-H in methylene and the asymmetric stretching vibration of C-H in methyl, and the latter is classified into the characteristic peak of quaternary ammonium group, thereby proving the success of QAPBI synthesis.
The performance tests were performed on the novel polybenzimidazole quaternary ammonium salt anion exchange membranes prepared in examples 1 to 4 and the polybenzimidazole membrane prepared in comparative example 1, respectively, by the following methods:
(1) Ion Exchange Capacity (IEC) test
The IEC (mmol/g) of an anion exchange membrane reflects the content of ion exchange groups in the membrane, and generally the more ion exchange groups in the membrane, the better the ion conductivity. The IEC test method comprises taking 1 × 5cm 2 Washing the anion exchange membrane, drying in an oven at 50 deg.C for 36h until the weight remains unchanged, weighing the dry membrane to weight m dry . Subsequently, the membrane was subjected to a temperature of 30 ℃ at a volume of V 1 0.1mol L of -1 Soaking in HCl solution for 24h, and adding OH - Ion exchange into solution, then with 1mol L -1 Titrating NaOH standard solution, and consuming the volume of the NaOH solution as V 2 . The IEC calculation formula for anion exchange membranes is as follows:
wherein, C 1 Is the HCl concentration, C 2 Is the NaOH concentration.
The IEC of the novel polybenzimidazole quat anion exchange membranes of examples 1-4 are shown in table 1.
(2)OH - Conductivity (σ) test
The ion conductivity reflects the OH anion exchange membrane pair - Of (2), OH - The higher the conductivity, the more electrocatalytic reduction of CO 2 The better the effect of (c). The soaked anion-exchange membrane is used for dividing the conductance cell into two compartments, and 1mol L of the anion-exchange membrane is filled into each compartment -1 KOH solution of (a). Finally, under the conditions that the constant current is 5.0mA and the frequency is 1.0Hz to 100kHz, the impedance of the conductance cell when the membrane is arranged is measured to be R by using a CHI660E type electrochemical workstation produced by Shanghai Chenghua instruments Limited 1 . The same conductivity cell, the distance between two electrodes and the volume of the electrolyte in two compartments are kept consistent, and the impedance of the conductivity cell without the membrane is measured to be R by the same test method 0 . The membrane ionic conductivity calculation formula is as follows:
wherein σ is the OH of the membrane - Conductivity (S cm) -1 ) And A is the effective area (cm) of the diaphragm 2 ) And d is the thickness (cm) of the separator.
σ of the novel polybenzimidazole quat anion exchange membranes of examples 1 to 4 and the novel polybenzimidazole membrane of comparative example 1 are shown in table 1.
| Film | IEC(mmol g -1 ) | σ(S cm -1 ) |
| PBI | / | 5.86×10 -5 |
| QAPBI-1 | 0.805 | 1.74×10 -2 |
| QAPBI-2 | 1.396 | 5.23×10 -2 |
| QAPBI-3 | 2.477 | 4.89×10 -2 |
| QAPBI-4 | 2.985 | 6.26×10 -2 |
The Faraday effects of the novel polybenzimidazole quat anion exchange membranes of examples 1-3 and the polybenzimidazole membrane of comparative example 1 at different voltages are shown in FIG. 3; wherein FIG. 3 (a) is PBI, FIG. 3 (b) is QAPBI-1, FIG. 3 (c) is QAPBI-2, and FIG. 3 (d) is QAPBI-3; as can be seen from the figure, QAPBI-2 at-3.8V Faraday efficiency is as high as 80.71%.
The faradaic effect of the novel polybenzimidazole quat anion exchange membranes of examples 2 and 4 at different voltages is shown in figure 4; as can be seen from the figure, the Faraday effect of QAPBI-4 at different voltages is better than that of QAPBI-2.
The current densities of CO at different voltages for the novel polybenzimidazole quat anion exchange membranes of examples 1-3 and the polybenzimidazole membrane of comparative example 1 are shown in fig. 5; among them, FIG. 5 (a) is PBI, FIG. 5 (b) is QAPBI-1, FIG. 5 (c) is QAPBI-2, and FIG. 5 (d) is QAPBI-3.
The electrolytic stability of the novel polybenzimidazole quat anion exchange membrane prepared in example 2 was tested by electrocatalytic reduction of CO as in example 2 2 Continuously electrolyzing at-3.8V, and recording data every 1h until the Faraday effect of CO is seriously reduced; the results are shown in FIG. 6; after 18h of electrolysis, the faradaic efficiency at-3.8V remained stable.
