CN108565476B - Preparation method and application of ternary CoAuPd @ AuPd core-shell catalyst for fuel cell - Google Patents

Preparation method and application of ternary CoAuPd @ AuPd core-shell catalyst for fuel cell Download PDF

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CN108565476B
CN108565476B CN201810113846.4A CN201810113846A CN108565476B CN 108565476 B CN108565476 B CN 108565476B CN 201810113846 A CN201810113846 A CN 201810113846A CN 108565476 B CN108565476 B CN 108565476B
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coaupd
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CN108565476A (en
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周新文
罗来明
陈迪
胡青云
张荣华
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China Three Gorges University CTGU
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention relates to a preparation method of a fuel cell catalyst, electrochemical dealloying and application thereof. The synthesis method adopts a continuous reduction method and comprises the following steps: triblock copolymer P123 acts as a protecting agent and sodium borohydride acts as a reducing agent. Dissolving a certain amount of P123 in secondary distilled water, adding cobalt chloride solution into the P123 solution, introducing nitrogen to remove oxygen before reaction, and continuously stirring, wherein the reaction temperature is controlled at room temperature (30 ℃). And slowly dropwise adding a sodium borohydride solution into the reaction liquid, and then slowly dropwise adding a mixed solution of chloroauric acid and potassium chloropalladate into the reaction liquid 30 minutes after the dropwise adding is finished, and stopping the reaction after 4 hours. And centrifuging and washing the reaction liquid for three to five times to obtain the ternary CoAuPd alloy catalyst for the fuel cell. The special ternary CoAuPd alloy catalyst has excellent methanol catalytic oxidation performance and oxygen reduction catalytic activity after electrochemical gradient dealloying, and is a fuel cell catalyst with great development prospect.

