CN115161686A - Ni monatomic catalyst and preparation method and application thereof - Google Patents
Ni monatomic catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 238000000197 pyrolysis Methods 0.000 claims description 49
- 239000000843 powder Substances 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 12
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 229920000557 Nafion® Polymers 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000011148 porous material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 8
- 239000001509 sodium citrate Substances 0.000 description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000001508 potassium citrate Substances 0.000 description 4
- 229960002635 potassium citrate Drugs 0.000 description 4
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 4
- 235000011082 potassium citrates Nutrition 0.000 description 4
- 230000004075 alteration Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000012113 quantitative test Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
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- 239000002078 nanoshell Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
- C25B11/032—Gas diffusion electrodes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/23—Carbon monoxide or syngas
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a Ni monatomic catalyst, which takes a hollow porous nano carbon shell with the aperture of 120-180nm as a carbon substrate, and metallic nickel is anchored on the surface of the hollow porous nano carbon shell in a monatomic form. The invention also discloses a preparation method and application of the Ni monatomic catalyst. The Ni monatomic catalyst provided by the invention can effectively promote the material transmission in the catalytic layer and expand the three-phase reaction interface, and is used for electrochemical CO 2 The reduction product CO has the characteristics of high catalytic activity, high CO product selectivity, good material stability and the like. The preparation method provided by the invention has the characteristics of simplicity, feasibility, wide raw material source, low price and the like, and is suitable for large-scale production and industrial applicationThe application is as follows.
Description
Technical Field
The invention belongs to the technical field of electrochemical catalyst nano material preparation, and particularly relates to a Ni monatomic catalyst and a preparation method and application thereof.
Background
CO generation using renewable power sources 2 The organic silicon-carbon composite material is converted into a chemical product with an additional value, so that the greenhouse gas emission can be effectively reduced, the environment is improved, and the energy crisis problem can be reduced. Electrochemical CO over the last decades 2 And the advantages of mild reaction conditions (normal temperature and normal pressure), controllable products and the like are widely concerned. Electrochemical reduction of CO 2 The preparation of CO has the advantages of high selectivity, large current density and the like, and has good industrial application prospect, however, the CO production electrochemical catalyst which is widely researched at present is basically noble metal and relative alloy thereof, such as Ag, au, pd and the like, and is expensive and poor in economical efficiency, so that the development of the CO production electrochemical catalyst which is environment-friendly, low in price and efficient is particularly important.
In recent years, ni monatomic catalyst has attracted much attention due to its low cost, high catalytic activity and high atom utilization rate, and some researchers use Ni monatomic catalyst for electrochemical reduction of CO 2 CO is prepared and high selectivity is obtained. However, the existing research basically supports Ni monatomic catalyst on carbon material substrate with the aperture of tens of nanometers, and the pore structure is not beneficial to CO 2 Local transport, reduction of CO near catalytically active sites 2 The concentration, the preparation process of the Ni monatomic catalyst is complex, and the stability is poor. For example, the document 1[ Yang H, et al. Nature communications,2019,10 (1): 1-9]It is proposed that a Ni monatomic catalyst is supported on carbon black by pyrolyzing nickel acetate, phenanthroline, and commercial carbon black, and that a CO faradaic efficiency of close to 100% is obtained between-0.8 to-1.4 v vs. The catalyst has low working current density, and meanwhile, the performance of the catalyst is attenuated after the catalyst works continuously for 24 hours, so that the stability of the catalyst is poor. Reference 2, zheng T, et al, joule,2019,3 (1): 265-278.]It is proposed to synthesize Ni monatomic catalyst on a large scale using commercial carbon black and obtain 100mA/cm at a cell voltage of less than 2.8V 2 High current density and near 100% CO faraday efficiency. C of the catalystO has a good faraday efficiency, but the cell voltage is higher at the same current density and the energy efficiency is lower.
