CN113430540A - Monoatomic catalyst, preparation method and application thereof - Google Patents
Monoatomic catalyst, preparation method and application thereof Download PDFInfo
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- CN113430540A CN113430540A CN202110710204.4A CN202110710204A CN113430540A CN 113430540 A CN113430540 A CN 113430540A CN 202110710204 A CN202110710204 A CN 202110710204A CN 113430540 A CN113430540 A CN 113430540A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- 125000004429 atom Chemical group 0.000 claims abstract description 35
- 239000011148 porous material Substances 0.000 claims abstract description 30
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 52
- 238000010438 heat treatment Methods 0.000 claims description 42
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 30
- 239000001569 carbon dioxide Substances 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 22
- 238000006722 reduction reaction Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 150000001722 carbon compounds Chemical class 0.000 claims description 13
- 238000004108 freeze drying Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- -1 nitrogen-containing compound Chemical class 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 5
- 239000011736 potassium bicarbonate Substances 0.000 claims description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 239000005539 carbonized material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 238000012546 transfer Methods 0.000 abstract description 7
- 230000001965 increasing effect Effects 0.000 abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 235000002639 sodium chloride Nutrition 0.000 description 14
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 13
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
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- 238000003917 TEM image Methods 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 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
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- 238000001075 voltammogram Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910003298 Ni-Ni Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004642 ferric ammonium citrate Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C25B1/50—Processes
-
- 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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
Abstract
The invention belongs to the technical field of catalyst preparation, and provides a monatomic catalyst, and a preparation method and application thereof. The monatomic catalyst provided by the invention comprises an ultrathin spatial three-dimensional open-pore carbon skeleton, and nitrogen atoms and metal monatomics which are anchored on the ultrathin spatial three-dimensional open-pore carbon skeleton; the nitrogen atom and the metal monoatomic atom form MNxA site structure wherein x is 3 or 4; the mass of the metal monoatomic atom is 0.5-6.76% of that of the ultrathin spatial three-dimensional open-pore carbon skeleton. The ultrathin spatial three-dimensional open-pore carbon skeleton in the monatomic catalyst can enhance mass transfer and improve the utilization rate of active sites of metal monatomic, thereby increasing the number of effective active sites and finally improving the catalytic activity of the monatomic catalyst.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a monatomic catalyst and a preparation method and application thereof.
Background
Since the first industrial revolution, fossil fuels were developed and used on a large scale to sustain rapid development of human society and economy. However, excessive consumption of fossil fuels not only poses a serious energy crisis, but also results in carbon dioxide (CO) in the earth's atmosphere2) The content increases sharply.This also leads to a number of environmental problems, such as: "greenhouse effect", ocean acidification, extreme weather, etc. Sustainable energy in nature such as solar energy, wind energy and the like can be converted into electric energy, and the electric energy drives the electrochemical electrolytic cell to convert CO into CO2And converting into other value-added high-energy chemical raw materials and fuels, such as ethanol, carbon monoxide and the like. The method can reduce the dependence of human society on fossil fuel, promote the carbon cycle of biosphere, and is a carbon dioxide recycling scheme with great prospect. However, due to the stable linear structure of carbon dioxide, the bonding energy of C ═ O is extremely high (806 kJ. mol)-1) The desire to achieve cleavage of carbon-oxygen bonds requires a high activation energy barrier, which ultimately results in a significant overpotential. At the same time, the potential at which the Hydrogen Evolution Reaction (HER) takes place is related to the CO2Reduction reaction (CO)2RR) occur very close in potential, causing a very strong competitive action. The low kinetic properties and the accompanying side reactions together hinder CO2The effective reduction of (2). Therefore, reasonably designing a high-efficiency catalyst to improve the catalytic activity and catalytic selectivity of the carbon dioxide reduction reaction is a key point for realizing carbon reduction and energy conservation. The Single-Atom catalyst (Single-Atom Catalysts) has great development prospect in the field of electrocatalytic carbon dioxide reduction. However, the metal monatomic catalyst which is successfully prepared at present is mostly loaded on bulk carbon or a two-dimensional graphene substrate which is easy to agglomerate, so that most active sites cannot contact with reactants in a catalytic process, and the catalytic activity is low.
