CN114540867A - Nano reactor for reducing acidic electrocatalytic carbon dioxide, preparation method and membrane electrode system - Google Patents

Nano reactor for reducing acidic electrocatalytic carbon dioxide, preparation method and membrane electrode system Download PDF

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CN114540867A
CN114540867A CN202210071840.1A CN202210071840A CN114540867A CN 114540867 A CN114540867 A CN 114540867A CN 202210071840 A CN202210071840 A CN 202210071840A CN 114540867 A CN114540867 A CN 114540867A
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康鹏
刘治坤
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Abstract

The invention relates to a nano reactor for reducing acidic electrocatalytic carbon dioxide, a preparation method and a membrane electrode system. Synthesizing phenolic resin coated silicon spheres by a hydrothermal method, adding an N source during high-temperature calcination, and removing silicon cores to obtain the N-doped carbon nanocages. NiO nano-particles grow inside the nano-cage by utilizing the capillary action of the micropores, and are reduced into Ni when negative potential is applied, so that the N-doped carbon nano-cage for packaging the Ni nano-particles is finally formed and used as a nano-counterA reactor; it can work in acidic electrolyte, and avoid CO2The raw gas is changed into useless carbonate; the Faraday efficiency of CO can reach 84.3% when the pH value is 2.5; in addition, compared with the traditional neutral membrane electrode system, the acidic membrane electrode system has stronger operation stability when the circulating electrolyte is not replaced (>15h) And has practical industrial application potential.

Description

Nano reactor for reducing acidic electrocatalytic carbon dioxide, preparation method and membrane electrode system
Technical Field
The invention belongs to the technical field of electric energy catalysis; relates to the preparation of a novel space-limited nano reactor capable of electrocatalysis of carbon dioxide to carbon monoxide in acid electrolyte and the design of an acid flow electrolysis system. In particular to a nano reactor for reducing acidic electrocatalytic carbon dioxide, a preparation method and a membrane electrode system.
Background
With the development of the industrialization process of modern society, carbon dioxide (CO) in the atmosphere2) The content is accumulated continuously, and the concentration thereof is increased from 280ppm (parts per million by volume) in 1750 years to more than 420ppm at present[1]. This increase in the concentration of greenhouse gases is mainly caused by the overuse of fossil energy sources such as coal, oil, and natural gas, and thus causes many environmental problems such as an increase in the global average temperature, a loss of polar ice caps, and an increase in the global average sea level due to the increase. While solar and wind power have been increasingly prevalent in global energy structures, there remains a need for energy storage systems to accommodate such intermittent and fluctuating renewable power. Electrocatalytic CO2Reduction (CO)2RR) technique can convert CO2Converted into high-value fuels and chemicals, and stored as energy sources for a long time. The technology creates a sustainable global-scale carbon neutralization economic system, gets rid of the dependence on fossil fuels, and realizes more innovative Carbon Capture and Utilization (CCU) rather than pure carbon capture and sequestration.
Electrocatalytic CO2RR can be performed at ambient temperature/pressure, and is of paramount importance in electrochemical and carbon chemistry. Albeit CO2Research on RR has progressed, but industrialization still faces obstacles. At present, CO2RR generally employs weakly or strongly alkaline electrolytes (e.g., KHCO)3Solution and KOH solution) and an Anion Exchange Membrane (AEM) is used as a separator between the cathode and anode. The alkaline condition can inhibit the competition of Hydrogen Evolution Reaction (HER), and realize higher Faradaic Efficiency (FE) of the product. But at the same time, in the alkaline electrolyte, CO in the raw material gas2Most of them are not reduced but are reacted with OH-Reaction to form Carbonate (CO)3 2-) Consumption (Eq.1), limiting CO2The utilization efficiency of (2). Furthermore, when AEM is used，CO3 2-Will migrate from the cathode to the anode by AEM to allow CO to migrate2Further lost. The technical economic analysis shows that if the carbonate in the alkaline electrolyte is tried to be regenerated into CO2Will consume a large amount of energy[2]. Thus, CO2Low efficiency CO of RR2The utilization problem is one of the core problems in the field, and the industrialized CO is greatly reduced2Feasibility of RR.
Figure BDA0003482357520000011
CO in acidic media2RR, CO can be avoided3 2-And (4) generating. In particular, any CO produced locally3 2-Will be converted back to CO by protons in the bulk electrolyte2. However, under acidic conditions with conventional electrocatalysts, the more kinetically favored HER will replace CO2RR becomes the main reaction. Aiming at the problems, a nano reactor is designed to be used as an electrocatalyst, and the H in the nano reactor is limited by using the space confinement effect of a yolk-shell (yolk-shell) structure+The concentration and the mass transfer rate of the catalyst form a micro chemical environment with local alkalization, and CO can be selectively removed under the acidic condition2Reducing to CO. In addition, the nano reactor is coupled with a Proton Exchange Membrane (PEM) to form a Membrane Electrode Assembly (MEA) system, so that the stable acid flow electrolytic reaction is realized, and the method has wide industrial development prospect.
