CN113976121B - Method for preparing electrocatalytic material by ion implantation and related application - Google Patents
Method for preparing electrocatalytic material by ion implantation and related application Download PDFInfo
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- CN113976121B CN113976121B CN202010651097.8A CN202010651097A CN113976121B CN 113976121 B CN113976121 B CN 113976121B CN 202010651097 A CN202010651097 A CN 202010651097A CN 113976121 B CN113976121 B CN 113976121B
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- 238000000034 method Methods 0.000 title claims abstract description 20
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- 230000003197 catalytic effect Effects 0.000 claims abstract description 73
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
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- -1 argon ion Chemical class 0.000 description 2
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- 229910017052 cobalt Inorganic materials 0.000 description 2
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- 239000003446 ligand Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
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- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
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- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- B01J35/33—
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- B01J35/394—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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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
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
A method and related applications for preparing an electrocatalytic material by ion implantation, the electrocatalytic material comprising a substrate and an electrocatalyst; the substrate surface layer is a catalytic layer, and the electrocatalyst is located in the catalytic layer and is dispersed in an atomic scale. The material can be applied to various electrocatalytic reactions, and can keep excellent activity and stability in long-term catalytic reactions.
Description
Technical Field
The application relates to a method for preparing an electrocatalytic material by ion implantation and related applications, and belongs to the technical field of preparation of catalytic materials and clean energy.
Background
In the modern chemical industry, about more than 90% of reactions require the use of catalysts, such as petrochemical, biochemical, environmental protection, etc. In the catalytic process, only the surface of the catalyst in contact with the reactants can exhibit catalytic activity, and sites inside the catalyst are wasted, so that the size of the catalyst is reduced and the exposed surface area of the catalyst is increased, which is one of important methods for improving catalytic efficiency. When this reduction is exerted to the utmost, it is to achieve a single dispersion of the catalytically active sites, i.e. an atom dispersed catalyst.
To date, there have been many reports demonstrating that when the catalyst size is reduced to the atomic level, it has higher activity than metal nanoclusters and nanoparticles. Metals such as platinum, iridium and gold are supported on oxides such as iron oxide, aluminum oxide and cerium oxide in a dispersed manner to prepare monoatomic catalysts, and these catalysts show very excellent catalytic activity in water gas shift (J.Am.chem.Soc.2013,135,15314-15317), nitro hydrogenation (Nature Communications 5,5634(2014)), CO oxidation (Nature Chemistry 3, 634-641 (2011)), and the like. However, in the preparation process of the catalysts, complex impregnation reaction and subsequent high-temperature heat treatment are often required, the preparation process is complex, the preparation methods only aim at some special carriers and atom dispersion, and the preparation methods have no universality; and the method can not realize highly ordered regulation and control preparation of the content of atomic dispersion, doping depth and the like. For example, in patent CN 109012732A and patent CN 109967113 a, when preparing the atomic dispersion catalyst, a large amount of organic substances and ligands are used, which causes environmental pollution and other problems, and large-scale preparation and application are difficult to achieve.
Disclosure of Invention
According to a first aspect of the present application, there is provided an electrocatalytic material comprising a substrate and an electrocatalyst; the surface layer of the substrate is a catalytic layer, and the electrocatalyst is positioned in the catalytic layer and is dispersed in an atomic level. The material can be applied to various electrocatalytic reactions, and can keep excellent activity and stability in long-term catalytic reactions.
In the present application, the atomic-level dispersion means that the electrocatalyst is dispersed in the catalytic layer, particles or clusters are not formed on the surface of the catalytic layer, and the electrocatalyst does not act with the substrate to form a periodic new phase or independently form a new phase inside the catalytic layer.
Optionally, the thickness of the catalytic layer is 0.05-0.5 μm; preferably 0.15 to 0.35 μm;
optionally, the lower limit of the thickness of the catalytic layer is selected from 0.05 μm, 0.06 μm, 0.07 μm, 0.08 μm, 0.09 μm, 0.10 μm, 0.11 μm, 0.12 μm, 0.13 μm, 0.14 μm, 0.15 μm, 0.16 μm, 0.17 μm, 0.18 μm, 0.19 μm, 0.20 μm, 0.21 μm, 0.22 μm, 0.23 μm, 0.24 μm, 0.25 μm, 0.26 μm, 0.27 μm, 0.28 μm, 0.29 μm, 0.30 μm, 0.31 μm, 0.32 μm, 0.33 μm, 0.34 μm, 0.35 μm, 0.36 μm, 0.37 μm, 0.38 μm, 0.39 μm, 0.40 μm, 0.43 μm, 0.46 μm, 0.48 μm, 0.47 μm, 0.48 μm, or 0.48 μm; the upper limit is selected from 0.06 μm, 0.07 μm, 0.08 μm, 0.09 μm, 0.10 μm, 0.11 μm, 0.12 μm, 0.13 μm, 0.14 μm, 0.15 μm, 0.16 μm, 0.17 μm, 0.18 μm, 0.19 μm, 0.20 μm, 0.21 μm, 0.22 μm, 0.23 μm, 0.24 μm, 0.25 μm, 0.26 μm, 0.27 μm, 0.28 μm, 0.29 μm, 0.30 μm, 0.31 μm, 0.32 μm, 0.33 μm, 0.34 μm, 0.35 μm, 0.36 μm, 0.37 μm, 0.38 μm, 0.39 μm, 0.40 μm, 0.41 μm, 0.42 μm, 0.34 μm, 0.35 μm, 0.36 μm, 0.37 μm, 0.38 μm, 0.39 μm, 0.48 μm, or 49 μm.
