CN111841663A - Electrochemical method for reducing size of carbon-supported metal nanoparticle electrocatalyst - Google Patents
Electrochemical method for reducing size of carbon-supported metal nanoparticle electrocatalyst Download PDFInfo
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- 238000002848 electrochemical method Methods 0.000 title claims abstract description 12
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- 238000000034 method Methods 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 70
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- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
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- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
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- 230000003213 activating effect Effects 0.000 description 2
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- QAKLCUQMLFFUHY-UHFFFAOYSA-N [N].[Pt] Chemical compound [N].[Pt] QAKLCUQMLFFUHY-UHFFFAOYSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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Abstract
The invention discloses an electrochemical method for reducing the size of a carbon-supported metal nanoparticle electrocatalyst, which is characterized in that an electrochemical two-electrode or three-electrode system is constructed, wherein a working electrode is a carbon-supported metal nanoparticle electrode, and then a negative potential lower than-1V is directly and continuously applied to the working electrode in an alkaline solution or a salt solution of which the electrolyte is alkali metal, so that the size of the carbon-supported metal nanoparticle electrocatalyst can be reduced. The method has the advantages of simple and convenient operation, low energy consumption and short time consumption, can be used for preparing the small-size metal catalyst and reactivating the agglomerated metal catalyst, well solves the problems that the prior art is difficult to convert large-size metal particles into small-size particles, or the conversion process involves high-temperature treatment conditions and is not suitable for application under electrochemical conditions, and provides a good preposed basis for the application of the small-size metal catalyst in the fields of water electrolysis, fuel cells and the like. Therefore, the invention is very suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to an electrochemical method for reducing the size of a carbon-supported metal nanoparticle electrocatalyst.
Background
The metal (such as platinum, palladium, copper and the like) nanoparticle electrocatalyst has good catalytic activity in electrocatalytic reactions such as a hydrogen evolution reaction, an oxygen reduction reaction, a carbon dioxide reduction reaction and the like, and has important application in the fields of hydrogen energy acquisition, fuel cells and the like. In order to enhance the dispersion and conductivity of the metal nanoparticle catalyst, the catalyst is usually supported on a carbon material (e.g., conductive carbon black, carbon cloth), and then coated on the surface of an electrode or directly used as a self-supporting electrode in an electrocatalytic reaction. In electrocatalytic reactions, the size of the metal nanoparticles has a large influence on the catalytic activity. Generally, the small-sized nanoparticles have larger specific surface area and higher surface energy, and can realize higher catalytic activity. If the metal nanoparticles are reduced in size to the atomic scale, higher catalytic activity and unique selectivity can be achieved for some electrocatalytic reactions. However, small-sized metal nanoparticles or metal atoms have high surface energy and are easy to aggregate, so that the preparation difficulty is extremely high. In addition, the metal nano particles are easy to migrate and agglomerate into large-size particles in the catalytic reaction process, so that the catalytic activity of the metal nano particles is reduced. If the size of the nanoparticles in these reduced activity catalyst systems is reduced again, reactivation to small size nanoparticles will greatly restore catalyst activity. Therefore, the development of a simple and effective technology for reducing the size of the metal nanoparticles has important significance in the fields of catalyst preparation and reactivation.
At present, the conversion of large-size metal particles into small-size metal particles mainly depends on an inverse Ostwald ripening process, namely, a proper substrate is introduced under a high-temperature condition, metal bonds are destroyed by thermal diffusion, and the small-size metal particles, atom clusters and even metal monoatomic atoms are stabilized by the aid of strong interaction between the substrate and metal. However, the method not only needs high-temperature treatment, but also has harsh conditions and serious energy waste; the method is mainly suitable for preparing powder materials, and when the method is applied to electrocatalysis reaction, a binder needs to be further introduced, so that the electrochemical active area of the catalyst is reduced, the transportation of electrolyte and gas reactants or products is hindered, the catalysis of reactions such as hydrogen evolution, oxygen reduction and the like is inconvenient, and particularly the catalytic activity and stability of the electrode under high current density are reduced. In addition, when the heat treatment method is applied to the process of activating the electrocatalyst, the operation involves a plurality of steps of stripping the catalyst from the electrode surface, activating the catalyst, re-coating the catalyst and the like due to the great difference between the using condition of the electrocatalyst and the heat treatment condition, so that the operation is complex and long in time consumption, the electrode surface and the whole electrocatalysis system are easily damaged in the process, and the practical application is severely limited.
Therefore, there is a need for a method for reducing the size of the carbon-supported metal nanoparticles and even obtaining atomic catalysts under electrochemical conditions.
Disclosure of Invention
The invention aims to provide an electrochemical method for reducing the size of a carbon-supported metal nanoparticle electrocatalyst, and mainly solves the problems that in the prior art, large-size metal particles are difficult to convert into small-size particles, or high-temperature treatment conditions are involved in the conversion process, so that the conversion process is not suitable for being applied under electrochemical conditions.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an electrochemical method for reducing the size of carbon-supported metal nanoparticle electrocatalyst is to construct an electrochemical two-electrode or three-electrode system, wherein a working electrode is a carbon-supported metal nanoparticle electrode, and then in an alkaline solution or a salt solution of which an electrolyte is an alkali metal, a negative potential lower than-1V is directly and continuously applied to the working electrode, so that the size of the carbon-supported metal nanoparticle catalyst can be reduced.
Preferably, a complex potential of less than-1V is continuously applied to the working electrode for a holding time of greater than 1 min.
Preferably, platinum or graphite is used as the counter electrode when constructing the electrochemical two-electrode system.
Or when an electrochemical three-electrode system is constructed, platinum or graphite is used as a back electrode, and any one of a mercury/mercury oxide electrode, a silver/silver chloride electrode and a calomel electrode is used as a reference electrode.
Specifically, in the carbon-supported metal nanoparticle electrode, the carbon material is any one of graphene, carbon nanotubes, carbon cloth, carbon paper, graphite foil and corresponding dopants.
Specifically, in the carbon-supported metal nanoparticle electrode, the metal is any one of platinum, palladium, gold, silver, iridium, copper, nickel, iron and cobalt.
Specifically, when the electrolyte is an alkali solution of an alkali metal, the alkali is a hydroxide of any one of lithium, sodium and potassium.
Or, when the electrolyte is a salt solution of an alkali metal, the salt is any one of sulfate, carbonate, hydrochloride and nitrate.
Specifically, the carbon-supported metal nanoparticle electrode is obtained by loading metal nanoparticles on a carbon material and then coating the carbon-supported metal nanoparticle electrode on the surface of the electrode; or the metal nano particles are loaded on the carbon material and then directly used as a self-supporting electrode, and the self-supporting electrode is the carbon-loaded metal nano particle electrode.
Alternatively, the carbon-supported metal nanoparticle electrode is a carbon-supported metal nanoparticle electrode that has been used and in which the metal particles have agglomerated.
The design principle of the invention is as follows: under an electrochemical two-electrode or three-electrode system, a carbon-supported metal catalyst is used as a working electrode, a larger negative potential is applied in an alkali metal salt solution, and a cathode corrosion phenomenon is utilized, so that large-size metal particles can be converted into small-size metal particles, even metal single atoms.
Compared with the prior art, the invention has the following beneficial effects:
(1) compared with the method for reducing the size of the catalyst by heat treatment, the method is carried out in a water phase system, does not relate to a high-temperature treatment process, and has short treatment time; and the damage of the surface of the electrode and the whole electro-catalytic system does not exist, and the treatment mode is simpler and more reliable. Thus being completely suitable for application under electrochemical conditions.
(2) Because the invention combines the continuous application of negative potential in the aqueous phase system to realize the reduction of the size of the metal catalyst, based on the characteristic, the invention is suitable for various carbon materials and adulterant matrixes thereof and is suitable for various metal nanoparticle systems; the method is suitable for powder materials and self-supporting electrode systems; the method can be used for preparing the metal catalyst and also can be used for reactivating the agglomerated metal nanoparticle catalyst; has the effect of reducing the size of metal nanoparticle systems with different sizes, and can prepare metal monatomic catalysts. Therefore, the invention has good universality, well breaks through the limitation of the prior art, meets the preparation of various carbon-supported metal (such as platinum, palladium, copper and the like) nano-particle electrocatalysts and the regeneration of catalytic activity, provides a good preposed foundation for the application of small-size metal catalysts in the fields of water electrolysis, fuel cells and the like, and is very suitable for popularization and application.
(3) The electrolyte has wide selection range, can directly change the potential to carry out in situ (such as the electrolytic water catalyst in an alkaline electrolytic cell) for some reactions without replacing the electrolyte, well considers the balance between the operation efficiency and the cost, and flexibly meets the requirements of practical application.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
FIG. 2 shows the present invention-example 1: (a) scanning electron microscope images of the platinum particles and the aza-carbon cloth before electrochemical treatment; (b) scanning electron microscope images of the platinum particles and the monoatomic mixture after electrochemical treatment for 5 minutes; (c) a transmission scanning electron microscope image of spherical aberration correction of the monatomic platinum after electrochemical treatment for 10 minutes; (d) scanning electron microscope images of the prepared single atom platinum-aza carbon cloth.
FIG. 3 shows a diagram of a single-atom Pt-AZA carbon cloth as a self-supporting electrode for catalyzing hydrogen evolution reaction in example 1 of the present invention: (a) a polarization curve graph; (b) tafel plot; (c) an accelerated degradation test schematic; (d) schematic diagram of potentiostatic testing.
FIG. 4 shows the present invention-example 2: (a, b) scanning electron micrographs of platinum particles-carbon cloth before electrochemical treatment; (c, d) scanning electron micrographs of platinum particles-carbon cloth reduced in size after electrochemical treatment.
FIG. 5 shows the present invention-example 3: (a, b) scanning electron micrographs of copper particles-carbon cloth before electrochemical treatment; (c, d) scanning electron micrographs of copper particles-carbon cloth reduced in size after electrochemical treatment.
FIG. 6 shows the present invention-example 4: (a) scanning electron microscope image of gold particle-carbon cloth before electrochemical treatment; (b) scanning electron microscopy of gold particles-carbon cloth with reduced size after electrochemical treatment.
Detailed Description
The invention provides a method for reducing the size of a plurality of carbon-supported metal nanoparticle electrocatalysts, which can be carried out under electrochemical conditions, has the advantages of simple and convenient operation, low energy consumption and short time consumption, and can be used for preparing small-size metal catalysts and reactivating agglomerated metal catalysts. The process of the invention is summarized and mainly divided into the construction of an electrolytic system and the reduction of the metal particle size by negative potential treatment, as shown in figure 1.
Firstly, an electrolytic system is constructed. In the invention, the carbon-supported metal nanoparticle catalyst is used as a working electrode to construct a three-electrode system or a two-electrode system, and an alkali or salt solution of an alkali metal is used as an electrolyte. Specifically, the carbon-supported metal nanoparticle electrode is obtained by loading metal nanoparticles on a carbon material (for example, carbon-supported metal nanoparticles are prepared by chemical reduction, electrodeposition and the like), and then coating the carbon-supported metal nanoparticle electrode on the surface of the electrode or directly using the carbon-supported metal nanoparticle electrode as a self-supporting electrode, or using a carbon-supported metal particle system in which metal particles are aggregated for a period of time. The carbon material has no special requirement, and can be graphene, carbon nanotubes, carbon cloth, carbon paper, graphite foil and other carbon materials and corresponding dopants of the carbon materials; the metal has wide application range and can be nanoparticles of metals such as platinum, palladium, gold, silver, iridium, copper, nickel, iron, cobalt and the like; the alkali metal alkali or salt solution is selected from a wide range, and can be hydroxide solution of alkali metals such as lithium, sodium, potassium and the like, and solution of sulfate, carbonate, hydrochloride, nitrate and the like. In a word, the electrolytic system has wide selection range, is suitable for various metal types, and is suitable for nano particles with different sizes.
Followed by negative potential treatment to reduce the metal particle size. In the invention, a larger negative potential is applied to the working electrode and is kept for a period of time, so that the size of the carbon-supported metal nanoparticle catalyst can be effectively reduced. Specifically, different negative potentials can be selected for different metals, and the magnitude of the negative potential affects the rate of size reduction of the metal particles and the rate of metal loss during processing. The negative potential adopted by the embodiment is lower than-1V, and the processing time is longer than 1 min. Under the treatment condition, the method has the characteristics of short electrochemical treatment time, relatively mild treatment condition, small influence on a carbon material carrier and small influence on an original electrolysis system, and can realize the reactivation of the catalyst in situ under some conditions.
The invention is further illustrated by the following description and examples in conjunction with the accompanying drawings.
Example 1
And performing 0.2V electro-deposition on the aza-carbon cloth in a chloroplatinic acid solution to prepare the platinum nano-particle-aza-carbon cloth self-supporting electrode. A three-electrode system is formed by taking platinum nano particles-nitrogen-doped carbon cloth as a working electrode, a platinum net as a counter electrode and mercury/mercury oxide as a reference electrode. Treating in 10mol/L sodium hydroxide solution at negative potential of-8V for 10min, and rinsing with deionized water to obtain the monatomic platinum-nitrogen-doped carbon cloth self-supporting electrode.
As can be seen from FIG. 2a, the platinum particle size in the platinum nanoparticle-aza-carbon cloth is about 2nm, and the size distribution is not uniform. After 5min of-8V treatment, the large size particles disappeared and platinum clusters (around 1 nm) co-existed with platinum single atoms (see FIG. 2 b). The electrochemical treatment is continued for 10min, and uniformly distributed platinum monoatomic atoms can be obtained (see fig. 2 c).
In addition, the existence of large-size platinum particles is not observed in the scanning electron micrograph, the surface morphology is not greatly influenced by the electrochemical treatment process, and the nitrogen-doped carbon cloth substrate still maintains the nano-array structure (see fig. 2 d). The prepared platinum monoatomic-aza-carbon cloth is used for catalyzing hydrogen evolution reaction, and the electrode can be found in the condition that the current density is 10mA cm-2The time overpotential is only 0.022V, and the platinum nanoparticle-aza-carbon cloth electrode (0.032V) before electrochemical treatment is superior to the commercial platinum nanoparticle-aza-carbon cloth electrodePlatinum charcoal catalyst (0.041V) (see FIG. 3 a). The Tafel slope of the reaction for hydrogen evolution catalyzed by platinum monoatomic-aza-carbon cloth is 29.5mV dec-1Is superior to a platinum nano particle-nitrogen-doped carbon cloth electrode (36.3mV dec) before electrochemical treatment-1) (see FIG. 3 b). Moreover, the platinum monoatomic-azacarbon cloth also shows good stability, and the polarization curve of the cloth is basically kept unchanged after 5000 circles of accelerated degradation experiments (see fig. 3c), and the current density of the cloth is basically kept unchanged under a constant potential test of 100h (see fig. 3 d).
Example 2
The gold nanoparticle-carbon cloth composite electrode prepared by a chemical reduction method is used as a working electrode, a platinum mesh is used as a counter electrode, and a silver/silver chloride electrode is used as a reference electrode to form a three-electrode system. Treating in 1mol/L sodium sulfate solution at-10 negative potential for 10min, and rinsing with deionized water to obtain gold particles with reduced size.
As can be seen from FIGS. 4a and b, the gold particle size of the gold nanoparticle-carbon cloth is about 500nm, and the size distribution and the spatial distribution are extremely uneven. After electrochemical treatment, the large-sized particles disappeared, and the gold nanoparticles of about 50nm size were uniformly dispersed on the surface of the carbon cloth (see fig. 4c, d).
Example 3
The copper nano particle-carbon cloth composite electrode prepared by an electrochemical reduction method is used as a negative electrode, and a platinum net is used as a positive electrode to form a two-electrode system. And (3) applying 10V voltage to a potassium sulfate solution of 1mol/L, treating for 20min, and then rinsing with deionized water to obtain the copper particles with reduced size.
As can be seen from FIGS. 5a and b, the size of copper particles in the copper nanoparticle-carbon cloth is about 800nm, and the spatial distribution is not uniform. After electrochemical treatment, the large-sized particles disappeared, and the copper nanoparticles having a size of about 40nm were uniformly dispersed on the surface of the carbon cloth (see fig. 5c, d).
