CN114540867B - Nano reactor for acidic electrocatalytic carbon dioxide reduction, preparation method and membrane electrode system - Google Patents

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

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CN114540867B
CN114540867B CN202210071840.1A CN202210071840A CN114540867B CN 114540867 B CN114540867 B CN 114540867B CN 202210071840 A CN202210071840 A CN 202210071840A CN 114540867 B CN114540867 B CN 114540867B
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康鹏
刘治坤
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Abstract

The invention relates to a nano-reactor for acidic electrocatalytic carbon dioxide reduction, a preparation method and a membrane electrode system. Synthesizing a phenolic resin coated silicon ball by a hydrothermal method, adding an N source during high-temperature calcination, and removing a silicon core to obtain the N-doped carbon nanocage. The NiO nano-particles grow in the nano-cage by utilizing micropore capillary action, and are reduced to Ni when negative potential is applied, so that the N-doped carbon nano-cage for encapsulating the Ni nano-particles is finally formed to serve as a nano-reactor; it can work in acid electrolyte to avoid CO 2 The feed gas becomes unusable carbonate; the Faraday efficiency of CO can reach 84.3% at pH value of 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) Has practical industrial application potential.

Description

Nano reactor for acidic electrocatalytic carbon dioxide reduction, 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 electrocatalytic reduction of carbon dioxide to carbon monoxide in an acid electrolyte and the design of an acid flow electrolysis system thereof. In particular to a nano-reactor for acidic electrocatalytic carbon dioxide reduction, a preparation method and a membrane electrode system.
Background
With the development of the industrial process of the modern society, carbon dioxide (CO 2 ) The content is continuously accumulated, and the concentration is increased from 280ppm (parts per million by volume) in 1750 to over 420ppm [1] . This increase in greenhouse gas concentration is mainly caused by excessive use of fossil energy sources mainly of coal, oil, and natural gas, and thus causes a number of environmental problems such as rise in global average temperature, loss of polar ice cover, rise in global average sea level caused thereby, and the like. While solar and wind energy have been an increasing proportion of global energy structures, energy storage systems are still needed to regulate such intermittent and fluctuating renewable power. Electrocatalytic CO 2 Reduction (C)O 2 RR) technology can convert CO 2 Is converted into high-value fuel and chemicals, and is stored as energy for a long time. The technology creates a sustainable global carbon neutralization economic system, gets rid of dependence on fossil fuels, and realizes Carbon Capture and Utilization (CCU) with more innovative value instead of pure carbon capture and sequestration.
Electrocatalytic CO 2 RR can be performed at ambient temperature/pressure and is of great importance in electrochemical and carbochemistry. Although CO 2 Many developments have been made in the research of RR, but industrialization thereof still faces a hurdle. CO at present 2 RR typically uses weakly or strongly alkaline electrolytes (e.g., KHCO 3 Solution and KOH solution) and an Anion Exchange Membrane (AEM) is used as a separator between the cathode and anode. Alkaline conditions can inhibit competition for Hydrogen Evolution Reactions (HER), achieving higher product Faraday Efficiencies (FE). At the same time, however, in the alkaline electrolyte, the CO in the feed gas 2 Most of which are not reduced but are combined with OH - The reaction generates Carbonate (CO) 3 2- ) Consumption (Eq.1), CO limitation 2 Is used for the utilization efficiency of the system. In addition, when AEM is used, CO 3 2- Will migrate from the cathode to the anode through the AEM to cause CO to be generated 2 Further loss. Technical economic analysis shows that if attempts are made to regenerate CO from carbonates in alkaline electrolytes 2 Will consume a great deal of energy [2] . Thus, CO 2 Low efficiency CO of RR 2 The utilization problem is one of the core problems in the field, and the realization of industrialized CO is greatly reduced 2 Feasibility of RR.