Disclosure of Invention
In view of the above, the present invention provides a monatomic catalyst, and a preparation method and an application thereof. The monatomic catalyst provided by the invention has high catalytic activity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a monatomic catalyst, which comprises an ultrathin spatial three-dimensional open-pore carbon skeleton, nitrogen atoms and metal monatomics, wherein the nitrogen atoms and the metal monatomic atoms are anchored on the ultrathin spatial three-dimensional open-pore carbon skeleton; the nitrogen atom and the metal monoatomic atom form MNXA site structure wherein x is 3 or 4; the metal monogenThe mass of the seed is 0.5-6.76% of that of the ultrathin spatial three-dimensional open-pore carbon skeleton.
Preferably, the metal monoatomic includes Ni.
The invention also provides a preparation method of the monatomic catalyst in the technical scheme, which comprises the following steps:
mixing a template agent, a nitrogen-containing compound, an organic carbon compound, water-soluble metal salt and water, and freeze-drying to obtain a precursor;
sequentially carrying out first heat treatment and template removal on the precursor to obtain a first heat treatment material;
and carrying out second heat treatment on the carbonized material to obtain the monatomic catalyst.
Preferably, the mass ratio of the template agent to the nitrogen-containing compound to the organic carbon compound is (8-9): (1.0-1.5): (0.6-0.7).
Preferably, the freeze-drying comprises: sequentially freezing and drying; the freezing temperature is-50 ℃, and the time is 12-18 h; the drying temperature is-50 ℃, the pressure is 1-10 Pa, and the time is 48-50 h.
Preferably, the first heat treatment is carried out under a protective atmosphere; the temperature of the first heat treatment is 750-760 ℃, and the time is 2-4 h.
Preferably, the second heat treatment is carried out under a protective atmosphere; the temperature of the second heat treatment is 900-1000 ℃, and the time is 1-1.5 h.
The invention also provides the application of the monatomic catalyst in the technical scheme or the monatomic catalyst obtained by the preparation method in the technical scheme in the electrocatalytic carbon dioxide reduction reaction.
Preferably, platinum is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, a glassy carbon electrode loaded with a catalyst is used as a working electrode, a potassium bicarbonate solution is used as an electrolyte, and reduction reaction is carried out under the condition of introducing carbon dioxide;
the loading capacity of the catalyst is 0.10-0.30 mg/cm2；
The catalyst is the monatomic catalyst described in the technical scheme or the monatomic catalyst obtained by the preparation method described in the technical scheme.
Preferably, the parameters of the reduction reaction include: the temperature is 25 ℃, the pressure is 1atm, and the reduction potential is-0.6 to-1.0V.
The invention provides a monatomic catalyst, which comprises an ultrathin spatial three-dimensional open-pore carbon skeleton, nitrogen atoms and metal monatomics, wherein the nitrogen atoms and the metal monatomic atoms are anchored on the ultrathin spatial three-dimensional open-pore carbon skeleton; the nitrogen atom and the metal monoatomic atom form MNXA site structure wherein x is 3 or 4; the mass of the metal monoatomic atom is 0.5-6.76% of that of the ultrathin spatial three-dimensional open-pore carbon skeleton. The ultrathin spatial three-dimensional open-pore carbon skeleton structure in the catalyst provided by the invention can enhance mass transfer and improve the utilization rate of active sites of metal single atoms, thereby increasing the number of effective active sites and finally improving the catalytic activity of the catalyst.
