CN111477889A - Monoatomic iron-nitrogen co-doped carbon electrocatalyst and preparation method and application thereof - Google Patents
Monoatomic iron-nitrogen co-doped carbon electrocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of electrocatalysts, and discloses a monatomic iron-nitrogen co-doped carbon electrocatalyst, a preparation method and application thereof, wherein iron in the catalyst is wrapped in holes of a metal organic framework ZIF-8 containing micropores and/or mesoporous structures in a monatomic iron-nitrogen coordination mode, and the catalyst comprises micropores with the pore diameter of less than 3nm, and mesopores with the pore diameters of 3-5nm and 29-32 nm; the preparation method comprises the following steps: (1) adding iron phthalocyanine into the 2-methylimidazole solution; (2) adding a zinc nitrate solution, and mixing to obtain a ZIF-8 packaged iron phthalocyanine composite material; (3) the composite material is calcined and acid-washed to obtain the electrocatalyst of the invention. The catalyst has a regular and good repeatability in a macroscopic morphology of a regular dodecahedron, and when the catalyst is applied, electrolyte can transfer mass through a rich mesoporous structure in the catalyst to realize electrocatalysisTo convert CO2High selectivity, high activity and low overpotential for preparing CO.
Description
Technical Field
The invention relates to the technical field of electrocatalysts, in particular to a monoatomic iron-nitrogen co-doped carbon electrocatalyst and a preparation method and application thereof.
Background
Traditional biological and chemical wastewater treatment technologies mainly oxidize organic pollutants in wastewater into CO2The chemical energy stored in the wastewater is wasted and a large amount of greenhouse gases are discharged. The bioelectrochemical system is one of the most promising technologies in recent years for converting chemical energy in wastewater into electrical energy, and is widely used for wastewater treatment, and the anode of the bioelectrochemical system generates active bacteria to oxidize organic matters into CO2The cathode undergoes a specific reduction reaction.
Electrocatalysis of CO in a number of reduction reactions2The reduction reaction can treat the waste water to generate CO2Reducing and converting into chemical fuels with high added value, such as methane, formic acid, CO and the like, and simultaneously realizing CO2Emission reduction and resource recycling. Thus, electrocatalytic CO2The coupling of the reduction reaction and the bioelectrochemical system can convert the chemical energy in the wastewater into electric energy and apply the electric energy to reduce the CO generated by the wastewater treatment2And the synchronous recovery of energy and resources is realized.
However, the coupled system has the defects that the electrons generated by the anode of the coupled system are difficult to drive the cathode to generate high-energy-barrier electro-catalysis CO due to the limitation of the metabolism rate of microorganisms and the low concentration of organic pollutants in the wastewater2And (4) carrying out reduction reaction. Therefore, the development and application of this coupled system is limited by electrocatalytic CO2Low activity, low selectivity and high overpotential for reduction reaction.
In the previous reports, researchers have studied the high selectivity of noble metal catalysts such as gold and silver in the electrocatalysis of CO under the condition of low overpotential2Reduction to CO, however, its high price and low reserves limit their widespread practical use. In recent years, the chemical bonding and CO-doping of the nano-carbon-based material by the monoatomic metal and the nonmetal heterogeneous atom becomes a research hotspot, and due to the unique physicochemical property and the atomic distribution state, the catalyst has the function of electrocatalysis of CO2Reduced high ofAnd (4) activity. In addition, the interaction force between the atomic-scale metal and the non-metal hetero-atom doped carbon carrier can change the electronic structure of the metal catalyst, thereby improving the stability of the catalyst and reducing the overpotential thereof.
For example, publication No. CN110067003A discloses a metal monatomic doped graphene material, and a preparation method and application thereof, wherein the method utilizes ammonium chloride, glucose, dicyanodiamine and metal salt as raw materials to synthesize the metal monatomic doped graphene material by utilizing a freeze drying and high-temperature calcination method, and the metal monatomic doped graphene material is applied to electrocatalysis of CO2The reduction is used for preparing CO, and the reduction and the activity are high; researchers can select different synthesis methods and precursors to obtain catalytic materials with higher selectivity and lower overpotential.