Figure BDA0003482357520000011
CO in an acidic Medium 2 RR, can avoid CO 3 2- Is generated. In particular, any CO produced locally 3 2- Will be converted back to CO by protons in the bulk electrolyte 2 . However, under acidic conditions, the more kinetically favored HER of conventional electrocatalysts will replace CO 2 RR becomes the dominant reaction. For upwardThe problem is that we design a nano-reactor as an electrocatalyst, and limit H in the nano-reactor by utilizing the space domain-limiting effect of the yolk-shell (yolk-shell) structure + Form a locally alkalized microchemical environment, and can highly selectively convert CO under acidic conditions 2 Reducing to CO. In addition, the nano reactor is coupled with a Proton Exchange Membrane (PEM) to form a Membrane Electrode (MEA) system, so that stable acid flow electrolysis 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,CO 2 electrolysis to multicarbon products in strong acid,Science,372(2021)1074-1078.
Disclosure of Invention
The invention relates to an electrochemical CO capable of realizing high selectivity under acidic condition 2 A preparation method of a space-limited nano-reactor of RR and a corresponding design of an acid flow electrolysis system.
The technical scheme of the invention is as follows:
the invention provides a nano reactor for acidic electrocatalytic carbon dioxide reduction; hollow porous N-doped carbon shell with diameter of 580-620 nm of nano reactor, thickness of carbon shell is 18-25 nm, ni nano particles with diameter smaller than 35nm are uniformly distributed in the cavity of nano reactor, and its catalytic active site is the connection position of Ni NPs and inner wall of N-doped shell layer, CO 2 The RR reaction will be confined to the interior of the nanoreactor; n-doped sheath selectively promotes CO 2 Is limited by adsorption and diffusion of H + Is adsorbed and diffused. The nano reactor can perform carbon dioxide reduction reaction in the acidic electrolyte, and the acidic condition can avoid CO 2 The feed gas is converted to unusable carbonate.
The invention provides a nanometer for acidic electrocatalytic carbon dioxide reductionThe preparation method of the reactor comprises the steps of synthesizing phenolic resin coated silicon Spheres (SiO) by a hydrothermal method 2 At RF), adding an N source during high temperature calcination, and removing the silicon core to obtain an N-doped carbon nanocage (NCN). And growing NiO NPs in the nano cage by utilizing micropore capillary action to form N-doped carbon nano cage (NiO@NCN) for packaging the NiO NPs, reducing the NiO NPs into Ni NPs when negative potential is applied, and finally forming N-doped carbon nano cage (Ni@NCN) for packaging the Ni NPs as a nano reactor. As shown in fig. 1.
A method for preparing a nano-reactor for acidic electrocatalytic carbon dioxide reduction, which comprises the following steps:
(1) Tetraethyl orthosilicate (TEOS) is added into ethanol solution and stirred to form solution A; adding ammonia water into a mixed solution of water and ethanol, and stirring to form a solution B; adding all the solution A into the solution B to obtain a solution C, adding formaldehyde and resorcinol into the solution C, and continuously stirring for 20-28 h at room temperature; 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 water, followed by drying in an oven to give phenolic resin coated silica spheres (SiO 2 @RF)；
(2) SiO is made of 2 Grinding and mixing @ RF and melamine in a mortar, and then mixing in N 2 Pyrolysis is carried out in a tube furnace in atmosphere, 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 Nano Cage (NCN);
(3) Dispersing NCN in water, adding aqueous solution of nickel nitrate, and performing ultrasonic dispersion; then heating the obtained suspension to 70-90 ℃ to completely evaporate the water; calcining the dried solid in a tubular furnace in Ar atmosphere at 300-400 ℃ for 1-3 h, wherein NiO NPs are encapsulated into N-doped carbon nanocages (NiO@NCN); after cathodic potential is applied, niO NPs are reduced in situ to Ni NPs, forming N-doped carbon nanocages (Ni@NCN) encapsulating the Ni NPs as a spatially confined nanoreactor.
In the method, in the step (1), the volume ratio of ethanol to TEOS in the solution A is 8-9:1.
In the method, 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
In 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 step (2), the SiO 2 The mass ratio of the @ RF to the melamine is 4-6:1.
In the method, in the step (3), the mass ratio of the nickel nitrate solution (43 mM) to NCN is 5-50:1.