Disclosure of Invention
The present invention is directed to solving, at least in part, one of the technical problems in the related art. Accordingly, it is a primary object of the present invention to provide a Ni monatomic catalyst which is mainly used for CO 2 The method aims to solve the problems of complex production process, low working current density, poor stability and/or low energy efficiency of the existing Ni monatomic catalyst. The invention also provides a preparation method and application of the Ni monatomic catalyst.
The purpose of the invention is realized by the following technical scheme:
in a first aspect:
a Ni monatomic catalyst takes a hollow porous nano carbon shell with the aperture of 120-180nm as a carbon substrate, and metallic nickel is anchored on the surface of the hollow porous nano carbon shell in a monatomic form.
Further, wherein the specific surface area of the hollow porous nanocarbon shell is 300 to 500m 2 /g。
A preparation method of the Ni monatomic catalyst comprises the following steps:
1) Putting sodium citrate in inert gas for high-temperature pyrolysis, and removing impurities from solid powder obtained by the high-temperature pyrolysis and drying to obtain the hollow porous nano carbon shell;
2) Dispersing the hollow porous nano carbon shell, nickel salt and 1,10-phenanthroline into an anhydrous solvent, uniformly stirring at room temperature, heating for reaction, and then drying to obtain powder;
3) And 3) putting the powder obtained in the step 2) into inert gas for high-temperature pyrolysis, and then removing impurities from the powder subjected to high-temperature pyrolysis and drying to obtain solid powder.
4) And (3) fully and uniformly mixing the obtained solid powder with an inorganic nitrogen source, putting the mixture into a porcelain ark for high-temperature pyrolysis, and cleaning, removing impurities and drying the solid powder subjected to high-temperature pyrolysis to obtain the Ni monatomic catalyst.
In one embodiment of the present invention, the pyrolysis temperature in step 1) is 600-1200 ℃, the pyrolysis time is 2-5h, and the pyrolysis temperature rise rate is 1-5 ℃/min.
In one embodiment of the present invention, the pyrolysis temperature in step 1) is 900 ℃, the pyrolysis time is 3 hours, and the pyrolysis temperature rise rate is 1 ℃/min.
In an embodiment of the present invention, the pyrolysis temperature in step 3) is 300-800 ℃, the pyrolysis time is 1-3h, and the pyrolysis temperature rise rate is 5-15 ℃/min.
In an embodiment of the present invention, the pyrolysis temperature in step 3) is 600 ℃, the pyrolysis time is 2 hours, and the pyrolysis temperature rise rate is 10 ℃/min.
In an embodiment of the present invention, the high-temperature pyrolysis temperature in step 4) is 500-1000 ℃, the high-temperature pyrolysis time is 0.5-2h, and the high-temperature pyrolysis temperature rise rate is 2-8 ℃/min.
In an embodiment of the present invention, the pyrolysis temperature in step 4) is 800 ℃, the pyrolysis time is 1h, and the pyrolysis temperature rise rate is 5 ℃/min.
In one embodiment of the invention, the mass ratio of the hollow porous nano carbon shell to the nickel salt to the 1,10-phenanthroline is (3-8) 1: (1-5).
In one embodiment of the invention, in the step 5), the mass ratio of the solid powder to the inorganic nitrogen source is 1 (3-15).
The Ni monatomic catalyst is applied to catalytic reduction of CO 2 To produce a CO compound.
In one embodiment of the invention, the Ni monatomic catalyst and the Nafion solution of the perfluorinated sulfonic acid resin are dispersed in absolute ethyl alcohol and fully and uniformly mixed, and then the Ni monatomic catalyst slurry is sprayed on hydrophobic carbon paper with a microporous layer to prepare the gas diffusion electrode.