Reference to the literature
[1]M.Ding,R.W.Flaig,H.-L.Jiang,O.M.Yaghi,Carbon capture and conversion using metal–organic frameworks and MOF-based materials,Chemical Society Reviews,48(2019)2783-2828.
[2]J.E.Huang,F.Li,A.Ozden,A.S.Rasouli,F.P.G.de Arquer,S.Liu,S.Zhang,M.Luo,X.Wang,Y.Lum,CO2 electrolysis to multicarbon products in strong acid,Science,372(2021)1074-1078.
Disclosure of Invention
The invention relates to a method for realizing high selection under acidic conditionElectrochemical CO of nature2A preparation method of a space-limited nano reactor of RR and the design of a corresponding acid flow electrolysis system.
The technical scheme of the invention is as follows:
the invention provides a nano reactor for reducing acidic electrocatalytic carbon dioxide; the hollow porous N-doped carbon shell with the diameter of 580-620 nm of the nano-reactor is 18-25 nm thick, Ni nano-particles with the diameter of less than 35nm are uniformly distributed in the cavity of the nano-reactor, the catalytic active sites of the carbon shell are the positions where Ni NPs are connected with the inner wall of the N-doped shell layer, and CO is added2The RR reaction will be confined inside the nanoreactor; n-doped shells selectively promote CO2Adsorption and diffusion of (3), limiting H+Adsorption and diffusion. The nano reactor can carry out carbon dioxide reduction reaction in acid electrolyte, and CO can be avoided under the acid condition2The feed gas is converted to a non-useful carbonate.
The invention provides a preparation method of a nano reactor for reducing acidic electrocatalytic carbon dioxide, which comprises the steps of firstly synthesizing silicon Spheres (SiO) coated with phenolic resin by a hydrothermal method2@ RF), adding an N source during high-temperature calcination, and removing the silicon core to obtain the N-doped carbon nanocages (NCN). And growing NiO NPs in the nanocages by utilizing the micropore capillary action to form N-doped carbon nanocages (NiO @ NCN) for encapsulating the NiO NPs, wherein the NiO NPs are reduced into Ni NPs when a negative potential is applied, and finally forming the N-doped carbon nanocages (Ni @ NCN) for encapsulating the Ni NPs as a nano reactor. As shown in fig. 1.
A preparation method of a nano reactor for acidic electrocatalytic carbon dioxide reduction comprises the following steps:
(1) adding tetraethyl orthosilicate (TEOS) into an ethanol solution, and stirring to form a solution A; adding ammonia water into a mixed solution of water and ethanol, and stirring to form a solution B; adding the solution A into the solution B completely to obtain a solution C, adding formaldehyde and resorcinol into the solution C, and continuously stirring at room temperature for 20-28 h; then transferring the liquid into a polytetrafluoroethylene lining stainless steel autoclave, and heating for 20-28 h at 90-110 ℃; after natural cooling, the precipitate was separated by centrifugation and washed with ethanol and waterAnd then dried in an oven to obtain phenolic resin coated silicon Spheres (SiO)2@RF)；
(2) Mixing SiO2@ RF was mixed with melamine in a mortar and then ground in N2Pyrolyzing at high temperature in an atmosphere tubular furnace, wherein the pyrolysis temperature is 850-950 ℃, and the pyrolysis time is 0.5-2 h; then putting the solid obtained by pyrolysis into an HF solution and stirring to obtain an N-doped carbon nanocage (NCN);
(3) dispersing NCN in water, adding an aqueous solution of nickel nitrate, and performing ultrasonic dispersion; then heating the obtained suspension to 70-90 ℃ to completely evaporate water; putting the dried solid into a tubular furnace in Ar atmosphere for calcining at the temperature of 300-400 ℃ for 1-3 h, wherein NiO NPs are packaged into the N-doped carbon nanocages (NiO @ NCN); after the cathode potential is applied, the NiO NPs are reduced to Ni NPs in situ to form N-doped carbon nanocages (Ni @ NCN) for packaging the Ni NPs, and the N-doped carbon nanocages serve as space confinement nanoreactors.
According to the method, in the step (1), the volume ratio of ethanol to TEOS in the solution A is 8-9: 1.
In the step (1), the volume ratio of water to ethanol to ammonia water (29 wt%) in the solution B is 4-5: 1-2: 1
According to the method, in the step (1), when the solution A is added into the solution B, the volume ratio of the solution A to the solution B is 1-1.5: 1.
In the method, in the step (1), the molar ratio of formaldehyde to resorcinol is 1.5-2.0: 1.