The invention also provides a preparation method of the monatomic catalyst in the technical scheme, which comprises the following steps: mixing a template agent, a nitrogen-containing compound, an organic carbon compound, water-soluble metal salt and water, and freeze-drying to obtain a precursor; sequentially carrying out first heat treatment and template removal on the precursor to obtain a first heat treatment material; and carrying out second heat treatment on the first heat-treated material to obtain the monatomic catalyst. The preparation method provided by the invention realizes the uniform dispersion of the raw materials by utilizing freeze drying, and obtains a homogeneous precursor; under the action of the template agent, the organic carbon compound is converted into the ultrathin spatial three-dimensional open-pore carbon skeleton in the first heat treatment process, so that the effective active sites of the catalyst are greatly improved, and the catalytic activity of the catalyst is greatly improved. Meanwhile, the preparation method provided by the invention can realize controllable synthesis of catalysts with different metal monatomic loads by adjusting the adding amount of the water-soluble metal salt and the organic carbon compound; and by adjusting the type of the water-soluble metal salt, a plurality of different metal monatomic supported catalysts can be prepared, and the universality is strong. In addition, the preparation method provided by the invention has the advantages of wide raw material source and low cost; and the preparation process is simple and easy to operate.
The invention also provides the application of the monatomic catalyst in the technical scheme or the monatomic catalyst obtained by the preparation method in the technical scheme in the electrocatalytic carbon dioxide reaction. Because the catalyst provided by the invention provides more reaction active sites, the catalytic efficiency of the catalyst on carbon dioxide is improved.
The data of the examples show that: the catalyst provided by the invention has the carbon monoxide Faraday efficiency of 78-100%.
Drawings
FIG. 1 is a scanning electron micrograph of a catalyst obtained in example 1;
FIG. 2 is a transmission electron micrograph of the catalyst obtained in example 1;
FIG. 3 is a Fourier transform spectrum of the Ni K-edge EXAFS spectrum of the catalyst obtained in example 1;
FIG. 4 is a high angle annular dark field image-scanning transmission electron microscope image of the catalyst obtained in example 1;
FIG. 5 shows different catalysts in CO2Saturated 0.5mol/L KHCO3Linear sweep voltammograms in solution, inset is a partial magnification of linear sweep voltammograms for electrodes using different catalysts over a potential range of-0.3 to-0.7V (vs RHE);
figure 6 is a graph of faradaic efficiency of the product carbon monoxide for different catalysts at various potentials (relative to RHE);
FIG. 7 is a schematic diagram of an ultra-thin spatial three-dimensional open-pore carbon skeleton model simulating an electrocatalytic carbon dioxide reduction reaction;
FIG. 8 is a schematic diagram of a two-dimensional layered structure carbon skeleton model simulating an electrocatalytic carbon dioxide reduction reaction
Fig. 9 is a schematic diagram of a carbon skeleton model of a bulk carbon substrate structure simulating an electrocatalytic carbon dioxide reduction reaction.
Detailed Description
The invention provides a monatomic catalyst, which comprises an ultrathin spatial three-dimensional open-pore carbon skeleton, nitrogen atoms and metal monatomics, wherein the nitrogen atoms and the metal monatomic atoms are anchored on the ultrathin spatial three-dimensional open-pore carbon skeleton; the nitrogen atom and the metal monoatomic atom form MNXA site structure wherein x is 3 or 4; the mass of the metal monoatomic atom is 0.5-6.76% of that of the ultrathin spatial three-dimensional open-pore carbon skeleton.
In the present invention, MNXWherein M represents a metal single atom and N is a nitrogen atom.
In the invention, the mass of the metal monoatomic atom is 0.5-6.76% of that of the ultrathin spatial three-dimensional open-pore carbon skeleton.
In the present invention, the metal monoatomic atom preferably includes Ni.
In the invention, the mass of the nitrogen atom is preferably 9.2-12.2% of that of the ultrathin spatial three-dimensional open-pore carbon skeleton.
In the invention, element N is filled in carbon vacancy defects of the ultrathin space three-dimensional open-pore carbon skeleton to form N-C bonds with surrounding C, and metal monoatomic atoms are coordinated with the surrounding N to form MNXSite structure.