CN108899556A discloses a method for preparing a carbon-nitrogen-based monatomic iron catalyst with the assistance of ball milling, which adopts a one-pot method to wrap ferriporphyrin in a monomolecular manner in holes of a metal organic framework by mechanical ball milling to form a host-guest structure. And then, carrying out high-temperature pyrolysis reaction, forming a nitrogen-doped porous carbon carrier by the metal organic framework object, keeping the original porous structure, and fixing the ferriporphyrin molecule in the porous structure by forming a monoatomic Fe-Nx structure. However, the catalyst prepared by the ball milling method has poor embedding effect of the iron monoatomic atom and the metal organic framework, and has the problems of low selectivity and insufficient activity of the catalyst.
Thus, the above-mentioned bioelectrochemical technique and electrocatalysis of CO2Matching of reduced coupling system, development of high activity and high selectivity catalyst, especially electrocatalysis CO with low over potential2Reducing catalysts remains a problem that continues to be investigated and solved.
Disclosure of Invention
The invention aims to provide a monatomic iron-nitrogen CO-doped carbon electrocatalyst, iron is wrapped in a metal organic framework in an iron monatomic-nitrogen coordination mode, and the catalyst can promote mass transfer of electrolyte due to more active sites and abundant mesoporous structures attached to the catalyst, so that the catalyst is applied to electrocatalysis of CO2When the CO is prepared by reduction, the method has the advantages of high selectivity, low overpotential and high catalytic activity.
In order to achieve the purpose, the invention adopts the technical scheme that:
a monoatomic iron-nitrogen co-doped carbon electrocatalyst is characterized in that iron is wrapped in holes of a metal organic framework ZIF-8 containing a micropore and/or mesoporous structure in a monoatomic iron-nitrogen coordination mode; the catalyst comprises micropores with the aperture smaller than 3nm, and mesopores with the aperture of 3-5nm and 29-32 nm.
The preparation method provided by the invention is a molecular confinement coupling high-temperature calcination method, wherein iron phthalocyanine molecules are confined in a cavity of a metal organic frame ZIF-8 compound and then calcined at high temperature in inert gas, the iron phthalocyanine molecules and a ZIF-8 framework are carbonized, iron-nitrogen bonds of the iron phthalocyanine are anchored in a ZIF-8 derived nanocarbon carrier, in addition, redundant metal iron can be agglomerated at high temperature to form iron oxide with mesoporous size, zinc can be sublimated at high temperature to form micropores, and the iron oxide and the residual zinc are etched by acid pickling to respectively form mesoporous and microporous structures, so that more active sites can be exposed, and the single-atom iron material of the three-dimensional nitrogen-doped hierarchical porous carbon anchor with the microporous-mesoporous structure is obtained. The material has a high specific surface area, can be attached with more active sites, and the abundant mesoporous structure can promote the mass transfer of electrolyte, thereby realizing the electrocatalysis of CO2High selectivity, high activity and low overpotential for preparing CO.
The BET specific surface area of the catalyst is 500-1100 m2g-1The pore volume is 0.36-0.97 cm3g-1。
The invention also provides a preparation method of the monatomic iron-nitrogen co-doped carbon electrocatalyst, which comprises the following steps:
(1) adding iron phthalocyanine into a methanol solution of 2-methylimidazole, and dissolving to obtain a mixed solution;
(2) adding a methanol solution of zinc nitrate into the mixed solution, and stirring to obtain a ZIF-8/iron phthalocyanine composite material;
(3) calcining and acid-washing the ZIF-8/iron phthalocyanine composite material obtained in the step (2) in a nitrogen atmosphere to obtain the monatomic iron-nitrogen co-doped carbon electrocatalyst.