The method, in the step (2), the SiO2The mass ratio of @ RF to melamine is 4-6: 1.
In the method, in the step (3), the mass ratio of the nickel nitrate solution (43mM) to the NCN is 5-50: 1.
A membrane electrode system of a nano reactor for reducing carbon dioxide by using acid electrocatalysis is characterized in that the nano reactor is coated on one side of a Nafion 115 Proton Exchange Membrane (PEM) as a cathode electrocatalyst and is sprayed with RuO2Ti network of nanoparticles (RuO)2/Ti) as anode catalyst is attached to the other side of the PEM to form MEA; during acid electrolysis, the catholyte is acidified by sulfuric acidNa of (2)2SO4Solution, anolyte is H2SO4The electrolytic voltage of the solution is 2.5-4.0V. As shown in fig. 2.
The invention provides a method for realizing high-selectivity electrochemical CO under acidic condition2A preparation method of a reduced space-limited nano reactor and a design of a corresponding acid flow electrolysis system. Tetraethyl orthosilicate, formaldehyde and resorcinol generate SiO coated by phenolic resin under hydrothermal condition2Adding melamine as N source, high-temp calcining to remove SiO2And (4) carrying out nucleation to form N-doped carbon nanocages. NiO nano-particles grow inside the nano-cage by utilizing the capillary action of the micropores, and are reduced into Ni when negative potential is applied, so that the N-doped carbon nano-cage for encapsulating the Ni nano-particles is formed and serves as a nano-reactor. CO 22RR reaction is limited in the inside of the nano-reactor, and the N-doped shell can selectively promote CO2Adsorption and diffusion of (3), limiting H+The adsorption and diffusion of (2) to generate a local alkalization phenomenon, thereby inhibiting the hydrogen evolution reaction in the acidic electrolyte. CO can be effectively avoided by using acid electrolyte2The feed gas becomes a useless carbonate. The nano reactor has the Faraday efficiency of CO up to 93.2% under neutral condition (pH-7.2) and 84.3% under acidic condition (pH-2.5). In addition, the novel acid flow MEA electrolysis system can achieve higher current density and greater stability than conventional neutral flow electrolysis systems.
Summarizing the significant advantages of the present invention:
(1) the invention firstly proposes the application of the catalyst in the electrochemical CO2A preparation method of a novel space-limited nano reactor of RR.
(2) The nano-reactor can inhibit H+Mass transfer process from the bulk solution into the nanoreactor, thereby inhibiting HER.
(3) CO Faraday Efficiency (FE) of the nanoreactors under neutral conditions (pH 7.2)CO) Can reach 93.2 percent.
(4) FE of a nanoreactor under acidic conditions (pH 2.5)COCan reach 84.3%, and acid electrolyte can be avoidedCO2The raw material gas is changed into carbonate to increase CO2The utilization ratio of (2).
(5) The invention provides an acidic flow MEA electrolysis system capable of continuously operating for the first time.
(6) The current density at the same cell pressure of an acid MEA electrolysis system will be greatly increased compared to a conventional neutral MEA electrolysis system.
(7) Compared with the traditional neutral MEA (membrane electrode assembly) electrolytic system, the acidic MEA electrolytic system has stronger operation stability (>15h) when circulating electrolyte is not replaced, and has practical industrial application potential.
Drawings
FIG. 1: schematic diagram of a synthetic method of a novel space-limited nano reactor (Ni @ NCN).
FIG. 2: schematic diagram of novel Membrane Electrode Assembly (MEA) system for acid flow electrolysis.
FIG. 3: (a) example 1, (b) example 2 and (c) Scanning Electron Micrograph (SEM) of example 3 nanoreactor.
FIG. 4: (a, b) Transmission Electron Micrographs (TEM) of example 1, (c) example 2, and (d) example 3 nanoreactors.
FIG. 5: example 1 high angle annular dark field-scanning projection electron microscopy (HAADF-STEM) and elemental Mapping (Mapping) of nanoreactors.
FIG. 6: x-ray diffraction patterns (XRD) of the nano-reactors of example 1, example 2 and example 3.
FIG. 7 is a schematic view of: example 1 nano-reactor X-ray photoelectron spectroscopy (XPS) of Ni element before and after CPE.
FIG. 8: example 1, example 2 and example 3 nanoreactors, (a) FE at different potentialsCO(neutral pH of 7.2), (b) FE in the range of acidic to neutral (pH 0.4 to 7.2) at-1.4V vs. Ag. AgClCO。
FIG. 9: example 1, example 2 and example 3 nanoreactors (a) FE in acidic (pH 2.5) MEA electrolysis cellsCO(b) CO local Current Density (j)CO)。
FIG. 10: example 1 nanoreactor (a) FE in MEA Electrolysis cellsCO(b) electrolysis of electricityStability test at 3.4V (without replacement of circulating electrolyte).
FIG. 11: example 1, example 2 and example 3 nanoreactors in acidic conditions with FE of other literature reported catalystsCOAnd (6) comparing.
Detailed description of the preferred embodiments
The present invention will be described in further detail with reference to the following examples and drawings, but the present invention is not limited thereto. It will be apparent to those skilled in the art that variations or modifications of the present invention can be made without departing from the spirit and scope of the invention, and these variations or modifications are also within the scope of the invention.
The invention discloses a nano reactor for acidic electrocatalysis carbon dioxide reduction; the hollow porous N-doped carbon shell with the diameter of 580-620 nm of the nano-reactor is 18-25 nm thick, Ni nano-particles with the diameter of less than 35nm are uniformly distributed in the cavity of the nano-reactor, the catalytic active sites of the carbon shell are the positions where Ni NPs are connected with the inner wall of the N-doped shell layer, and CO is added2The RR reaction will be confined inside the nanoreactor; n-doped shells selectively promote CO2Adsorption and diffusion of (3), limiting H+Adsorption and diffusion.
The embodiment of the invention uses a membrane electrode system of a nano reactor for reducing acidic electrocatalytic carbon dioxide; the nano reactor is used as a cathode electrocatalyst to be coated on one side of a Nafion 115 Proton Exchange Membrane (PEM) and is sprayed with RuO2Ti network of nanoparticles (RuO)2/Ti) as anode catalyst is attached to the other side of the PEM to form MEA; in acid electrolysis, the catholyte is Na acidified by sulfuric acid2SO4Solution, anolyte is H2SO4The electrolytic voltage of the solution is 2.5-4.0V.
The specific preparation method and test process are as follows:
example 1
The preparation process of the nano reactor comprises the following steps:
(1) 3.4mL of TEOS was added to 30mL of ethanol to form solution A (volume ratio of ethanol to TEOS: 8.8:1), and 3.45mL of aqueous ammonia (29 wt%) was added to a mixed solution of 6mL of water and 15mL of ethanolSolution B was formed (volume ratio of ethanol to water to ammonia water 4.3:1.7: 1). Then the solution A was added to the solution B in its entirety and stirred. Subsequently, 0.56mL of formaldehyde and 0.4g of resorcinol (molar ratio of the two is 1.8:1) are added and stirring is continued at room temperature for 24 h. The liquid was transferred to a teflon lined stainless steel autoclave and heated at 100 ℃ for 24 h. After natural cooling, the precipitate was separated by centrifugation, washed with ethanol and water, and then dried in an oven to obtain SiO2@RF。
(2) 2g of melamine were mixed with 0.4g of SiO2@ RF (mass ratio of the two: 5:1) is put into a mortar for grinding and mixing, and then N is added2And (3) pyrolyzing at high temperature of 900 ℃ in an atmosphere tubular furnace for 1 h. The solid obtained by pyrolysis was then put into an HF solution (10 wt%) and stirred to obtain NCN.
(3) 200mg of NCN was dispersed in 15mL of water. Then, 5g of 43mM nickel nitrate aqueous solution (mass ratio of nickel nitrate aqueous solution to NCN 25:1) was added, and sonication was performed for 30 min. The resulting suspension was then heated to 80 ℃ to completely evaporate the water. And (3) putting the dried solid into an Ar atmosphere tubular furnace for heating at 350 ℃ for 2 hours to obtain the novel space-limited nano reactor.
As shown in the SEM of fig. 3a, the appearance of the nano-reactor obtained in example 1 was spherical with a diameter of about 600nm, and no metallic NPs were observed outside the shell of the nano-reactor, indicating that the NPs were not distributed outside the shell. Fig. 4a, b is TEM of the nano-reactor of example 1, which exhibits a unique hollow structure, a shell thickness of N-doping is 20nm, and mesopores are distributed on the shell, and metallic NPs having an average particle size of 17.3nm are distributed inside the hollow structure. FIG. 5 is HAADF-STEM and Mapping of the nano-reactor of example 1, the bright spots in the picture further confirming that NPs are fixed inside the hollow structure, C and N elements are uniformly distributed on the catalyst, and Ni elements are mainly distributed on the NPs. Combining the above results, the metal NPs are successfully encapsulated in the N-doped carbon nanocages, forming a novel space-limited nanoreactor. In XRD of the nanoreactor of example 1 in FIG. 6, two broad peaks at 24.9 ° and 44.1 ° 2 θ values were (002) and (100) of graphitic carbon, but no distinct NiO peak was observed, probably due to the carbonThe diffraction peaks cover the diffraction peaks of the NiO NPs. FIG. 7 is X-ray photoelectron spectroscopy (XPS) of Ni element before and after potentiostatic electrolysis (CPE) in the nanoreactor of example 1. Prior to CPE, the Ni 2p3/2 band can be deconvoluted to NiII(856.3eV) and the corresponding satellite peaks. After CPE, Ni 2p3/2 is mixed with Ni0(853.8eV) as the main peak, and NiIIIs a secondary peak, which indicates that NiO NPs are reduced into Ni under the cathode potential0NPs, form the final Ni @ NCN. A method of making a working electrode comprising the steps of:
(1) 0.5mg of the novel space-limited nanoreactor was dispersed in 0.5mL of ethanol, and 10. mu.L of Nafion solution (5 wt%) was added thereto, and ultrasonic treatment was performed for 30min to obtain a dispersion. 5 mul of the dispersion was applied dropwise to a glassy carbon electrode for electrocatalytic reduction of carbon dioxide in an H-type electrolytic cell.