The ultrathin spatial three-dimensional open-pore carbon skeleton in the catalyst provided by the invention can enhance mass transfer and improve the utilization rate of active sites of metal single atoms, so that the number of effective active sites is increased, and the catalytic activity of the catalyst is finally improved.
The invention also provides a preparation method of the monatomic catalyst in the technical scheme, which comprises the following steps:
mixing a template agent, a nitrogen-containing compound, an organic carbon compound, water-soluble metal salt and water, and freeze-drying to obtain a precursor;
sequentially carrying out first heat treatment and template removal on the precursor to obtain a first heat treatment material;
and carrying out second heat treatment on the first heat-treated material to obtain the monatomic catalyst.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The method comprises the steps of mixing a template agent, a nitrogen-containing compound, an organic carbon compound, a water-soluble metal salt and water, and freeze-drying to obtain a precursor.
In the present invention, the template agent preferably includes one or more of sodium chloride, ammonium chloride and silicon dioxide, and more preferably sodium chloride. In the present invention, the nitrogen-containing compound preferably includes one or more of dicyandiamide, melamine and ammonia gas, and more preferably dicyandiamide. In the present invention, the organic carbon compound preferably includes one or more of glucose, melamine, cellulose and citric acid, and further preferably glucose. In the present invention, the water-soluble metal salt preferably includes one or more of nickel acetate tetrahydrate, nickel chloride and nickel nitrate, and more preferably nickel acetate tetrahydrate. In the present invention, the water is preferably deionized water.
In the present invention, the mass ratio of the template agent, the nitrogen-containing compound, the organic carbon compound, and the water-soluble metal salt is preferably (8000 to 9000): (1000-1500): (600-700): (2.7-60), and more preferably 8500: 1200: 620: (2.7-60). In the invention, the dosage ratio of the water to the organic carbon compound is preferably (60-80) mL: 0.62 g.
In the present invention, the freeze-drying preferably includes sequentially freezing and drying. In the present invention, the temperature of the freezing is preferably-50 ℃; the time is preferably 12-18 h. In the present invention, the temperature of the drying is preferably-50 ℃; the pressure is preferably 1-10 Pa; the time is preferably 48-50 h.
In the invention, freeze drying realizes the uniform dispersion of the raw materials, and a homogeneous precursor is obtained.
After the precursor is obtained, the precursor is sequentially subjected to first heat treatment and template removal to obtain a first heat treatment material.
In the present invention, the first heat treatment is preferably performed under a protective atmosphere; the protective atmosphere preferably comprises nitrogen or argon, more preferably argon. In the invention, the temperature of the first heat treatment is preferably 750-760 ℃, and the rate of raising the temperature from room temperature to the temperature of the first heat treatment is preferably 4-5 ℃/min; the time is preferably 2-4 h. In the present invention, the first heat treatment is preferably performed in a high-temperature tube furnace.
In the present invention, the organic carbon compound is in the first heat placeCoating the surface of the template agent crystal in the treatment process to form an ultrathin spatial three-dimensional open-pore carbon skeleton; nitrogen atoms generated by the decomposition of the nitrogen-containing compound are anchored on the ultrathin spatial three-dimensional open-pore carbon skeleton; metal monoatomic atoms generated by the decomposition of the water-soluble metal salt are also anchored on the ultrathin spatial three-dimensional open-pore carbon skeleton; meanwhile, the metal monoatomic atom anchored on the ultrathin spatial three-dimensional open-pore carbon skeleton and the nitrogen atom form MNxSite structure.
In the present invention, the removal template preferably includes: the resulting first heat-treated product is mixed with water. In the present invention, the water is preferably deionized water, and the amount of the water used in the present invention is not particularly limited as long as the template agent is completely dissolved. In the invention, the first heat treatment product is mixed with water, so that the template agent crystals in the first heat treatment product are dissolved, and the removal of the template agent is realized.
