CN109881213B - Efficient coupling method for producing hypochlorite through anodic oxidation and reducing carbon dioxide through cathode - Google Patents
Efficient coupling method for producing hypochlorite through anodic oxidation and reducing carbon dioxide through cathode Download PDFInfo
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- CN109881213B CN109881213B CN201910202183.8A CN201910202183A CN109881213B CN 109881213 B CN109881213 B CN 109881213B CN 201910202183 A CN201910202183 A CN 201910202183A CN 109881213 B CN109881213 B CN 109881213B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 85
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 48
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 40
- 230000003647 oxidation Effects 0.000 title claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 13
- 238000010168 coupling process Methods 0.000 title claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910052742 iron Inorganic materials 0.000 claims abstract description 48
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- 238000002360 preparation method Methods 0.000 claims description 12
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Images
Abstract
The invention provides a method for coupling production of hypochlorite by anodic oxidation and reduction of carbon dioxide by a cathode. The inventionElectrocatalytic reduction of CO using monatomic iron-loaded nitrogen-doped carbon material as catalyst2Meanwhile, the method can be used for producing hypochlorite through anodic oxidation with hypochlorite anodic production, thereby realizing efficient production of hypochlorite and reducing carbon dioxide to carbon monoxide; the nitrogen-doped carbon electrocatalytic material loaded by the monatomic iron has a polyhedral microstructure with the length and the width both in nanoscale, and the loaded metal in the nitrogen-doped carbon electrocatalytic material loaded by the monatomic iron is dispersed in a monatomic form. The electrochemical reduction method is used for electrochemically reducing carbon dioxide, the current efficiency of selectively reducing carbon dioxide to carbon monoxide can reach more than 99.63%, and the stability is good. Meanwhile, the current efficiency of the anode for producing the hypochlorite is as high as 99.47 percent, and the higher faradaic efficiency can be maintained for a long time.
Description
Technical Field
The invention belongs to the field of catalysis, and particularly relates to a method for coupling production of hypochlorite by anodic oxidation and reduction of carbon dioxide by a cathode.
Background
In recent decades, rapid development of economy brings great convenience to people, and simultaneously creates a series of environments, a large amount of carbon dioxide gas is discharged while fossil fuels are utilized, and negative effects of greenhouse effect on the living environment of the earth are increasingly aggravated. How to recover and utilize carbon dioxide is currently an important research topic.
Electrocatalytic reduction of CO2Renewable energy sources are utilized to generate electric energy, and the energy is converted into high-energy-state-density compounds such as CO, formic acid, alcohols, hydrocarbons and the like to be stored so as to be reused, so that the method has very important significance for coping with environmental problems and relieving energy crisis. However, in the conventional electrocatalytic reduction of carbon dioxide, oxygen evolution reaction occurs at the anode, and the generation of oxygen is not commercially valuable. Unfortunately, only cathodic reactions are used to produce value added products in electrolytic processes. If certain anodic reactions can be combined with the reduction of carbon dioxide while also producing useful chemicals, it will allow for efficient use of electrical energy. Inspired by this idea, we thought that the electrolysis of neutral chloride solutions at the anode produced hypochlorite, a commonly used chemical, which could allow the anode to produce value added products. Sodium hypochlorite can be used for bleachingIndustrial waste water treatment, papermaking, weaving, pharmacy, fine chemistry industry, numerous fields such as sanitary disinfection specifically are: sodium hypochlorite can be used as a bleaching agent for bleaching paper pulp, textiles, chemical fibers and starch; can be used as a bleaching agent of grease in the soap making industry; can be used for producing hydrazine hydrate, monochloramine and dichloroamine in the chemical industry; can be used as water purifying agent, bactericide and disinfectant for water treatment; in the field of organic industry, the method can be used for manufacturing a cleaning agent for preparing acetylene by the hydration of chloropicrin and calcium carbide; in agriculture and animal husbandry, it can be used as disinfectant and deodorant for vegetables, fruits, farm and animal house; the food grade sodium hypochlorite can be used for sterilizing drinking water, fruits and vegetables and sterilizing food manufacturing equipment and appliances. If we could couple the anodic oxidation to produce hypochlorite with the cathodic reduction of carbon dioxide, a simultaneous efficient production of hypochlorite and reduction of carbon dioxide could be achieved. However, carbon dioxide is introduced into the sodium chloride solution until the sodium chloride solution is saturated, and the pH of the solution is acidic and is not favorable for reducing the carbon dioxide. Furthermore, the chloride ions are liable to form complexes with the metals in the catalyst, which is deactivation of the catalyst. How to efficiently remove CO in a sodium chloride solution2The conversion to industrial chemicals of practical value is a difficult challenge.