Compared with the prior art, the invention has at least the following advantages:
the carbon substrate of the Ni monatomic catalyst adopts the hollow porous nano carbon shell, the carbon substrate has a macroporous structure with the diameter of 120-180nm, the porosity is high, the specific surface area is large, the connectivity of the internal pore structure is high, and the hollow porous nano carbon shell with the pore size is used as the carbon substrate, so that sufficient reaction active area can be ensured, and CO can be effectively reduced 2 Collision between molecules and the carbon substrate wall surface, thereby increasing CO 2 Effective diffusion coefficient of molecules in the catalytic layer, and finally CO on the surface of the active site is improved 2 Molecular concentration and improving catalyst activity and current density; the metal nickel is anchored on the hollow porous nano carbon shell in a monoatomic form to form a Ni monoatomic catalyst, which can effectively promote the material transmission in a catalytic layer and expand a three-phase reaction interface and is used for electrochemical CO 2 The reduction product CO has the characteristics of high catalytic activity, high CO product selectivity, good material stability and the like.
The preparation method of the Ni monatomic catalyst provided by the invention has the advantages of simple preparation method, wide raw material source and low price, and is suitable for large-scale production and industrial application.
Drawings
In order to more clearly illustrate the embodiments of the present invention, reference will now be made briefly to the embodiments or to the accompanying drawings that are needed in the description of the prior art.
FIG. 1 is a process flow diagram of a method for preparing a Ni monatomic catalyst according to the present invention;
FIG. 2 is a scanning electron microscope image of the Ni monatomic catalyst provided by the present invention;
FIG. 3 is a diagram of the distribution of elements of a high-resolution transmission electron microscope of the Ni monatomic catalyst provided by the present invention;
FIG. 4 is an electron microscope image of spherical aberration correction of Ni monatomic catalyst provided by the present invention;
FIG. 5 shows the electrocatalytic CO of the Ni monatomic catalyst provided by the invention 2 Faradaic efficiency plot of reduced CO;
FIG. 6 shows the electrocatalytic CO of the Ni monatomic catalyst provided by the invention 2 Stability test plots of reduced CO;
FIG. 7 shows electrocatalytic CO of Ni monatomic catalyst provided by the invention 2 Performance profile of reduced CO.
Detailed Description
The present invention will be further described with reference to the following drawings and examples, which are illustrative only and not intended to be limiting, and the scope of the present invention is not limited thereby.
In the following examples, the raw materials used in the present application are commercially available, unless otherwise specified.
Wherein, the citrate refers to a kind of salt which has stronger capability of chelating calcium ions at low temperature but has reduced chelating capability when the temperature is increased, and further, the citrate in the application includes but is not limited to one or a mixture of sodium citrate and potassium citrate;
the nickel salt refers to a salt containing nickel, namely a compound formed by nickel and acid radical, and the nickel salt in the application includes but is not limited to nickel acetate, nickel chloride or a mixture thereof.
The anhydrous solvent mainly has the effects of fully dissolving and dispersing the hollow porous nano carbon shell, the nickel salt, the 1,10-phenanthroline and the like, and can be used as long as the solvent capable of fully dissolving and dispersing the hollow porous nano carbon shell, the nickel salt and the 1,10-phenanthroline is adopted, and the anhydrous solvent in the application comprises but is not limited to anhydrous ethanol, anhydrous isopropanol and the like;
wherein the inorganic nitrogen source mainly serves to provide sufficient NH in the high-temperature pyrolysis process 3 That is, the inorganic nitrogen source in the present application includes, but is not limited to, urea, melamine, pure nitrogen, and the like.
