CN115275217A - Semi-continuous core-shell structure catalyst preparation device - Google Patents
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Abstract
The invention provides a semi-continuous core-shell structure catalyst preparation device which comprises a palladium surface cleaning reactor, a copper underpotential deposition reactor and a copper platinum replacement reactor which are sequentially connected through a pipeline, wherein the pipeline is provided with a valve and a pump, and the palladium surface cleaning reactor, the copper underpotential deposition reactor and the copper platinum replacement reactor are respectively provided with a feeding hole and a discharging hole. The semi-continuous core-shell structure catalyst preparation device provided by the invention has the advantages that the time required for large-batch preparation is similar to that of a small batch, the core-shell catalyst can be conveniently prepared in an enlarged manner, and the product catalyst has the same grade or better performance while the batch preparation is enlarged.
Description
Technical Field
The invention belongs to the field of fuel cells, and relates to a semi-continuous core-shell structure catalyst preparation device.
Background
In the field of pem fuel cells, the performance of the cathode catalyst is critical in determining whether a device can be commercialized on a large scale. The palladium platinum core-shell catalyst (hereinafter referred to as core-shell catalyst) has good catalytic quality specific activity and durability, and is known as a fuel cell catalyst of the next generation. The preparation of core-shell catalysts was first proposed by the Adzic team of the Brookhaven National Laboratory, USA, where three main steps are involved: (1) Cleaning the surface of the palladium nano-particles by an electrochemical method to remove impurities; (2) Generating a copper monolayer on the surface of the palladium nano-particles by a copper underpotential deposition (UPD) method; (3) Platinum ions are added to perform a surface redox reaction (SLRR) with the copper monolayer to form a structure in which the palladium core is coated with a platinum monolayer (Zhang, J., vukmicrovic, M.B., xu, Y., malrikakis, M., & Adzic, R.R. (2005). This fabrication technique was first implemented on a Rotating Disk Electrode (RDE), with single batches on the order of micrograms only. Subsequently, based on The three reaction steps described above, a number of methods for scale-up of production batches (e.g. in The development laboratory on The gram scale (Naohara, h.; sasaki, K.; adzic, R.R.platinum Monolayer catalysts for The Oxygen Reduction reaction.216th ECS Meeting; vienna, austria,2009.; khateeb, S., guerreo, S., su, D., darling, R.M., protsailo, L.V.and Shao, M.2016. Fuel cell performance of palladium-platinum core-shell catalysts, J.J.Joule of The Electrochemical catalysts 163 (7), P.F708; zhou, W.P., P.Sasaki, K.K., suzeki, D.S., zhang, Y.Wacker, W.P.S.J.S.S.S. Pat. No. 4332; U.S. Pat. No. 4,3232; U.S. Pat. No. 3,3232; see, J.S. Ser. No. 4,32; J.;. 4,32; U.S. Ser. 4,32; U.S. No. 2,32; J.;,32; U.S. Pat,32; U.S. Ser. Pat No. Ser. No. 2,32; I. Ser. 2,32; incorporated by No. 2,32, U.A. patents) for example, U.S. patents). The key for determining the performance of the core-shell catalyst is the thickness and coating uniformity of the platinum shell layer, and the three reaction steps can influence the appearance of the platinum shell layer in the preparation process. The surface cleaning and the copper UPD mainly use an electrochemical workstation to perform potential control on the surface of the palladium nanoparticle, and recently, the two reactions are also realized by a chemical method and electroless plating (electrolytic deposition). The surface displacement chemical reaction does not need potential control, and additives (such as citric acid and ethylene diamine tetraacetic acid) are added at the same time when the platinum salt solution is added, and the low temperature is controlled to slow down the copper-platinum SLRR reaction rate, so that a platinum shell layer with uniform thickness can be generated. However, as with many chemical processes, the core-shell catalyst produced by the process of scaling up is significantly inferior to the core-shell catalyst produced on RDE in terms of catalytic activity and durability because of problems of uneven mixing of materials, uneven heat transfer (concentration and temperature gradient are different from those of small batches), and uneven potential control. Considering that the core-shell catalyst is the key for reducing the cost of the new generation of fuel cells, the amplification preparation technology of the core-shell catalyst is very important for the fuel cell industry.
The existing core-shell catalyst preparation technology uses a single batch reactor, namely the three main reaction steps are carried out in time sequence in the same reactor. Essentially different reactions require different considerations in the amplification of production batches, such as surface cleaning involving potential control, copper underpotential deposition reactions, to promote good contact between the palladium nanoparticles and the electrodes while ensuring uniform potential distribution throughout the electrodes in the reactor. In the mass preparation (a large amount of carbon-supported palladium corresponds to a relatively small electrode active area, and a large current generates a polarization voltage difference), the requirements of the two points on the potential control reaction are difficult to realize. For another example, in the surface displacement reaction, the carbon-supported palladium dispersion and the platinum salt solution should be mixed quickly and efficiently to facilitate the formation of a platinum shell layer with uniform thickness. If the stirring and mixing are not intense enough, the concentration of platinum ions in the partial area of the reactor is higher, the replacement reaction rate is higher, and a platinum shell layer with partial thickness and poor coating property is easily generated. In view of the above, it is very difficult to optimize each reaction in the same reactor while considering various considerations specific to each reaction.
For the reasons mentioned above, the mass activity and durability of core-shell catalysts prepared in large batches in a single batch reactor currently still differ from those prepared by the RDE method (Shao, m., chang, q., dodelet, j.p., & Chenitz, r. (2016.). Recent advances in electrochemical catalysts for oxidative benzene reduction reactions.chemical reviews,116 (6), 3594-36).
Disclosure of Invention
The invention aims to provide a device for preparing a core-shell structure catalyst, which is more favorable for the amplification preparation of the core-shell catalyst, aiming at the technical problems to be solved.
In order to achieve the purpose, the invention provides a semi-continuous core-shell structure catalyst preparation device which comprises a palladium surface cleaning reactor, a copper underpotential deposition reactor and a copper platinum displacement reactor which are sequentially connected through a pipeline, wherein a valve and a pump are arranged on the pipeline, and the palladium surface cleaning reactor, the copper underpotential deposition reactor and the copper platinum displacement reactor are respectively provided with a feeding hole and a discharging hole.
According to the semi-continuous core-shell structure catalyst preparation device, preferably, a feed inlet of the palladium surface cleaning reactor is connected with a discharge outlet of the copper-platinum replacement reactor through a recovery pipeline.
According to the semi-continuous core-shell structure catalyst preparation apparatus of the present invention, preferably, one or more of the palladium surface cleaning reactor, the copper underpotential deposition reactor and the copper platinum displacement reactor has an agitator.
According to the semi-continuous core-shell structure catalyst preparation device, the pipeline is preferably a polytetrafluoroethylene pipe.
According to the semi-continuous core-shell structure catalyst preparation device, preferably, the pump is a peristaltic pump or an electronic injection pump.
According to the semi-continuous core-shell structure catalyst preparation device, preferably, one or more of the palladium surface cleaning reactor, the copper underpotential deposition reactor and the copper platinum replacement reactor is/are provided with at least one air inlet.
According to the semi-continuous core-shell structure catalyst preparation device, preferably, the number of the gas inlets is two.
According to the semi-continuous core-shell structure catalyst preparation device of the present invention, preferably, the gas inlet is connected to a gas supply source.
Compared with the prior art, the semi-continuous core-shell structure catalyst preparation device can realize independent optimization of individual reaction, and is more favorable for solving the difficult problem of core-shell catalyst in amplification preparation. The novel reactor design is more suitable for industrialized continuous production, and a recovery line can be added after proper treatment (removal of excessive chlorine, iron, platinum ions and the like), so that the preparation cost is further reduced.
Drawings
FIG. 1 is a schematic flow diagram of the main reaction steps for preparing a core-shell catalyst.
FIG. 2 is a schematic structural diagram of a semicontinuous core-shell structure catalyst preparation device according to the present invention.
Fig. 3 is a result comparing the specific activity of platinum group metal mass obtained by a mea (membrane electrode single cell) test of 10 g batch (left) of the semi-continuous core-shell catalyst preparation apparatus of the present invention and 1 g batch (right) of the core-shell catalyst prepared by the conventional batch single reactor.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
It is noted that some conventional technical procedures, reagents and apparatuses are not described in detail in the following examples for the sake of brevity and clarity, but it is understood that the conventional technical procedures, reagents and apparatuses are obvious to those skilled in the art if not specifically stated.