Example 5:
in the embodiment, the polybenzimidazole quaternary ammonium salt anion exchange membrane is used for reducing CO in electrocatalysis 2 The procedure of the application in (1) is the same as in example 1;
the preparation method of the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in the embodiment comprises the following steps:
step one, weighing 1mmol of polybenzimidazole, placing the polybenzimidazole in a three-neck flask, adding 40mL of dimethyl sulfoxide, and stirring in an oil bath at 80 ℃ until the polybenzimidazole is completely dissolved. Then, adding 0.2mmol 2, 3-epoxypropyltrimethylammonium chloride, continuously stirring and reacting for 24 hours at the temperature of 80 ℃ to obtain a brown viscous solution, pouring the brown viscous solution into 200mL acetone for precipitation, carrying out suction filtration and deionized water washing for 5 times, and carrying out vacuum drying for 48 hours at room temperature to obtain a precursor;
weighing a certain precursor, dissolving the precursor in dimethyl sulfoxide to prepare brown viscous liquid with the mass ratio of 10wt%, pouring the viscous liquid on a dry and clean glass plate for casting to form a film, and then drying for 24 hours at the temperature gradient condition of 120 ℃ to obtain the novel polybenzimidazole quaternary ammonium salt anion exchange membrane;
and step three, soaking the prepared novel polybenzimidazole quaternary ammonium salt anion exchange membrane in ethanol for 24 hours, washing with deionized water, and drying.
Step four, putting the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in 1mol L -1 Soaking in KOH solution for 24h to realize the exchange of chloride ions and hydroxide radicals; finally, washing with deionized water and drying.
Example 6:
in the embodiment, the polybenzimidazole quaternary ammonium salt anion exchange membrane is used for reducing CO in electrocatalysis 2 The procedure of application (2) was the same as in example 1.
The preparation method of the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in the embodiment comprises the following steps:
step one, weighing 1mmol of polybenzimidazole, placing the polybenzimidazole in a three-neck flask, adding 40mL of dimethyl sulfoxide, and stirring in an oil bath at 80 ℃ until the polybenzimidazole is completely dissolved. Then, adding 0.4mmol 2, 3-epoxypropyltrimethylammonium chloride, continuously stirring and reacting for 24h at 80 ℃ to obtain brown viscous solution, pouring the brown viscous solution into 200mL acetone for precipitation, carrying out suction filtration and deionized water washing for 5 times, and carrying out vacuum drying for 48h at room temperature to obtain a precursor;
weighing a certain precursor, dissolving the precursor in dimethyl sulfoxide to prepare brown viscous liquid with the mass ratio of 10wt%, pouring the viscous liquid on a dry and clean glass plate for casting to form a film, and then drying for 24 hours at the temperature gradient condition of 120 ℃ to obtain the novel polybenzimidazole quaternary ammonium salt anion exchange membrane;
and step three, soaking the prepared novel polybenzimidazole quaternary ammonium salt anion exchange membrane in ethanol for 24 hours, washing with deionized water, and drying.
Step four, putting the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in 1mol L -1 Soaking in KOH solution for 24h to realize the exchange of chloride ions and hydroxide radicals; finally, washing with deionized water and drying.
Example 7:
in the embodiment, the polybenzimidazole quaternary ammonium salt anion exchange membrane is used for reducing CO in electrocatalysis 2 The procedure of the application in (1) was the same as in example 1.
The preparation method of the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in the embodiment comprises the following steps:
step one, weighing 1mmol of polybenzimidazole, placing the polybenzimidazole in a three-neck flask, adding 40mL of dimethyl sulfoxide, and stirring in an oil bath at 80 ℃ until the polybenzimidazole is completely dissolved. Then, adding 0.6mmol of 2, 3-epoxypropyltrimethylammonium chloride, continuously stirring and reacting for 24 hours at the temperature of 80 ℃ to obtain a brown viscous solution, pouring the brown viscous solution into 200mL of acetone for precipitation, carrying out suction filtration and deionized water washing for 5 times, and then carrying out vacuum drying for 48 hours at room temperature to obtain a precursor;
weighing a certain precursor, dissolving the precursor in dimethyl sulfoxide to prepare brown viscous liquid with the mass ratio of 10wt%, pouring the viscous liquid on a dry and clean glass plate for casting to form a film, and then drying for 24 hours at the temperature gradient of 120 ℃ to obtain the novel polybenzimidazole quaternary ammonium salt anion exchange membrane;
and step three, soaking the prepared novel polybenzimidazole quaternary ammonium salt anion exchange membrane in ethanol for 24 hours, washing with deionized water, and drying.