[ example 1 ] preparation of Ni monatomic catalyst
Embodiment mode 1
A preparation method of a Ni monatomic catalyst comprises the following steps:
1) Grinding the sodium citrate with the crystal water to fine particles, and then drying the ground sodium citrate at 160 ℃ overnight for 24 hours to remove the crystal water;
2) Putting the sodium citrate without crystal water in inert gas argon for high-temperature pyrolysis at 600 ℃ for 5h, wherein the heating rate is 3 ℃/min, then respectively putting the powder after high-temperature pyrolysis in 1mol/L hydrochloric acid solution, absolute ethyl alcohol and deionized water to remove impurities, and filtering the impurities to obtain powder, and drying the powder overnight to obtain a hollow porous nano carbon shell;
3) Dispersing 39.6mg of hollow porous nano carbon shell, 12.4mg of nickel acetate and 18.3mg of 1, 10-phenanthroline in 2ml of absolute ethyl alcohol, fully stirring for 15min at room temperature, reacting for 4h in a water bath at 60 ℃, and then drying overnight at 80 ℃ to obtain powder;
4) Putting the dried powder into inert gas argon for pyrolysis at 300 ℃ for 3h, wherein the heating rate is 5 ℃/min, removing impurities from the powder by using hydrochloric acid and deionized water respectively, and drying overnight to obtain solid powder;
5) Fully and uniformly mixing the solid powder with the mass ratio of 1:3 and melamine, putting the mixture into a porcelain ark, pyrolyzing the mixture for 2 hours at the high temperature of 500 ℃, wherein the heating rate is 5 ℃/min, washing the solid powder with hydrochloric acid at the temperature of 80 ℃ to remove oxides, impurities and drying the solid powder overnight, thus obtaining the Ni monatomic catalyst with the aperture of 120-180 nm.
Embodiment mode 2
A preparation method of a Ni monatomic catalyst comprises the following steps:
1) Grinding the potassium citrate with the crystal water to fine particles, and then drying the ground potassium citrate at 160 ℃ overnight for 24 hours to remove the crystal water;
2) Putting the potassium citrate without crystal water in inert gas argon for high-temperature pyrolysis at 900 ℃ for 3h, wherein the heating rate is 1 ℃/min, then respectively putting the powder after high-temperature pyrolysis in 1mol/L hydrochloric acid solution, absolute ethyl alcohol and deionized water to remove impurities, and filtering the impurities to obtain powder, and drying the powder overnight to obtain a hollow porous nano carbon shell;
3) Dispersing 69.6mg of hollow porous nano carbon shell, 12.4mg of nickel chloride and 29.7mg of 1,10-phenanthroline in 2mL of anhydrous isopropanol, fully stirring for 15min at room temperature, reacting for 4h in a water bath at 60 ℃, and then drying overnight at 80 ℃ to obtain powder;
4) Putting the dried powder into inert gas argon for high-temperature pyrolysis at 600 ℃ for 2h, wherein the heating rate is 10 ℃/min, removing impurities from the powder by using hydrochloric acid and deionized water respectively, and drying overnight to obtain solid powder;
5) And (2) fully and uniformly mixing the solid powder with the mass ratio of 1.
Embodiment 3
A preparation method of a Ni monatomic catalyst comprises the following steps:
1) Grinding the sodium citrate with the crystal water to fine particles, and then drying the ground sodium citrate at 160 ℃ overnight for 24 hours to remove the crystal water;
2) Putting the sodium citrate without crystal water in an inert gas argon gas for pyrolysis at 1200 ℃ for 2h, wherein the heating rate is 3 ℃/min, then respectively putting the powder after pyrolysis in a 1mol/L hydrochloric acid solution, absolute ethyl alcohol and deionized water to remove impurities, and filtering the impurities to obtain powder, and drying the powder overnight to obtain a hollow porous nano carbon shell;
3) Dispersing 84.1mg of hollow porous carbon nano-shell, 12.4mg of nickel acetate and 51.3mg of 1, 10-phenanthroline in 2ml of absolute ethyl alcohol, fully stirring for 15min at room temperature, reacting in a water bath at 60 ℃ for 4h, and then drying at 80 ℃ overnight to obtain powder;
4) Putting the dried powder into inert gas argon for pyrolysis at 800 ℃ for 1h, wherein the heating rate is 15 ℃/min, removing impurities from the powder by using hydrochloric acid and deionized water respectively, and drying overnight to obtain solid powder;
5) And (2) fully and uniformly mixing the solid powder with the mass ratio of 1.