FIG. 1 is a schematic flow diagram of the main reaction steps for preparing the core-shell catalyst. As shown, core-shell catalyst preparation typically involves three main reactions: palladium surface cleaning, copper underpotential deposition and copper platinum displacement reaction.
As shown in fig. 2, the semicontinuous core-shell catalyst preparation apparatus of the present invention comprises a palladium surface cleaning reactor 1, a copper underpotential deposition reactor 2 and a copper platinum displacement reactor 3, which are connected in sequence via a pipeline, wherein the pipeline is provided with a valve 4 and a pump 5. The palladium surface cleaning reactor 1, the copper underpotential deposition reactor 2 and the copper platinum displacement reactor 3 are all provided with an upper feed inlet and a lower discharge outlet. The feed may be introduced into the respective reactor via a feed inlet (e.g. located in the upper part, which may be one or more) and the product may be withdrawn via a discharge outlet located, for example, in the lower part.
As shown in fig. 2, the apparatus for preparing a core-shell catalyst of the present invention is formed by connecting three reactors in series, and is used for performing palladium surface cleaning, copper underpotential deposition, and copper-platinum displacement reaction, respectively. By this design, individual optimization can be made for each reaction, which is beneficial to maintaining catalyst performance when scaling up production batches. The design of the core-shell structure catalyst preparation device is closer to a continuous process (still in a semi-continuous mode), the three reactors work and operate simultaneously, a recovery line can recycle partial raw materials, and the preparation cost is reduced. In contrast, the core-shell catalyst preparation process commonly used in the prior art allows three main reactions to be performed in a single reactor (batch type single reactor) in time sequence, and in the process of preparing a batch in an enlarged manner, the design limits some schemes for improving the reactor, so that the optimization of the preparation process becomes complicated and difficult. For example, in a batch type single reactor, when a platinum salt solution is added in the copper-platinum replacement reaction, a copper electrode should not be disposed in the reactor, and if copper simultaneous underpotential deposition is performed by the electroless plating method, the copper electrode must be removed and then the next copper-platinum replacement reaction can be performed. Therefore, the existing process is complicated and inconvenient.
The feed inlet of the palladium surface cleaning reactor 1 can be connected with the discharge outlet of the copper platinum displacement reactor 3 through a recovery pipeline 9. Thereby realizing the reaction again after the liquid phase solution is recovered, and being more environment-friendly and energy-saving. The recovery conduit 9 may be provided with a valve 4 and a pump 5.
One or more of the palladium surface cleaning reactor 1, the copper underpotential deposition reactor 2 and the copper platinum displacement reactor 3 may have a stirrer 8, such as a cantilever stirrer, to improve the reaction efficiency in the reactor.
The pipe 4 may be a teflon pipe, but is not limited thereto, and one skilled in the art may select any suitable material according to actual needs. The pump 5 may be, but is not limited to, a peristaltic pump or an electronic syringe pump. The pipeline 4 and the pump 5 are matched for use, so that the pollution to the catalyst and the pipeline blockage can be reduced.
The transfer of the catalyst dispersion between the reactors can be achieved by peristaltic pumps or electronic injection pumps, which are required to ensure gas tightness and avoid organic contamination.
One or more of the palladium surface cleaning reactor 1, the copper underpotential deposition reactor 2 and the copper platinum displacement reactor 3 has at least one gas inlet for introducing oxygen, argon, nitrogen, etc. The air inlet is arranged at the top of each reactor. The gas inlets may be one or two so as to pass one or two gases. The gas inlet may be connected by a conduit to a gas supply source such as an oxygen cylinder 6, an argon cylinder 7, etc. The gas supply conduit may be provided with a valve to control the gas flow.