Membrane electrode system using an acidic electrocatalytic carbon dioxide reduction nanoreactor coated as a cathodic electrocatalyst on one side of a Nafion 115 Proton Exchange Membrane (PEM) with RuO spray coating 2 Ti network of nanoparticles (RuO) 2 Ti) is attached to the other side of the PEM as an anode catalyst to form an MEA; in acid electrolysis, the catholyte is sodium sulfate acidified 2 SO 4 Solution, anolyte is H 2 SO 4 The solution has an electrolysis voltage of 2.5-4.0V. As shown in fig. 2.
The invention provides the electrochemical CO with high selectivity under the acidic condition 2 A preparation method of a reduced space-limited nano-reactor and a corresponding design of an acid flow electrolysis system. Tetraethyl orthosilicate, formaldehyde and resorcinol generate SiO coated by phenolic resin under hydrothermal condition 2 Microballoons, adding melamine as N source, high temperature calcining to remove SiO 2 And (3) a core, and forming the N-doped carbon nanocage. And utilizing micropore capillary action to enable NiO nano particles to grow in the nano cage, and reducing the NiO nano particles into Ni when negative potential is applied to form the N-doped carbon nano cage for packaging the Ni nano particles as a nano reactor. CO 2 The RR reaction is limited to the interior of the nanoreactor, and the N-doped shell can selectively promote CO 2 Is limited by adsorption and diffusion of H + Adsorption and diffusion of (2) to cause local alkalization, therebyCan inhibit hydrogen evolution reaction in the acid electrolyte. The use of the acid electrolyte can effectively avoid CO 2 The feed gas becomes unusable carbonate. The Faraday efficiency of the nano reactor under neutral condition (pH-7.2) can reach 93.2%, and under acidic condition (pH-2.5) can reach 84.3%. In addition, the novel acid flow MEA electrolysis system may achieve higher current densities and greater stability than conventional neutral flow electrolysis systems.
Summarizing the remarkable advantages of the invention are:
(1) The invention provides the method for electrochemical CO for the first time 2 A preparation method of a novel space-limited nano reactor of RR.
(2) The nano-reactor can inhibit H + Mass transfer from the bulk solution into the nanoreactor thereby inhibiting HER.
(3) At neutral conditions (ph=7.2), the CO Faradaic Efficiency (FE) of the nanoreactor CO ) Can reach 93.2 percent.
(4) FE of the nanoreactor under acidic conditions (ph=2.5) CO Can reach 84.3%, and the acid electrolyte can avoid CO 2 The raw material gas is changed into carbonate to improve CO 2 Is used for the utilization of the system.
(5) The invention provides an acid flow MEA electrolysis system capable of continuously running for the first time.
(6) The current density at the same cell pressure of an acidic MEA electrolysis system will be greatly increased compared to a conventional neutral MEA electrolysis system.
(7) Compared with the traditional neutral MEA electrolysis system, the acidic MEA electrolysis system has stronger operation stability (> 15 h) when the circulating electrolyte is not replaced, and has practical industrial application potential.
Drawings
Fig. 1: a schematic diagram of a synthesis method of a novel space-limited nano-reactor (Ni@NCN).
Fig. 2: schematic of a novel acid flow electrolytic Membrane Electrode (MEA) system.
Fig. 3: (a) example 1, (b) example 2 and (c) scanning electron microscope photographs (SEM) of the nanoreactors of example 3.
Fig. 4: (a, b) example 1, (c) example 2 and (d) Transmission Electron Microscope (TEM) photographs of the nanoreactors of example 3.
Fig. 5: example 1 high angle annular dark field-scanning projection electron micrographs (HAADF-STEM) and elemental Mapping (Mapping) of nanoreactors.
Fig. 6: x-ray diffraction patterns (XRD) for the example 1, example 2 and example 3 nanoreactors.
Fig. 7: example 1 the nanoreactor was 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 potentials CO (neutral pH-7.2), (b) acidic to neutral range (pH 0.4-7.2), FE at-1.4V vs. Ag|AgCl CO 。
Fig. 9: example 1, example 2 and example 3 nanoreactors in an acidic (ph=2.5) MEA cell (a) FE CO (b) CO local current density (j) CO )。
Fig. 10: example 1 nanoreactor (a) FE in MEA cell CO (b) stability test at an electrolysis voltage of 3.4V (without replacement of circulating electrolyte).