The content of the electrocatalyst is distributed in a quasi-normal manner from the surface to the inside in the thickness direction of the catalytic layer.
In the present application, the normal distribution is a trend of increasing first and then decreasing.
Optionally, the mass content of the electrocatalyst in the catalytic layer is 0.05-5 wt%. In the present application, the mass content of the electrocatalyst in the catalytic layer is 100% of the total mass of electrocatalyst in the catalytic layer/total mass of electrocatalytic layer.
Optionally, the electrocatalyst is present in the catalytic layer at a mass concentration having a lower limit selected from 0.05 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 2.6 wt%, 3 wt%, 3.5 wt%, 4 wt%, or 4.5 wt%; an upper limit selected from 0.05 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 2.6 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%;
preferably, the mass content of the electrocatalyst reaches the maximum in the thickness of 0.07-0.28 mu m on the surface of the catalytic layer, and is 1.0-3.5 wt%.
Optionally, the electrocatalyst is a metallic element;
the metal element is selected from at least one of iron, cobalt, nickel, manganese, vanadium, chromium, copper, molybdenum, tungsten, platinum, iridium, ruthenium, cerium and lanthanum;
the metal element is different from the metal element contained in the substrate;
in the present application, the substrate serves to stabilize the injected electrocatalyst, acting as a support; the substrate may or may not have electrocatalytic properties.
The substrate is a pure metal substrate or an alloy substrate;
the substrate is selected from at least one of a plate-shaped structure, a block-shaped structure, a foam structure, a net-shaped structure and a powder-shaped structure; preferably a plate-like, foam structure or a net-like structure;
in an alternative embodiment, the substrate is selected from at least one of copper foam, nickel foam, iron foam, titanium foam, nickel mesh, wire mesh, titanium mesh, nickel powder, and iron powder.
The metal element in the pure metal substrate is selected from one of nickel, iron, titanium and copper;
the alloy substrate is selected from at least one of nickel-iron alloy, nickel-aluminum alloy, nickel-chromium alloy and iron-chromium alloy.
In one embodiment, the invention provides an electrocatalytic material containing an atom dispersion catalyst layer, which comprises a substrate material and the atom dispersion catalyst layer, wherein the surface layer material containing the atom dispersion is a catalytic active layer, and the substrate material provides a guest for stabilizing the atom dispersion and provides a support for the catalyst layer.
In a second aspect of the present application, there is provided a method for preparing an electrocatalytic material as described in any one of the above, wherein the method for preparing the atomically dispersed catalytic material is extremely limited by the type of the electrocatalytic agent and the base material, and has very wide universality; in addition, the preparation method has the advantages of simple process, low preparation cost and environmental friendliness, can realize accurate control on the catalyst layer, and has very great application potential.
The preparation method of the electrocatalytic material comprises the following steps:
and introducing an electrocatalyst into the surface layer of the substrate through ion implantation to form a catalytic layer with the electrocatalyst dispersed at an atomic level, so as to obtain the electrocatalytic material.
In the present application, the ion implantation does not cause significant changes to the topography of the substrate.
Optionally, pre-treating the substrate prior to ion implantation;
the pretreatment is at least one selected from cleaning, oxidation, reduction, nitridation, vulcanization, etching, impact and cutting.
Optionally, the specific conditions of the cleaning include:
and cleaning the substrate by using a solvent, wherein the solvent is selected from at least one of acetone, ethanol and water.
Optionally, specific conditions of the oxidation include:
in an oxygen-containing atmosphere;
the oxidation temperature is 100-500 ℃;
the oxidation time is 0.5-3 h.
Optionally, the specific conditions of the reduction include:
under an atmosphere containing hydrogen;
the reduction temperature is 200-600 ℃;
the reduction time is 0.5-6 h.
Optionally, specific conditions of the nitridation reaction include:
under the atmosphere containing ammonia gas;
the nitriding temperature is 300-600 ℃;
the nitriding time is 0.5-6 h.
Alternatively, the specific conditions of the sulfurization reaction include:
under an atmosphere containing hydrogen sulfide gas;
the vulcanization temperature is 300-600 ℃;
the vulcanization time is 0.5-6 h.
Herein, the oxygen-containing atmosphere comprises oxygen, air or a mixture of oxygen with nitrogen and/or an inert gas;
the hydrogen-containing atmosphere is a mixture of hydrogen and nitrogen and/or inert gas;
the ammonia-containing atmosphere is a mixture of ammonia and nitrogen and/or inert gas;
the hydrogen sulfide-containing atmosphere is a mixture of hydrogen sulfide and nitrogen and/or an inert gas.
By pretreating the substrate, the activity and stability of the catalytic layer formed after ion implantation can be increased.
Optionally, specific conditions of the ion implantation include:
vacuum degree 1 x 10 -4 ～5*10 -3 Pa；
The accelerating voltage is 10-100 kV;
ion implantation agentThe amount is 1 x 10 14 ～1*10 17 ions/cm 2 ；
The arc current is 5-200A;
the time is 1-600 min.
Optionally, the thickness of the catalytic layer is 0.05-0.5 μm; preferably 0.15 to 0.35 μm;
optionally, the lower limit of the thickness of the catalytic layer is selected from 0.05 μm, 0.06 μm, 0.07 μm, 0.08 μm, 0.09 μm, 0.10 μm, 0.11 μm, 0.12 μm, 0.13 μm, 0.14 μm, 0.15 μm, 0.16 μm, 0.17 μm, 0.18 μm, 0.19 μm, 0.20 μm, 0.21 μm, 0.22 μm, 0.23 μm, 0.24 μm, 0.25 μm, 0.26 μm, 0.27 μm, 0.28 μm, 0.29 μm, 0.30 μm, 0.31 μm, 0.32 μm, 0.33 μm, 0.34 μm, 0.35 μm, 0.36 μm, 0.37 μm, 0.38 μm, 0.39 μm, 0.40 μm, 0.43 μm, 0.46 μm, 0.48 μm, 0.47 μm, 0.48 μm, or 0.48 μm; the upper limit is selected from 0.06 μm, 0.07 μm, 0.08 μm, 0.09 μm, 0.10 μm, 0.11 μm, 0.12 μm, 0.13 μm, 0.14 μm, 0.15 μm, 0.16 μm, 0.17 μm, 0.18 μm, 0.19 μm, 0.20 μm, 0.21 μm, 0.22 μm, 0.23 μm, 0.24 μm, 0.25 μm, 0.26 μm, 0.27 μm, 0.28 μm, 0.29 μm, 0.30 μm, 0.31 μm, 0.32 μm, 0.33 μm, 0.34 μm, 0.35 μm, 0.36 μm, 0.37 μm, 0.38 μm, 0.39 μm, 0.40 μm, 0.41 μm, 0.42 μm, 0.34 μm, 0.35 μm, 0.36 μm, 0.37 μm, 0.38 μm, 0.39 μm, 0.48 μm, or 49 μm.
Along the thickness direction of the catalyst layer, from the surface layer to the inside, the content of the electrocatalyst is in a quasi-normal distribution which increases and then decreases.
Optionally, the mass content of the electrocatalyst in the catalyst layer is 0.05-5 wt%.
Optionally, the lower limit of the mass content of the electrocatalyst in the catalytic layer is selected from 0.05 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 2.6 wt%, 3 wt%, 3.5 wt%, 4 wt% or 4.5 wt%; the upper limit is selected from 0.05 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 2.6 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%;
preferably, the mass content of the electrocatalyst reaches the maximum in the thickness of 0.07-0.28 mu m on the surface of the catalytic layer, and is 1.0-3.5 wt%.
Optionally, the electrocatalyst is a metal element;
the metal element is selected from at least one of transition metal or rare earth element; the metal element is different from the metal element contained in the substrate;
wherein the transition metal element is at least one of iron, cobalt, nickel, manganese, vanadium, chromium, copper, molybdenum, tungsten, platinum, iridium and ruthenium, and the rare earth element is cerium and lanthanum;
the substrate is a pure metal substrate or an alloy substrate;
the substrate is selected from at least one of a plate-shaped structure, a block-shaped structure, a foam structure, a net-shaped structure and a powder-shaped structure;
the metal element in the pure metal substrate is selected from one of nickel, iron, titanium and copper;
the alloy substrate is selected from at least one of ferronickel alloy, nickel-aluminum alloy, nickel-chromium alloy and iron-chromium alloy.
In a third aspect of the present application, there is provided a use of at least one of the electrocatalytic materials described in any one of the above and the electrocatalytic materials prepared by the preparation method described in any one of the above in the field of electrocatalysis.
Optionally, the electrocatalytic material of any one of the above items and the electrocatalytic material prepared by the preparation method of any one of the above items are applied to alkaline electrolyzed water hydrogen evolution/oxygen evolution reaction, acidic electrolyzed water hydrogen evolution/oxygen evolution reaction, carbon dioxide reduction reaction, nitrogen fixation reaction, and oxygen reduction reaction.