The molar ratio of the 2-methylimidazole to the zinc nitrate is 7.5-8.5: 1, and the excessive ligand 2-methylimidazole can be ensured in the range, so that the ligand can be effectively combined with zinc ions to generate a ZIF-8 precursor.
The concentration of the 2-methylimidazole in the methanol solution of the 2-methylimidazole is 0.75-0.85 mol/L, and the concentration of the zinc nitrate in the methanol solution of the zinc nitrate is 0.09-0.11 mol/L.
Preferably, the molar ratio of the 2-methylimidazole to the zinc nitrate is 8:1, each zinc ion in the ZIF-8 structure is combined with 4 2-methylimidazole molecules, the amount of the 2-methylimidazole determines the particle size of the ZIF-8, and the molar ratio of the 2-methylimidazole to the zinc nitrate is 8:1, so that the particle size of the ZIF-8 can be effectively controlled to be 60-70 nm, and the simultaneous existence of mesoporous and microporous structures is facilitated.
The addition amount of the iron phthalocyanine is 0.2-1.2 g/L, when the addition amount is too small, the amount of the metal iron is insufficient, the number of active sites is too small, and when the addition amount is too large, the generation of metal iron particles or the generation of iron carbide is caused, so that the amount of the monatomic iron is reduced, and the number of the active sites is also reduced.
In the step (2), the stirring temperature is 15-30 ℃, the stirring time is 20-30 hours, the preparation process of the ZIF-8 can be realized at normal temperature without heating or low temperature, iron phthalocyanine is fully and uniformly packaged into holes of the ZIF-8, the nucleating size of the ZIF-8 is in a certain relation with the stirring time, the stirring time is selected from 20-30 hours, and the particle size of the ZIF-8 in the range is about 60-70 nm.
Preferably, in the step (2), the stirring temperature is 20-25 ℃, and the stirring time is 20-25 hours.
In the step (3), the calcining temperature is 700-1050 ℃, and the heating rate is 2-10 ℃ for min-1The calcination time is 2-4 h; the acid washing is carried out by using 0.5-1.0M sulfuric acid, and the acid washing time is 20-30 h.
Wherein the calcining temperature directly influences the type and content of nitrogen and the coordination form of iron and nitrogen in the monatomic iron-nitrogen co-doped carbon electrocatalyst, and the percentage of the content of iron-nitrogen bonds in the total nitrogen content is increased by controlling the calcining temperature, so that the catalyst has more excellent catalytic activity, higher selectivity and higher catalytic activityLower overpotential. The calcination temperature is within 700-1050 ℃, the precursor can be ensured to be carbonized uniformly and fully, the iron-nitrogen bond of the iron phthalocyanine breaks through the limit domain of the original macrocyclic molecule and is embedded into the carbonized ZIF-8 frame, the acid pickling is carried out for 10-30 h by adopting 0.5-1.0M sulfuric acid, the removal of iron oxide and residual metal zinc in the calcined product can be ensured, so that the micropore and mesoporous structure of the catalyst is increased, the increase of the number of active sites and the CO in the reaction process are facilitated, and the removal of the iron oxide and the residual metal zinc in the calcined product is ensured2And the mass transfer of the electrolyte, the stability of the monoatomic iron-nitrogen coordination structure is improved, and the high activity and the low overpotential of the catalyst are finally realized.
Preferably, in the step (3), the calcination temperature is 900-1050 ℃, and the catalyst obtained at the calcination temperature has better pore size distribution and higher catalytic activity.
Further preferably, the calcination temperature is 950-1000 ℃, and the BET specific surface area of the prepared monoatomic iron-nitrogen co-doped carbon electrocatalyst is 1011m2g-1Left and right.
Still more preferably, the molar ratio of 2-methylimidazole in step (1) to zinc nitrate in step (2) is 8:1, the concentration of 2-methylimidazole is 0.8 mol/L, the concentration of zinc nitrate is 0.1 mol/L, the addition amount of iron phthalocyanine is 0.3 g/L, the stirring temperature in step (2) is 25 ℃, the stirring time is 24 hours, the calcination temperature is 1000 ℃, the calcination time is 3 hours, the concentration of sulfuric acid in step (3) is 0.5M, and the acid washing time is 24 hours.
The invention also provides the application of the monatomic iron-nitrogen CO-doped carbon electrocatalyst in electrocatalysis of CO2The application of reduction to prepare CO is characterized in that carbon paper loaded with the monatomic iron-nitrogen CO-doped carbon electrocatalyst is used as a working electrode, a saturated silver/silver chloride electrode is used as a reference electrode, a platinum column is used as a counter electrode, a potassium bicarbonate solution is used as an electrolyte, and the CO is electrocatalyzed through a three-electrode system2And (4) reducing. The Faraday efficiency of CO reduction preparation is high, the highest efficiency can reach about 96%, and the catalyst has high catalytic activity.
The invention also provides the monatomic iron-nitrogen CO-doped carbon electrocatalyst for electrocatalysis of CO in a bioelectrochemical system2Use of reduction to prepare CO, to support said monoCarbon paper of atomic iron-nitrogen CO-doped carbon electrocatalyst is used as cathode material of Microbial Electrolysis Cell (MEC) and is driven by Microbial Fuel Cell (MFC) to generate electrocatalysis CO2The reaction for preparing CO by reduction is stable and efficient in the whole electrocatalysis process, external energy input is not needed, and the electrocatalysis CO is driven by only utilizing the energy in the wastewater under the action of the catalyst2The highest output current of the current for preparing CO by reduction is 1.54 +/-0.05 mA, and the highest CO generation rate is 33.66 +/-0.58 mmol g-1 cath-1. Compared with the prior art, the invention has the following beneficial effects:
(1) the catalyst provided by the invention wraps iron in holes of a metal organic framework ZIF-8 in a monatomic iron-nitrogen coordination mode, removes iron oxide and zinc by utilizing the calcining and pickling processes, and manufactures a hierarchical micropore and mesoporous structure for the metal organic framework, so that when the catalyst is applied, electrolyte can transfer mass through the abundant mesoporous structure, thereby realizing electrocatalysis of CO2High selectivity, high activity and low overpotential for preparing CO.
(2) The preparation method of the monatomic iron-nitrogen co-doped carbon electrocatalyst provided by the invention is easy to operate, the macroscopic morphology of the catalyst is regular dodecahedron, the catalyst is regular and good in repeatability, the raw materials are cheap and easy to obtain, and the industrial production is easy to realize.
(3) The monatomic iron-nitrogen CO-doped carbon electrocatalyst provided by the invention has good catalytic stability in neutral electrolyte, and can realize efficient electrocatalysis of CO under the normal temperature condition2The reduction is used for preparing CO, the initial voltage is as low as-0.2V (relative to a standard reversible hydrogen electrode), and the lowest gradient of Tafel (Tafel) is 92mV dec-1Faradaic efficiency of CO can reach up to 96% at-0.5V (relative to a standard reversible hydrogen electrode) applied voltage.
(4) The monatomic iron-nitrogen CO-doped carbon electrocatalyst provided by the invention is applied to electrocatalysis of CO in a bioelectrochemical system2The CO is prepared by reduction, the electrocatalysis process is stable and efficient, external energy input is not needed, and the effect is good.
Drawings
Fig. 1 is a TEM image of a monoatomic iron-nitrogen co-doped carbon electrocatalyst prepared in example 1 of the present invention;
FIG. 2 is an AC-STEM diagram of a monatomic iron-nitrogen co-doped carbon electrocatalyst prepared in example 1 of the present invention;
FIG. 3 is a BET plot of a monatomic iron-nitrogen-co-doped carbon electrocatalyst prepared in example 1 of the present invention;
fig. 4 is a pore size distribution diagram of a monatomic iron-nitrogen co-doped carbon electrocatalyst prepared in example 1 of the present invention;
FIG. 5 is an XPS spectrum of a monatomic iron-nitrogen co-doped carbon electrocatalyst prepared in example 1 of the present invention;
FIG. 6 shows that the monatomic Fe-N CO-doped carbon electrocatalyst prepared in example 1 of the present invention electrocatalysts CO2Faraday efficiency graph for reduction preparation of CO;
FIG. 7 shows that the monatomic iron-nitrogen CO-doped carbon electrocatalyst prepared in example 1 of the present invention electrocatalysis CO in a bioelectrochemical system2And (3) reducing the output current and the output voltage of the prepared CO.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
Example 1
(1) Adding 32mmol 2-methylimidazole and 24mg iron phthalocyanine (FePc) into 40m L methanol, magnetically stirring for 10min to mix well to obtain a mixed solution, and adding 4mmol zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) is added into 40m L methanol, and the mixture is stirred for 10min by magnetic force until the mixture is mixed evenly, thus obtaining the methanol solution of zinc nitrate;
(2) adding a methanol solution of zinc nitrate into the mixed solution, magnetically stirring for 24 hours at room temperature, performing centrifugal separation, washing for 3 times by using methanol and deionized water respectively, and performing vacuum drying for 12 hours at 70 ℃ to obtain a metal organic framework ZIF-8 packaged iron phthalocyanine composite material;
(3) calcining the prepared composite material at 1000 ℃ in nitrogen atmosphere at the heating speed of 5 ℃ for min-1The calcination time is 3h, and the obtained calcination product is a monoatomic iron-nitrogen co-doped carbon electrocatalyst containing iron oxide and metal zinc; and washing the calcined product with 0.5M dilute sulfuric acid for 24 hours, removing ferric oxide and residual metal zinc, filtering and drying to obtain the monatomic iron-nitrogen co-doped carbon electrocatalyst.
The morphology of the prepared monatomic iron-nitrogen co-doped carbon electrocatalyst is observed by a transmission scanning electron microscope (TEM) and a spherical aberration correction transmission electron microscope (AC-STEM), and the result is shown in fig. 1 and fig. 2, fig. 1 shows that the monatomic iron-nitrogen co-doped carbon electrocatalyst prepared in the embodiment has rich mesoporous and microporous structures and presents a hierarchical microporous-mesoporous structure; as shown in fig. 2, the iron element in the prepared monatomic iron-nitrogen co-doped carbon electrocatalyst exists in the material in the form of a monatomic atom.
The nitrogen adsorption and desorption curve of the prepared catalyst is shown in figure 3, and the BET specific surface area of the catalyst is 1011m2g-1The pore volume is 0.97cm3g-1. The pore size distribution is shown in fig. 4, it can be seen that the catalyst comprises micropores with pore sizes less than 3nm, mesopores with pore sizes of 3-5nm and 29-32nm, wherein the amount of micropores with pore sizes less than 3nm is the largest, the amount of mesopores with pore sizes of about 3.7nm is the largest in the mesopores with pore sizes of 3-5nm, and the amount of mesopores with pore sizes of 31.2nm is the largest in the mesopores with pore sizes of 29-32nm, and the catalyst containing a large amount of micropores and mesopores is successfully obtained; when X-ray photoelectron spectroscopy (XPS) was observed, it was found that iron and nitrogen elements exist in the prepared catalyst in the form of an iron-nitrogen coordination structure, as shown in fig. 5.
Examples 2 to 4
According to the preparation method of example 1, the calcination temperatures in the step (3) were changed to 700 deg.C, 800 deg.C and 900 deg.C, respectively, and the remaining steps were not changed, and the BET specific surface areas of the obtained catalysts were 469m, respectively2g-1、693m2g-1And 775m2g-1Pore volumes of 0.36cm respectively3g-1、0.50cm3g-1And 0.69cm3g-1Pore diameter ofThe distribution was the same as the catalyst of example 1, including micropores having a pore size of less than 3nm, mesopores of 3 to 5nm and mesopores of 29 to 32 nm.
