CN117564265A - 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 79
- 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 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000013335 mesoporous material Substances 0.000 claims abstract description 12
- 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
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [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
- 238000005554 pickling Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 9
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- 238000006722 reduction reaction Methods 0.000 description 13
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- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
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- 150000003624 transition metals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 2
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- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- 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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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
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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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
The invention is thatThe preparation method and application of the porous carbon supported Ni nanoparticle catalyst are provided, and 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 supported Ni nanoparticle catalyst is used for electrocatalytic reduction of CO 2 Is used in the field of applications.
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
The global power source mainly depends on fossil energy, but unconditioned exploitation causes a series of energy crisis and environmental problems, such as energy exhaustion, annual rising of air temperature, climate deterioration, ocean acidification and the like, which threatens the sustainable development of human beings, so that the searching of renewable energy sources and the slowing of carbon dioxide emission become the key problems at present, and the relatively mild reaction condition of electrocatalytic carbon dioxide reduction reaction can lead to CO 2 Is converted into a product with industrial value. Currently, CO 2 The conversion of (c) can be achieved by photochemical, biological, mineral and electrochemical methods. In recent years, electrochemical reduction of CO 2 The method is considered as a transformation 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, and only water and CO are consumed in the reaction process 2 No additional burden is imposed on the environment. Thus, CO 2 RR has potential realityThe application value is a 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 activity towards HER, so that it is necessary to prepare a composite of transition metal and other active substances to increase CO 2 Catalytic activity of RR. In recent years, under mild conditions, the non-noble metal catalyst with a core-shell structure has high selectivity for CO 2 Reduction to CO is one of the hot spots of research due to its low cost and significant catalytic activity. 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.
Chinese patent ZL 201910877936.5, patent name "a catalyst for electrocatalytic reduction of CO 2 Preparation method and application of iron-nitrogen CO-doped carbon catalyst, discloses a method for electrocatalytic reduction of CO 2 A method for preparing a doped carbon catalyst and application thereof, wherein the carbon-based catalyst is doped with iron nitrogen atoms and contains intrinsic carbon defects. The Faraday efficiency of the CO reaches 95%, and the maximum current density is about 1.9mA cm -2 The current density is smaller, the preparation time is longer, the industrial level cannot be achieved, and the process is required to be further improved.
Although one is electrocatalytic reduction of CO 2 Many efforts are made in the aspect of catalysts, but the existing catalysts still have the problems of complex preparation technology, high cost, poor catalyst activity and stability, and the like, which are 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 to load the porous carbon supported Ni nano-particle catalyst material to 1cm 2 The working electrode is prepared on the carbon paper.
Further, the particle size of the nickel nano particles is 4-50 nm.
Further, the porous carbon-supported Ni nanoparticle catalyst is used for electrocatalytic reduction of CO 2 Is used in the field of applications.
Further, the porous carbon-supported Ni nanoparticle catalyst reduces CO in electrocatalysis 2 To the application of CO.
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 is used for electrocatalytic reduction of CO 2 The catalyst has excellent catalytic performance, the CO partial current density of the catalyst can reach industrial current density, and meanwhile, 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 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 Linear sweep voltammogram.
FIG. 4 shows 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 Middle electrocatalytic CO 2 Faraday efficiency plot for CO reduction.
FIG. 5 shows 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 Middle electrocatalytic CO 2 Stability test chart for reduced CO.
FIG. 6 shows the electrocatalytic CO in 1M KOH in a flowing cell at room temperature for a porous carbon supported Ni nanoparticle catalyst (Ni@N-C) prepared in accordance with an embodiment of the present invention 2 Faraday efficiency of CO reduction and CO partial current density plot.
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 at concentration of 5mg/ml, and adding 0.05mol/L Ni (NO) 3 ) 2 Then 2.75g of 2-methylimidazole aqueous solution is added, the reaction is carried out for 24 hours at 30 ℃, and the product is subjected to centrifugation and washing treatment, and is dried in a 60 ℃ oven to obtain the precursor material. The method comprises the steps of carrying out a first treatment on the surface of the
(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 concentration of 3mg/ml, and adding 0.07mol/L Ni (NO) 3 ) 2 Then 0.82g of 2-methylimidazole aqueous solution is added, the reaction is carried out for 24 hours at 30 ℃, and the product is subjected to centrifugation and washing treatment, and is dried in a 60 ℃ oven to obtain the precursor material. The method comprises the steps of carrying out a first treatment on the surface of the
(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 concentration of 8mg/ml, and adding 0.1mol/L Ni (NO) 3 ) 2 Then 2.75g of 2-methylimidazole aqueous solution was added thereto, and the reaction was carried out at 30℃for 12 hours, followed by centrifugationAnd washing, and drying in a 60 ℃ oven to obtain the precursor material. The method comprises the steps of carrying out a first treatment on the surface of the
(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 concentration of 10mg/ml, and adding 0.05mol/L Ni (NO) 3 ) 2 1.64g of 2-methylimidazole aqueous solution was then added, and the reaction was carried out at 30℃for 24 hours, followed by centrifugation and washing of the resultant, and oven drying at 60℃to obtain a precursor material. The method comprises the steps of carrying out a first treatment on the surface of the
(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 at concentration of 7mg/ml, and adding 0.1mol/L Ni (NO) 3 ) 2 2.75g of 2-methylimidazole aqueous solution is added, the reaction is carried out for 12 hours at 30 ℃, and the product is subjected to centrifugation and washing treatment, and is dried in a 60 ℃ oven to obtain the precursor material. The method comprises the steps of carrying out a first treatment on the surface of the
(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 to load the catalyst material to 1cm 2 The working electrode is prepared on the carbon paper.
(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 of CO 2 Catalytic performance test:
first tested in an H-cell, using a three electrode system, in CO 2 Saturated 0.5 MKHO 3 In the process, linear cyclic voltammetry scanning is carried out at a scanning speed of 5mV/s, the result is shown in the figure 3, and the result is shown by the test result, so that the material can be used for electrocatalytic reduction of CO 2 In the system, the initial potential is lower, the current density is larger, and the system has excellent conductivity.
In CO 2 Saturated 0.5M KHCO 3 In the electrocatalytic reduction of CO at different potentials 2 The result of the test of the Faraday efficiency of CO is shown in fig. 4, and the performance test shows that the material has 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, the result is shown in figure 6, the material can be seen to have a CO Faraday efficiency of more than 90% and a current density of 237mAcm in a wide voltage range of-0.5 to-1.5V (vs. RHE) through the test -2 。
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 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.
2. The method for preparing a porous carbon supported Ni nanoparticle catalyst according to claim 1, wherein in the step (1), the ordered mesoporous material is SBA-15, and the concentration of the ordered mesoporous material is 3-10mg/ml.
3. The method for preparing a porous carbon-supported Ni nanoparticle catalyst by a hard template method according to claim 1, wherein in the step (1), the metal nickel 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 primary temperature is raised to 250-350 ℃ at a temperature raising rate of 2-4 ℃/min, the heat is preserved for 20-30min, and the secondary temperature is raised to 600-1000 ℃ at a temperature raising rate of 6-8 ℃/min, and the heat is preserved for 120-180min.
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. The porous carbon-supported Ni nanoparticle catalyst of any of claims 1-7 for electrocatalytic reduction of CO 2 Is used in the field of applications.
9. The use of claim 8, wherein the porous carbon-supported Ni nanoparticle catalyst reduces CO in electrocatalysis 2 To the application of CO.
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