Disclosure of Invention
The invention aims to provide a method for producing hypochlorite by anodic oxidation and coupling with cathode reduction of carbon dioxide.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
providing an electrocatalytic reduction of CO2The method utilizes a nitrogen-doped carbon material loaded by monatomic iron as a catalyst to carry out electrocatalytic reduction on CO2The nitrogen-doped carbon loaded by the monatomic iron has a polyhedral microstructure with the length, the width and the height of the polyhedron of the nanoscale, and the loaded metal in the nitrogen-doped carbon electrocatalytic material loaded by the monatomic iron is dispersed in the monatomic form.
According to the scheme, the length, the width and the height of the polyhedron with the nanoscale size are all 50-200 nm.
According to the scheme, the load amount of the metal Fe is 0.1-2.16%, and preferably 0.5-1.08%.
According to the scheme, the preparation method of the nitrogen-doped carbon material loaded by the monatomic iron comprises the following steps:
1) adding ZIF-8 into the solution of ferric acetylacetonate, and performing ultrasonic treatment to fully and uniformly mix the mixture; vacuum drying to obtain solid powder;
2) calcining the powder in an inert atmosphere at 900-1000 ℃, naturally cooling to room temperature, and collecting a reaction product to obtain the nitrogen-doped carbon loaded by the monatomic iron.
According to the scheme, the solution of the iron acetylacetonate in the step 1) is a tetrahydrofuran solution of the iron acetylacetonate, and the ultrasonic time is 1-2 h.
According to the scheme, the vacuum drying time in the step 1) is 1-2 h.
According to the scheme, the calcination in the step 2) is carried out for 2-4 hours.
According to the scheme, the preparation method of the ZIF-8 comprises the following steps: dissolving 0.5-0.6 g of zinc nitrate hexahydrate in 10-20 mL of methanol to obtain solution A, dissolving 0.55-0.65 g of dimethyl imidazole in 10-20 mL of methanol to obtain solution B, adding the solution A into the solution B, performing ultrasonic treatment, reacting at 30-40 ℃ for 10-15 h, and performing post-treatment to obtain ZIF-8.
According to the scheme, the ultrasonic time in the preparation of the ZIF-8 is 10-20 min; the post-treatment in the preparation of the ZIF-8 is to centrifugally collect a solid product after reaction, centrifugally wash the solid product with DMF for 3 times, wash the solid product with methanol for 3 times, and dry the solid product for 6 hours at 40 ℃ in vacuum to obtain the ZIF-8; and the solid is obtained by centrifuging at a low rotating speed of 5000-8000 r/min for 5-10 min in the preparation of the ZIF-8.
A method for coupling production of hypochlorite by anodic oxidation and reduction of carbon dioxide by a cathode comprises the following specific steps: in an electrolytic cell with a proton exchange membrane divided into an anode tank and a cathode tank, a catalyst electrode prepared by nitrogen-doped carbon electrocatalytic materials loaded by monatomic iron is taken as a working electrode, a cathode is taken, a ruthenium-titanium electrode is taken as an auxiliary electrode, an anode is taken, electrolyte solutions are respectively filled in the electrolytic cells of the anode tank and the cathode tank, carbon dioxide is introduced into the cathode tank until the cathode tank is saturated, then the carbon dioxide is continuously introduced, the tank pressure is 1V-3V, preferably 1.5V-2.5V, the carbon dioxide is reduced by a cathode, and hypochlorite is produced by the anode.
According to the scheme, the electrolyte solution is 0.05-0.2M sodium chloride solution.
According to the scheme, the preparation method of the nitrogen-doped carbon catalyst electrode loaded by the monatomic iron comprises the following steps: and weighing the nitrogen-doped carbon material loaded by the monatomic iron, ultrasonically dispersing the nitrogen-doped carbon material into a mixed solution of Nafion and isopropanol, then dripping the suspended liquid of the nitrogen-doped carbon loaded by the monatomic iron on the surface of a glassy carbon electrode, and drying the glassy carbon electrode under an infrared lamp to obtain the nitrogen-doped carbon/glassy carbon electrode loaded by the monatomic iron.
According to the scheme, the ratio of the nitrogen-doped carbon loaded by the monatomic iron to the mixed solution of Nafion and isopropanol is 5-10 mg: 0.5-1 mL.
According to the scheme, the loading amount of the catalyst in the nitrogen-doped carbon catalyst electrode loaded by the monatomic iron is 1-2 mg/cm2。
According to the scheme, the ruthenium-titanium electrode can be obtained by spraying a layer of ruthenium on a titanium net, and has the characteristics of high activity, high stability and corrosion resistance when used for anodic oxidation.
The invention has the advantages that:
1. according to the invention, the MOF material and the single atom are combined together, so that the high-efficiency electrocatalytic reduction carbon dioxide catalyst is successfully prepared, the catalyst can be used for effectively electrocatalytic reduction of carbon dioxide for a long time under an acidic condition, the Faraday efficiency of electrocatalytic reduction of carbon dioxide to carbon monoxide can be up to 99.63%, and the Faraday efficiency of chlorine production and alkali production of a ruthenium-titanium electrode is also up to 99.47%.
2. The method skillfully couples the hypochlorite produced by anodic oxidation with the carbon dioxide reduced by the cathode, the hypochlorite can be produced efficiently by the anode, the carbon dioxide can be reduced to carbon monoxide efficiently by the cathode, and the effect of simultaneously producing the hypochlorite efficiently and reducing the carbon dioxide to the carbon monoxide is realized
3. The catalyst has the advantages of cheap and easily obtained raw materials, easily realized synthesis conditions, no need of complex devices, simple operation, no danger and no need of hiring professional personnel for operation.
4. The metal load in the nitrogen-doped carbon electrocatalytic material loaded by the monatomic iron is surface substitution load, and the metal load is less, so that the material cost is reduced, and the economic benefit of the material is improved.
5. The material is environment-friendly, does not cause secondary pollution and has certain cyclicity.
Drawings
FIG. 1 is an XRD pattern of monatomic iron-supported nitrogen-doped carbon of example 1;
fig. 2 is an SEM image of nitrogen-doped carbon synthesized in example 1 and a monatomic iron-supported nitrogen-doped carbon;
FIG. 3 is a graph of a monoatomic iron-supported nitrogen-doped carbon TEM, Mapping and HAADF-STEM;
FIG. 4 is an EXAFS plot and fitted curve for monatomic iron-loaded nitrogen-doped carbon;
FIG. 5 is a TEM of nano-iron loaded nitrogen doped carbon;
FIG. 6 is a schematic view of an experimental setup;
FIG. 7 shows electrocatalytic reduction of CO by nitrogen-doped carbon, nano-iron-loaded nitrogen-doped carbon, and monoatomic iron-loaded nitrogen-doped carbon material2An efficiency map of (c);
FIG. 8 is a graph of the current efficiency of the single atom iron loaded nitrogen doped carbon electrocatalytic reduction of carbon dioxide and ruthenium titanium electrodes to produce hypochlorite at different cell pressures;
FIG. 9 is a graph of the stability performance of ruthenium titanium and monatomic iron-supported nitrogen-doped carbon catalysts at a cell pressure of 2.5V.
Detailed Description
Example 1
Preparation of nitrogen-doped carbon material loaded by monatomic iron:
dissolving 0.5g of zinc nitrate hexahydrate in 10mL of methanol to obtain solution A, dissolving 0.55g of dimethyl imidazole in 10mL of methanol to obtain solution B, adding the solution A into the solution B, performing ultrasonic treatment, reacting at 30 ℃ for 10 hours, centrifuging, collecting a solid product after reaction, washing with DMF (dimethyl formamide) and methanol for three times respectively, centrifuging, collecting a washed solid product, and drying in a vacuum drying oven at 80 ℃ to obtain ZIF-8; adding 0.1g of ZIF-8 powder into 10ml of 0.01% ferric acetylacetonate tetrahydrofuran solution, and performing ultrasonic treatment for 1h to fully and uniformly mix the powder; vacuum for 1h to obtain solid powder; calcining the powder for 2 hours at 950 ℃ in Ar atmosphere, and collecting reaction products after naturally cooling to room temperature to obtain the nitrogen-doped carbon loaded by the monatomic iron. The iron loading was 1.08% by IPC-OES test.
FIG. 1 is an XRD pattern of monatomic iron-supported nitrogen-doped carbon; according to XRD patterns, the main component of the synthesized material is nitrogen-doped carbon.
Fig. 2 SEM images of nitrogen-doped carbon and monatomic iron-loaded nitrogen-doped carbon: the SEM pictures show that the morphology of the material before and after loading the metal is not changed. (before doping in FIG. a and after doping in FIG. b)
FIG. 3 is a graph of a monoatomic iron-supported nitrogen-doped carbon TEM, Mapping and HAADF-STEM; it can be seen from fig. 3(a) that the material is polyhedral and has a length, width and height of about 50-200 nm, and fig. 3(b) that the material is mainly composed of carbon and nitrogen, iron is indeed loaded on the surface of the material, and it is apparent from fig. 3(c) and (d) that Fe on the surface is dispersed in a monoatomic form by HAADF-STEM.
Fig. 4 is an EXAFS plot of monatomic iron-loaded nitrogen-doped carbon, from which the bonding of monatomic iron to nitrogen is evident in the left plot of fig. 4, and from which the measured data and the fitted data are in good agreement in the right plot of fig. 4.
Preparation of nitrogen-doped carbon material as a control material:
dissolving 0.5g of zinc nitrate hexahydrate in 10mL of methanol to obtain solution A, dissolving 0.55g of dimethyl imidazole in 10mL of methanol to obtain solution B, adding the solution A into the solution B, performing ultrasonic treatment, reacting at 30 ℃ for 10 hours, centrifuging, collecting a solid product after reaction, washing with DMF (dimethyl formamide) and methanol for three times respectively, centrifuging, collecting a washed solid product, and drying in a vacuum drying oven at 80 ℃ to obtain ZIF-8; calcining for 2 hours at 950 ℃ in Ar atmosphere, and collecting reaction products to obtain the nitrogen-doped carbon after naturally cooling to room temperature.
Preparation of a control material, namely a nano-iron-loaded nitrogen-doped carbon material:
dissolving 0.5g of zinc nitrate hexahydrate in 10mL of methanol to obtain solution A, dissolving 0.55g of dimethyl imidazole in 10mL of methanol to obtain solution B, adding the solution A into the solution B, performing ultrasonic treatment, reacting at 30 ℃ for 10 hours, centrifuging, collecting a solid product after reaction, washing with DMF (dimethyl formamide) and methanol for three times respectively, centrifuging, collecting a washed solid product, and drying in a vacuum drying oven at 80 ℃ to obtain ZIF-8; adding 0.1g of the ZIF-8 powder into 10ml of 0.05% ferric acetylacetonate tetrahydrofuran solution, and performing ultrasonic treatment for 1 hour to fully and uniformly mix the mixture; vacuum for 1h to obtain solid powder; calcining the powder for 2 hours at 950 ℃ in Ar atmosphere, and collecting reaction products to obtain the iron-loaded nitrogen-doped carbon after naturally cooling to room temperature. Fig. 5 is a TEM of nano-iron supported nitrogen doped carbon, from which it can be seen that iron clusters are formed after the iron loading is increased.
Example 2
Construction of an electrolytic system:
weighing 10mg of nitrogen-doped carbon loaded by monatomic iron as a precursor, ultrasonically dispersing the precursor into 1mL of mixed solution of Nafion (2 wt%) and isopropanol, and then dripping 150 mu L of nitrogen-doped carbon suspension loaded by monatomic iron on the surface of 1cm2Drying the surface of the glassy carbon electrode under an infrared lamp to prepare the nitrogen-doped carbon/glassy carbon electrode loaded with the monatomic iron, wherein the loading amount of the catalyst in the electrode is 1.5mg/cm2。
In an electrolytic cell with a proton exchange membrane divided into an anode tank and a cathode tank, a nitrogen-doped carbon catalyst electrode loaded by monatomic iron is taken as a working electrode (cathode), ruthenium titanium is taken as an auxiliary electrode (anode), anode and cathode electrolyte solutions are 0.1M sodium chloride solutions, carbon dioxide is introduced into the cathode tank until the solution is saturated, then the electrical reaction is carried out under the condition of continuously introducing the carbon dioxide, and the reaction equation is as follows:
cathode is CO2+2H++2e-→CO+H2O
Anode Cl-+2OH-→ClO-+H2O+2e-
Carrying out a total reaction; CO22+Cl-→CO+ClO-
The experimental setup is shown in fig. 6, where CE is the auxiliary electrode, RE is the reference electrode, and WE is the working electrode. Electrocatalytic reduction of CO from nitrogen-doped carbon, nano-iron-loaded nitrogen-doped carbon and monatomic iron-loaded nitrogen-doped carbon material2The efficiency map of (2) is shown in FIG. 7Shown in the figure. As can be seen in fig. 7: the efficiency of the monatomic iron-supported nitrogen-doped carbon material for the electrocatalytic reduction of CO2 is significantly higher than the efficiency of the nitrogen-doped carbon material, which is not supported and supports nano-iron particles, for the electrocatalytic reduction of CO 2.
Example 3
The electrocatalytic cathode reduces CO2 and the anode produces hypochlorite:
reducing carbon dioxide under the bath pressure of 1.0V, wherein the current efficiency of carbon monoxide is 33.99 percent, and the current efficiency of the anode for producing the hypochlorite is 23.75 percent; reducing carbon dioxide under the pressure of 1.5V, wherein the current efficiency of carbon monoxide is 55.63 percent, and the current efficiency of the anode for producing the hypochlorite is 51.47 percent; the carbon dioxide is reduced under the bath pressure of 2.0V, the current efficiency of the carbon monoxide is 81.22 percent, and the current efficiency of the anode for producing the hypochlorite is 78.195 percent; the current efficiency of carbon monoxide is 99.63 percent and the current efficiency of hypochlorite production by the anode is 99.47 percent when the carbon dioxide is reduced under the pressure of 2.5V, the current efficiency of carbon monoxide is 99.21 percent and the current efficiency of hypochlorite production by the anode is 99.08 percent when the carbon dioxide is reduced under the pressure of 3.0V. The experimental results are shown in fig. 8: when the groove pressure is 2.5V, the Faraday efficiency is best. FIG. 9 shows the stability test results of the catalyst under the optimum cell pressure, and it can be seen that the catalyst still has higher activity after 20 hours of reaction.
Claims (9)
1. Electrocatalytic reduction of CO2The method of (2), characterized by: electrocatalytic reduction of CO using monatomic iron-loaded nitrogen-doped carbon material as catalyst2The nitrogen-doped carbon loaded by the monatomic iron has a polyhedral micro-morphology structure with the length, the width and the height of the polyhedron of the nanoscale size, the loaded metal in the nitrogen-doped carbon electrocatalytic material loaded by the monatomic iron is dispersed in a monatomic form, and the loading amount of the metal Fe is 0.1% -2.16%.