Fig. 11: examples 1,2 and 3 nanoreactors FE with other literature reported catalysts under acidic conditions CO And (5) comparing.
Detailed description of the preferred embodiments
The invention will be described in further detail with reference to examples and drawings, but the method of practicing the 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 such variations or modifications are intended to be included within the scope of the invention.
The embodiment of the invention discloses a nano reactor for acidic electrocatalytic carbon dioxide reduction; hollow porous N-doped carbon shell with diameter of 580-620 nm of nano reactor, thickness of carbon shell is 18-25 nm, ni nano particles with diameter smaller than 35nm are uniformly distributed in the cavity of nano reactor, and its catalytic active site is the connection position of Ni NPs and inner wall of N-doped shell layer, CO 2 The RR reaction will be confined to the interior of the nanoreactor; n-doped sheath selectively promotes CO 2 Is limited by adsorption and diffusion of H + Is adsorbed and diffused.
The embodiment of the invention uses a membrane electrode system of a nano reactor for acidic electrocatalytic carbon dioxide reduction; 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 RuO 2 Ti network of nanoparticles (RuO) 2 Ti) is attached to the other side of the PEM as an anode catalyst to form an MEA; in acid electrolysis, the catholyte is sodium sulfate acidified 2 SO 4 Solution, anolyte is H 2 SO 4 The solution has an electrolysis voltage of 2.5-4.0V.
The specific preparation method and the test process are as follows:
example 1
A process for preparing a nanoreactor comprising the steps of:
(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 ammonia (29 wt%) was added to a mixed solution of 6mL of water and 15mL of ethanol to form solution B (volume ratio of ethanol to water to ammonia water=4.3:1.7:1). Solution a was then added fully to solution B and stirred. Subsequently, 0.56mL of formaldehyde and 0.4g of resorcinol (molar ratio=1.8:1) were added and stirring was continued at room temperature for 24h. The liquid was transferred to a polytetrafluoroethylene-lined stainless steel autoclave and heated at 100 ℃ for 24h. Naturally cooling, separating precipitate by centrifugation, washing with ethanol and water, and drying in an oven to obtain SiO 2 @RF。
(2) 2g of melamine are reacted with 0.4g of SiO 2 Grinding and mixing @ RF (mass ratio of two=5:1) in a mortar, and then grinding and mixing in N 2 Pyrolysis is carried out in a tube furnace in atmosphere, the pyrolysis temperature is 900 ℃, and the pyrolysis time is 1h. 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 ultrasonic treatment was performed for 30 minutes. The resulting suspension was then heated to 80 ℃ to allow the water to evaporate completely. And (3) placing the dried solid into an Ar atmosphere tube furnace for heating at the temperature of 350 ℃ for 2 hours to obtain the novel space-limited nano-reactor.
As shown in the SEM of fig. 3a, the external appearance of the nano-reactor obtained in example 1 was spherical with a diameter of about 600nm, and no metallic NPs was observed outside the shell of the nano-reactor, indicating that NPs would not be distributed outside the shell. FIGS. 4a, b are TEM of the nanoreactor of example 1, which exhibits a unique hollow structure, an N-doped shell layer having a thickness of 20nm, and mesopores distributed on the shell, and metal NPs having an average particle diameter of 17.3nm distributed inside the hollow structure. Fig. 5 is HAADF-STEM and Mapping of the nano-reactor of example 1, and the bright spots in the pictures further confirm 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 NPs. By combining the results, the metal NPs are successfully encapsulated in the N-doped carbon nanocages, and the novel space-limited-domain nano-reactor is formed. The XRD of the example 1 nanoreactor in fig. 6, where the two broad peaks at 2 theta values of 24.9 deg. and 44.1 deg. are (002) and (100) for graphitic carbon, but no distinct NiO peaks were observed, probably due to the fact that the diffraction peaks of carbon covered the diffraction peaks of NiO NPs. FIG. 7 is X-ray photoelectron spectroscopy (XPS) of Ni element before and after potentiostatic electrolysis (CPE) in a nano-reactor of example 1. The Ni 2p3/2 band can be deconvolved to Ni before CPE II (856.3 eV) and corresponding satellite peaks. After CPE, ni 2p3/2 is Ni 0 (853.8 eV) as the main peak, ni II Is a secondary peak, which indicates that NiO NPs are reduced to Ni under the cathode potential 0 NPs, forming the final ni@ncn. The preparation method of the working electrode comprises the following steps:
(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, followed by sonication for 30min to obtain a dispersion. mu.L of the dispersion was applied dropwise to a glassy carbon electrode for electrocatalytically reduced carbon dioxide in an H-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 sonicated for 30min to obtain a dispersion. The dispersion is then sprayedIs coated on 5cm 2 Is sprayed with RuO on Nafion 115 film 2 Ti network of nanoparticles (RuO) 2 Ti) is attached to the other side of the membrane, constituting the MEA for electrocatalytically reduced carbon dioxide in a flow electrolyser. To verify the sustainability of the acid MEA flow electrolysis, the circulating electrolyte was not replaced during the stability test.
The operating conditions for electrocatalytic carbon dioxide reduction are as follows:
(1) When in electrolysis in an H-type battery, a glassy carbon electrode loaded with a catalyst is used as a working electrode, a platinum sheet electrode is used as a counter electrode, an Ag|AgCl electrode is used as a reference electrode, and an electrolyte is CO 2 Saturated 0.5M KHCO 3 Solution (neutral conditions) or sulfuric acid acidified 0.25MNA 2 SO 4 The pH value of the solution (acid condition) is 0.4-7.2, and the electrolysis potential is-0.5 to-1.0V vs. Reversible Hydrogen Electrode (RHE).
Example 1 nanoreactor in fig. 8a FE at neutral electrolyte ph=7.2 CO 93.2% was reached at-0.8V vs. RHE. The example 1 nanoreactor in FIG. 8b shows excellent CO over a range from neutral to more acidic pH (7.2-1.0) 2 RR Selectivity, FE of example 1 at pH 2.5 CO Can reach 84.3%, which shows that the nano reactor can realize higher CO selectivity under the acidic condition.
In CO 2 In RR process (Eq.2), OH around catalytic site - Will gradually accumulate while when the proton consumption rate in the nanoreactor exceeds the rate of transfer of protons from bulk solution to nanoreaction, the proton concentration will start to drop, resulting in a local pH rise within the reactor, thus inhibiting HER in the acidic electrolyte. In addition, to balance OH - Is H, H + And metal cations (M) + ) Will diffuse into the nanoreactor but a majority of H + By OH - Neutralization of M + Will increase the local concentration of (c), which will further promote CO 2 Is activated by the activation of (a). Thus, the spatially confined structure contributes to achieving high selectivity of CO under acidic conditions 2 RR。
CO 2 +2e - +H 2 O→CO+2OH - (Eq.2)
(2) In the flowing MEA device, under neutral condition, the electrolyte of the anode and the cathode is 0.5M KHCO 3 A solution; under acidic conditions, the catholyte was sulfuric acid acidified 0.25M Na 2 SO 4 Solution, anolyte of 0.25M H 2 SO 4 The solution has an electrolysis voltage of 2.5-4.0V.
In FIG. 9, the nano-reactor of example 1 was used to produce FE at an electrolysis voltage of 3.4V in an acidic MEA cell CO Can reach 80%, j CO Can reach 78mA cm -2 . FIG. 10 is a comparison of the results of the acid electrolysis and neutral electrolysis of the example 1 nanoreactor in an MEA cell, with higher current densities being achievable at the same voltage as compared to neutral conditions (pH 7.2) due to the high proton conductivity of the PEM. In order to examine the sustainability of the acid electrolysis, an electrolytic stability test was performed without renewing the circulating electrolyte, and the results are shown in fig. 10 b. After 15h electrolysis, the current density of the acid system shows a stable and slowly increasing trend, and meanwhile, the selectivity of CO is not obviously reduced, so that higher stability is shown. Whereas in conventional neutral electrolytes (KHCO 3 ) The current density tends to decrease with time because in neutral systems, K + Migration from the anode to the cathode and acidification of the anolyte due to Oxygen Evolution (OER) results in a decrease in the net concentration of the electrolyte, and thus a decrease in current density and an increase in electrolysis voltage. In contrast, in an acidic system, protons are conducted through the PEM, H on both sides + The concentration can be kept 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, sustainable electrochemical CO 2 RR method.