[ example 2 ] detection of Ni monatomic catalyst
This example will be described in detail by taking the Ni monatomic catalyst prepared in embodiment 2 of example 1 as an example:
1) Micro-morphology characteristics of Ni monatomic catalyst:
scanning an electron microscope (Hitachi-4800, japan) on the Ni monatomic catalyst prepared by the method specifically comprises the following steps: as shown in fig. 2, fig. 2 is a scanning electron microscope topography of the Ni monatomic catalyst anchored by the hollow porous nanocarbon shell, from which it can be seen that the prepared Ni monatomic catalyst material has a developed pore structure; the pore diameter of the Ni-based catalyst is 120-180nm, the integral framework is highly communicated, the porosity is extremely high and is not less than 75% according to the test result of a focused ion beam micro-tomography reconstruction technology (Helios Nanolab-650 (FEI, USA)), and the specific surface area of the Ni-based catalyst is 341.5m according to the specific surface area test (McTriStar II 3020) 2 /g。
The Ni monatomic catalyst prepared by the method is scanned by a transmission electron microscope (the model is Tecnai G2F20 microscope), the result is shown in figure 3, figure 3 is a high-resolution transmission electron microscope element distribution diagram of the Ni monatomic catalyst anchored by the hollow porous nano carbon shell, and the Ni monatomic catalyst prepared by the method has rich Ni and N, and meanwhile, the Ni is uniformly distributed on the surface of the carbon shell, and no obvious particles or agglomeration appear;
scanning a spherical aberration correction electron microscope picture (model number is JEM ARM 200F) of the Ni monatomic catalyst prepared by the method, wherein the result is shown in figure 4, the figure 4 is the spherical aberration correction electron microscope picture of the Ni monatomic catalyst anchored by the hollow porous nano carbon shell, a white bright point in the picture is Ni with atomic-level dispersion, the particle diameter of the Ni is about 0.2nm, the size of the Ni monatomic catalyst is very close to the diameter of one Ni monatomic, and the prepared material is proved to be Ni monatomic dispersion;
2) Catalytic reduction of CO by Ni monatomic catalyst 2 Faradaic efficiency plot for reducing CO compounds:
after 20mg of the Ni monatomic catalyst prepared in embodiment 2 of example 1 and 200. Mu.L of a perfluorosulfonic acid resin Nafion solution (5 wt% in mass) were dispersed in 5mL of absolute ethanol and mixed well, the Ni monatomic catalyst was preparedSpraying the reagent slurry on hydrophobic carbon paper with a microporous layer to prepare a gas diffusion electrode; the loading capacity of the Ni monatomic catalyst gas diffusion electrode is 1mg/cm through weighing and calculating the loading capacity before and after loading the catalyst 2 。
Electrochemical reduction of CO over Ni monatomic catalyst 2 And (3) testing the performance:
in a double-chamber H-type reactor, the loading of the catalyst material (Ni monatomic catalyst) on the carbon cloth electrode is 1mg/cm 2 The electrolyte is 0.1M KHCO 3 ，CO 2 The flow rate is 30sccm, and the pressure is normal temperature and normal pressure. The anode used was 1cm 2 The cathode of the platinum sheet electrode adopts a glassy carbon electrode clamp to fix a carbon cloth electrode loaded with a Ni monatomic catalyst, a silver-silver chloride electrode is used as a reference electrode, and a cation exchange membrane is used for separating a cathode chamber and an anode chamber. Electrochemical workstation (ParSTAT MC, princeton, USA) for electrochemical CO 2 Specific test for reduction. During the test, CO is continuously introduced into the electrolyte firstly 2 Removing dissolved oxygen in the electrolyte for more than 30min, and then carrying out CV cyclic activation under the potential of 0-2V vs. Ag/AgCl, wherein the sweep rate is 200mV/s, and the cycle times are 20 times, so that the working electrode reaches the optimal working state. Finally, constant potential electrolysis test is carried out in a potential range of-1.3V to-2.0V vs. Ag/AgCl, each potential is electrolyzed for 30min, gas products after electrolysis are quantitatively tested by gas chromatography, and the Faraday efficiency of each product is calculated according to current density and electrolysis time; the results are shown in FIG. 5, FIG. 5 is an electrocatalytic CO of Ni monatomic catalyst anchored by a hollow porous nanocarbon shell 2 The performance graph of the reduced CO shows that when the potential is-1.3Vvs.Ag/AgCl, the Faraday efficiency of the CO can reach 77.4 percent, and the overpotential is lower; meanwhile, along with more negative potential, the Faraday efficiency of CO is gradually increased, and the highest value of the Faraday efficiency is 96.5% when the Faraday efficiency is-1.8V.s.Ag/AgCl, so that extremely high selectivity is shown.