The preparation method of the core-shell structure catalyst by using the core-shell structure catalyst preparation device comprises the following steps: firstly, carbon-supported nano palladium/dilute sulfuric acid solution which is uniformly dispersed is added into a palladium surface cleaning reactor 1, quantitative recovery line solution (containing copper sulfate, citric acid and palladium ions) can be simultaneously introduced, and the carbon-supported nano palladium is subjected to cyclic voltammetry potential scanning (CV) surface cleaning in an oxygen-free environment. In order to optimize the reaction and shorten the reaction time, a graphite net and carbon cloth can be selected as a working electrode and a counter electrode. Then, carbon-supported nano palladium dispersion liquid (a certain amount of copper sulfate solution is added when needed) with the surface cleaned is added into the copper underpotential deposition reactor 2, and copper underpotential deposition is carried out by a potentiostatic method (an external electrochemical workstation) or an electroless plating method (a copper counter electrode and a working electrode) in an oxygen-free environment. The electrode with high specific surface area can be selected to shorten the reaction time. Then, the catalyst which is deposited under the underpotential is added into a copper-platinum replacement reactor 3, a platinum salt solution (containing citric acid or ethylene diamine tetraacetic acid) which is deoxidized in advance is dripped under the environment of violent stirring and no oxygen to carry out surface oxidation reduction replacement reaction, the replacement reaction rate can be controlled by selecting cantilever type high-speed stirring matched with a baffle and controlling the temperature of ice water bath, and finally the palladium dissolution amount and the thickness of a platinum shell layer can be controlled by adjusting the oxygen content of the atmosphere in the reactor. After the reaction is finished, carrying out solid-liquid phase separation on the product of the copper-platinum replacement reactor 3, and drying the solid-phase catalyst after the solid-phase catalyst is cleaned by ammonium bicarbonate solution and ultrapure water to obtain the core-shell catalyst; the liquid phase product can be recycled and introduced into the palladium surface cleaning reactor 1 after being treated (for example, removing chloride ions, iron ions and platinum ions).
For the above process, considering that the initial current of the first step palladium surface cleaning is large, the counter electrode has high potential and tends to generate oxygen evolution reaction, the graphite counter electrode can be preferably selected and separated from the carbon-supported nano palladium dispersion liquid by a high number of sand cores. If the copper underpotential deposition is carried out by an external electrochemical workstation in the same way, a graphite counter electrode is used and carbon-loaded nano palladium dispersion liquid is separated; if the copper mesh working electrode and the counter electrode are used, an external workstation is not needed, but the copper counter electrode is gradually dissolved along with the reaction time, and the copper mesh working electrode and the copper mesh counter electrode are timely supplemented. The copper ion content in the liquid phase is properly adjusted according to the batch size, the mass ratio of the liquid phase copper ions to the solid phase palladium is between 0.5 and 20, and the copper ion content can be adjusted by a recovery line and an external copper sulfate solution. The thickness of the platinum shell and the platinum/palladium mass ratio of the final core-shell catalyst are determined by the copper-platinum displacement reaction and the post-treatment in the third step, and the adjustment of the thickness of the platinum shell and the platinum/palladium mass ratio of the final core-shell catalyst can be realized by regulating and controlling the mass ratio of an additive (citric acid or ethylene diamine tetraacetic acid) to an oxidant (ferric nitrate, ferric bromide or ferric chloride) and the atmospheric oxygen content. According to the added additive and oxidant, the recovery line is correspondingly post-treated to remove part of ions, and then the solution of the recovery line can be added into the palladium surface cleaning reactor.
Examples
The technical effects of the semicontinuous core-shell structure catalyst preparation apparatus of the present invention will be further described below by way of specific examples.
1. The raw materials for preparing the core-shell catalyst are as follows:
nuclear material, carbon supported nano palladium TKK TM TECPd (ONLY) F35; electrolyte solution (50 mM sulfuric acid aqueous solution); copper sulfate (Sigma-Aldrich) TM ) (ii) a Potassium chloroplatinite (Sigma-Aldrich) TM ) (ii) a Citric acid (Sigma-Al)drich TM ) (ii) a Ferric chloride (Sigma-Aldrich) TM )。
2. The device for preparing the semi-continuous core-shell structure catalyst is used for preparing the catalyst in 10 g-level batch, and comprises the following specific steps:
(1) 10.0g of carbon-supported nano palladium is uniformly dispersed in 700ml of ultrapure water, and a proper amount of concentrated sulfuric acid is added so that the liquid phase concentration is 50mM sulfuric acid. The carbon-supported nano palladium/sulfuric acid dispersion was added to the palladium surface cleaning reactor 1, and argon gas was introduced into the palladium surface cleaning reactor 1 for 30 minutes or more to remove oxygen, during which the dispersion was mixed at 300rpm using a cantilever stirrer. Connecting a palladium surface cleaning reactor 1 with an electrochemical workstation (a working electrode is connected with a bottom plate graphite plate of the reactor, a counter electrode is connected with carbon cloth, a reference electrode is connected with an Ag/AgCl electrode), stopping stirring, performing CV scanning to clean the palladium surface (0.36-0.45V vs. RHE reversible hydrogen electrode, 5mV/s scanning speed), stirring for 1 minute every 30 minutes in the process, performing CV scanning for 120 minutes totally, and conveying a product dispersion liquid to a copper underpotential deposition reactor 2 through a peristaltic pump (introducing argon to remove oxygen for 30 minutes in advance).
