CN117564265B - Preparation method and application of porous carbon supported Ni nanoparticle catalyst - Google Patents
Preparation method and application of porous carbon supported Ni nanoparticle catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
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- 239000002184 metal Substances 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 239000013335 mesoporous material Substances 0.000 claims abstract description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 239000012300 argon atmosphere Substances 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention provides a preparation method and application of a porous carbon supported Ni nanoparticle catalyst, wherein the preparation method comprises the following steps: 1. mixing the ordered mesoporous material with water, adding a metal nickel salt aqueous solution and a 2-methylimidazole aqueous solution for reaction, centrifuging and washing to obtain a precursor material; 2. calcining the precursor material at 600-1000 ℃, and cooling along with a furnace to prepare the nitrogen-doped carbon-coated nickel catalyst with the core-shell structure; 3. the nitrogen-doped carbon-coated nickel catalyst with the core-shell structure is washed by hydrofluoric acid to prepare the porous carbon-supported Ni nanoparticle catalyst, wherein the particle size of the nickel nanoparticle is 4-50 nm. The dispersion of metal active sites is improved by a hard template method, the catalytic activity is enhanced, and the prepared porous carbon-loaded Ni nanoparticle catalyst is applied to electrocatalytic reduction of CO 2.
Description
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a preparation method and application of a porous carbon supported Ni nanoparticle catalyst.
Background
Worldwide power sources mainly depend on fossil energy, but unconditionally mined causes a series of energy crisis and environmental problems, such as energy exhaustion, annual rise in air temperature, climate deterioration, ocean acidification and the like, which threatens sustainable development of human beings, so that searching for renewable energy sources and slowing down carbon dioxide emission become key problems at present, and relatively mild reaction conditions of electrocatalytic carbon dioxide reduction reactions can convert CO 2 into products with industrial value. Currently, conversion of CO 2 can be achieved by photochemical, biological, mineral, electrochemical, and the like. In recent years, the electrochemical reduction method of CO 2 is considered as a conversion method with very good application prospect, and has the following advantages: (1) The electrochemical reduction process can be regulated and controlled by regulating the applied voltage; (2) Can be combined with renewable energy sources such as wind energy, solar energy, hydroelectric power generation, geothermal energy and the like to provide an effective storage method for the renewable energy sources; (3) The reaction condition is mild, the operation process is simple, the conversion rate is higher, the reaction raw materials are easy to obtain, the large-scale production is convenient, only water and CO 2 are consumed in the reaction process, and no extra burden is caused to the environment. Therefore, the CO 2 RR has potential practical application value and is a very promising energy conversion technology.
The high cost of noble metals and the low reserves in nature limit their application in the catalytic direction, and the development of alternative low cost, high efficiency and high stability catalysts is the focus of current research. The transition metal is abundant and low-priced, so it becomes an excellent metal catalyst that can replace noble metals. Common transition metals are Fe, co, ni, cu and Zn, etc., however, when pure metals are used as catalysts, they exhibit higher activities for HER, so that it is necessary to prepare a composite of transition metal and other active substances to increase the catalytic activity of CO 2 RR. In recent years, under mild conditions, non-noble metal catalysts of core-shell structure reduce CO 2 to CO with high selectivity, because of their low cost and remarkable catalytic activity are one of the hot spots of research. The M@N-C catalyst reported still consisted of larger metal nanoparticles, which reduced the exposure of the active sites on the N-doped carbon shell. More importantly, the source of the synergy between the N-doped carbon shell and the metal nanoparticle core is not yet clear, and the reaction mechanism is even controversial, e.g. whether the N-C unit acts as an active site, whether the metal NPs affects catalytic activity.
The patent name of China patent ZL 201910877936.5, a preparation method and application of an iron-nitrogen CO-doped carbon catalyst for electrocatalytic reduction of CO 2, discloses a preparation method and application of a doped carbon catalyst for electrocatalytic reduction of CO 2, wherein the carbon-based catalyst is doped with iron-nitrogen atoms and contains intrinsic carbon defects. The Faraday efficiency of the CO reaches 95%, the maximum current density is about 1.9mA cm -2, the current density is smaller, meanwhile, the preparation time is longer, the industrial level cannot be reached, and the CO needs to be further improved.