Example 2
A process for preparing a nanoreactor comprising the steps of:
(1) 3.9mL of TEOS was added to 35mL of ethanol to form 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 solution B (volume ratio of ethanol to water to aqueous ammonia=5:2:1).Solution a was then added fully to solution B 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 28h. The liquid was transferred to a polytetrafluoroethylene-lined stainless steel autoclave and heated at 110℃for 28h. Naturally cooling, centrifuging to separate precipitate, washing with ethanol and water, and drying in oven at 60deg.C to obtain SiO 2 @RF。
(2) 2.4g of melamine are reacted with 0.4g of SiO 2 Grinding and mixing @ RF (mass ratio of two=6:1) in a mortar, and then grinding and mixing in N 2 Pyrolysis is carried out in a tube furnace in atmosphere, the pyrolysis temperature is 950 ℃, and the pyrolysis time is 2h. 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 ultrasonic treatment was performed for 30 minutes. The resulting suspension was then heated to 90 ℃ to allow complete evaporation of the water. And (3) placing the dried solid into an Ar atmosphere tube furnace for heating at 400 ℃ for 3 hours to obtain the novel space confinement nano-reactor.
FIG. 3b is an SEM of the nanoreactor obtained in example 2, which is seen to have a spherical shape with a diameter of about 620nm, and no metallic NPs were observed outside the shell of the nanoreactor, indicating that the NPs were not distributed outside the shell. FIG. 4b is a TEM of the nanoreactor 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 metal NPs having an average particle diameter of 33nm distributed inside the hollow structure. The XRD pattern of example 2 in fig. 6 has a distinct NiO peak, indicating the formation of larger particles, consistent with the TEM results (fig. 4 c).
The preparation method of the working electrode comprises the following steps:
(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, followed by sonication for 30min to obtain a dispersion. mu.L of the dispersion was applied dropwise to a glassy carbon electrode for electrocatalytically reduced carbon dioxide in an H-cell.
(2) 10mg of novel space-limited domain nano-meterThe reactor was dispersed in a mixed solution of 920. Mu.L of isopropyl alcohol and 80. Mu.L of Nafion solution (5 wt%) and sonicated for 30min to obtain a dispersion. The dispersion was then sprayed at 5cm 2 Is sprayed with RuO on Nafion 115 film 2 Ti network of nanoparticles (RuO) 2 Ti) is attached to the other side of the membrane, constituting the MEA for electrocatalytically reduced carbon dioxide in a flow electrolyser.
The operating conditions for electrocatalytic carbon dioxide reduction are as follows:
(1) When in electrolysis in an H-type battery, a glassy carbon electrode loaded with a catalyst is used as a working electrode, a platinum sheet electrode is used as a counter electrode, an Ag|AgCl electrode is used as a reference electrode, and an electrolyte is CO 2 Saturated 0.5M KHCO 3 Solution (neutral conditions) or sulfuric acid acidified 0.25M Na 2 SO 4 The pH value of the solution (acid condition) is 0.4-7.2, and the electrolysis potential is-0.5 to-1.0V vs. RHE.
FIG. 8a shows FE's for the example 2 nanoreactor at neutral pH 7.2 CO At 80.6%, example 2 of FIG. 8b shows a good CO in the acidic to neutral range (pH 1.7-7.2) 2 RR Selectivity, FE of example 1 at pH 2.5 CO Can reach 75%, which shows that the catalyst can realize higher CO selectivity under acidic conditions.
(2) In the flowing MEA device, under neutral condition, the electrolyte of the anode and the cathode is 0.5M KHCO 3 A solution; under acidic conditions, the catholyte was sulfuric acid acidified 0.25M Na 2 SO 4 Solution, anolyte of 0.25M H 2 SO 4 The solution has an electrolysis voltage of 2.5-4.0V.