After the template is removed, the method preferably further comprises the steps of carrying out solid-liquid separation on the obtained feed liquid and drying the obtained solid. In the invention, the solid-liquid separation mode is preferably suction filtration; the present invention does not specifically limit the drying parameters, as long as water can be completely removed.
After the first heat treatment material is obtained, the invention carries out second heat treatment on the first heat treatment material to obtain the monatomic catalyst.
In the present invention, the second heat treatment is preferably performed under a protective atmosphere, and the protective atmosphere preferably includes nitrogen or argon, and more preferably argon. In the invention, the temperature of the second heat treatment is preferably 900-1000 ℃, and more preferably 950 ℃; the rate of raising the temperature from room temperature to the temperature of the second heat treatment is preferably 4-5 ℃/min; the time is preferably 1 to 1.5 hours.
According to the invention, the second heat treatment can reduce the oxygen content in the material subjected to the first heat treatment, and improve the crystallinity of the ultrathin spatial three-dimensional open-pore carbon skeleton, so that the conductivity is improved, and the catalytic activity is favorably improved.
The invention also provides the application of the monatomic catalyst in the technical scheme or the monatomic catalyst obtained by the preparation method in the technical scheme in the electrocatalytic carbon dioxide reduction reaction.
In the invention, the catalyst provided by the invention has excellent catalytic activity and selectivity, so that the catalyst can be used for electrocatalytic carbon dioxide reduction reaction.
In the invention, the application preferably comprises the steps of taking platinum as a counter electrode, an Ag/AgCl electrode as a reference electrode, a glassy carbon electrode loaded with a catalyst as a working electrode, and taking a potassium bicarbonate solution as an electrolyte, and carrying out a reduction reaction under the condition of introducing carbon dioxide.
In the invention, the catalyst is the monatomic catalyst described in the above technical scheme or the monatomic catalyst obtained by the preparation method described in the above technical scheme. In the invention, the loading amount of the catalyst is preferably 0.10-0.30 mg/cm2More preferably 0.28mg/cm2。
In the present invention, the concentration of the potassium bicarbonate solution is preferably 0.1 to 0.5mol/L, and more preferably 0.5 mol/L.
In the present invention, the flow rate of carbon dioxide is preferably 20 sccm.
In the present invention, the parameters of the reduction reaction include: the temperature is preferably 25 ℃, the pressure is preferably 1atm, and the reduction potential is preferably in the range of-0.6 to-1.0V.
The monatomic catalyst, the preparation method and the application thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
First, sodium chloride (8.5g), dicyanodiamide (1.2g), glucose (0.62g), and nickel acetate tetrahydrate (12mg) were dissolved in 75mL of deionized water, and frozen at-50 ℃ for 12 hours, followed by drying at-50 ℃ under 1Pa for 48 hours to obtain a precursor. Then placing the precursor in a high-temperature tube furnace, heating to 760 ℃ at a speed of 4 ℃/min under Ar atmosphere, and preserving heat for 2 h; and dispersing the first heat treatment product into deionized water, carrying out suction filtration and drying to obtain a first heat treatment material. And then placing the first heat treatment material in a high-temperature tubular furnace, heating to 900 ℃ at a speed of 4 ℃/min under Ar atmosphere, and preserving heat for 1h to obtain the nickel monatomic catalyst, which is marked as catalyst 1.
The mass of the nickel single atom in the obtained catalyst is 1.41 percent of the mass of the carbon skeleton by XPS measurement, and the mass of the nitrogen atom is 10.65 percent of the mass of the carbon skeleton.
FIG. 1 is a scanning electron micrograph of a catalyst obtained in example 1; FIG. 2 is a transmission electron micrograph of the catalyst obtained in example 1. As can be seen from fig. 1 and 2: the nickel monoatomic species is supported on an ultra-thin spatial open-porous carbon skeleton, and no macroscopic metal particles are present in the transmission electron micrograph.