FIG. 6 is electrocatalytic CO of Ni monatomic catalyst anchored by hollow porous nanocarbon shells, as shown in FIG. 6 2 And (3) testing the stability of the reduced CO under the specific test conditions: in a dual-chamber H-type reactor, the catalyst material (Ni monatomic catalyst) is supported on a carbon cloth electrodeThe amount is 1mg/cm 2 The electrolyte is 0.1M KHCO 3 ，CO 2 The flow rate is 30sccm, and the pressure is normal temperature and normal pressure. The anode used was 1cm 2 The cathode of the platinum sheet electrode adopts a glassy carbon electrode clamp to fix a carbon cloth electrode loaded with a Ni monatomic catalyst, a silver-silver chloride electrode is used as a reference electrode, and a cation exchange membrane is used for separating a cathode chamber and an anode chamber. And (3) carrying out stability test through constant potential, setting the potential to be-1.8V vs. Ag/AgCl, periodically carrying out quantitative test on outlet gas by using a gas chromatograph, and calculating the Faraday efficiency. As can be seen from the figure, under the constant potential operation condition of 80 hours, the performance of the Ni monatomic catalyst is not reduced basically, the CO Faraday efficiency of more than 90 percent is still maintained after 80 hours, and the extremely high stability is displayed;
in the membrane electrode flow type reactor, the loading capacity of the catalyst material (Ni single atom catalyst) on the carbon cloth electrode is 1mg/cm 2 The cathode adopts a glassy carbon electrode clamp to fix a carbon cloth electrode loaded with a Ni monatomic catalyst, the anolyte is 1mol/L KOH solution, foamed nickel is used as the anode, an anion exchange membrane is used for separating a cathode chamber and an anode chamber, and humidified CO is directly introduced into the cathode 2 The gas participates in the reaction and runs by adopting a two-electrode system with constant current (50-200 mA/cm) 2 ) Electrochemical workstation (ParSTAT MC, princeton, USA) for electrochemical CO 2 Specific test for reduction, (cathode reaction is CO) 2 +H 2 O+2e - →CO+2OH - Competing side reaction is 2H 2 O+2e - →H 2 +2OH - ) In the testing process, the constant operation is carried out for 30min under each current, the gas product after electrolysis is quantitatively tested by using gas chromatography, and the inlet CO is controlled by a mass flowmeter 2 The flow rate is constant at 100mL/min, and after constant operation for 30min under each current, the gas collected at the outlet is injected into a gas chromatograph to obtain CO and H products 2 Carrying out quantitative test, and calculating the Faraday efficiency of each product according to the current density and the electrolysis time; the results are shown in FIG. 7, which is a graph of the electrocatalytic CO of the Ni monatomic catalyst anchored by the hollow porous nanocarbon shell in the membrane electrode flow reactor in FIG. 7 2 The performance diagram of CO reduction shows that the catalyst can reach the performance close to that of CO200mA/cm 2 And exhibits a very low cell voltage (-2.2V), with a corresponding energy efficiency (energy efficiency is the product of theoretical cell voltage and faradaic efficiency compared to the actual cell voltage) of up to 60%, exhibiting very high electrochemical performance.