In FIG. 9, the nano-reactor of example 2 was used to produce FE at an electrolysis voltage of 3.4V in an acidic MEA cell CO Can reach 72.4%, j CO Can reach 62.4mA cm -2 。
Example 3
A process for preparing a nanoreactor comprising the steps of:
(1) 3.1mL of TEOS was added with 25mL of ethanol to form solution A (volume ratio of ethanol to TEOS=8:1), 3.75mL of ammonia (29 wt%) was added with a mixed solution of 3.75mL of water and 15mL of ethanol to form solution B (body of ethanol and water and ammonia)Product ratio = 4:1:1). Solution a was then added fully to solution B and stirred. Subsequently, 0.5mL of formaldehyde and 0.3g of resorcinol (molar ratio=1.5:1) were added and stirring was continued at room temperature for 20h. The liquid was transferred to a polytetrafluoroethylene-lined stainless steel autoclave and heated at 90 ℃ for 20h. Naturally cooling, separating precipitate by centrifugation, washing with ethanol and water, and drying in an oven to obtain SiO 2 @RF。
(2) 1.6g of melamine are reacted with 0.4g of SiO 2 Grinding and mixing @ RF (mass ratio of two=4:1) in a mortar, and then grinding and mixing in N 2 Pyrolysis is carried out in a tube furnace in atmosphere, the pyrolysis temperature is 850 ℃, and the pyrolysis time is 0.5h. 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 ultrasonic treatment was performed for 30 minutes. The resulting suspension was then heated to 90 ℃ to allow complete evaporation of the water. And (3) placing the dried solid into an Ar atmosphere tube furnace for heating at 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 is seen to be spherical 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 layer thickness of 18nm, and mesopores distributed on the shell, no metallic NPs was observed in the TEM because the content of synthetically added Ni was too small.
The preparation method of the working electrode comprises the following steps:
(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, followed by sonication for 30min to obtain a dispersion. mu.L of the dispersion was applied dropwise to a glassy carbon electrode for electrocatalytically reduced carbon dioxide in an H-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 sonicated for 30min to obtain a dispersion. The dispersion was then sprayed at 5cm 2 Is sprayed with RuO on Nafion 115 film 2 Ti network of nanoparticles (RuO) 2 Ti) is attached to the other side of the membrane, constituting the MEA for electrocatalytically reduced carbon dioxide in a flow electrolyser.
The operating conditions for electrocatalytic carbon dioxide reduction are as follows:
(1) When the H-type battery is electrolyzed, the glassy carbon electrode is a working electrode, the platinum sheet electrode is a counter electrode, the Ag|AgCl electrode is a reference electrode, and the electrolyte is CO 2 Saturated 0.5M KHCO 3 Solution (neutral conditions) or sulfuric acid acidified 0.25M Na 2 SO 4 The pH value of the solution (acid condition) is 0.4-7.2, and the electrolysis potential is-0.5 to-1.0V vs. RHE.
FIG. 8a shows FE's for example 3 nanoreactors at neutral pH 7.2 CO at-0.8V vs. RHE 69%, FIG. 8b, example 3 nanoreactor FE CO The pH value of the electrolyte is slightly changed (7.2-3.2) along with the decrease of the pH value, which shows that the electrolyte has better stability under the acidic condition.
In FIG. 11, the example 1,2,3 nanoreactors achieve higher FE's at lower pH values than reported in the prior art CO Exhibits excellent acidic electrolytic performance.
(2) In the flowing MEA device, under neutral condition, the electrolyte of the anode and the cathode is 0.5M KHCO 3 A solution; under acidic conditions, the catholyte was sulfuric acid acidified 0.25M Na 2 SO 4 Solution, anolyte of 0.25M H 2 SO 4 The solution has an electrolysis voltage of 2.5-4.0V.
In FIG. 9, example 3 nanoreactor FE was used at an electrolysis voltage of 3.4V in an acid MEA cell CO Can reach 60.1%, j CO Can reach 43mA cm -2 。
While the present invention has been described in terms of the preferred embodiments in situ, it will be apparent to those skilled in the relevant art that the methods described herein can be modified or appropriately adapted and combined to practice the technology without departing from the spirit, scope and aspects 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 included within the spirit, scope and content of the invention.