FIG. 3 is a Fourier transform of the EXAFS spectrum of the Ni K-edge of the catalyst obtained in example 1. from FIG. 3, it can be seen that the catalyst has only Ni-N bonds, no Ni-Ni bonds corresponding to Ni Foil, and no NiO bonds in NiO, which together indicate that the Ni atoms in the catalyst are all in the form of single atoms.
FIG. 4 is a high angle annular dark field image-scanning transmission electron microscope image of the catalyst obtained in example 1, as can be seen from FIG. 4: the white bright spots are nickel atoms which are dispersed on the carbon skeleton in the form of single atoms, and no nickel particles are found.
Comparative example 1
Firstly, dissolving nickel acetate tetrahydrate (3mg), dicyandiamide (0.9g) and graphene oxide (100mg) in 75mL of deionized water in a certain proportion, stirring for 4 hours on a magnetic stirrer, and then placing the mixed solution in a vacuum freeze dryer for freeze-drying to obtain precursor solid powder. And then placing the precursor in a tubular furnace for heat preservation for 2h at 320 ℃ under the protection of argon flow, then placing the precursor in the tubular furnace for heat preservation for 2h at 520 ℃, and then naturally cooling to room temperature to obtain the catalyst, namely the catalyst 2.
Comparative example 2
First, a certain proportion of nickel acetate tetrahydrate (12mg), dicyandiamide (1.2g), ammonium chloride (6.0g), glucose (0.62g) was dissolved in 75mL of deionized water and stirred on a magnetic stirrer for 4 h. And then putting the mixed solution into a vacuum freeze dryer for freeze-drying to obtain precursor solid powder. And finally, under the protection of argon flow, placing the precursor in a tubular furnace at 800 ℃ for heat preservation for 3h, and then naturally cooling to room temperature to obtain the catalyst, namely the catalyst 3.
Comparative example 3
Firstly, dicyanodiamine (1.2g), sodium chloride (8.5g) and glucose (0.62g) in a certain proportion are dissolved in 75mL deionized water, and after stirring for 4 hours on a magnetic stirrer, the mixed solution is placed in a vacuum freeze dryer for freeze-drying to obtain precursor solid powder. Then the precursor is placed in a tube furnace for heat preservation for 3h at 760 ℃ under the protection of argon gas flow. After cooling to room temperature, the sodium chloride was washed out with deionized water, and the solid powder was dried and recovered. And finally, placing the washed and dried solid powder in a tubular furnace, preserving the heat for 1h under the protection of argon flow and at the temperature of 900 ℃, and naturally cooling to room temperature to obtain the catalyst, namely the catalyst 4.
Electrochemical testing
Respectively mixing 4mg of the catalyst obtained in example 1 and comparative examples 1-3 with 0.7mL of deionized water, 0.25mL of ethanol and 0.05mL of 5 wt% Nafion 117 solution to obtain a catalyst dispersion liquid; then dropwise adding the catalyst dispersion liquid onto a glassy carbon electrode (diameter of 3mm), and drying in the air to finally obtain the catalyst loading amount of 0.28mg/cm2The working electrode of (1).
The test adopts a three-electrode electrolytic cell structure, the glassy carbon electrode loaded with the catalyst is used as a working electrode, and a platinum foil (1 multiplied by 1 cm)2) As a counter electrode, an Ag/AgCl electrode (E ═ 0.204V) was used as a reference electrode; measurements were performed in a type H cell at room temperature (25 ℃) and ambient pressure using the CHI 760e electrochemical workstation.
Carbon dioxide gas flow was at a constant 20mL min throughout the test-1At a rate of 0.5mol/LKHCO3Electrolyte (CO)2Saturation, pH 7.2).
When testing the Linear Sweep Voltametry (LSV) curve, the electrochemical workstation measured at 10 mV. s-1The scan rate of (a) was used to collect data, and the scan voltage ranged from 0.2V to-1.0V, with the results shown in fig. 5. As can be seen from fig. 5: in the range of-0.3 to-1.0V (vs. RHE), with catalysisCompared with the catalyst 3, the catalyst 1 obviously shows higher current density and higher catalytic activity; as can be seen from the inset: the initial potential of the catalyst 1 is superior to that of the other three catalysts, and the dynamic performance is more excellent.