Examples 5 to 7
According to the preparation method of example 1, the addition amounts of iron phthalocyanine in step (1) were changed to 8mg, 16mg and 48mg, respectively, and the remaining steps were not changed.
Application example 1 application of monatomic iron-nitrogen CO-doped carbon electrocatalyst to electrocatalysis of CO2Reduction test
Step (1) of adding 5mg of the monatomic iron-nitrogen co-doped carbon electrocatalyst prepared in example 1 into a mixed solution of a perfluorosulfonic acid polymer solution (Nafion) (0.5 wt%) and 450 μ L absolute ethyl alcohol, and then performing ultrasonic treatment for 2 hours and performing magnetic stirring for 2 hours to form a uniform catalyst suspension;
step (2) selecting 100 mu L of catalyst suspension liquid drop in step (1) at 1 × 1cm2Drying the carbon paper under an infrared lamp to obtain the carbon paper with the loading capacity of 1.0mg cm-2The catalyst working electrode of (1);
and (3): taking the loaded catalyst carbon paper obtained in the step (2) as a working electrode, a saturated silver/silver chloride electrode as a reference electrode, a platinum column as a counter electrode, 0.5M potassium bicarbonate solution as electrolyte, and electrocatalysis of CO through a three-electrode system2And (3) reducing, selecting a tail gas sample every 20min under different applied voltages, entering a gas chromatograph, analyzing the content of CO in the tail gas sample, and calculating to obtain the Faraday efficiency of the CO.
As shown in FIG. 6, the monatomic iron-nitrogen CO-doped carbon electrocatalyst prepared in example 1 electrocatalyzes CO2The maximum Faraday efficiency of CO reduction is about 96%.
Application example 2 application of monatomic iron-nitrogen co-doped carbon electrocatalyst to bioelectrochemical system
Step (1): electrochemically active bacteria (Shewanella oneidensis MR-1) acclimatized with acetate as an organic substance were inoculated in Microbial Fuel Cells (MFC) and Microbial Electrolyzers (MEC) and stably operated for 6 months with an open-circuit voltage of MFC of 680 mV.
And (2) in the step (1), the cathode and anode electrode materials of the MFC device are respectively carbon felt (6 × 3 × 1cm)And carbon brush, the anode electrolyte of MFC is composed of phosphate buffer solution (6g L)-1Disodium hydrogen phosphate, 3g L-1Potassium dihydrogen phosphate, 1g L-1Ammonium chloride and 0.5g L-1Sodium chloride), 5m L L-1Vitamin solution, 12.5m LL-1Mineral solution and 15mM L-1Acetate, the cathode electrolyte of MFC is composed of 16.64g of potassium ferricyanide added into 1L phosphate buffer solution, and the cathode chamber and the anode chamber of MFC are separated by proton exchange membrane.
And (3) in the step (1), the anode electrode material and the anolyte of the MEC device are the same as those of the MFC device, and the cathode material of the MEC is 1 × 1cm prepared to support the monatomic iron-nitrogen co-doped carbon electrocatalyst prepared in the example 12Carbon paper, the catholyte is 0.5M potassium bicarbonate solution;
and (4): the MFC is used as a driving energy source, the MEC is used as a driven device, an additional auxiliary resistor with the resistance value of 20 omega is connected in series at the same time, the current in the whole MFC-MEC coupling system is measured, and a universal meter is used for measuring the voltage in the coupling system;
the monatomic iron-nitrogen CO-doped carbon electrocatalyst of the MEC cathode in the coupling device can be driven by an MFC to generate electrocatalysis CO2Reduction to produce CO. As shown in FIG. 7, the output voltage of the monatomic Fe-N CO-doped C electrocatalyst applied to the MFC-MEC coupling device is 1.14 +/-0.02V, the output current is 1.54 +/-0.05 mA, and the CO generation rate is 33.66 +/-0.58 mmol g-1 cath-1。
Application examples 3 to 5
According to the steps of application example 1, the atomic iron-nitrogen CO-doped carbon electrocatalyst prepared in examples 2 to 4 is respectively used as a cathode material to electrocatalysis CO2Reduction Performance test, electrocatalysis of CO2The maximum faradaic efficiency for reduction to CO is about 58%, 82%, and 89%, respectively. Therefore, in the preparation process of the catalyst, the calcination temperature has a great influence on the catalytic activity of the catalyst. When the calcination temperature is above 800 ℃, the catalytic activity of the catalyst is better.
Application examples 6 to 8
The atomic iron-nitrogen copolymers prepared in examples 5 to 7 were each prepared according to the procedure of application example 1Carbon-doped electrocatalyst as cathode material for electrocatalysis of CO2Reduction Performance test, electrocatalysis of CO2The maximum faradaic efficiency for reduction to CO is around 92%, 93% and 94%, respectively.
Claims (10)
1. A monatomic iron-nitrogen co-doped carbon electrocatalyst is characterized in that iron is wrapped in holes of a metal organic framework ZIF-8 containing a micropore and/or a mesoporous structure in a monatomic iron-nitrogen coordination mode; the catalyst comprises micropores with the aperture smaller than 3nm, and mesopores with the aperture of 3-5nm and 29-32 nm.
2. The monatomic iron-nitrogen co-doped carbon electrocatalyst according to claim 1, wherein the BET specific surface area of the catalyst is 500-1100 m2g-1The pore volume is 0.36-0.97 cm3g-1。
3. The preparation method of the monatomic iron-nitrogen-codoped carbon electrocatalyst according to claim 1 or 2, characterized by comprising the steps of:
(1) adding iron phthalocyanine into a methanol solution of 2-methylimidazole, and dissolving to obtain a mixed solution;
(2) adding a methanol solution of zinc nitrate into the mixed solution, mixing, and then carrying out centrifugal separation, washing and drying to obtain the ZIF-8 packaged iron phthalocyanine composite material;
(3) calcining and acid-washing the ZIF-8/iron phthalocyanine composite material obtained in the step (2) in a nitrogen atmosphere to obtain the monatomic iron-nitrogen co-doped carbon electrocatalyst.
4. The preparation method of the monatomic iron-nitrogen co-doped carbon electrocatalyst according to claim 3, wherein the molar ratio of 2-methylimidazole in step (1) to zinc nitrate in step (2) is 7.5-8.5: 1.
5. The preparation method of the monatomic iron-nitrogen co-doped carbon electrocatalyst, according to claim 3, wherein the molar concentration of 2-methylimidazole in the methanol solution of 2-methylimidazole is 0.75-0.85 mol/L, and the molar concentration of zinc nitrate in the methanol solution of zinc nitrate is 0.09-0.11 mol/L.
6. The preparation method of the monatomic iron-nitrogen co-doped carbon electrocatalyst according to claim 3, wherein in the step (1), the mass concentration of the iron phthalocyanine in the mixed solution after the iron phthalocyanine is added is 0.2-1.2 g/L.
7. The preparation method of the monatomic iron-nitrogen co-doped carbon electrocatalyst according to claim 3, wherein in the step (2), the stirring temperature is 15-30 ℃ and the stirring time is 20-30 hours.
8. The preparation method of the monatomic iron-nitrogen co-doped carbon electrocatalyst according to claim 3, wherein in the step (3), the calcination temperature is 700-1050 ℃, and the temperature rise rate is 2-10 ℃ min-1The calcination time is 2-4 h; the acid washing is carried out by using 0.5-1.0M sulfuric acid, and the acid washing time is 10-30 h.
9. The use of the monatomic iron-nitrogen CO-doped carbon electrocatalyst according to claim 1 or 2 for electrocatalysis of CO2Application of reduction to CO preparation.
10. The monatomic iron-nitrogen CO-doped carbon electrocatalyst according to claim 1 or 2, electrocatalysis of CO in a bioelectrochemical system2Application of reduction to CO preparation.
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