According to the application of the provided electrocatalytic material containing the atomic dispersion catalytic layer, when the material is used as different electrocatalytic reaction electrodes, the matched appropriate electrocatalytic species and substrate material species which are dispersed in the catalytic layer in an atomic level can be selected according to the reaction species.
Optionally, the electrocatalytic material is subjected to an activation treatment before use; the activation treatment includes chemical activation and/or electrochemical activation.
In the application, the activity and the stability of the catalytic layer formed after ions are implanted can be improved by activating the electrocatalytic material.
Optionally, the chemical activation is selected from at least one of a soaking activation, a pickling activation, an oxidation activation, a reduction activation.
Optionally, the electrochemical activation is selected from at least one of potentiostatic activation, cyclic voltammetric activation, potentiometric step activation;
optionally, the chemical activation specifically comprises:
the acid washing activation is to immerse the electrocatalytic material in an acid solution for 0.5 to 12 hours, wherein the acid solution is an aqueous solution of sulfuric acid, hydrochloric acid and nitric acid, and the concentration of the acid solution is 0.01 to 6M;
the oxidation activation is to activate the electrocatalytic material in an oxygen-containing atmosphere, wherein the activation temperature is 100-500 ℃, and the oxidation time is 0.5-6 hours;
the reduction activation is to activate the electrocatalytic material in an atmosphere containing hydrogen, wherein the activation temperature is 200-600 ℃, and the reduction time is 0.5-6 h.
Optionally, the electrochemical activation specifically comprises:
the constant potential activation is that the electrocatalytic material is put into a test solution and is subjected to constant potential treatment for 0.5-24 hours at any potential within-1.5-2V;
the cyclic voltammetry activation is that the electrocatalytic material is put into a test solution, and is activated for 100-300 circles within the potential range of 0-1.6V at the scanning speed of 100 mV/s;
the potential step activation is that the electrocatalytic material is put into a test solution, and the step constant potential is processed for 0.5-24 hours within any potential range of-1.5-2V.
In the present application, the test solution is selected from the group of electrolytes used in electrochemical tests, including but not limited to potassium hydroxide (KOH) solution, sodium hydroxide (NaOH) solution, sulfuric acid (H) 2 SO 4 ) Solution, perchloric acid (HClO) 4 ) Solution, sodium carbonate (NaCO) 3 ) At least one of the solutions.
The beneficial effect that this application can produce includes:
(1) the invention can realize the preparation of the catalyst layer containing the electro-catalyst dispersed at atomic level on various metal substrates by an ion implantation method. The preparation method is extremely limited by the types of the substrate material and the electrocatalyst, has very wide universality and has very good application and research significance.
(2) Compared with the existing preparation method of the catalytic material containing the atomic-scale dispersed catalyst, the preparation method provided by the invention has the advantages of simple process, low preparation cost and convenience for scale-up preparation; in the preparation process, a large amount of organic matters and ligand materials are not needed, so that the preparation method is environment-friendly, the preparation loss is less, and the material utilization rate is high; in addition, the method can realize the accurate control of the atom dispersion catalyst layer, including the atom content, the doping depth and the like in the catalyst layer.
(3) The electrocatalytic material containing the atomic-level dispersed catalytic layer can be applied to various electrocatalytic reactions, and can be applied to various electrocatalytic reaction systems through reasonable selection and matching of the type of the electrocatalysts in the atomic-level dispersed catalytic layer and the substrate material, and the electrocatalytic material can show excellent catalytic activity and stability; therefore, the preparation method and the material provided by the invention have very large application potential.
Drawings
FIG. 1 is a scanning electron micrograph of sample S-1# in example 1.
FIG. 2 is a graph showing the electron spectrum EDX detection of the sample S-1# in example 1 for the element content.
FIG. 3 is an X-ray diffraction (XRD) pattern of sample S-1# in example 1.
FIG. 4 is a spectrum of XPS Fe2p as an iron element in the catalytic layer of sample S-1# in example 1.
FIG. 5 is a XPS Ni2p spectrum of the nickel element in the catalytic layer of sample S-1# in example 1.
FIG. 6 is a graph showing the variation of the content of elements in the catalytic layer with depth of sample S-1# in example 1.
FIG. 7 is a graph showing the performance of oxygen evolution test under three-electrode conditions for the sample S-1# in example 1 and the comparative example D-1 #.
FIG. 8 is a graph showing hydrogen evolution test performance under three-electrode conditions for the sample S-1# in example 1 and the comparative example D-1 #.
FIG. 9 is a graph showing the stability test curves of the sample S-2# in example 2 and the sample S-1# in example 1 under the three-electrode condition.
Detailed Description
The invention will now be further described by way of specific examples, it being emphasized that in applications where the invention provides an electrocatalytic material comprising an atomically dispersed catalytic layer, the material can be used in a variety of electrocatalytic reaction electrodes, and the following examples are given only by way of example of the use of the material as an electrolytic water electrode. The following examples are provided by way of illustration only and not by way of limitation. Unless otherwise stated, the raw materials in the examples are all purchased commercially and used directly without special treatment; the test instrument uses manufacturer recommended parameters.