(2) 10mg of the novel space-limited nano-reactor was dispersed in a mixed solution of 920. mu.L of isopropanol and 80. mu.L of Nafion solution (5 wt%), and subjected to ultrasonic treatment for 30min to obtain a dispersion. The dispersion was then sprayed to 5cm2Coated with RuO on Nafion 115 film2Ti network of nanoparticles (RuO)2/Ti) is attached to the other side of the membrane, constituting an MEA for electrocatalytic reduction of carbon dioxide in a flow electrolytic device. To verify the sustainability of the flow electrolysis of the acidic MEA, the circulating electrolyte was not replaced during the stability test.
The operating conditions for electrocatalytic carbon dioxide reduction were as follows:
(1) when electrolyzing in H-type cell, the glassy carbon electrode carrying catalyst is working electrode, the platinum sheet electrode is counter electrode, Ag | AgCl electrode is reference electrode, and the electrolyte is CO2Saturated 0.5M KHCO3Solution (neutral condition) or sulphuric acid acidified 0.25MNa2SO4The pH value of the solution (acidic condition) is 0.4-7.2, and the electrolytic potential is-0.5 to-1.0V vs. Reversible Hydrogen Electrode (RHE).
In fig. 8a, the example 1 nanoreactor has FE at pH 7.2 of neutral electrolyteCORHE reached 93.2% at-0.8V vs. In FIG. 8b, the nano-reactor of example 1 shows excellent CO in a wide pH range (7.2-1.0) from neutral to acidic2RR is selective atFE of example 1 at pH 2.5COCan reach 84.3 percent, which shows that the nano reactor can realize higher CO selectivity under the acidic condition.
In CO2RR Process (Eq.2), OH around the catalytic site-Gradually accumulates, and when the proton consumption rate in the nanoreactor exceeds the proton transfer rate from the bulk solution to the nanoreactor, the proton concentration begins to decrease, resulting in an increase in the local pH in the reactor, thereby enabling HER inhibition in the acid electrolyte. In addition, to balance OH-Negative charge of, H+And a metal cation (M)+) Will diffuse into the nanoreactor, but most of the H+Is covered with OH-Neutralization, M+Will increase the local concentration of CO, which will further contribute to CO2And (4) activating. Therefore, the steric confinement structure helps to realize highly selective CO under acidic conditions2RR。
CO2+2e-+H2O→CO+2OH- (Eq.2)
(2) In a flow MEA device, the electrolyte of the cathode and the anode are 0.5M KHCO under neutral conditions3A solution; under acidic conditions, the catholyte was 0.25M Na acidified with sulfuric acid2SO4Solution, anolyte 0.25M H2SO4The electrolytic voltage of the solution is 2.5-4.0V.
In FIG. 9, example 1 nanoreactor FE was measured at an electrolytic voltage of 3.4V in an acid MEA electrolytic cellCOCan reach 80%, jCOCan reach 78mA cm-2. Figure 10 is a comparison of acid and neutral electrolysis results for the nanoreactor of example 1 in an MEA cell, and higher current densities can be achieved at the same voltage compared to neutral conditions (pH 7.2) due to the high proton conductivity of the PEM. To investigate the sustainability of acid electrolysis, an electrolytic stability test was performed without refreshing the circulating electrolyte, and the results are shown in fig. 10 b. After 15h of electrolysis, the current density of the acidic system shows a stable and slowly increasing trend, and meanwhile, the selectivity of CO is not obviously reduced, and the acidic system shows higher stability. In conventional neutral electrolyte (KHCO)3)，The current density tends to decrease with time, since in a neutral system, K is+The migration from the anode to the cathode is lost and the anolyte is acidified by Oxygen Evolution Reaction (OER), resulting in a decrease in the net concentration of the electrolyte, resulting in a decrease in current density and an increase in electrolysis voltage. In contrast, in an acidic system, protons are conducted through the PEM and H on both sides+The concentration can be balanced throughout the electrolysis process, achieving a sustainable pattern. These results indicate that the combination of a spatially confined nanoreactor as an electrocatalyst with an acidic MEA electrolysis system is a viable and sustainable electrochemical CO2RR method.
Example 2
The preparation process of the nano reactor comprises the following steps:
(1) 3.9mL of TEOS was added to 35mL of ethanol to form a solution a (volume ratio of ethanol to TEOS: 9:1), and 3mL of aqueous ammonia (29 wt%) was added to a mixed solution of 6mL of water and 15mL of ethanol to form a solution B (volume ratio of ethanol to water to aqueous ammonia: 5:2: 1). Then the solution A was added to the solution B in its entirety and stirred. Subsequently, 0.6mL of formaldehyde and 0.5g of resorcinol (molar ratio 2:1) were added and stirring was continued at room temperature for 28 h. The liquid was transferred to a teflon lined stainless steel autoclave and heated at 110 ℃ for 28 h. After natural cooling, the precipitate was separated by centrifugation, washed with ethanol and water, and then dried in an oven at 60 ℃ to give SiO2@RF。
(2) 2.4g of melamine were mixed with 0.4g of SiO2Mixing with @ RF (6: 1) in a mortar, and grinding in N2Pyrolyzing at 950 ℃ for 2h in a tubular furnace in the atmosphere. The solid obtained by pyrolysis was then put into an HF solution (10 wt%) and stirred to obtain NCN.
(3) 200mg of NCN was dispersed in 15mL of water. Then, 10g of 43mM nickel nitrate aqueous solution (mass ratio of nickel nitrate aqueous solution to NCN: 50:1) was added, and sonication was performed for 30 min. The resulting suspension was then heated to 90 ℃ to completely evaporate the water. And (3) putting the dried solid into an Ar atmosphere tubular furnace for heating at 400 ℃ for 3 hours to obtain the novel space-limited nano reactor.
FIG. 3b is an SEM of the nano-reactor obtained in example 2, and it can be seen that the appearance thereof is spherical with a diameter of about 620nm and that no metallic NPs are observed outside the shell of the nano-reactor, indicating that the NPs are not distributed outside the shell. Fig. 4b is a TEM of the nano-reactor of example 2, which exhibits a unique hollow structure, an N-doped shell layer having a thickness of 25nm, and mesopores distributed on the shell, and metallic NPs having an average particle size of 33nm distributed inside the hollow structure. The XRD pattern of example 2 in fig. 6 shows a distinct NiO peak indicating the formation of larger particles, consistent with TEM results (fig. 4 c).
A method of making a working electrode comprising the steps of:
(1) 0.5mg of the novel space-limited nanoreactor was dispersed in 0.5mL of ethanol, and 10. mu.L of Nafion solution (5 wt%) was added thereto, and the dispersion was subjected to ultrasonic treatment for 30 min. 5 mul of the dispersion was applied dropwise to a glassy carbon electrode for electrocatalytic reduction of carbon dioxide in an H-type electrolytic cell.
(2) 10mg of the novel space-limited nano-reactor was dispersed in a mixed solution of 920. mu.L of isopropanol and 80. mu.L of Nafion solution (5 wt%), and subjected to ultrasonic treatment for 30min to obtain a dispersion. The dispersion was then sprayed to 5cm2Coated with RuO on Nafion 115 film2Ti network of nanoparticles (RuO)2/Ti) is attached to the other side of the membrane, constituting an MEA for electrocatalytic reduction of carbon dioxide in a flow electrolytic device.
The operating conditions for electrocatalytic carbon dioxide reduction were as follows:
(1) when the catalyst is electrolyzed in an H-type battery, the glassy carbon electrode loaded with the catalyst is a working electrode, the platinum sheet electrode is a counter electrode, the Ag | AgCl electrode is a reference electrode, and the electrolyte is CO2Saturated 0.5M KHCO3Solution (neutral condition) or sulfuric acid acidified 0.25M Na2SO4The pH value of the solution (acidic condition) is 0.4-7.2, and the electrolytic potential is-0.5 to-1.0V vs.
Example 2 nanoreactors in FIG. 8a FE at neutral pH 7.2CO80.6%, example 2 in FIG. 8b shows better CO in the acidic to neutral range (pH 1.7-7.2)2RR Selectivity, at pH 2.5, FE of example 1COCan reach 75 percent, which shows that the catalyst can realize higher CO selectivity under acidic conditions.
(2) In a flow MEA device, the electrolyte of the cathode and the anode are 0.5M KHCO under neutral conditions3A solution; under acidic conditions, the catholyte was 0.25M Na acidified with sulfuric acid2SO4Solution, anolyte 0.25M H2SO4The electrolytic voltage of the solution is 2.5-4.0V.