Claims (9)

1. The preparation process of nanometer reactor for acid electrocatalytic carbon dioxide reduction features that phenolic resin coated silicon ball (SiO) is first synthesized through hydrothermal process 2 At RF), adding an N source during high-temperature calcination, and removing the silicon core to obtain an N-doped carbon nanocage (NCN); growing NiO NPs in the nano cage by utilizing micropore capillary action to form N-doped carbon nano cage (NiO@NCN) for encapsulating the NiO NPs, reducing the NiO NPs into Ni NPs when negative potential is applied, and finally forming N-doped carbon nano cage (Ni@NCN) for encapsulating the Ni NPs as a nano reactor; the method comprises the following steps:
(1) Tetraethyl orthosilicate (TEOS) is added into ethanol solution and stirred to form solution A; adding ammonia water into a mixed solution of water and ethanol, and stirring to form a solution B; adding all the solution A into the solution B to obtain a solution C, adding formaldehyde and resorcinol into the solution C, and continuously stirring for 20-28 h at room temperature; 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 water, followed by drying in an oven to give phenolic resin coated silica spheres (SiO 2 @RF)；
(2) SiO is made of 2 Grinding and mixing @ RF and melamine in a mortar, and then mixing in N 2 Pyrolysis is carried out in a tube furnace in atmosphere, 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 Nano Cage (NCN);
(3) Dispersing NCN in water, adding aqueous solution of nickel nitrate, and performing ultrasonic dispersion; then heating the obtained suspension to 70-90 ℃ to completely evaporate the water; calcining the dried solid in a tubular furnace in Ar atmosphere at 300-400 ℃ for 1-3 h, wherein NiO NPs are encapsulated into N-doped carbon nanocages (NiO@NCN); after cathodic potential is applied, niO NPs are reduced in situ to Ni NPs, forming N-doped carbon nanocages (Ni@NCN) encapsulating the Ni NPs as a spatially confined nanoreactor.
2. The method of claim 1, wherein in step (1), the volume ratio of ethanol to TEOS in solution a is 8-9:1.
3. The method of claim 1, wherein in step (1), the volume ratio of water to ethanol to 29wt% ammonia water in solution B is 4-5:1-2:1.
4. The method of claim 1, wherein in step (1), the volume ratio of solution a to solution B is 1 to 1.5:1 when solution a is added to solution B.
5. The method of claim 1, wherein in step (1), the molar ratio of formaldehyde to resorcinol is 1.5 to 2.0:1.
6. The method of claim 1, wherein in step (2), the SiO 2 The mass ratio of the @ RF to the melamine is 4-6:1.
7. The method according to claim 1, wherein in step (3), the mass ratio of the 43mM nickel nitrate solution to NCN is 5-50:1.
8. The method as claimed in claim 1, wherein the nano reactor for acidic electrocatalytic carbon dioxide reduction has a hollow porous N-doped carbon shell with a diameter of 580-620 nm, the carbon shell has a thickness of 18-25 nm, ni nano particles with a diameter of less than 35nm are uniformly distributed in the cavity of the nano reactor, and the catalytic active sites are the positions where Ni NPs are connected with the inner wall of the N-doped shell, and CO 2 The RR reaction will be confined to the interior of the nanoreactor; n-doped sheath selectively promotes CO 2 Is limited by adsorption and diffusion of H + The nano reactor can carry out carbon dioxide reduction reaction in acid electrolyte, and the acid condition is thatCan avoid CO 2 The feed gas is converted to unusable carbonate.
9. A membrane electrode system of a nano-reactor for acidic electrocatalytic carbon dioxide reduction prepared using the method of any one of claims 1 to 8; characterized in that the nano reactor is used as a cathode electrocatalyst to be coated on one side of a PEM of a Nafion 115 proton exchange membrane, and is sprayed with RuO 2 Nanoparticulate Ti (RuO) 2 Ti is used as anode catalyst to be attached to the other side of the PEM to form MEA; in acid electrolysis, the catholyte is sodium sulfate acidified 2 SO 4 Solution, anolyte is H 2 SO 4 The solution has an electrolysis voltage of 2.5-4.0V.
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