In the examples, a three-electrode test was performed using a Garmy model INTERFACE 5000 electrochemical workstation.
In the examples, the morphology and surface elemental analysis of the samples were determined using a Quanta 200FEG scanning electron microscope with energy spectroscopy.
In the examples, the X-ray diffraction (XRD) patterns of the samples were measured using a Rigaku model D/Max-2500X-ray diffractometer using Cu Ka radiation
In the examples, XPS analysis of samples was determined using a VG ESCALAB MK2 type X-ray spectrometer;
in the examples, the ion implantation was performed using a high-energy metal ion implanter (HEMII-80) available from hong Kong plasma technology, Inc.
Comparative example 1:
an electrocatalytic material is provided, which is a nickel metal material and is a plate-shaped structural material with the thickness of 10 x 5 x 1mm, and the comparative example is named as D-1 #.
Example 1:
the embodiment provides an electrocatalytic material, wherein a substrate material selected for the electrocatalytic material is a nickel metal substrate plate-shaped structure (i.e., the electrocatalytic material in comparative example 1, hereinafter referred to as a nickel substrate for short), and a selected electrocatalyst is metallic iron. The preparation method of the material specifically comprises the following steps:
(1) cleaning a nickel substrate:
cleaning a nickel substrate in acetone, ethanol and water in sequence to remove oil stains on the surface, and naturally airing the cleaned nickel substrate;
(2) preparing a catalyst layer by ion implantation:
performing iron ion implantation on the cleaned nickel substrate to obtain an electrocatalytic material containing iron elements dispersed at atomic level in the surface layer (catalytic layer), and performing single-side implantation with the implantation vacuum degree of 1 × 10 -3 Pa, accelerating voltage of 60kV, arc current of 100A, and implanted ion dose of 5 × 10 16 ions/cm 2 The injection time is 350 min.
And (3) performing electrode activation on the prepared electrocatalytic material:
chemically activating the electrocatalytic material (hereinafter referred to as electrode) obtained in the step (2), which specifically comprises the following steps: and (4) immersing the electrode into 0.5M sulfuric acid solution, taking out after half an hour, and washing to be clean, wherein the name of the electrode is sample S-1 #.
And (3) carrying out morphology characterization on the sample S-1 #:
and (3) performing morphology characterization on the sample S-1# by using a scanning electron microscope, wherein the result is shown in figure 1, and the element composition in the electrode is determined by using an electron energy spectrum EDX, and the result is shown in figure 2.
The results show that: in sample S-1#, the introduction of the iron element of the electrocatalyst has no obvious change to the appearance of the substrate material, and all the injected elements enter the inside of the substrate, and particles and clusters are not formed on the surface of the substrate. Because the introduced iron element is in an atom dispersion form in the catalytic layer and the content is very low, the existence of iron cannot be detected in the EDX;
the catalyst layer containing the electrocatalyst iron was characterized (XRD) with an X-ray diffractometer, and the results are shown in fig. 3, which shows that the injected sample only shows the peak of the nickel substrate, indicating that the injected iron element does not react with the substrate to form a new phase, nor does it form a new phase alone.
The iron element and the nickel element in the catalytic layer of sample S-1# were subjected to element XPS characterization, and the results are shown in fig. 4 and 5, where the presence of the iron element and the nickel element was detected in the catalytic layer; and from the XPS atlas analysis of the iron element, compared with a single iron compound in the data, the 2p peak of the Fe element in the iron-containing species in the sample shifts to high binding energy, which indicates that strong interaction exists between iron and nickel, and the relatively strong electron-withdrawing action of nickel enables the iron to present higher valence state and binding energy, and the injected iron element does not form a new phase independently in the substrate; in addition, it is judged from the XPS signal of the nickel element that the chemical environment of the bulk nickel species of the substrate is not significantly changed. According to the EDX, XPS and XRD results of the samples and the principle of the ion implantation method, the content of the introduced iron element in the catalyst layer, particularly the surface layer where the contact solution participates in the catalytic reaction, is extremely low, a new phase is not formed independently, and the new phase exists in an atomic level dispersion form.
Stripping a sample S-1# layer by using XPS (X-ray diffraction) and an argon ion sputtering gun, so as to obtain the component information of the sample in the depth direction, wherein the change condition of the content of iron elements in a plane with different depths from the surface is given in Table 1:
table 1: XPS surface test depth and iron element content table of sample S-1#
Wherein, the content of the iron element is equal to the mass of the iron element in the catalytic layer at any depth/the mass of the total elements in the catalytic layer at the depth is 100 percent.
FIG. 6 shows the curve of the content of iron element in sample S-1# as a function of relative depth, from which the content of iron element in the catalytic layer shows a trend of increasing first and then decreasing in a near-class normal distribution as a function of depth; in the application, the catalytic layer is an outer surface layer of a substrate material containing iron element, the thickness of the catalytic layer of the sample S-1# is 0.35 μm, and the mass content of the iron element in the catalytic layer is 0.05-2.63 wt%.
The sample S-1# was characterized:
in a three-electrode system, a sample S-1# is used as a working electrode, mercury/mercury oxide is used as a reference electrode, a platinum sheet is used as a counter electrode, potassium hydroxide (KOH) with the concentration of 1M is used as electrolyte, the electrochemical activity of the electrode used as an oxygen evolution electrode is tested by a cyclic voltammetry method at the scanning speed of 20mV/S, and the ohmic compensation is 90%. Under the same conditions, the electrochemical activity of the electrode as an oxygen evolution electrode was tested by using D-1# provided in the comparative example as a working electrode; as a result, as shown in fig. 7 and table 2, it was found that the electrocatalytic oxygen evolution activity of sample S-1# was significantly improved after the surface layer was introduced with the atomic-level dispersed iron element to form the catalytic layer.
In a three-electrode system, a sample S-1# is used as a working electrode, mercury/mercury oxide is used as a reference electrode, a graphite sheet is used as a counter electrode, potassium hydroxide (KOH) with the concentration of 1M is used as an electrolyte, the electrochemical activity of the electrode serving as a hydrogen evolution electrode is tested by a linear scanning method at the scanning speed of 5mV/S, and the ohmic compensation is 90%. Under the same conditions, the electrochemical activity of the electrode as a hydrogen evolution electrode under alkaline conditions was tested with the D-1# provided in the comparative example as a working electrode; as a result, as shown in fig. 8, it was found that the electrocatalytic hydrogen evolution activity of sample S-1# was significantly improved after the surface layer was introduced with the atomic-scale dispersed iron element to form the catalytic layer.
Example 2:
the embodiment provides an electrocatalytic material, wherein a substrate material selected for the electrocatalytic material is a nickel metal substrate plate-shaped structure (i.e., the electrocatalytic material in comparative example 1, hereinafter referred to as a nickel substrate for short), and a selected electrocatalyst is metallic iron. The preparation method of the material specifically comprises the following steps:
(1) reduction pretreatment of a nickel substrate:
reducing the nickel substrate for 2 hours at the high temperature of 450 ℃ in a mixed atmosphere of hydrogen and nitrogen containing 5 vol.% of hydrogen, and naturally cooling to obtain a nickel substrate with a pretreated surface;
(2) preparing a catalyst layer by ion implantation:
injecting iron ions into the nickel substrate with the surface pretreated to obtain the electrocatalytic material containing the iron element dispersed in atomic scale in the surface layer, and adopting a single-layer materialSurface implantation with vacuum degree of 1 × 10 -3 Pa, accelerating voltage of 20kV, arc current of 30A, and implanted ion dose of 5 × 10 15 ions/cm 2 The injection time is 150 min.
The electrocatalytic material was named sample # S-2.
And (3) carrying out morphology characterization on the sample S-2 #:
the characterization method is the same as that of the embodiment 1, the appearance of the sample S-2# is similar to that of the sample S-1#, the iron element is distributed in the catalytic layer in an atomic scale mode, the thickness of the catalytic layer of the sample S-2# is 0.2 mu m, and the mass content of the iron element in the catalytic layer of the sample S-2# is 0.1-1.2 wt%.
The sample S-2# was subjected to performance characterization:
in the three-electrode system, the sample S-2# was used as the working electrode, and other test conditions were the same as in example 1, the electrochemical activity of the electrode as an oxygen evolution electrode under alkaline conditions was tested, and the test results are shown in table 2, and it can be seen that, in comparison with the sample S-1#, the sample activity can be improved by the method of pretreating the substrate material even if the sample is activated without ion implantation.
In a three-electrode system, a sample S-2# is taken as a working electrode, other test conditions are the same as those in example 1, the electrochemical activity of the electrode as a hydrogen evolution electrode under an alkaline condition is tested, and as a result, similar to example 1, after a catalyst layer is formed by introducing an iron element dispersed at an atomic level into a surface layer, the electrocatalytic hydrogen evolution activity of the sample S-2# is obviously improved.
FIG. 9 shows a comparison of the stability test for sample S-1# and sample S-2#, the test method comprising:
the same as the oxygen evolution activity device tested under the three-electrode condition, the testing method is a constant voltage test, and the catalytic stability of the sample is tested under the constant potential of 1.65V.
As seen from fig. 9, the catalytic electrode prepared after the surface reduction pretreatment of the base material is more advantageous in stability, and thus, the catalytic layer formed after ion implantation can be increased in stability by the pretreatment of the base material.