In testing the Faraday efficiency, the working electrode was kept at a constant potential for 30min, potential current data was collected using an electrochemical workstation, and the resulting gas products were detected with a Shimadzu GC-2030 gas chromatograph (Shimadzu corporation, Japan). The range of the applied voltage during the test is-0.6V to-1.0V; only CO and H in gas phase products2Was detected and no product was detected in the liquid phase, the results are shown in figure 6. As can be seen from fig. 6: the faradaic efficiency of catalyst 1 is significantly higher than the other three catalysts, indicating that catalyst 1 is more selective to carbon monoxide.
All potentials are relative to the Reversible Hydrogen Electrode (RHE), and the associated potential calculations are calculated according to the nernst equation (equation 1):
e (vs. rhe) ═ E (vs. ag/AgCl) +0.204V +0.0591 × pH formula 1.
Example 2
The differences from example 1 are: the mass of nickel acetate tetrahydrate was 3 mg. The mass of the nickel monoatomic atom in the obtained catalyst was 0.51% of the mass of the carbon skeleton.
Example 3
The differences from example 1 are: the mass of nickel acetate tetrahydrate was 6 mg. The mass of the nickel single atom in the obtained catalyst is 0.89% of the mass of the carbon skeleton.
Example 4
The differences from example 1 are: the mass of nickel acetate tetrahydrate was 24 mg. The mass of the nickel monoatomic atom in the obtained catalyst is 3.88% of the mass of the carbon skeleton.
Example 5
The differences from example 1 are: the mass of nickel acetate tetrahydrate was 48 mg. The mass of the nickel monoatomic atom in the obtained catalyst is 6.76% of the mass of the carbon skeleton.
Comparative example 4
The differences from example 1 are: 12mg of nickel acetate tetrahydrate was replaced by 10mg of cobalt acetate tetrahydrate. The mass of the cobalt single atom in the obtained catalyst was 1.52% of the mass of the carbon skeleton.
Comparative example 5
The differences from example 1 are: 12mg of nickel acetate tetrahydrate was replaced by 10.6mg of ferric ammonium citrate. The mass of the iron single atom in the obtained catalyst is 1.83 percent of the mass of the carbon skeleton.
Comparative example 6
The differences from example 1 are: 12mg of nickel acetate tetrahydrate was replaced with 5.4mg of ammonium chloroplatinate. The mass of platinum monoatomic atoms in the obtained catalyst was 1.92% of the mass of the carbon skeleton.
Comparative example 7
The differences from example 1 are: 12mg of nickel acetate tetrahydrate was replaced by 9.4mg of copper acetate monohydrate. The mass of copper single atom in the obtained catalyst is 1.48% of the mass of the carbon skeleton.
The electrochemical performance of the catalysts obtained in examples 1 to 5 and comparative examples 4 to 7 was tested by the above electrochemical test method, and the results are shown in table 1.
TABLE 1 results of electrochemical Performance test of catalysts obtained in examples 1 to 5 and comparative examples 4 to 7
As can be seen from table 1: the current density of-1.0V shows the mass transfer effect and catalytic activity of metal single atoms in the catalyst, and the current density of-1.0V of the catalyst obtained in example 1 is 75mA/cm2The fact shows that the ultrathin spatial three-dimensional open-pore carbon skeleton in the catalyst enhances the mass transfer effect of metal single atoms, so that the catalytic activity of the catalyst is increased; in examples 2 and 3, however, the low content of the monoatomic atom resulted in a current density of 34mA/cm at-1.0V2Thereby making the mass transfer enhancing effect insignificant; but the faradaic carbon monoxide efficiency of the final catalyst was 90% probably due to the high availability of active sites.