Although many efforts are made to reduce the CO 2 catalyst by electrocatalytic reaction, the existing catalyst still has the problems of complex preparation technology, high cost, poor catalyst activity and stability, and the like, which is unfavorable for industrial production. In view of this, the present invention has been made.
Disclosure of Invention
In view of the above, the present invention proposes a method for preparing a porous carbon-supported Ni nanoparticle catalyst and application thereof, which solve the above-mentioned problems.
The technical scheme of the invention is realized as follows:
the preparation method of the porous carbon supported Ni nanoparticle catalyst comprises the following steps:
(1) Mixing the ordered mesoporous material with water, adding a metal nickel salt aqueous solution and a 2-methylimidazole aqueous solution for reaction, centrifuging and washing to obtain a precursor material;
(2) Calcining the precursor material at 600-1000 ℃, and cooling along with a furnace to prepare the nitrogen-doped carbon-coated nickel catalyst with the core-shell structure;
(3) And washing the nitrogen-doped carbon-coated nickel catalyst with the core-shell structure by adopting hydrofluoric acid to prepare the porous carbon-supported Ni nanoparticle catalyst.
Further, in the step (1), the ordered mesoporous material is SBA-15, and the concentration of the ordered mesoporous material is 3-10mg/ml.
Further, in the step (1), the metal nickel is nickel nitrate, and the molar ratio of the nickel nitrate to the 2-methylimidazole is 1:6 to 20, the concentration of the metal nickel salt in the aqueous solution is 0.05 to 0.1mol/L.
Further, in the step (1), the reaction temperature of the reaction is 30-60 ℃ and the reaction time is 10-30 h.
Further, in the step (2), the calcination is sintering in an argon atmosphere.
Further, in the step (2), the primary temperature is raised to 250-350 ℃ at a temperature raising rate of 2-4 ℃/min, the temperature is kept for 20-30min, and the secondary temperature is raised to 600-1000 ℃ at a temperature raising rate of 5-8 ℃/min, and the temperature is kept for 120-180min.
Further, in the step (3), the concentration of the hydrofluoric acid is 10-40 wt% and the pickling time is 6-24h.
Further, a nafion solution is used as a binder, and a porous carbon-supported Ni nanoparticle catalyst material is supported on carbon paper of 1cm 2 to prepare the working electrode.
Further, the particle size of the nickel nano particles is 4-50 nm.
Further, the porous carbon-supported Ni nanoparticle catalyst is applied to electrocatalytic reduction of CO 2.
Further, the porous carbon-supported Ni nanoparticle catalyst is used for reducing CO 2 to CO in electrocatalysis.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the method for preparing the porous carbon supported Ni nanoparticle catalyst by the hard template method, disclosed by the invention, the porous carbon supported Ni nanoparticle catalyst is prepared by the template SBA-15, so that the novel efficient electrocatalyst is obtained, and the synthesis mode is simple and efficient, the operation is simple and convenient, and the synthesis process is environment-friendly;
(2) The porous catalyst is prepared by adopting a template method, a precursor material is prepared by a one-step coprecipitation method, and then a porous carbon-supported Ni-N carbon-based catalyst is prepared by utilizing high-temperature pyrolysis; finally, the template is removed by HF solution.
(3) The catalyst prepared by the invention has excellent catalytic performance on electrocatalytic reduction of CO 2, the CO partial current density of the catalyst can reach industrial current density, and the catalyst has good stability.
(4) According to the catalyst for preparing the porous carbon supported Ni nano particles through the template SBA-15, the size of the nano particles can be regulated and controlled by changing the amount of metal salt on the template SBA-15 and the sintering temperature, the particle size is firstly reduced and then increased along with the increase of the metal salt, the size of the metal particles is gradually increased along with the increase of the sintering temperature, the performance of the catalyst is obviously reduced along with the increase of the size of the nano particles, and the moderate particle size can reach the optimal catalytic performance.
Drawings
Fig. 1 is SEM (a) and TEM images (b, C) of a porous carbon-supported Ni nanoparticle catalyst (ni@n-C) prepared in the first embodiment of the present invention.
FIG. 2 is an XRD pattern of a porous carbon-supported Ni nanoparticle catalyst (Ni@N-C) prepared in accordance with example one of the present invention.
FIG. 3 shows a linear sweep voltammogram of a porous carbon-supported Ni nanoparticle catalyst (Ni@N-C) prepared in accordance with example one of the present invention at room temperature, 0.5M KHCO 3.
FIG. 4 is a Faraday plot of the electrical catalytic reduction of CO 2 to CO in 0.5M KHCO 3 at room temperature for a porous carbon supported Ni nanoparticle catalyst (Ni@N-C) prepared in accordance with example one of the present invention.
FIG. 5 is a graph showing the stability test of the porous carbon-supported Ni nanoparticle catalyst (Ni@N-C) prepared in the first embodiment of the invention for electrocatalytic CO 2 reduction of CO in 0.5M KHCO 3 at room temperature.
FIG. 6 is a graph showing the Faraday efficiency and the partial current density of CO for electrocatalytic reduction of CO 2 in 1M KOH in a flow cell at room temperature for a porous carbon-supported Ni nanoparticle catalyst (Ni@N-C) prepared in accordance with example one of the present invention.
Detailed Description
In order to better understand the technical content of the present invention, the following provides specific examples to further illustrate the present invention.
The experimental methods used in the embodiment of the invention are conventional methods unless otherwise specified.
Materials, reagents, and the like used in the examples of the present invention are commercially available unless otherwise specified.
Example 1
The preparation method of the porous carbon-supported Ni nanoparticle catalyst comprises the following steps:
(1) Dispersing ordered mesoporous material SBA-15 into deionized water with the concentration of 5mg/ml, adding 0.05mol/L Ni (NO 3)2 aqueous solution, then adding 2.75g 2-methylimidazole aqueous solution, reacting at 30 ℃ for 24 hours, centrifuging and washing the reacted product, and drying in a 60 ℃ oven to obtain a precursor material;
(2) And (3) placing the obtained precursor material in an argon atmosphere for high-temperature heat treatment, wherein the primary heating is performed at a heating rate of 3 ℃/min to 300 ℃, the temperature is kept for 20-30min, the secondary heating is performed at a heating rate of 5 ℃/min to 800 ℃ and the temperature is kept for 150min, and the carbon-loaded Ni nano-particle catalyst is obtained after cooling along with a furnace.
(3) The material obtained through high-temperature treatment is washed for 12 hours by an HF solution with the concentration of 20wt percent to remove the template, and the porous carbon supported Ni nano-particle catalyst is obtained, wherein the outer layer of the Ni particles is coated by a carbon layer.
The porous carbon supported Ni nanoparticle catalyst of this embodiment has a clear tubular structure, wherein the Ni nanoparticles are the inner core (particle size of 6 nm) and the nitrogen-doped carbon is the outer shell
Example 2
The preparation method of the porous carbon-supported Ni nanoparticle catalyst comprises the following steps:
(1) Dispersing ordered mesoporous material SBA-15 into deionized water with the concentration of 3mg/ml, adding 0.07mol/L Ni (NO 3)2 aqueous solution, then adding 0.82g 2-methylimidazole aqueous solution, reacting at 30 ℃ for 24 hours, centrifuging and washing the reacted product, and drying in a baking oven at 60 ℃ to obtain a precursor material;
(2) And (3) placing the obtained precursor material in an argon atmosphere for high-temperature heat treatment, wherein the primary heating is carried out at a heating rate of 2 ℃/min to 250 ℃, the temperature is kept for 20min, the secondary heating is carried out at a heating rate of 6 ℃/min to 700 ℃ and the temperature is kept for 120min, and the carbon-loaded Ni nano-particle catalyst is obtained after cooling along with a furnace.
(3) The material obtained through high-temperature treatment is washed by HF solution with concentration of 20wt% for 24 hours to remove the template, and the porous carbon supported Ni nano-particle catalyst is obtained, wherein the outer layer of the Ni particles is coated by a carbon layer.
The porous carbon supported Ni nanoparticle catalyst of this embodiment has a tubular structure of stacked porous carbon material, wherein the nickel nanoparticles are the inner core (particle size 10 nm) and the nitrogen doped carbon is the outer shell.
Example 3
The preparation method of the porous carbon-supported Ni nanoparticle catalyst comprises the following steps:
(1) Dispersing ordered mesoporous material SBA-15 into deionized water with the concentration of 8mg/ml, adding 0.1mol/L Ni (aqueous solution of NO 3)2, then adding 2.75g of 2-methylimidazole aqueous solution, reacting at 30 ℃ for 12 hours, centrifuging and washing the reacted product, and drying in a baking oven at 60 ℃ to obtain a precursor material;
(2) And (3) placing the obtained precursor material in an argon atmosphere for high-temperature heat treatment, wherein the primary heating is performed at a heating rate of 4 ℃/min to 350 ℃, the temperature is kept for 30min, the secondary heating is performed at a heating rate of 8 ℃/min to 1000 ℃ and the temperature is kept for 180min, and the carbon-loaded Ni nano-particle catalyst is obtained after cooling along with a furnace.
(3) The material obtained through high-temperature treatment is washed for 12 hours by an HF solution with the concentration of 20wt percent to remove the template, and the porous carbon supported Ni nano-particle catalyst is obtained, wherein the outer layer of the Ni particles is coated by a carbon layer.
The porous carbon supported Ni nanoparticle catalyst of this embodiment has a clear tubular structure, wherein the Ni nanoparticles are the inner core (particle size 40 nm) and the nitrogen-doped carbon is the outer shell.
Example 4
The preparation method of the porous carbon-supported Ni nanoparticle catalyst comprises the following steps:
(1) Dispersing ordered mesoporous material SBA-15 into deionized water with the concentration of 10mg/ml, adding 0.05mol/L Ni (NO 3)2 aqueous solution, then adding 1.64g 2-methylimidazole aqueous solution, reacting at 30 ℃ for 24 hours, centrifuging and washing the reacted product, and drying in a baking oven at 60 ℃ to obtain a precursor material;
(2) And (3) placing the obtained precursor material in an argon atmosphere for high-temperature heat treatment, wherein the primary heating is performed at a heating rate of 4 ℃/min to 300 ℃, the temperature is kept for 20-30min, the secondary heating is performed at a heating rate of 8 ℃/min to 900 ℃ and the temperature is kept for 180min, and the carbon-loaded Ni nano-particle catalyst is obtained after cooling along with a furnace.
(3) The material obtained through high-temperature treatment is washed for 12 hours by an HF solution with the concentration of 10wt% to remove the template, and the porous carbon supported Ni nano-particle catalyst is obtained, wherein the outer layer of the Ni particles is coated by a carbon layer.
The porous carbon supported Ni nanoparticle catalyst of this embodiment has a clear tubular structure, wherein the Ni nanoparticles are inner cores (particle size 25 nm) and the nitrogen-doped carbon is outer shells.
Example 5
The preparation method of the porous carbon-supported Ni nanoparticle catalyst comprises the following steps:
(1) Dispersing ordered mesoporous material SBA-15 into deionized water with the concentration of 7mg/ml, adding 0.1mol/L Ni (aqueous solution of NO 3)2, then adding 2.75g of 2-methylimidazole aqueous solution, reacting at 30 ℃ for 12 hours, centrifuging and washing the reacted product, and drying in a baking oven at 60 ℃ to obtain a precursor material;
(2) And (3) placing the obtained precursor material in an argon atmosphere for high-temperature heat treatment, wherein the primary heating is performed at a heating rate of 4 ℃/min to 350 ℃, the temperature is kept for 30min, the secondary heating is performed at a heating rate of 8 ℃/min to 1000 ℃ and the temperature is kept for 180min, and the carbon-loaded Ni nano-particle catalyst is obtained after cooling along with a furnace.
(3) The material obtained through high-temperature treatment is washed for 12 hours by an HF solution with the concentration of 20wt percent to remove the template, and the porous carbon supported Ni nano-particle catalyst is obtained, wherein the outer layer of the Ni particles is coated by a carbon layer.
The porous carbon supported Ni nanoparticle catalyst of the embodiment has a clear tubular structure, wherein the nickel nanoparticle is an inner core (particle size is 50 nm), and the nitrogen-doped carbon is an outer shell.
Test example 1
The structural morphology characterization and performance detection of the porous carbon-loaded Ni nanoparticle catalyst prepared in the embodiment I are carried out.
The nafion solution is used as a binder, and the catalyst material is loaded on carbon paper of 1cm 2 to prepare the working electrode.