Example 3:
the embodiment provides an electrocatalytic material, wherein a substrate material selected for the electrocatalytic material is a nickel metal substrate plate-shaped structure (i.e., the electrocatalytic material in comparative example 1, hereinafter referred to as a nickel substrate for short), and a selected electrocatalyst is metallic iron. The preparation method of the material specifically comprises the following steps:
(1) reduction pretreatment of a nickel substrate:
reducing the nickel substrate for 2 hours at the high temperature of 600 ℃ in the mixed atmosphere of hydrogen and nitrogen with the hydrogen being 5 vol.%, and naturally cooling to obtain the nickel substrate with the surface being pretreated;
(2) preparing a catalyst layer by ion implantation:
performing iron ion implantation on the nickel substrate with the surface pretreated to obtain the electrocatalytic material containing the iron element with atomic-level dispersion in the surface layer, adopting single-side implantation, and ensuring the implantation vacuum degree to be 1 x 10 -3 Pa, accelerating voltage of 40kV, arc current of 60A, and implanted ion dose of 3 × 10 16 ions/cm 2 The injection time is 300 min.
And (3) performing electrode activation on the prepared electrocatalytic material:
carrying out electrochemical activation on the electrocatalytic material (hereinafter referred to as electrode) obtained in the step 2), and specifically comprising the following steps: in 1M potassium hydroxide solution, the electrode is activated for 200 circles in cyclic voltammetry at a scanning speed of 100mV/S within a potential range of 1.2-1.6V, and the electrode is taken out and washed clean, and is named as a sample S-3 #.
And (3) carrying out morphology characterization on the sample S-3 #:
the characterization method is the same as that of the example 1, the appearance of the sample S-3# is similar to that of the sample S-1#, the iron element is distributed in the catalytic layer in an atomic scale mode, the thickness of the catalytic layer of the sample S-3# is 0.28 mu m, and the mass content of the iron element in the catalytic layer of the sample S-3# is 0.5-2.1 wt%.
The sample S-3# was characterized:
in the three-electrode system, the sample S-3# was used as the working electrode, and other test conditions were the same as in example 1, and the results of the electrochemical activity test of this electrode as an oxygen evolution electrode under alkaline conditions are shown in table 2. Compared with an electrode containing an atom dispersion catalyst layer, the electrode has excellent catalytic activity no matter chemical activation or electrochemical activation is adopted.
In a three-electrode system, a sample S-3# is taken as a working electrode, other test conditions are the same as those in example 1, the electrochemical activity of the electrode as a hydrogen evolution electrode under an alkaline condition is tested, and as a result, similar to example 1, after a catalyst layer is formed by introducing an iron element dispersed at an atomic level into a surface layer, the electrocatalytic hydrogen evolution activity of the sample S-3# is obviously improved.
Table 2 shows the test performance of sample S-3# in example 3, compared with the test performance of sample S-1# in example 1 and the test performance of sample S-2# in example 2 under the three-electrode condition.
Table 2: comparative table of activity of samples S-1#, S-2#, S-3#
Example 4:
in this embodiment, an electrocatalytic material is provided, in which a base material is a 60-mesh iron wire mesh material with a specification of 10 × 1mm, and implanted ions are chromium elements.
(1) Pretreating the iron wire mesh substrate:
nitriding the wire netting substrate in the mixed atmosphere of 5 vol.% ammonia gas and nitrogen gas at the high temperature of 500 ℃ for 4 hours, and naturally cooling to obtain the wire netting substrate with the surface being pretreated;
(2) preparing a catalyst layer by ion implantation:
performing chromium ion implantation on the cleaned wire mesh substrate to obtain an electrocatalytic material containing the atomically dispersed chromium element in the surface layer, and performing single-side implantation with the implantation vacuum degree of 1 × 10 -3 Pa, accelerating voltage of 50kV, arc current of 60A, and implanted ion dose of 5 × 10 16 ions/cm 2 The injection time is 200 min.
And (3) performing electrode activation on the prepared electrocatalytic material:
chemically activating the electrocatalytic material (hereinafter referred to as electrode) obtained in the step 2), which specifically comprises the following steps: and (4) immersing the electrode into a 3M sulfuric acid solution, taking out after half an hour, and washing to be clean, wherein the name of the electrode is sample S-4 #.
And (3) carrying out morphology characterization on the sample S-4 #:
the characterization method is the same as that of the embodiment 1, the appearance of the sample S-4# is similar to that of the sample S-1#, the chromium element is distributed in the catalytic layer in an atomic scale mode, the thickness of the catalytic layer of the sample S-4# is 0.3 mu m, and the mass content of the chromium element in the catalytic layer of the sample S-4# is 0.5-2.7 wt%.
The sample S-4# was characterized:
in the three-electrode system, sample S-4# is used as the working electrode, and other test conditions are the same as in example 1, the electrochemical activity of the electrode as an oxygen/hydrogen evolution electrode under alkaline conditions is tested, and the electrode shows excellent electrocatalytic activity compared with the electrocatalytic activity of a wire mesh substrate material, which is very critical to the formation of a chromium element monodisperse catalyst layer on the surface of the substrate material in comparison with the chromium ion implantation.