Step four, putting the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in 1mol L -1 Soaking in KOH solution for 24h to realize the exchange of chloride ions and hydroxide radicals; finally, washing with deionized water and drying.
Example 8:
in the embodiment, the polybenzimidazole quaternary ammonium salt anion exchange membrane is used for reducing CO in electrocatalysis 2 The procedure of the application in (1) was the same as in example 1.
The preparation method of the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in the embodiment comprises the following steps:
step one, weighing 1mmol of polybenzimidazole, placing the polybenzimidazole in a three-neck flask, adding 40mL of dimethyl sulfoxide, and stirring in an oil bath at 80 ℃ until the polybenzimidazole is completely dissolved. Then, adding 0.8mmol of 2, 3-epoxypropyltrimethylammonium chloride, continuously stirring and reacting for 24h at the temperature of 80 ℃ to obtain a brown viscous solution, pouring the brown viscous solution into 200mL of acetone for precipitation, carrying out suction filtration and deionized water washing for 5 times, and carrying out vacuum drying for 48h at room temperature to obtain a precursor;
weighing a certain precursor, dissolving the precursor in dimethyl sulfoxide to prepare brown viscous liquid with the mass ratio of 10wt%, pouring the viscous liquid on a dry and clean glass plate for casting to form a film, and then drying for 24 hours at the temperature gradient of 120 ℃ to obtain the novel polybenzimidazole quaternary ammonium salt anion exchange membrane;
and step three, soaking the prepared novel polybenzimidazole quaternary ammonium salt anion exchange membrane in ethanol for 24 hours, washing with deionized water, and drying.
Step four, putting the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in 1mol L -1 Soaking in KOH solution for 24h to realize the exchange of chloride ions and hydroxide radicals; finally, washing with deionized water and drying.
Example 9:
in the embodiment, the polybenzimidazole quaternary ammonium salt anion exchange membrane is used for reducing CO in electrocatalysis 2 The procedure of the application in (1) was the same as in example 1.
The preparation method of the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in the embodiment comprises the following steps:
step one, weighing 1mmol of polybenzimidazole, placing the polybenzimidazole in a three-neck flask, adding 40mL of dimethyl sulfoxide, and stirring in an oil bath at 80 ℃ until the polybenzimidazole is completely dissolved. Then, adding 1.2mmol of 2, 3-epoxypropyltrimethylammonium chloride, continuously stirring and reacting for 24 hours at the temperature of 80 ℃ to obtain a brown viscous solution, pouring the brown viscous solution into 200mL of acetone for precipitation, carrying out suction filtration and deionized water washing for 5 times, and carrying out vacuum drying for 48 hours at room temperature to obtain a precursor;
weighing a certain precursor, dissolving the precursor in dimethyl sulfoxide to prepare brown viscous liquid with the mass ratio of 10wt%, pouring the viscous liquid on a dry and clean glass plate for casting to form a film, and then drying for 24 hours at the temperature gradient of 120 ℃ to obtain the novel polybenzimidazole quaternary ammonium salt anion exchange membrane;
and step three, soaking the prepared novel polybenzimidazole quaternary ammonium salt anion exchange membrane in ethanol for 24 hours, washing with deionized water, and drying.
Step four, putting the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in 1mol L -1 Soaking in KOH solution for 24h to realize the exchange of chloride ions and hydroxide radicals; finally, washing with deionized water and drying.
Example 10:
in the embodiment, the polybenzimidazole quaternary ammonium salt anion exchange membrane is used for reducing CO in electrocatalysis 2 The procedure of the application in (1) was the same as in example 1.
The preparation method of the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in the embodiment comprises the following steps:
step one, weighing 1mmol of polybenzimidazole, placing the polybenzimidazole in a three-neck flask, adding 40mL of dimethyl sulfoxide, and stirring in an oil bath at 80 ℃ until the polybenzimidazole is completely dissolved. Then, adding 1.4mmol of 2, 3-epoxypropyltrimethylammonium chloride, continuously stirring and reacting for 24 hours at the temperature of 80 ℃ to obtain a brown viscous solution, pouring the brown viscous solution into 200mL of acetone for precipitation, carrying out suction filtration and deionized water washing for 5 times, and carrying out vacuum drying for 48 hours at room temperature to obtain a precursor;
weighing a certain precursor, dissolving the precursor in dimethyl sulfoxide to prepare brown viscous liquid with the mass ratio of 10wt%, pouring the viscous liquid on a dry and clean glass plate for casting to form a film, and then drying for 24 hours at the temperature gradient of 120 ℃ to obtain the novel polybenzimidazole quaternary ammonium salt anion exchange membrane;
and step three, soaking the prepared novel polybenzimidazole quaternary ammonium salt anion exchange membrane in ethanol for 24 hours, washing with deionized water, and drying.
Step four, putting the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in 1mol L -1 Soaking in KOH solution for 24h to realize the exchange of chloride ions and hydroxide radicals; finally, washing with deionized water and drying.
Example 11:
the polybenzimidazole quaternary ammonium salt anion exchange membrane of the embodiment is used for reducing CO in electrocatalysis 2 The procedure of the application in (1) was the same as in example 1.
The preparation method of the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in the embodiment comprises the following steps:
step one, weighing 1mmol of polybenzimidazole, placing the polybenzimidazole in a three-neck flask, adding 40mL of dimethyl sulfoxide, and stirring in an oil bath at 80 ℃ until the polybenzimidazole is completely dissolved. Then, adding 1.6mmol of 2, 3-epoxypropyltrimethylammonium chloride, continuously stirring and reacting for 24h at the temperature of 80 ℃ to obtain a brown viscous solution, pouring the brown viscous solution into 200mL of acetone for precipitation, carrying out suction filtration and deionized water washing for 5 times, and carrying out vacuum drying for 48h at room temperature to obtain a precursor;
weighing a certain precursor, dissolving the precursor in dimethyl sulfoxide to prepare brown viscous liquid with the mass ratio of 10wt%, pouring the viscous liquid on a dry and clean glass plate for casting to form a film, and then drying for 24 hours at the temperature gradient condition of 120 ℃ to obtain the novel polybenzimidazole quaternary ammonium salt anion exchange membrane;
and step three, soaking the prepared novel polybenzimidazole quaternary ammonium salt anion exchange membrane in ethanol for 24 hours, washing with deionized water, and drying.
Step four, putting the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in 1mol L -1 Soaking in KOH solution for 24h to realize the exchange of chloride ions and hydroxide radicals; finally, washing with deionized water and drying.
Example 12:
in the embodiment, the polybenzimidazole quaternary ammonium salt anion exchange membrane is used for reducing CO in electrocatalysis 2 The procedure of the application in (1) was the same as in example 1.
The preparation method of the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in the embodiment comprises the following steps:
step one, weighing 1mmol of polybenzimidazole, placing the polybenzimidazole in a three-neck flask, adding 40mL of dimethyl sulfoxide, and stirring in an oil bath at 80 ℃ until the polybenzimidazole is completely dissolved. Then, adding 1.8mmol 2, 3-epoxypropyltrimethylammonium chloride, continuously stirring and reacting for 24h at the temperature of 80 ℃ to obtain brown viscous solution, pouring the brown viscous solution into 200mL acetone for precipitation, carrying out suction filtration and deionized water washing for 5 times, and carrying out vacuum drying for 48h at room temperature to obtain a precursor;
weighing a certain precursor, dissolving the precursor in dimethyl sulfoxide to prepare brown viscous liquid with the mass ratio of 10wt%, pouring the viscous liquid on a dry and clean glass plate for casting to form a film, and then drying for 24 hours at the temperature gradient condition of 120 ℃ to obtain the novel polybenzimidazole quaternary ammonium salt anion exchange membrane;
and step three, soaking the prepared novel polybenzimidazole quaternary ammonium salt anion exchange membrane in ethanol for 24 hours, washing with deionized water, and drying.
Step four, putting the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in 1mol L -1 Soaking in KOH solution for 24h to realize the exchange of chloride ions and hydroxide radicals; finally, washing with deionized water and drying.
While embodiments of the invention have been described above, it is not intended to be limited to the details shown, described and illustrated herein, but is to be accorded the widest scope consistent with the principles and novel features herein disclosed, and to such extent that such modifications are readily available to those skilled in the art, and it is not intended to be limited to the details shown and described herein without departing from the general concept as defined by the appended claims and their equivalents.