2. Electrocatalytic reduction of CO according to claim 12The method of (2), characterized by: the length, width and height of the polyhedron with the nanoscale size are all 50-200 nm.
3. Electrocatalysis according to claim 1Reduction of CO2The method of (2), characterized by: the loading amount of the metal Fe is 0.5-1.08%.
4. Electrocatalytic reduction of CO according to claim 12The method of (2), characterized by: the preparation method of the nitrogen-doped carbon material loaded by the monatomic iron comprises the following steps:
1) adding ZIF-8 into the solution of ferric acetylacetonate, and performing ultrasonic treatment to fully and uniformly mix the mixture; vacuum drying to obtain solid powder;
2) calcining the powder for 2-4 hours at 900-1000 ℃ in an inert atmosphere, and collecting reaction products after naturally cooling to room temperature to obtain the nitrogen-doped carbon loaded by the monatomic iron.
5. Electrocatalytic reduction of CO according to claim 42The method of (2), characterized by: the solution of the iron acetylacetonate in the step 1) is a tetrahydrofuran solution of the iron acetylacetonate, and the ultrasonic time is 1h-2 h; the vacuum drying time in the step 1) is 1-2 h; calcining for 2-4 h in the step 1);
the preparation method of the ZIF-8 comprises the following steps: dissolving 0.5-0.6 g of zinc nitrate hexahydrate in 10-20 mL of methanol to obtain solution A, dissolving 0.55-0.65 g of dimethyl imidazole in 10-20 mL of methanol to obtain solution B, adding the solution A into the solution B, performing ultrasonic treatment, reacting at 30-40 ℃ for 10-15 h, and performing post-treatment to obtain ZIF-8.
6. A method for coupling production of hypochlorite by anodic oxidation and reduction of carbon dioxide by a cathode is characterized by comprising the following steps: in an electrolytic cell with a proton exchange membrane divided into an anode tank and a cathode tank, a catalyst electrode prepared from the monatomic iron-supported nitrogen-doped carbon electrocatalytic material as claimed in claim 1 is used as a working electrode, the working electrode is used as a cathode, a ruthenium-titanium electrode is used as an auxiliary electrode, the working electrode is used as an anode, electrolyte solutions are respectively filled in the electrolytic cells of the anode tank and the cathode tank, carbon dioxide is introduced into the cathode tank until the cathode tank is saturated, then the carbon dioxide is continuously introduced, the cathode at the tank pressure of 1V-3V is used for reducing the carbon dioxide, and the chlorite is produced by the anode.
7. The method for coupling the anodic oxidation for the production of hypochlorite and the cathodic reduction of carbon dioxide as claimed in claim 6, wherein the specific method comprises: the cell pressure is 1.5V-2.5V, and the electrolyte solution of the anode and the cathode is 0.05-0.2M of sodium chloride solution.
8. The method of claim 6, wherein the anodic oxidation to produce hypochlorite is coupled with cathodic reduction of carbon dioxide, wherein: the preparation method of the nitrogen-doped carbon catalyst electrode loaded by the monatomic iron comprises the following steps: and weighing the nitrogen-doped carbon material loaded by the monatomic iron, ultrasonically dispersing the nitrogen-doped carbon material into a mixed solution of Nafion and isopropanol, then dripping the suspended liquid of the nitrogen-doped carbon loaded by the monatomic iron on the surface of a glassy carbon electrode, and drying the glassy carbon electrode under an infrared lamp to obtain the nitrogen-doped carbon/glassy carbon electrode loaded by the monatomic iron.
9. The method as claimed in claim 6, wherein the loading amount of the catalyst in the monatomic iron-supported nitrogen-doped carbon catalyst electrode is 1-2 mg/cm2。
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