Example 5:
in this example, an electrocatalytic material is provided, which uses a base material of 10 × 1mm nickel-chromium (chromium 15 wt%) alloy foam structure material, and the implanted ions are platinum elements.
(1) Pretreating a nickel-chromium alloy substrate:
oxidizing the nickel-chromium alloy substrate in the air at the high temperature of 300 ℃ for two hours, and naturally cooling to obtain a nickel-chromium alloy substrate with a pretreated surface;
(2) preparing a catalyst layer by ion implantation:
performing platinum ion implantation on the surface-pretreated nichrome substrate to obtain an electrocatalytic material containing atomically dispersed platinum elements in the surface layer, adopting single-side implantation with the implantation vacuum degree of 2 x 10 -3 Pa, accelerating voltage of 30kV, arc current of 30A, and implanted ion dose of 1 × 10 15 ions/cm 2 The injection time is 20 min.
And (3) performing electrode activation on the prepared electrocatalytic material:
carrying out electrochemical activation on the electrocatalytic material (hereinafter referred to as electrode) obtained in the step 2), and specifically comprising the following steps: in 1M potassium hydroxide solution, the electrode is activated for 50 circles in cyclic voltammetry at a scanning speed of 100mV/S within a potential range of 0-1.2V, and the electrode is taken out and washed clean, namely a sample S-5 #.
And (3) carrying out morphology characterization on the sample S-5 #:
the characterization method is the same as that of the example 1, the appearance of the sample S-5# is similar to that of the sample S-1#, the platinum element is distributed in the catalytic layer in an atomic scale mode, the thickness of the catalytic layer of the sample S-5# is 0.15 mu m, and the mass content of the platinum element in the catalytic layer of the sample S-5# is 0.08-1.0 wt%.
The sample S-5# was characterized:
in a three-electrode system, sample S-5# is taken as a working electrode, other test conditions are the same as example 1, the electrochemical activity of the electrode as an oxygen/hydrogen evolution electrode is tested to be superior to that of a nichrome base material under an alkaline condition, the electrode shows superior electrocatalytic activity, a platinum ion implantation is carried out on the surface of the nichrome to form an atom dispersed platinum catalyst layer, and highly dispersed platinum shows superior catalytic activity under an electrochemical environment.
Although the present invention has been described with reference to a few preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A method of preparing an electrocatalytic material, comprising:
introducing an electrocatalyst into the surface layer of the substrate through ion implantation to form a catalyst layer with the electrocatalyst dispersed in an atomic level to obtain the electrocatalytic material;
the electrocatalytic material includes a substrate and an electrocatalyst;
the surface layer of the substrate is a catalytic layer, and the electrocatalyst is positioned in the catalytic layer and is dispersed in an atomic level;
the electrocatalyst is a metal element;
the metal element is selected from at least one of transition metal or rare earth element;
the metal element is different from the metal element contained in the substrate;
the substrate is a pure metal substrate or an alloy substrate;
the substrate is selected from at least one of a plate-shaped structure, a block-shaped structure, a foam structure, a net-shaped structure and a powder-shaped structure;
the metal element in the pure metal substrate is selected from one of nickel, iron, titanium and copper;
the alloy substrate is selected from at least one of ferronickel alloy, nickel-aluminum alloy, nickel-chromium alloy and iron-chromium alloy.
2. The preparation method of the electrocatalytic material as set forth in claim 1, wherein the thickness of the catalytic layer is 0.05-0.5 μm;
the content of the electrocatalyst is distributed in a quasi-normal distribution from the surface inward in the thickness direction of the catalytic layer.
3. The preparation method of the electrocatalytic material as set forth in claim 1, wherein the mass content of the electrocatalysts in the catalytic layer is 0.05-5 wt%.
4. The method of claim 1, wherein the substrate is pretreated prior to ion implantation;
the pretreatment is at least one selected from cleaning, oxidation, reduction, nitridation, vulcanization, etching, impact and cutting.
5. The method for preparing an electrocatalytic material as set forth in claim 1, wherein the specific conditions of the ion implantation include:
vacuum degree of 1 x 10 -4 ~5*10 -3 Pa；
The accelerating voltage is 10-100 kV;
implantation ionSub-doses of 1 x 10 14 ~1*10 17 ions/cm 2 ;
The arc current is 5-200A;
the time is 1-600 min.
6. The application of at least one of the electrocatalytic materials prepared by the preparation method of any one of claims 1-5 in the field of electrocatalysis.
7. The use according to claim 6, in alkaline electrolysis water hydrogen evolution/oxygen evolution reactions, acidic electrolysis water hydrogen evolution/oxygen evolution reactions, carbon dioxide reduction reactions, nitrogen fixation reactions, oxygen reduction reactions.
8. Use according to claim 6, wherein the electrocatalytic material is subjected to an activation treatment prior to use; the activation treatment includes chemical activation and/or electrochemical activation.
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