Claims (8)
1. Application of polybenzimidazole quaternary ammonium salt anion exchange membrane in electrocatalytic reduction of CO 2 The use of (a), wherein the polybenzimidazole quaternary ammonium salt anion exchange membrane has the structural formula:
the preparation method of the polybenzimidazole quaternary ammonium salt anion exchange membrane comprises the following steps:
step one, weighing 1mmol of polybenzimidazole, placing the polybenzimidazole in a three-neck flask, adding 40mL of dimethyl sulfoxide, and stirring in an oil bath at 80 ℃ until the polybenzimidazole is completely dissolved; then, 2.0mmol of 2, 3-epoxypropyltrimethylammonium chloride is added, the mixture is continuously stirred and reacted for 24 hours at the temperature of 80 ℃, a brown viscous solution is obtained, the brown viscous solution is poured into 200mL of acetone for precipitation, and after the acetone is filtered and washed for 5 times by deionized water, the mixture is dried for 48 hours in vacuum at room temperature, and a precursor is obtained;
weighing a certain precursor, dissolving the precursor in dimethyl sulfoxide to prepare brown viscous liquid with the mass ratio of 10wt%, pouring the viscous liquid on a dry and clean glass plate for casting to form a film, and then drying for 24 hours at the temperature gradient of 120 ℃ to obtain the novel polybenzimidazole quaternary ammonium salt anion exchange membrane;
step three, soaking the prepared novel polybenzimidazole quaternary ammonium salt anion exchange membrane in ethanol for 24 hours, washing with deionized water, and drying;
step four, putting the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in 1mol L -1 Soaking in KOH solution for 24h to realize the exchange of chloride ions and hydroxide radicals; finally, washing and drying by using deionized water;
fifthly, placing the novel polybenzimidazole quaternary ammonium salt anion exchange membrane obtained in the fourth step into a treatment cavity of a low-temperature plasma treatment instrument, pumping the system air pressure in the treatment cavity to 3Pa, introducing ammonia gas at the speed of 30L/min for washing, introducing ammonia gas into the treatment cavity again after washing to ensure that the pressure in the treatment cavity is constant to 30Pa, turning on a radio frequency power supply of the low-temperature plasma treatment instrument, adjusting the discharge power of the radio frequency power supply, and performing ammonia gas plasma treatment on the surface of the novel polybenzimidazole quaternary ammonium salt anion exchange membrane in the treatment cavity for 3min with the discharge power of 100W.
2. The polybenzimidazole quat anion exchange membrane as claimed in claim 1 for the electrocatalytic reduction of CO 2 Characterized in that said polybenzimidazole quat anion exchange membrane is used as an electrocatalytic reduction membrane for CO 2 Diaphragm of middle H type electrolytic cell.
3. The polybenzimidazole quat anion exchange membrane of claim 2 for the electrocatalytic reduction of CO 2 The method is characterized in that electrolyte is added into an H-type electrolytic cell and is added for 50-70 mL min -1 Introducing CO into the electrolyte at a flow rate 2 To discharge oxygen from the electrolyte to make the electrolyte reach CO 2 A saturated state; taking a silver foil with a surface formed with a microporous structure as a working electrode, taking Ag/AgCl as a reference electrode and a platinum sheet as a counter electrode; 15-25 mL min -1 Continuously introducing CO into the electrolyte at a speed of 2 Then applying a voltage to promote CO 2 A reduction reaction occurs at the surface of the working electrode.
4. Use of a polybenzimidazole quat anion exchange membrane as claimed in claim 3 for the electrocatalytic reduction of CO 2 The method is characterized in that the process of forming the micropore structure on the surface of the silver foil is as follows: silver foil with the thickness of 0.5mm is used as a cathode catalytic material, the constant-voltage electrolysis function of a CHI660E type electrochemical workstation is used, the surface of the silver foil is oxidized for 3min under the condition of 2.6V, and then is reduced for 3min under the condition of-2.6V, so that a microporous structure is formed on the surface of the silver foil.
5. The polybenzimidazole quat anion exchange membrane of claim 3 for the electrocatalytic reduction of CO 2 The method is characterized in that a microporous structure is formed on the surface of the silver foil, and then a glassy carbon electrode clamp is used for clamping to form a working electrode.
6. The polybenzimidazole quat anion exchange membrane of claim 3 for the electrocatalytic reduction of CO 2 The application of (1), characterized in that the electrolyte is 0.1mol L -1 KHCO of 3 And (3) solution.
7. The polybenzimidazole quat anion exchange membrane of claim 1 for the electrocatalytic reduction of CO 2 The application of (1) is characterized in that the thickness of the polybenzimidazole quaternary ammonium salt anion exchange membrane is 10-50 mu m.
8. Use of a polybenzimidazole quat anion exchange membrane as claimed in claim 2 in electrocatalytic reduction of CO 2 The polybenzimidazole quaternary ammonium salt anion exchange membrane is soaked by deionized water, clamped between rubber gaskets and installed in the middle of an H-shaped electrolytic cell to serve as a diaphragm.
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