Example 4
A commercial Pt/C catalyst with reduced activity is used as a working electrode, graphite is used as a counter electrode, and a calomel electrode is used as a reference electrode to form a three-electrode system. Treating at-5V for 10min in 2mol/L potassium chloride solution, and rinsing with deionized water to obtain platinum particles with reduced size.
As can be seen from FIG. 6a, the Pt/C catalyst with reduced activity had a very uneven size distribution of the platinum particles, and a large number of the platinum particles were agglomerated into particles of about 20nm in size. After the electrochemical treatment, the large-sized particles disappeared, and the platinum nanoparticles having a size of about 3nm were uniformly dispersed on the surface of the carbon substrate (see fig. 6 b).
The above examples are only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the technical problems solved by the present invention should be consistent with the present invention, and should be included in the scope of the present invention, unless there is any meaningful change or retouching in the spirit and concept of the subject invention.
Claims (10)
1. An electrochemical method for reducing the size of carbon-supported metal nanoparticle electrocatalyst is characterized by constructing an electrochemical two-electrode or three-electrode system, wherein a working electrode is a carbon-supported metal nanoparticle electrode, and then in an alkaline solution or a salt solution of which the electrolyte is an alkali metal, a negative potential lower than-1V is directly and continuously applied to the working electrode, so that the size of the carbon-supported metal nanoparticle catalyst can be reduced.
2. An electrochemical process for reducing the size of a carbon-supported metal nanoparticle electrocatalyst according to claim 1, wherein a complex potential of less than-1V is applied to the working electrode continuously for a retention time greater than 1 min.
3. An electrochemical process for reducing the size of carbon-supported metal nanoparticle electrocatalysts as in claim 2, wherein platinum or graphite is used as the counter electrode when constructing the electrochemical two-electrode system.
4. An electrochemical method for reducing the size of carbon-supported metal nanoparticle electrocatalysts according to claim 2, wherein platinum or graphite is used as a back electrode and any one of mercury/mercury oxide electrode, silver/silver chloride electrode and calomel electrode is used as a reference electrode when an electrochemical three-electrode system is constructed.
5. The electrochemical method for reducing the size of the carbon-supported metal nanoparticle electrocatalyst according to any one of claims 1 to 4, wherein in the carbon-supported metal nanoparticle electrode, the carbon material is any one of graphene, carbon nanotubes, carbon cloth, carbon paper, graphite foil and corresponding dopants.
6. An electrochemical process for reducing the size of a carbon-supported metal nanoparticle electrocatalyst according to claim 5, wherein the metal in the carbon-supported metal nanoparticle electrode is any one of platinum, palladium, gold, silver, iridium, copper, nickel, iron, cobalt.
7. An electrochemical method for reducing the size of carbon-supported metal nanoparticle electrocatalysts according to claim 6, wherein when the electrolyte is an alkali solution of an alkali metal, the alkali is a hydroxide of any one of lithium, sodium and potassium.
8. An electrochemical method for reducing the size of carbon supported metal nanoparticle electrocatalysts according to claim 6, wherein when the electrolyte is a solution of a salt of an alkali metal, the salt is any one of a sulfate, a carbonate, a hydrochloride and a nitrate.
9. An electrochemical method for reducing the size of a carbon-supported metal nanoparticle electrocatalyst according to claim 1, 2, 3, 4, 6, 7 or 8, wherein the carbon-supported metal nanoparticle electrode is obtained by supporting metal nanoparticles on a carbon material and then coating the carbon-supported metal nanoparticle electrode surface; or the metal nano particles are loaded on the carbon material and then directly used as a self-supporting electrode, and the self-supporting electrode is the carbon-loaded metal nano particle electrode.
10. An electrochemical process for reducing the size of a carbon-supported metal nanoparticle electrocatalyst according to claim 1, 2, 3, 4, 6, 7 or 8, wherein the carbon-supported metal nanoparticle electrode is a carbon-supported metal nanoparticle electrode that has been used and in which metal particles have agglomerated.
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