Description

Preparation method and application of ternary CoAuPd @ AuPd core-shell catalyst for fuel cell
Technical Field
The invention belongs to the technical field of fuel cells, relates to a preparation method and dealloying of a catalyst, and particularly relates to a preparation method and an electrochemical gradient dealloying method of a fuel cell catalyst CoAuPd.
Background
The wide application of traditional fossil energy petroleum, coal, natural gas and the like not only aggravates the energy crisis, but also has low energy conversion efficiency, and can discharge a large amount of toxic and harmful gases in the use process, thereby causing environmental pollution, global warming and haze. The fuel cell takes combustible gas such as hydrogen, natural gas, coal gas and the like and liquid such as methanol, ethanol, formic acid and the like as raw materials, chemical energy in the fuel is directly converted into electric energy through electrode reaction, and the energy conversion efficiency is not limited by Carnot cycle because the reaction process does not involve combustion, and reaches 60% -80%. The direct methanol fuel cell uses methanol as a cell fuel, has the advantages of low raw material price, convenient storage, clean exhaust, low noise, small environmental pollution, high theoretical specific energy density, quick response and the like, and is a mainstream power supply of future portable electronic products and fuel cell automobiles. Compared with a hydrogen fuel cell, the direct methanol fuel cell does not need an external reforming and hydrogen purification device, is convenient to carry and store, solves the problem of hydrogen source, but also has the problems of catalyst poisoning, fuel permeation and the like. For example, methanol fuel can generate CO-like intermediate products in the oxidation process, and the CO-like intermediate products can be strongly adsorbed on the surface of the catalyst and occupy catalytic active sites, so that the activity of the catalyst and the performance of a battery are reduced. The development of more efficient methanol oxidation and oxygen reduction catalysts is therefore the most critical aspect of the direct methanol fuel cell research field.
At present, the Pt-based catalyst is still the mainstream catalyst of the direct methanol fuel cell, but the noble metal Pt has large using amount, small storage amount, high price, easy poisoning by intermediate products, slow kinetics of oxygen reduction reaction, low stability of the catalyst, fuel permeation and the like. Compared with Pt-based catalysts, Pd and Pt have very similar properties, belong to the same main group on the periodic table of elements, have crystal structures of face-centered cubic structures and similar atomic radii, have Pd reserves 50 times that of Pt, are low in price and have good activity on oxygen reduction. On the basis of a pure Pd catalyst, another metal Au is introduced to form a binary PdAu alloy catalyst, so that the dosage of Pd can be reduced, the catalytic activity can be improved by utilizing the alloy effect (lattice deformation effect and surface ligand effect), and the structural stability of the catalyst can be enhanced. Dealloying can cause the active metal on the surface of the catalyst to be dissolved, so that a rough surface and more reactive active sites are formed, and the dealloying method is an effective means for regulating and controlling the surface composition and the electronic effect of the catalyst. According to the invention, on the basis of the binary PdAu catalyst, non-noble metal Co is introduced to form a ternary CoAuPd alloy catalyst, so that the use amount of noble metal is further reduced, and the catalytic activity of the catalyst is improved. Meanwhile, the characteristic that non-noble metal Co is easily dissolved in acid is utilized to carry out dealloying on the ternary CoAuPd alloy catalyst, so that the catalytic activity of the ternary CoAuPd alloy catalyst is improved.
Aiming at the technical problems, the preparation method is a simple continuous reduction synthesis technology, the protective agent is a triblock copolymer P123, the reducing agent is sodium borohydride, firstly, the Co nanocrystalline is reduced by the sodium borohydride, then, the Co nanocrystalline is used as a seed crystal, and the potential difference between Co and Pd as well as Au is utilized to carry out potential displacement reaction. The ternary CoAuPd alloy catalyst with two special structures including a novel three-dimensional nanometer thorn structure, a three-dimensional nanometer framework cluster structure and a hollow structure is prepared by utilizing ferromagnetism of Co crystal seeds and multi-stage self-assembly. The post-treatment method of the catalyst is an electrochemical gradient dealloying technology, an electrochemical test system is a three-electrode system, the dealloying method is carried out in an acid electrolyte by adopting a cyclic voltammetry method, and the gradient dealloying test result is detected by a methanol oxidation reaction and an oxygen reduction reaction. The CoAuPd @ AuPd core-shell structure and the rough binary AuPd alloy surface are formed after electrochemical de-alloying, so that the methanol catalysis and oxygen reduction catalysis performance of the catalyst is further improved, and the more efficient methanol oxidation and oxygen reduction catalyst for the direct methanol fuel cell is prepared.
Disclosure of Invention
The invention aims to synthesize a ternary CoAuPd alloy nano catalyst with two special morphological structures including a novel three-dimensional nano thorn structure and/or a three-dimensional nano cluster structure by a continuous reduction method, and the ternary CoAuPd alloy nano catalyst has excellent catalytic activity and stability, and then the catalytic performance of the catalyst can be further improved by an electrochemical gradient dealloying method. If two self-assembly structures are included, the content distribution ratio of the two super three-dimensional self-assembly structures is the nano thorn structure: the nano-cluster structure is 1: 1-100.
The fuel cell catalyst CoAuPd has a super three-dimensional nanometer thorn structure, and the structure is formed by multi-stage self-assembly; wherein the average particle size of the three-dimensional nano thorn structure is 130.65 +/-45.73 nm; assembled into nano-particlesThe average length of the two-dimensional nano feather-like particles of the thorn is 19.76 +/-5.44 nm; the electrochemical active area (ECSA) after electrochemical gradient dealloying is 1-200 m2/gPdThe atomic content molar ratio of Co, Au and Pd is close to 1: 1-x: 1-y, wherein x and y are 5% and 5%.
Further preferably, the atomic content molar ratio of Co, Au and Pd is 1:1: 1.
the fuel cell catalyst CoAuPd has a super three-dimensional nano cluster structure, and the structure is formed by multi-stage self-assembly; wherein the average grain diameter of the three-dimensional nano cluster structure is 26.10 +/-4.30 nm; the average grain diameter of the nano particles which are assembled into a hollow structure and a solid structure of the nano cluster is 7.18 +/-1.21 nm; the electrochemical active area (ECSA) after electrochemical gradient dealloying is 1-200 m2/gPdThe atomic content molar ratio of Co, Au and Pd is close to 1: 1-x: 1-y, wherein x and y are 5% and 5%.
Further preferably, the atomic content molar ratio of Co, Au and Pd is 1:1: 1.
the technical scheme adopted by the invention for realizing the purpose is as follows:
a preparation method of a fuel cell catalyst CoAuPd adopts a continuous reduction synthesis method, firstly, a nanoparticle Co seed crystal is synthesized, then, the Co seed crystal is used as a sacrificial template, chloroauric acid and potassium chloropalladate solution are used as metal precursors, and Au and Pd elements are replaced by utilizing an electronic position exchange reaction; the ternary CoAuPd alloy nano catalyst which has good dispersity, two special morphologies including a three-dimensional self-assembly nano thorn structure and a three-dimensional nano cluster structure and excellent catalytic activity and stability is prepared through the ferromagnetism of the Co seed crystal and multi-stage self assembly. By utilizing the characteristic that non-noble metal Co on the surface layer of the ternary CoAuPd alloy catalyst can be dissolved in an acid electrolyte, Co atoms on the surface layer of the ternary CoAuPd alloy catalyst are dissolved by adopting an electrochemical gradient dealloying method to form a CoAuPd @ AuPd core-shell structure. The catalytic activity of the catalyst is further improved by a double-function mechanism of the surface layer AuPd alloy, a rough surface after dealloying, a special three-dimensional nanometer thorn, a nanometer cluster structure and a hollow structure.
The method comprises the following steps:
(1) dissolving a triblock copolymer P123 in secondary distilled water by ultrasonic waves; adding a cobalt chloride solution into the triblock copolymer P123 solution, introducing nitrogen, and magnetically stirring, wherein the temperature is controlled to be 10-100 ℃, the concentration of P123 in the mixed solution is 1-100 mg/mL, and the concentration of cobalt chloride is 0.01-5 mmol/L. Slowly dropwise adding a sodium borohydride solution, wherein the concentration of sodium borohydride is 0.1-100 mg/mL; after reacting for 30-60 minutes, slowly dropwise adding a mixed solution of chloroauric acid and potassium chloropalladate, wherein the concentration of the chloroauric acid is 0.01-0.2 mmol/L, and the concentration of the potassium chloropalladate is 0.01-0.2 mmol/L. And after the dripping is finished, continuing to react for 120-720 min, and stopping the reaction, wherein the reaction solution finally becomes a black suspension. And (3) centrifugally separating the reaction solution at 1000-10000 r/min, washing with water and absolute ethyl alcohol for 3-5 times, and finally adding the product after washing into the absolute ethyl alcohol for dispersion protection to obtain the ternary CoPdAu alloy catalyst for the fuel cell.
(2) