CN113136600B - Electrocatalyst and preparation method and application thereof - Google Patents
Electrocatalyst and preparation method and application thereof Download PDFInfo
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- CN113136600B CN113136600B CN202110255260.3A CN202110255260A CN113136600B CN 113136600 B CN113136600 B CN 113136600B CN 202110255260 A CN202110255260 A CN 202110255260A CN 113136600 B CN113136600 B CN 113136600B
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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Abstract
The invention discloses an electrocatalyst and a preparation method and application thereof. The electrocatalytic active units on the electrocatalyst are distributed in a periodic array, so that when external voltage is applied to the electrocatalyst, the electrocatalytic active units can spontaneously generate an electric field enhancement effect, thereby improving the electrocatalytic performance and reducing the using amount of electrocatalytic active materials.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to an electrocatalysis electrode and a preparation method and application thereof.
Background
Under the large background of global carbon neutralization requirements, in order to solve the problems of environmental pollution and energy shortage around the world, energy systems mainly using fossil fuels need to be transformed. Electrochemical energy technology is considered as a main technology of future energy systems due to the advantages of cleanness, high efficiency and the like. Electrochemical energy technologies such as electrochemical hydrogen production, electrochemical nitrogen reduction and electrochemical carbon dioxide reduction can be coupled with new energy technologies such as wind energy and solar energy, clean electric energy is converted into chemical energy to be stored in hydrogen, ammonia and organic compounds, clean conversion and large-scale transportation and application of energy are achieved, and energy waste is avoided. Meanwhile, the efficiency of electrochemical energy technologies such as fuel cells is not limited by Carnot cycle, and the efficient conversion of chemical energy stored in compounds into electric energy can be realized. However, the efficiency of current electrochemical energy technologies is low due to the high kinetic energy barrier of electrochemical reactions, which hinders their large-scale application. The electrochemical reaction energy barrier is reduced by the electro-catalyst, so that the energy conversion efficiency is improved, and the premise of large-scale application of various electrochemical technologies is provided. Currently, increasing the efficiency of electrocatalysts and reducing the amount of electrocatalytically active materials containing expensive metals is one of the core problems that needs to be addressed by electrochemical energy technology.
In recent years, researchers change the chemical properties and electronic structures of electrocatalysts in modes of chemical component regulation, defect regulation, stress regulation, substrate regulation and the like, and further improve the catalytic performance of the electrocatalysts. By accurately controlling the synthesis conditions of the materials, adopting relatively complex technical means such as plasma treatment, high-temperature sintering and the like and adopting different strategies aiming at different electrocatalysts and electrochemical reaction systems, the improvement of the performance of the electrocatalysts can be effectively realized, and the cost and the dosage of electrocatalysis active components in the electrocatalysts are reduced.
For example, the patent application reports a method for regulating the electrocatalytic hydrogen evolution performance of nickel-iron-based hydroxide through cadmium doping, and the patent application reports a method for improving the electrocatalytic performance of metal oxide through quenching modification. However, these methods based on chemical regulation require precise control of reaction conditions, the technical means for implementing these chemical regulations are relatively complex, and the versatility of these means for different electrocatalysts and electrochemical reactions is poor, thus the implementation difficulty is large.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides an electrocatalyst, a preparation method and application thereof.
In a first aspect of the invention, an electrocatalyst is presented comprising:
an electrically conductive non-catalytically active support member,
and each electrocatalytic active unit is arranged on the conductive non-catalytic active support and is distributed in a periodic array.
The electrocatalytic electrode according to the embodiment of the invention has at least the following beneficial effects: the electric catalyst is provided with a plurality of electric catalytic active units on a conductive non-catalytic active support member in a periodic array arrangement, wherein the electric field intensity on the surface of the electric catalytic active unit on the electric catalyst can be spontaneously enhanced when external voltage is applied to the electric catalyst through the periodic array arrangement of the electric catalytic active units, so that the electric catalytic performance is improved; the excellent catalytic performance of the electrocatalyst in the electrochemical reaction can be realized while the dosage of the electrocatalytic active material on the electrocatalytic active unit can be reduced; harsh reaction conditions are not required to be controlled, the requirements on the reaction conditions are loose, and the large-scale production and application are facilitated; the structure is simple, the preparation is easy, the universality is good, and corresponding electrocatalysis active materials can be processed and prepared according to the requirements of electrochemical reaction; the current density of the electrocatalyst can be 1-5000 m A/cm under the service state 2 The method is adjustable and is suitable for various industrial-grade electrochemical applications.
In some embodiments of the invention, the periodic array distribution is at least one of an N-fold rotational axis symmetric distribution, an inverted centrosymmetric distribution, a mirror symmetric distribution, a slip plane symmetric distribution; wherein N is an integer of 3-6. The N-time rotation axis symmetric distribution specifically means that one N-time rotation axis exists in the electrocatalytic activity units which are arranged in a periodic array, and the whole electrocatalytic activity units which are arranged in a periodic array coincide with a graph before rotation every time the whole electrocatalytic activity units rotate 360 degrees/N around the axis; the N rotation axes are symmetrically distributed and can be 3 rotation axes (C) 3 ) Symmetrically distributed, 4 rotation axes (C) 4 ) Symmetrically distributed, 5 rotation axes (C) 5 ) Symmetrically distributed or 6 axes of rotation (C) 6 ) And are symmetrically distributed. The sliding plane symmetry means that the electrocatalytic active units arranged in a periodic array are reflected by a mirror surface and slide for a certain distance parallel to the mirror surface, and each electricity in the whole arrayThe catalytically active units will occupy the same position as the surroundings before conversion, i.e. the electrocatalytically active units arranged in a periodic array can coincide by themselves, via shifting of the slip plane.
In some embodiments of the invention, the distance between adjacent electrocatalytically-active cells is between 10nm and 20 cm. For example, the pitch between adjacent electrocatalytically-active cells may be set to 500nm, 0.005cm, 0.006cm, 0.008cm, 0.01cm, 0.015cm, 0.02cm, 0.025cm, 0.03cm, 0.05cm, 0.06cm, 0.08cm, 0.1cm,0.15cm, 0.2cm, 0.25cm, 0.3cm, 0.4cm, 0.5cm, 0.8cm, 1cm, 2cm, 2.5cm, 5cm, or the like.
In some embodiments of the invention, the electrocatalytically-active cells are disposed on a surface of the electrically-conductive, non-catalytically-active support; and/or the electrocatalytically-active cells are embedded within the electrically-conductive non-catalytically-active support.
In some embodiments of the present invention, the electrically conductive non-catalytic support member includes a plurality of electrically conductive non-catalytically active support members, the electrocatalytically active units are sandwiched between the electrically conductive non-catalytically active support members, and each of the electrocatalytically active units is distributed on the electrically conductive non-catalytically active support member in a periodic array.
In some embodiments of the present invention, the material of the electrocatalytically-active unit is an electrocatalytically-active material; or the electrocatalytic active unit comprises a template unit and an electrocatalytic active material layer made of electrocatalytic active materials, and the electrocatalytic active material layer is arranged on the surface of the template unit.
The electrocatalytically-active cell may be used to catalyze electrochemical reactions, particularly three-phase solid-liquid-gas electrochemical reactions. In some embodiments of the invention, the electrocatalytically-active material comprises at least one of an element, a compound, and a composition having electrocatalytic activity; the electrocatalytic activity includes at least one of electrochemical hydrogen evolution reaction catalytic activity, electrochemical oxygen evolution reaction catalytic activity, electrochemical hydrogen oxidation reaction catalytic activity, electrochemical methanol oxidation reaction catalytic activity, electrochemical formic acid oxidation reaction catalytic activity, electrochemical carbon dioxide reduction reaction catalytic activity and electrochemical nitrogen reduction reaction catalytic activity.
In some embodiments of the present invention, the electrocatalytically-active material is selected from any one of elemental metals, metal compounds, and carbon materials having the electrocatalytic activity; preferably, the metal element in the simple metal and the metal compound is at least one selected from aluminum, titanium, vanadium, chromium, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, ruthenium, rhodium, palladium, silver, antimony, hafnium, tantalum, tungsten, iridium, platinum, gold, bismuth, lanthanum, and cerium. The carbon material may be a pure carbon material or a carbon material containing a dopant substance.
In addition, the total projected area of each electrocatalytically-active element onto the electrically-conductive substrate is generally less than the area (θ) of the electrically-conductive substrate c ) Preferably, the total projected area of each electrocatalytic active unit on the conductive substrate accounts for 0.5% -85% of the area of the conductive substrate; for example, it may be 1%, 2.5%, 5%, 6.25%, 10%, 12.5%, 20%, 25%, 50%, 75%, etc.
In some embodiments of the invention, the electrically conductive non-catalytically active support is made of an electrically conductive electrochemically inert material, in particular a material that is not catalytically active for an electrochemical reaction that the electrocatalytically active unit is capable of catalyzing. Preferably, the electrically conductive, electrochemically inert material is selected from at least one of graphite, glassy carbon, titanium, copper, nickel, gold, stainless steel. The conductive non-catalytically active support member may be in the form of a planar plate, a foam, a fabric, a mesh, or the like, for example, a sheet of glassy carbon, a sheet of titanium, a mesh of titanium, a titanium foam, or the like may be used.
In a second aspect of the present invention, there is provided a method for preparing any one of the electrocatalysts set forth in the first aspect of the present invention, comprising: constructing template units distributed in a periodic array on a conductive non-catalytic active support, and then arranging an electrocatalytic active material layer on the surface of each template unit; specifically, template units which are periodically arranged in an array are constructed on the conductive non-catalytic active support member in the modes of mask plate assistance, 3D printing and the like, and then mask plates with through holes which are periodically arranged in an array are correspondingly arranged on the conductive non-catalytic active support member, wherein the through holes correspond to the template units; then arranging an electrocatalytic active material layer on the template unit by at least one of the modes of dipping, spraying, vapor deposition, physical coating, chemical coating, atomic layer deposition, electrochemical deposition and the like;
alternatively, the preparation method of the electrocatalytic electrode comprises the following steps: the electrocatalytic active units distributed in a periodic array are directly arranged on the conductive non-catalytic active support by adopting an electrocatalytic active material; specifically, electrocatalytic active units which are distributed in a periodic array can be directly arranged on the conductive non-catalytic active support by adopting an electrocatalytic active material directly through modes of 3D printing, laser cutting, silk-screen printing, electrostatic ink-jet printing and the like;
alternatively, the method of preparing the electrocatalyst comprises: constructing electrocatalytic active units distributed in a periodic array on a conductive substrate; an electrically conductive non-catalytically active support is then arranged between adjacent ones of said electrocatalytically active cells.
The preparation method of the electrocatalyst is suitable for the preparation of various electrochemical reaction catalysts, is particularly suitable for solid-liquid-gas three-phase electrochemical reactions, and can be used for preparing the corresponding electrocatalyst by adopting corresponding electrocatalytic active materials according to the requirements of the electrochemical reactions.
In a third aspect of the present invention, there is provided a use of any one of the electrocatalysts set forth in the first aspect of the present invention in catalyzing an electrochemical reaction comprising at least one of an electrochemical hydrogen evolution reaction, an electrochemical oxygen evolution reaction, an electrochemical hydrogen oxidation reaction, an electrochemical methanol oxidation reaction, an electrochemical formic acid oxidation reaction, an electrochemical carbon dioxide reduction reaction, and an electrochemical nitrogen reduction reaction.
In a fourth aspect of the invention, there is provided an electrocatalytic electrode comprising any one of the electrocatalysts set forth in the first aspect of the invention. In addition, the electrocatalytic electrode may further include an electrically conductive substrate, the electrocatalyst being disposed on a surface of the electrically conductive substrate. The electrocatalytic electrode is suitable for catalyzing alkaline electrochemical reactions.
In a fifth aspect of the invention, there is provided an electrochemical reactor comprising any one of the electrocatalytic electrodes set forth in the fourth aspect of the invention; or, comprising a membrane layer and any one of the electrocatalysts set forth in the first aspect of the invention, the electrocatalyst being disposed on the membrane layer, the membrane layer being selected from an ion exchange membrane or a gas membrane. The ion exchange membrane may be a cation exchange membrane or an anion exchange membrane. Wherein the electrochemical reactor comprising the membrane layer is suitable for acidic electrochemical reactions.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a photograph of an electrocatalytic electrode prepared in example 1;
FIG. 2 is a schematic view of the structure of an electrocatalytic electrode of example 1;
FIG. 3 is a graph of current density versus electrode potential for the electrocatalytic electrodes of example 1 and comparative example 1 in an electrochemical hydrogen evolution reaction;
FIG. 4 is a comparison graph of the reaction principle of the electrocatalytic electrodes of example 1 and comparative example 1 in the electrochemical hydrogen evolution reaction;
FIG. 5 is a photograph of an electrocatalytic electrode prepared in example 2;
FIG. 6 is a graph of current density versus electrode potential for the electrocatalytic electrodes of example 2 and comparative example 4 in an electrochemical hydrogen evolution reaction;
FIG. 7 is a photograph of an electrocatalytic electrode in service during an electrochemical hydrogen evolution reaction process in example 2;
FIG. 8 is a photograph of an electrocatalytic electrode prepared in example 3;
FIG. 9 is a graph of current density versus electrode potential for the electrocatalytic electrode of example 3 in an electrochemical oxygen evolution reaction;
FIG. 10 is a photograph of an electrocatalytic electrode prepared in example 4;
FIG. 11 is a graph of current density versus electrode potential for the electrocatalytic electrodes of example 4 and comparative example 2 in an electrochemical hydrogen evolution reaction;
FIG. 12 is a front view of an electrocatalytic electrode prepared in example 5;
FIG. 13 is a side view of an electrocatalytic electrode made in example 5;
FIG. 14 is a graph of current density versus electrode potential for electrocatalytic electrodes of example 5 and comparative example 3 in an electrochemical hydrogen evolution reaction;
FIG. 15 is a photograph of the electrocatalytic electrode of example 5 in service during the electrochemical hydrogen evolution reaction.
Reference numerals: an electrically conductive non-catalytically active support 100, an electrocatalytically active cell 200.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment prepares the electrocatalyst, and the specific process comprises the following steps:
(1) constructing a mask plate corresponding to the electrocatalyst shown in the figure 1 by laser cutting, wherein the mask plate is provided with a plurality of square through holes with the side length of 0.0125cm, the through holes are periodically arrayed according to 4 times of rotating shaft (C4) point groups, and the distance between every two adjacent through holes is 0.025 cm; the area of the through holes accounts for 25 percent of the total area of the mask plate (theta) c ＝25％)。
(2) Selecting a glassy carbon sheet without electrocatalytic activity in an electrochemical hydrogen production reaction as a conductive non-catalytic activity support and simultaneously as a conductive substrate, covering the mask plate constructed in the step (1) on the glassy carbon sheet, sputtering an electrocatalytic active material platinum (Pt) on the glassy carbon by a sputtering deposition method, depositing the electrocatalytic active material platinum on the glassy carbon sheet through holes on the mask plate to form electrocatalytic activity units, then stripping the mask plate, and loading the electrocatalytic activity units which are periodically arranged according to C4 point groups on the glassy carbon sheet as shown in figure 1 to prepare the platinum/glassy carbon electrocatalyst which can be used as an electrocatalytic electrode. As shown in fig. 2, the electrocatalyst includes a conductive non-catalytic active support member 100, and a plurality of electrocatalytic active units 200 distributed on the surface of the conductive non-catalytic active support member 100 at intervals and in a periodic array, wherein the electrocatalytic active units 200 are made of an electrocatalytic active material platinum, and are specifically distributed on the conductive non-catalytic active support member 100 in a 4-order rotational symmetry manner.
Comparative example 1
This comparative example prepared an electrocatalyst which differed from example 1 in that: in this comparative example, the mask plate was omitted, and Pt was directly sputter-deposited on the glassy carbon sheet by the operation similar to the step (2) in example 1, and a continuous platinum sheet as an electrocatalytic active material layer was formed on the glassy carbon sheet, to prepare an electrocatalyst, which was also used as an electrocatalytic electrode.
The electrocatalysts (i.e. electrocatalysis electrodes) prepared in example 1 and comparative example 1 are respectively used for carrying out the electrolytic water hydrogen evolution reaction in 0.5mol/L sulfuric acid aqueous solution, and the current density-electrode potential curve of each electrocatalysis electrode in the hydrogen evolution reaction is shown in figure 3. As can be seen from fig. 3, the electrocatalytic active units on the electrocatalytic electrode in example 1 are arranged in a periodic array on the conductive non-catalytic active support, so that the electrocatalytic electrode has a strong catalytic activity for the electrochemical hydrogen evolution reaction. In addition, a comparison graph of the reaction principle of the electrocatalytic electrode in the electrolytic water hydrogen evolution reaction of the example 1 and the comparative example 1 is shown in fig. 4, wherein (a) in fig. 4 shows a schematic diagram of the reaction principle of the electrocatalytic electrode in the electrolytic water hydrogen evolution reaction of the comparative example 1; (b) the reaction principle of the electrocatalytic electrode in the electrolytic water hydrogen evolution reaction is shown as a schematic diagram in example 1. As can be seen from fig. 4, the electrocatalytic electrode in example 1 spontaneously generates an electric field enhancement effect on the surface of the electrocatalytic active unit during the electrolytic water hydrogen evolution reaction, while the electrocatalytic electrode in comparative example 1 has no electric field enhancement effect on the surface of the electrocatalytic active material layer. As can be seen from fig. 3 and 4, in the electrocatalytic electrode of example 1, the electrocatalytic active units are periodically arrayed on the conductive non-catalytic active support, and in the service state, the electrocatalytic active units can spontaneously generate the electric field enhancement effect, so that the electrocatalytic performance can be improved, and the amount of the electrocatalytic active material can be reduced.
Example 2
The embodiment prepares the electrocatalyst, and the specific process comprises the following steps:
(1) by laser cuttingConstructing a mask plate corresponding to the shape of the electrocatalyst shown in fig. 5, wherein the mask plate is provided with a plurality of isosceles triangle-shaped through holes with the bottom side length of 0.03cm and the height of 0.6cm, the through holes are arranged in a line along the bottom side direction and are periodically arranged, and the minimum distance between every two adjacent through holes is 0.074 cm; the area of the through holes accounts for 25 percent of the area of the mask plate (theta) c ＝25％)。
(2) Covering the mask plate constructed in the step (1) on a glassy carbon sheet conductive substrate, sputtering an electrocatalytic active material platinum (Pt) on the glassy carbon sheet by a sputtering deposition method, depositing the electrocatalytic active material platinum on the glassy carbon sheet through each through hole on the mask plate to form an electrocatalytic active unit, coating soluble PMMA on the electrocatalytic active units, and then stripping the mask plate; a layer of amorphous carbon film is sputtered again, the PMMA and the amorphous carbon on the electrocatalytic activity units are removed by acetone, and the amorphous carbon between the adjacent electrocatalytic activity units forms a conductive non-catalytic activity support, so that the platinum/amorphous carbon catalyst is prepared on the conductive substrate glassy carbon sheet, as shown in figure 5, the electrocatalytic activity units which are periodically arranged are loaded on the conductive substrate glassy carbon sheet, the amorphous carbon conductive non-catalytic activity support surrounds the electrocatalytic activity units, and the whole can form an electrocatalytic electrode.
The electrocatalytic electrode prepared by the embodiment is used for carrying out the electrolytic water hydrogen evolution reaction in a 0.5mol/L sulfuric acid aqueous solution, the current density-electrode potential curve of the electrocatalytic electrode in the hydrogen evolution reaction is shown in fig. 6, and the photo of the electrocatalytic electrode in a service state is shown in fig. 7. As can be seen from fig. 6, the electrocatalytic electrode of the present embodiment has a strong catalytic activity for the electrochemical hydrogen evolution reaction; as can be seen from figure 7, in the service process, the bubbles are easy to desorb on the surface of the electrocatalytic active unit arranged on the electrocatalytic electrode, and the electrocatalytic electrode is proved to have good mass transfer when used for hydrogen evolution reaction.
Example 3
The embodiment prepares the electrocatalyst, and the specific process comprises the following steps:
(1) a mask plate corresponding to the shape of the electrocatalyst shown in FIG. 8 was constructed by laser cutting, wherein the mask plate had a number of square through holes with a side length of 0.0125cmEach through hole is arranged according to a 4-time rotating shaft (C4) point group periodic array, and the distance between every two adjacent through holes is 0.05 cm; the area of the through hole accounts for 6.25 percent of the area of the mask plate (theta) c ＝6.25％)。
(2) Covering the mask plate constructed in the step (1) on a glassy carbon conductive substrate, evaporating an electrocatalytic active material ruthenium (Ru) on the glassy carbon sheet by an electron beam assisted evaporation method, loading the electrocatalytic active material ruthenium on the glassy carbon sheet through each through hole on the mask plate to form electrocatalytic active units, coating soluble PMMA on the electrocatalytic active units, and then stripping the mask plate; and sputtering a layer of amorphous carbon again, removing the PMMA and the gold film on the electrocatalytic active units by using acetone, and forming a conductive non-catalytic active supporting sub-component by using the amorphous carbon between the adjacent electrocatalytic active units, so that the ruthenium/amorphous carbon catalyst is prepared on a conductive substrate, namely a glassy carbon sheet, as shown in figure 8, the electrocatalytic active units which are periodically arranged are loaded on the glassy carbon substrate, the amorphous carbon conductive non-catalytic active supporting sub-component surrounds the electrocatalytic active units, and the whole electrocatalytic electrode can be formed. That is, the electrocatalyst in this embodiment includes a conductive non-catalytic active support member and a plurality of electrocatalytic active units, where the conductive non-catalytic active support member includes a plurality of conductive non-catalytic active support sub-members, the electrocatalytic active units are sandwiched between the conductive non-catalytic active support sub-members, and each electrocatalytic active unit is periodically distributed in an array on the conductive non-catalytic active support member.
The electrocatalytic electrode prepared in this example was subjected to an electrolytic water oxygen evolution reaction in a 1mol/L aqueous solution of potassium hydroxide, and the current density-electrode potential curve of the electrocatalytic electrode in the oxygen evolution reaction is shown in fig. 9. As can be seen from fig. 9, the electrocatalytic electrode of the present example has a strong catalytic activity for the electrochemical oxygen evolution reaction.
Example 4
The embodiment prepares the electrocatalyst, and the specific process comprises the following steps:
(1) a mask plate corresponding to the shape of the electrocatalyst shown in FIG. 10 was constructed by laser cutting, wherein the mask plate had several isosceles triangle-shaped through holes with a bottom side length of 0.03cm and a height of 0.6cm, and each through hole was alongThe bottom edges are arranged in a line and periodically arranged, and the minimum distance between adjacent through holes is 0.074 cm; the area of the through holes accounts for 15 percent of the area of the mask plate (theta) c ＝15％)。
(2) Covering the mask plate constructed in the step (1) on a conductive non-catalytic active support glass carbon sheet (simultaneously serving as a conductive substrate), evaporating an electrocatalytic active material platinum (Pt) on the glass carbon sheet by a sputtering deposition method, putting the whole prepared material on a tubular furnace, and carrying out H treatment at a flow rate of 30sccm 2 Treating the glass substrate with S gas and Ar gas at a flow rate of 500sccm at 750 ℃ for 30min, taking out the glass substrate, and peeling off the mask plate, wherein electrocatalytic active units (containing charged catalytic active material PtS) are loaded on the glass substrate in a periodic arrangement as shown in FIG. 10 2 ) Form PtS 2 A glassy carbon electrocatalyst which can also act as an electrocatalytic electrode.
Comparative example 2
This comparative example prepared an electrocatalyst which differed from example 4 in that: in the comparative example, a mask plate was omitted, Pt was directly sputter-deposited on a glassy carbon plate in an operation similar to that in the step (2) in example 4, and the whole of the obtained material was placed on a tube furnace at a flow rate of 30sccm in H 2 Treating at 750 deg.C for 30min in the atmosphere of S gas and Ar gas with flow rate of 500sccm to obtain electrocatalyst which can be used as electrocatalytic electrode.
The electrocatalytic electrodes prepared in example 4 and comparative example 2 were used to perform the electrolytic water oxygen evolution reaction in 0.5mol/L sulfuric acid aqueous solution, and the current density-electrode potential curve of the electrocatalytic electrode in the hydrogen evolution reaction is shown in FIG. 11. As can be seen from fig. 11, the electrocatalytic electrode of example 4 has a strong catalytic activity for the electrochemical hydrogen evolution reaction.
Example 5
The embodiment prepares the electrocatalyst, and the specific process comprises the following steps:
(1) conical template units which are distributed in a periodic array and correspond to the template units shown in figure 12 in a front view and the template units shown in figure 13 in a top view are constructed on a resin/platinum composite conductive non-catalytic active support (simultaneously serving as a conductive substrate) through 3D printing, and each template unit is attached to a conductive substrateHas a bottom section diameter of 0.125cm and a height of 0.1cm, and each template unit has a rotation axis (C) of 3 times 3 ) The point groups are arranged in a periodic array, the distance between every two adjacent template units is 0.025cm, and the projection area of each template unit on the conductive substrate accounts for 15.1% of the area of the conductive substrate.
(2) Correspondingly arranging a mask plate with a C3 periodic array of through holes on the conductive non-catalytic active support, wherein the through holes correspond to the mask plate units; then, platinum (Pt) serving as an electrocatalytic active material is sputtered on the side, on which the template unit is arranged, of the conductive substrate prepared in the step (1) by a sputtering deposition method, so that electrocatalytic active units periodically arranged according to a C3 point group are formed on the conductive non-catalytic active support corresponding to the template unit, specifically, as shown in fig. 12 and 13, an electrocatalyst is prepared, and the electrocatalyst can also be used as an electrocatalytic electrode. The electrocatalyst comprises a conductive non-catalytic active support member and a plurality of electrocatalytic active units periodically distributed on the surface of the conductive non-catalytic active support member in an array manner, wherein each electrocatalytic active unit comprises a template unit and an electrocatalytic active material layer arranged on the surface of the template unit, and each electrocatalytic active unit is specifically distributed on a conductive substrate in a 3-time rotation axis symmetry manner.
Comparative example 3
This comparative example prepared an electrocatalyst which differed from example 5 in that: in this comparative example, the arrangement of the template unit and the mask plate was omitted, and an electrocatalytic active material layer (platinum layer) was sputter-deposited on the resin/platinum composite conductive non-catalytic active support by a sputter deposition method directly according to the step (2) in example 5, to prepare an electrocatalyst, which can also be used as an electrocatalytic electrode.
The electrocatalytic electrodes prepared in example 5 and comparative example 3 are respectively adopted to carry out electrolytic water hydrogen evolution reaction in 0.5mol/L sulfuric acid aqueous solution, the current density-electrode potential curve of the electrocatalytic electrode in the hydrogen evolution reaction is shown in fig. 14, the picture of the electrocatalytic electrode in the service state of example 5 is shown in fig. 15, and the finely-divided fuzzy tailing-shaped area in fig. 15 is air bubbles. As can be seen from fig. 14, the electrocatalytic electrode of example 5 has a strong catalytic activity for the electrochemical hydrogen evolution reaction; as can be seen from fig. 15, in the service process, the bubbles are easily desorbed on the surface of the electrocatalytic active unit arranged on the electrocatalytic electrode in example 5, which proves that the electrocatalytic electrode has good mass transfer for the hydrogen evolution reaction.
Example 6
The embodiment prepares the electrocatalyst, and the specific process comprises the following steps:
(1) constructing truncated spherical template units distributed in a periodic array on a resin/platinum composite conductive non-catalytic active support (which can be used as a conductive substrate at the same time) through 3D printing, wherein the diameter of the bottom section, which is attached to a conductive substrate, of each template unit is 0.125cm, the height of each template unit is 0.1cm, and each template unit is specifically arranged according to 6-time rotating shafts (C) 6 ) The point groups are arranged in a periodic array, and the distance between the adjacent template units is 0.025 cm.
(2) Correspondingly arranging a mask plate with a C6 periodic array of through holes on the conductive non-catalytic active support, wherein the through holes correspond to the mask plate units; sputtering electro-catalytic active material platinum (Pt) to one side of the template unit on the conductive substrate prepared in the step (1) by a sputtering deposition method, and further forming a template unit on the conductive non-catalytic active support according to C 6 The electrocatalytic active units which are periodically arranged in a dot group form the electrocatalyst, and the electrocatalyst can also be used as an electrocatalytic electrode.
Comparative example 4
This comparative example prepared an electrocatalyst which differed from example 1 in that: in this comparative example, a mask plate was removed, and an electrocatalytic active material platinum was sputter-deposited on a glassy carbon plate by a sputter deposition method directly in accordance with the operation similar to the step (2) in example 1, to form an electrocatalytic active material layer (platinum layer) uniformly supported on the glassy carbon plate of the conductive non-catalytically active support, and to prepare an electrocatalyst, which can also be used as an electrocatalytic electrode.
The same procedure as in example 2 was followed using the comparative example electrocatalytic electrode to conduct an electrolytic water hydrogen evolution reaction in a 0.5mol/L aqueous sulfuric acid solution, and the current density-electrode potential curve of the electrocatalytic electrode in the hydrogen evolution reaction is shown in FIG. 6.
Comparative example 5
The comparative example prepared an electrocatalyst, the specific process included the following steps:
(1) directly electrodepositing cobalt hydroxide on a titanium sheet by using an electrochemical deposition method and taking the titanium sheet as a working electrode (a conductive non-catalytic active support) and 1mol/L cobalt nitrate solution as electrolyte to obtain a cobalt hydroxide film uniformly loaded on the titanium sheet and in aperiodic array arrangement;
(2) and (2) placing the titanium sheet loaded with the cobalt hydroxide prepared in the step (1) into a tube furnace, and calcining for 2h at 300 ℃ in an air atmosphere to convert the cobalt hydroxide loaded on the titanium sheet into cobaltosic oxide to form the electrocatalyst.
Comparative example 6
The comparative example prepared an electrocatalyst, the specific process included the following steps:
(1) dispersing iridium dioxide powder in isopropanol by ultrasonic to prepare iridium dioxide dispersion liquid;
(2) and (2) dropwise coating the iridium dioxide dispersion liquid prepared in the step (1) on carbon cloth, and then drying to form an iridium dioxide coating on the carbon cloth, so as to prepare the electrocatalyst.
From the above, the electrocatalyst prepared in each of the above embodiments includes the conductive non-catalytic active support and the electrocatalytic active units periodically arranged on the conductive non-catalytic active support, and the electrocatalyst is in a film shape, wherein the electrocatalytic active units are distributed in a periodic array, so that when an external voltage is applied to the electrocatalyst, the electrocatalytic active units can spontaneously generate an electric field enhancement effect, thereby improving the electrocatalytic performance and reducing the amount of the electrocatalytic active material. The preparation method of the electrocatalyst is suitable for preparation of various electrochemical reaction catalysts, and in the specific production preparation process, the corresponding electrocatalyst can be prepared by adopting the corresponding electrocatalytic active material according to the requirements of electrochemical reactions, and the prepared electrocatalyst can be applied to catalyzing the corresponding electrochemical reactions, specifically comprising electrochemical hydrogen evolution reaction, electrochemical oxygen evolution reaction, electrochemical hydrogen oxidation reaction, electrochemical methanol oxidation reaction, electrochemical formic acid oxidation reaction, electrochemical carbon dioxide reduction reaction, electrochemical nitrogen reduction reaction and the like. The electrocatalyst can be used as an electrocatalyst electrode or can be further prepared into an electrocatalyst electrode, so the invention also provides the electrocatalyst electrode, which comprises any one of the electrocatalysts provided by the invention, and further can comprise a conductive substrate, wherein the electrocatalyst is arranged on the surface of the conductive substrate; the electrocatalytic electrode is suitable for catalyzing alkaline electrochemical reactions. In addition, the above electrocatalytic electrode can also be applied to the preparation of an electrochemical reactor, and further, the invention also provides an electrochemical reactor, wherein the electrochemical reactor comprises any one of the electrocatalytic electrodes provided by the invention, and the electrochemical reactor is suitable for alkaline electrochemical reaction; in addition, the invention also provides an electrochemical reactor, which comprises a membrane layer and any one of the electrocatalysts provided by the invention, wherein the electrocatalysts are arranged on the membrane layer, the membrane layer can be selected from an ion exchange membrane or a gas diaphragm, the ion exchange membrane can be a cation exchange membrane or an anion exchange membrane, and the electrochemical reactor is particularly suitable for acidic electrochemical reaction.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (16)
1. An electrocatalyst, comprising:
an electrically conductive non-catalytically active support member,
the electrocatalytic activity units are arranged on the surface of the conductive non-catalytic activity support and are distributed in a periodic array.
2. The electrocatalyst according to claim 1, wherein the periodic array distribution is at least one of N-fold rotationally symmetric distribution, inverted centrosymmetric distribution, mirror symmetric distribution, slip plane symmetric distribution, wherein N is an integer from 3 to 6.
3. The electrocatalyst according to claim 2, wherein the spacing between adjacent electrocatalytically active cells is in the range of 10nm to 20 cm.
4. The electrocatalyst according to claim 1, wherein the material of the electrocatalytically active element is an electrocatalytically active material; or, the electrocatalytic active unit comprises a template unit and an electrocatalytic active material layer composed of electrocatalytic active materials, wherein the electrocatalytic active material layer is arranged on the surface of the template unit, and the template unit is arranged on the surface of the conductive non-catalytic active support.
5. The electrocatalyst according to claim 4, wherein the electrocatalytically-active material comprises at least one of elements, compounds and compositions having electrocatalytic activity; the electrocatalytic activity includes at least one of electrochemical hydrogen evolution reaction catalytic activity, electrochemical oxygen evolution reaction catalytic activity, electrochemical hydrogen oxidation reaction catalytic activity, electrochemical methanol oxidation reaction catalytic activity, electrochemical formic acid oxidation reaction catalytic activity, electrochemical carbon dioxide reduction reaction catalytic activity and electrochemical nitrogen reduction reaction catalytic activity.
6. The electrocatalyst according to claim 5, wherein the electrocatalytically-active material is selected from any one of elemental metals, metal compounds and carbon materials having the electrocatalytic activity.
7. The electrocatalyst according to claim 6, wherein the elemental metal and the metal element in the metal compound are selected from at least one of aluminum, titanium, vanadium, chromium, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, ruthenium, rhodium, palladium, silver, antimony, hafnium, tantalum, tungsten, iridium, platinum, gold, bismuth, lanthanum, and cerium.
8. Electrocatalyst according to any one of claims 1 to 7, wherein the electrically conductive, non-catalytically active support is made of an electrically conductive, electrochemically inert material.
9. Electrocatalyst according to claim 8, characterized in that the electrically conductive, electrochemically inert material is selected from at least one of graphite, glassy carbon, titanium, copper, nickel, gold, stainless steel.
10. An electrocatalyst, comprising:
an electrically conductive non-catalytically active support;
the electrocatalytic activity units are embedded in the conductive non-catalytic activity support and are distributed in a periodic array, and the electrocatalytic activity units are solid electrocatalytic activity units formed by sputtering deposition by means of a mask plate.
11. The electrocatalyst according to claim 10 wherein the electrically conductive non-catalyst support members comprise electrically conductive non-catalytically active support sub-members, the electrocatalytically active cells being sandwiched between the electrically conductive non-catalytically active support sub-members.
12. A method of preparing an electrocatalyst according to any one of claims 1 to 9, comprising: constructing template units distributed in a periodic array on the surface of the conductive non-catalytic active support, and then arranging an electrocatalytic active material layer on the surface of each template unit;
alternatively, the method of preparing the electrocatalyst comprises: the method comprises the following steps that an electrocatalytic active material is adopted to directly arrange electrocatalytic active units distributed in a periodic array on the surface of a conductive non-catalytic active support;
alternatively, the method of preparing the electrocatalyst comprises: the method comprises the steps of constructing electrocatalytically-active cells distributed in a periodic array on an electrically-conductive substrate, and then arranging an electrically-conductive non-catalytically-active support member between adjacent electrocatalytically-active cells.
13. A method of preparing an electrocatalyst according to any one of claims 7 to 9, comprising: solid electrocatalytic active units distributed in a periodic array are constructed on a conductive substrate through sputtering deposition by means of a mask plate, and then a conductive non-catalytic active support is arranged between the adjacent solid electrocatalytic active units.
14. Use of the electrocatalyst of any one of claims 1 to 9 to catalyse an electrochemical reaction comprising at least one of an electrochemical hydrogen evolution reaction, an electrochemical oxygen evolution reaction, an electrochemical hydrogen oxidation reaction, an electrochemical methanol oxidation reaction, an electrochemical formic acid oxidation reaction, an electrochemical carbon dioxide reduction reaction and an electrochemical nitrogen reduction reaction.
15. An electrocatalytic electrode comprising the electrocatalyst according to any one of claims 1 to 9.
16. An electrochemical reactor comprising the electrocatalytic electrode of claim 15; alternatively, comprising a membrane layer on which the electrocatalyst according to any one of claims 1 to 9 is disposed and an electrocatalyst selected from an ion exchange membrane or a gas membrane.
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