(2) Adding 100ml of 400mM copper sulfate solution into a copper underpotential deposition reactor 2 (introducing argon to remove oxygen for 30 minutes in advance), stirring until the mixture is uniformly mixed, stopping stirring to enable carbon-supported nano palladium to settle and contact a bottom plate, performing constant potential control on the bottom plate of the reactor by an electrochemical workstation for 0.36V vs. RHE (hydrogen ion) every 30 minutes, stirring for 1 minute every 30 minutes, controlling copper underpotential deposition for 360 minutes in total by constant potential, and transferring a product dispersion to a copper platinum replacement reactor 3 by a peristaltic pump (introducing argon to remove oxygen for 30 minutes in advance).
(3) 600ml of a platinum salt solution in which the concentration of platinum (II) ions was 17mM, citric acid was 0.2M, and sulfuric acid was 50mM was prepared, argon was introduced to remove oxygen for 30 minutes or more, and then it was introduced into a copper-platinum displacement reactor 3 by a peristaltic pump, and the carbon-supported nano-palladium dispersion for depositing copper was added dropwise while mixing the dispersion at 400rpm using a cantilever stirrer in conjunction with a baffle, and this step was continued until 40 minutes after the completion of the addition of the platinum salt solution. 410mg of ferric chloride was dissolved in 10ml of 50mM dilute sulfuric acid, and the above solution was added to the copper-platinum substitution reactor 3 to mix with the catalyst dispersion (stirring at 300 rpm), and oxygen was introduced into the copper-platinum substitution reactor 3, and the reaction was stopped after 12 hours.
(4) Stopping stirring to enable the catalyst to naturally settle, separating the catalyst from a liquid phase in a vacuum filtration mode on a lower layer, sequentially washing the catalyst by ultrapure water, an ammonium bicarbonate solution and the ultrapure water for multiple times, and drying the catalyst in vacuum at 80 ℃ to obtain the 10 g-grade core-shell catalyst. The solution in the upper layer of the copper platinum displacement reactor 3, after being treated (except for platinum, iron and chloride ions), can be introduced into the palladium surface cleaning reactor 1 again for the next synthesis.
Comparative example
The following comparative experiment using a conventional batch single reactor of the prior art (see US10,497,942, fig. 1) for a batch of 1 gram, a core-shell catalyst was prepared as follows:
1.0g of carbon-supported nano palladium was dispersed in 600ml of ultrapure water, and an appropriate amount of concentrated sulfuric acid was added to make the liquid-phase sulfuric acid concentration 50mM. The carbon-supported nano palladium/sulfuric acid dispersion was poured into a batch-type single reactor, argon gas was introduced to remove oxygen for over 30 minutes, during which time the dispersion was mixed at 300rpm using magnetic stirring. Connecting the reactor with an electrochemical workstation (a working electrode is connected with a graphite plate at the bottom plate of the reactor, a counter electrode is connected with carbon cloth, a reference electrode is connected with an Ag/AgCl electrode), stopping magnetic stirring, starting CV scanning to clean the palladium surface (0.36-0.45V vs. RHE reversible hydrogen electrode, 5mV/s sweep speed), stirring for 1 minute every 30 minutes, and CV scanning for 120 minutes. 100ml of 350mM copper sulfate solution was prepared, argon gas was introduced to remove oxygen for 30 minutes or longer, and the mixture was introduced into a reactor by a peristaltic pump and mixed with the carbon-supported nano palladium dispersion. And (3) carrying out constant potential control on the bottom plate of the reactor by using an electrochemical workstation at 0.36V vs. RHE, stopping magnetic stirring to enable the carbon-supported nano palladium to settle and contact with the bottom plate, and stirring for 1 minute every 30 minutes, wherein the constant potential controls copper underpotential deposition to last for 360 minutes. 500ml of a platinum salt solution in which the platinum (II) ion concentration was 2mM, citric acid was 0.2M, and sulfuric acid was 50mM was prepared, and deoxygenated by introducing argon gas for 30 minutes or more, and introduced into a reactor by a peristaltic pump, and the carbon-supported nano-palladium dispersion for copper deposition was added dropwise while mixing the dispersion at 400rpm using magnetic stirring, and this step was continued until 40 minutes after the completion of the addition of the platinum salt solution. 350mg of ferric chloride was dissolved in 10ml of 50mM dilute sulfuric acid, and the solution was added to a reactor and mixed with a catalyst dispersion (magnetically stirred at 300 rpm), and oxygen gas was introduced into the reactor, and the reaction was stopped after 12 hours. Separating the catalyst from the liquid phase in a vacuum filtration mode, washing the catalyst with ultrapure water, ammonium bicarbonate solution and ultrapure water for multiple times in sequence, and drying the catalyst in vacuum at the temperature of 80 ℃ to obtain the batch type single-reactor 1 g-grade core-shell catalyst.