(A) Structural morphology and elemental characterization of the catalyst:
An image of the porous carbon-supported Ni nanoparticle catalyst (ni@n-C) was observed using a Transmission Electron Microscope (TEM) (fig. 1), and a tubular structure was clearly observed from fig. 1a, and the particle size of the porous carbon-supported Ni nanoparticle catalyst prepared by example one was about 6nm. And as is obvious from fig. 1, the middle black is nickel particles, the outer layer is a carbon layer shell, and the catalyst material prepared by the invention has a structure that the carbon layer is obviously coated with metal nickel particles.
The elemental composition information of the porous carbon supported Ni nanoparticle catalyst (ni@n-C) was characterized by X-ray diffraction (XRD) (fig. 2). As can be seen from fig. 2, the prepared material exhibits remarkable XRD diffraction peak information of nickel element.
(B) Electrocatalytic reduction CO 2 catalytic performance test:
firstly, testing in an H-type electrolytic cell, adopting a three-electrode system, and carrying out linear cyclic voltammetry scanning at a scanning speed of 5mV/s in 0.5MKHCO 3 saturated by CO 2, wherein the result is shown in a test result in FIG. 3, and the material can be seen to have lower initial potential, larger current density and excellent conductivity in an electrocatalytic reduction CO 2 system.
In CO 2 saturated 0.5M KHCO 3, the result of CO Faraday efficiency test of electrocatalytic reduction CO 2 under different potentials is shown in figure 4, and through performance test, the material can be seen to have excellent catalytic performance in a wider voltage range, and the Faraday efficiency of CO is up to about 90%. Further, the stability of the material is tested, and the result is shown in fig. 5, and the material has higher stability through no attenuation of the long-time test performance.
The material is tested in a flow cell and in 1M KOH electrolyte, and the result is shown in figure 6, and the material can be seen to have a CO Faraday efficiency of more than 90% and a current density of 237mAcm -2 in a wide voltage range of-0.5 to-1.5V (vs. RHE) through testing.
The catalyst according to the present invention was tested for current density and catalyst stability by the same test methods as above, except for the specific description.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. A preparation method of a porous carbon supported Ni nanoparticle catalyst is characterized by comprising the following steps of: the method comprises the following steps:
(1) Mixing the ordered mesoporous material SBA-15 with water, adding metal nickel salt aqueous solution and 2-methylimidazole aqueous solution for reaction, centrifuging and washing to obtain a precursor material;
(2) Heating and calcining the precursor material twice, heating to 250-350 ℃ once, preserving heat for 20-30min, heating to 600-1000 ℃ twice, preserving heat for 120-180min, and cooling along with a furnace to prepare the nitrogen-doped carbon-coated nickel catalyst with a core-shell structure;
(3) And washing the nitrogen-doped carbon-coated nickel catalyst with the core-shell structure by adopting hydrofluoric acid to prepare the porous carbon-supported Ni nanoparticle catalyst.
2. The method for preparing a porous carbon supported Ni nanoparticle catalyst according to claim 1, wherein in the step (1), the concentration of the ordered mesoporous material SBA-15 is 3-10mg/ml.
3. The method for preparing a porous carbon supported Ni nanoparticle catalyst according to claim 1, wherein in step (1), the metal nickel salt is nickel nitrate, and the molar ratio of nickel nitrate to 2-methylimidazole is 1:6 to 20, the concentration of the metal nickel salt in the aqueous solution is 0.05 to 0.1mol/L.
4. The method for preparing a porous carbon supported Ni nanoparticle catalyst according to claim 1, wherein in the step (1), the reaction temperature is 30-60 ℃ and the reaction time is 10-30 h.
5. The method for preparing a porous carbon-supported Ni nanoparticle catalyst according to claim 1, wherein in step (2), the calcination is sintering in an argon atmosphere.
6. The method for preparing a porous carbon supported Ni nanoparticle catalyst according to claim 1, wherein in the step (2), the temperature rising rate of the primary temperature rising is 2-4 ℃/min, and the temperature rising rate of the secondary temperature rising is 6-8 ℃/min.
7. The method for preparing a porous carbon supported Ni nanoparticle catalyst according to claim 1, wherein in the step (3), the concentration of hydrofluoric acid is 10-40 wt% and the pickling time is 6-24 hours.
8. Use of a porous carbon-supported Ni nanoparticle catalyst as in any of claims 1-7 for electrocatalytic reduction of CO 2.
9. The use of claim 8, wherein the porous carbon-supported Ni nanoparticle catalyst is used for reduction of CO 2 to CO in electrocatalysis.
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