A model that a carbon framework is an ultrathin spatial three-dimensional open-pore carbon framework, a two-dimensional layered structure and a block-shaped carbon substrate structure is constructed, and the mass transfer and active site utilization rate of the three carbon frameworks in the electrocatalytic carbon dioxide reduction reaction process are simulated by using a COMSOLULTIPHIS fine-element-based solution, and the result is shown in FIGS. 7-9.
As can be seen from fig. 7: the diffusion time was changed from 0 ms to 24ms (FIGS. a-i), and it can be clearly seen that CO is present2Diffuse rapidly throughout the ultra-thin spatial open-porous carbon skeleton structure and stabilize very quickly (within 12 ms) at the carbon skeleton-electrolyte interface.
As can be seen from fig. 8: the diffusion time was changed from 0 ms to 24ms (figures a-i), the diffusion of the reactants was severely slowed down due to the obstruction of the carbon skeleton layer; even with an increased simulation duration (24 ms), the reactant can only be utilized in the region close to the outer layer of the carbon skeleton having a 2D layered structure.
As can be seen from fig. 9: diffusion time changed from 0 ms to 24ms (fig. a-i); similar to the two-dimensional layered structure, the diffusion of the reactants is severely impeded by the layer of the bulk carbon skeleton within the aggregated bulk structure; even if the simulation duration (time ═ 24ms) is increased, the reactant can be utilized only at the outermost layer of the carbon skeleton having an agglomerated bulk structure.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A monatomic catalyst comprising an ultrathin spatially-stereo open-pore carbon skeleton, nitrogen atoms and metal monatomics anchored to the ultrathin spatially-stereo open-pore carbon skeleton; the nitrogen atom and the metal monoatomic atom form MNXA site structure wherein x is 3 or 4; the mass of the metal monoatomic atom is 0.5-6.76% of that of the ultrathin spatial three-dimensional open-pore carbon skeleton.
2. The monatomic catalyst of claim 1 wherein said metal monatomic comprises Ni.
3. A method of preparing the monatomic catalyst of claim 1, comprising the steps of:
mixing a template agent, a nitrogen-containing compound, an organic carbon compound, water-soluble metal salt and water, and freeze-drying to obtain a precursor;
sequentially carrying out first heat treatment and template removal on the precursor to obtain a first heat treatment material;
and carrying out second heat treatment on the carbonized material to obtain the monatomic catalyst.
4. The preparation method according to claim 3, wherein the mass ratio of the template agent to the nitrogen-containing compound to the organic carbon compound is (8-9): (1.0-1.5): (0.6-0.7).
5. The method of claim 3, wherein the freeze-drying comprises: sequentially freezing and drying; the freezing temperature is-50 ℃, and the time is 12-18 h; the drying temperature is-50 ℃, the pressure is 1-10 Pa, and the time is 48-50 h.
6. The production method according to claim 3, wherein the first heat treatment is performed under a protective atmosphere; the temperature of the first heat treatment is 750-760 ℃, and the time is 2-4 h.
7. The production method according to claim 3, wherein the second heat treatment is performed under a protective atmosphere; the temperature of the second heat treatment is 900-1000 ℃, and the time is 1-1.5 h.
8. Use of the monatomic catalyst according to any one of claims 1 to 2 or the monatomic catalyst obtained by the production method according to any one of claims 3 to 7 in an electrocatalytic carbon dioxide reduction reaction.
9. The application of the catalyst as claimed in claim 8, wherein platinum is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, a glassy carbon electrode loaded with the catalyst is used as a working electrode, a potassium bicarbonate solution is used as an electrolyte, and reduction reaction is carried out under the condition of introducing carbon dioxide;
the loading capacity of the catalyst is 0.10-0.30 mg/cm2；
The catalyst is the monatomic catalyst described in any one of claims 1 to 2 or the monatomic catalyst obtained by the production method described in any one of claims 3 to 7.
10. Use according to claim 9, wherein the parameters of the reduction reaction comprise: the temperature is 25 ℃, the pressure is 1atm, and the reduction potential is-0.6 to-1.0V.
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