The core-shell catalysts obtained in the above examples and comparative experiments were prepared as membrane electrodes (core-shell catalyst at cathode and commercial TKK Pt/C catalyst at anode with loading of 0.10mg Pt /cm 2 ) At 25cm 2 And testing by a single cell method. Specific mass activity test conditions: 0.9V, hydrogen/oxygen, 100/100% RH,80 ℃,150/150kPa (abs) Backpressure, compensated by high frequency impedance and permeation current. Aging test conditions: hydrogen/nitrogen 100/100% RH,80 deg.C, atmospheric pressure, constant voltage of 0.60, 0.95V each for 3 seconds, 3 ten thousand cycles of square wave.
The results of the experiment are shown in FIG. 3. The platinum specific activity of the catalyst of example reached 1.23A/mg Pt The specific mass activity of Platinum Group Metal (PGM) is 0.56A/mg PGM After an aging test (3 ten thousand cycles of square wave circulation, 0.60V and 0.95V constant voltage for 3 seconds) formulated by the United states department of energy (DOE), the activity is attenuated by 29 percent; the specific activity of platinum mass for the comparative experimental catalyst was 1.07/mg Pt PGM specific mass activity was 0.52A/mg PGM Activity decays by 38% after DOE aging test. The experimental result proves that compared with the conventional batch single reactor, the semi-continuous core-shell structure catalyst preparation device has the advantages that the preparation time required by a large batch is similar to that of a small batch, the amplification preparation of the core-shell catalyst is more facilitated, and the product catalyst has the same grade or better performance while the preparation batch is amplified.
The above embodiments are merely exemplary and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (8)
1. A semi-continuous core-shell structure catalyst preparation device is characterized in that: the device for preparing the core-shell structure catalyst comprises a palladium surface cleaning reactor, a copper underpotential deposition reactor and a copper platinum displacement reactor which are sequentially connected through a pipeline, wherein a valve and a pump are arranged on the pipeline, and the palladium surface cleaning reactor, the copper underpotential deposition reactor and the copper platinum displacement reactor are both provided with a feeding hole and a discharging hole.
2. The apparatus for preparing a core-shell structured catalyst according to claim 1, characterized in that: and the feed inlet of the palladium surface cleaning reactor is connected with the discharge outlet of the copper-platinum displacement reactor through a recovery pipeline.
3. The apparatus for preparing a core-shell structured catalyst according to claim 1, characterized in that: one or more of the palladium surface cleaning reactor, the copper underpotential deposition reactor and the copper platinum displacement reactor has an agitator.
4. The apparatus for preparing a core-shell structured catalyst according to claim 1, characterized in that: the pipeline is a polytetrafluoroethylene pipe.
5. The apparatus for preparing a catalyst having a core-shell structure according to claim 1, wherein: the pump is a peristaltic pump or an electronic syringe pump.
6. The apparatus for preparing a core-shell structured catalyst according to claim 1, characterized in that: one or more of the palladium surface cleaning reactor, the copper underpotential deposition reactor and the copper platinum displacement reactor has at least one gas inlet.
7. The apparatus for preparing a core-shell structured catalyst according to claim 6, characterized in that: the number of the air inlets is two.
8. The core-shell structure catalyst preparation apparatus according to claim 6 or 7, characterized in that: the air inlet is connected with an air supply source.
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