In FIG. 9, example 2 nanoreactor FE was measured in an acid MEA cell at an electrolytic voltage of 3.4VCOCan reach 72.4%, jCOCan reach 62.4mA cm-2。
Example 3
The preparation process of the nano reactor comprises the following steps:
(1) solution a was prepared by adding 3.1mL of TEOS to 25mL of ethanol (volume ratio of ethanol to TEOS: 8:1), and solution B was prepared by adding 3.75mL of aqueous ammonia (29 wt%) to a mixed solution of 3.75mL of water and 15mL of ethanol (volume ratio of ethanol to water to aqueous ammonia: 4:1: 1). Then the solution A was added to the solution B in its entirety and stirred. Subsequently, 0.5mL of formaldehyde and 0.3g of resorcinol (molar ratio of the two is 1.5:1) were added and stirring was continued at room temperature for 20 h. The liquid was transferred to a teflon lined stainless steel autoclave and heated at 90 ℃ for 20 h. After natural cooling, the precipitate was separated by centrifugation, washed with ethanol and water, and then dried in an oven to obtain SiO2@RF。
(2) 1.6g of melamine were mixed with 0.4g of SiO2@ RF (mass ratio of the two: 4:1) is put into a mortar for grinding and mixing, and then N is added2Pyrolyzing at 850 deg.C for 0.5h in a tubular furnace under atmosphere. The solid obtained by pyrolysis was then put into an HF solution (10 wt%) and stirred to obtain NCN.
(3) 200mg of NCN was dispersed in 15mL of water. Then, 1g of 43mM nickel nitrate aqueous solution (mass ratio of nickel nitrate aqueous solution to NCN: 5:1) was added, and sonication was performed for 30 min. The resulting suspension was then heated to 90 ℃ to completely evaporate the water. And (3) putting the dried solid into an Ar atmosphere tubular furnace for heating at the temperature of 300 ℃ for 1h to obtain the novel space-limited nano reactor.
FIG. 3c is a Scanning Electron Micrograph (SEM) of the nanoreactor obtained in example 3, which can be seen to be spherical in shape with a diameter of about 580 nm. Fig. 4c is a TEM of the nano-reactor of example 3, which exhibits a unique hollow structure, an N-doped shell thickness of 18nm, and mesopores distributed on the shell, and no metallic NPs were observed in the TEM because the amount of Ni added synthetically was too small.
A method of making a working electrode comprising the steps of:
(1) 0.5mg of the novel space-limited nanoreactor was dispersed in 0.5mL of ethanol, and 10. mu.L of Nafion solution (5 wt%) was added thereto, and ultrasonic treatment was performed for 30min to obtain a dispersion. 5 mul of the dispersion was applied dropwise to a glassy carbon electrode for electrocatalytic reduction of carbon dioxide in an H-type electrolytic cell.
(2) 10mg of the novel space-limited nano-reactor was dispersed in a mixed solution of 920. mu.L of isopropanol and 80. mu.L of Nafion solution (5 wt%), and subjected to ultrasonic treatment for 30min to obtain a dispersion. The dispersion was then sprayed to 5cm2Coated with RuO on Nafion 115 film2Ti network of nanoparticles (RuO)2/Ti) is attached to the other side of the membrane, constituting an MEA for electrocatalytic reduction of carbon dioxide in a flow electrolytic device.
The operating conditions for electrocatalytic carbon dioxide reduction were as follows:
(1) in the H-type cell, the glassy carbon electrode is used as working electrode, the platinum sheet electrode is used as counter electrode, the Ag | AgCl electrode is used as reference electrode, and the electrolyte is CO2Saturated 0.5M KHCO3Solution (neutral condition) or sulfuric acid acidified 0.25M Na2SO4The pH value of the solution (acidic condition) is 0.4-7.2, and the electrolytic potential is-0.5 to-1.0V vs.
Example 3 nanoreactors in FIG. 8a FE at neutral pH 7.2COat-0.8V vs. RHE of 69%, FIG. 8b, example 3 nanoreactor FECOThe change is not large along with the reduction (7.2-3.2) of the pH value of the electrolyte, which shows that the electrolyte has better stability under an acidic condition.
In FIG. 11, the example 1,2,3 nano-reactor can be operated under lower pH condition than the existing acidic literature reportAchieving higher FECOAnd excellent acid electrolysis performance is shown.
(2) In a flow MEA device, the electrolyte of the cathode and the anode are 0.5M KHCO under neutral conditions3A solution; under acidic conditions, the catholyte was 0.25M Na acidified with sulfuric acid2SO4Solution, anolyte 0.25M H2SO4The electrolytic voltage of the solution is 2.5-4.0V.
In FIG. 9, example 3 nanoreactor FE was measured in an acid MEA electrolytic cell at an electrolytic voltage of 3.4VCOCan reach 60.1%, jCOCan reach 43mA cm-2。
While the acid electrocatalytic carbon dioxide reduction nanoreactors and methods of making and membrane electrode systems of the present invention have been described in terms of preferred embodiments in the field, it will be apparent to those of ordinary skill in the art that modifications to, variations of, or appropriate alterations to, the methods described herein may be made to practice the techniques of the present invention without departing from the spirit, scope, or concept of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.

Claims (10)

1. A nano-reactor for acidic electrocatalytic carbon dioxide reduction; the method is characterized in that a hollow porous N-doped carbon shell with the diameter of 580-620 nm of a nano reactor is provided, the thickness of the carbon shell is 18-25 nm, Ni nano particles with the diameter smaller than 35nm are uniformly distributed in a cavity of the nano reactor, catalytic active sites of the Ni nano particles are the positions where Ni NPs are connected with the inner wall of an N-doped shell layer, and CO is added2The RR reaction will be confined inside the nanoreactor; n-doped shells selectively promote CO2Adsorption and diffusion of (3), limiting H+Adsorption and diffusion. The nano reactor can carry out carbon dioxide reduction reaction in acid electrolyte, and CO can be avoided under the acid condition2The feed gas is converted to a non-useful carbonate.
2. The preparation method of the nano reactor for acidic electrocatalytic carbon dioxide reduction is characterized in that firstly, hydrothermal reaction is carried outMethod for synthesizing silicon ball (SiO) coated by phenolic resin2@ RF), adding an N source during high-temperature calcination, and removing a silicon core to obtain an N-doped carbon nanocage (NCN); and growing NiO NPs in the nanocages by utilizing the micropore capillary action to form N-doped carbon nanocages (NiO @ NCN) for encapsulating the NiO NPs, wherein the NiO NPs are reduced into Ni NPs when a negative potential is applied, and finally forming the N-doped carbon nanocages (Ni @ NCN) for encapsulating the Ni NPs as a nano reactor.
3. The method of claim 2, comprising the steps of:
(1) adding tetraethyl orthosilicate (TEOS) into an ethanol solution, and stirring to form a solution A; adding ammonia water into a mixed solution of water and ethanol, and stirring to form a solution B; adding the solution A into the solution B completely to obtain a solution C, adding formaldehyde and resorcinol into the solution C, and continuously stirring at room temperature for 20-28 h; then transferring the liquid into a polytetrafluoroethylene lining stainless steel autoclave, and heating for 20-28 h at 90-110 ℃; after natural cooling, the precipitate was separated by centrifugation, washed with ethanol and water, and then dried in an oven to obtain phenolic resin-coated silica Spheres (SiO)2@RF)；
(2) Mixing SiO2@ RF was mixed with melamine in a mortar and then ground in N2Pyrolyzing at high temperature in an atmosphere tubular furnace, wherein the pyrolysis temperature is 850-950 ℃, and the pyrolysis time is 0.5-2 h; then putting the solid obtained by pyrolysis into an HF solution and stirring to obtain an N-doped carbon nanocage (NCN);
(3) dispersing NCN in water, adding an aqueous solution of nickel nitrate, and performing ultrasonic dispersion; then heating the obtained suspension to 70-90 ℃ to completely evaporate water; putting the dried solid into a tubular furnace in Ar atmosphere for calcining at the temperature of 300-400 ℃ for 1-3 h, wherein NiO NPs are packaged into the N-doped carbon nanocages (NiO @ NCN); after the cathode potential is applied, the NiO NPs are reduced to Ni NPs in situ to form N-doped carbon nanocages (Ni @ NCN) for packaging the Ni NPs, and the N-doped carbon nanocages serve as space confinement nanoreactors.
4. The method of claim 1, wherein in step (1), the volume ratio of ethanol to TEOS in the solution A is 8-9: 1.
5. The method of claim 1, wherein in the step (1), the volume ratio of water to ethanol to ammonia water (29 wt%) in the solution B is 4-5: 1-2: 1.
6. The method according to claim 1, wherein in the step (1), when the solution A is added to the solution B, the volume ratio of the solution A to the solution B is 1-1.5: 1.
7. The method according to claim 1, wherein the molar ratio of formaldehyde to resorcinol in step (1) is 1.5 to 2.0: 1.
8. The method as set forth in claim 1, wherein, in the step (2), the SiO is2The mass ratio of @ RF to melamine is 4-6: 1.
9. The method according to claim 1, wherein in the step (3), the mass ratio of the nickel nitrate solution (43mM) to the NCN is 5-50: 1.
10. A membrane electrode system of a nanoreactor using acidic electrocatalytic carbon dioxide reduction; it is characterized in that the nano reactor is used as a cathode electrocatalyst to be coated on one side of a Nafion 115 Proton Exchange Membrane (PEM) and is coated with RuO2Ti network of nanoparticles (RuO)2/Ti) as anode catalyst is attached to the other side of the PEM to form MEA; in acid electrolysis, the catholyte is sulfuric acid-acidified Na2SO4Solution, anolyte is H2SO4The electrolytic voltage of the solution is 2.5-4.0V.
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