The Ni monatomic catalyst provided by the application also prepares a catalyst with the pore diameter of less than 120nm and the pore diameter of more than 180nm and carries out related tests on the catalyst; it was found that when the pore diameter of the catalyst is less than 120nm, the reaction active area is too large but CO is hindered 2 Molecular transport, however, is increased when the catalyst has a pore size of greater than 180nm 2 The transport coefficient of the molecule, but the reaction active area is greatly reduced, i.e. for catalysts with pore sizes below 120nm and with pore sizes above 180nm, its CO is 2 The transfer and total reactive area of the reactor cannot be taken into consideration to reach the optimum value.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being covered by the appended claims and their equivalents.
Claims (10)
1. The Ni monatomic catalyst is characterized in that a hollow porous nano carbon shell with the aperture of 120-180nm is used as a carbon substrate, and metallic nickel is anchored on the surface of the hollow porous nano carbon shell in a monatomic form.
2. The Ni monatomic catalyst of claim 1 wherein the hollow porous nanocarbon shell has a specific surface area of 300-500m 2 /g。
3. A method for preparing the Ni monatomic catalyst according to claim 1, characterized by comprising the steps of:
1) Putting citrate in inert gas for high-temperature pyrolysis, and removing impurities from powder obtained by the high-temperature pyrolysis and drying to obtain the hollow porous nano carbon shell;
2) Dispersing the hollow porous nano carbon shell, nickel salt and 1,10-phenanthroline into an anhydrous solvent, uniformly stirring at room temperature, heating for reaction, and then drying to obtain powder;
3) Putting the powder obtained in the step 2) into inert gas for high-temperature pyrolysis, then removing impurities from the powder subjected to high-temperature pyrolysis, and drying to obtain solid powder;
4) And fully and uniformly mixing the obtained solid powder with an inorganic nitrogen source, putting the mixture into a porcelain ark for high-temperature pyrolysis, and cleaning, removing impurities and drying the solid powder subjected to high-temperature pyrolysis to obtain the Ni monatomic catalyst.
4. The method for preparing the Ni monatomic catalyst according to claim 3, wherein the pyrolysis temperature in the step 1) is 600 to 1200 ℃, the pyrolysis time is 2 to 5 hours, and the temperature rise rate of the pyrolysis is 1 to 5 ℃/min.
5. The method for preparing the Ni monatomic catalyst according to claim 3, wherein the pyrolysis temperature in the step 3) is 300 to 800 ℃, the pyrolysis time is 1 to 3 hours, and the pyrolysis temperature rise rate is 5 to 15 ℃/min.
6. The method for preparing the Ni monatomic catalyst as recited in claim 3, wherein the pyrolysis temperature in the step 4) is 500 to 1000 ℃, the pyrolysis time is 0.5 to 2 hours, and the temperature increase rate of the pyrolysis is 2 to 8 ℃/min.
7. The Ni monatomic catalyst preparation method of claim 3, wherein the mass ratio of the hollow porous nanocarbon shell, the nickel salt, and the 1,10-phenanthroline is (3-8) to 1: (1-5).
8. The method for preparing the Ni monatomic catalyst according to claim 7, wherein the mass ratio of the solid powder to the inorganic nitrogen source in the step 5) is 1 (3-15).
9. Use of the Ni monatomic catalyst according to claim 1 or 2 for the catalytic reduction of CO 2 To produce a CO compound.
10. Application of the Ni monatomic catalyst according to claim 9 to catalytic reduction of CO 2 And generating a CO compound, wherein the Ni monatomic catalyst and the Nafion solution of the perfluorinated sulfonic acid resin are dispersed in absolute ethyl alcohol and fully and uniformly mixed, and then the Ni monatomic catalyst slurry is sprayed on hydrophobic carbon paper with a microporous layer to prepare the gas diffusion electrode.
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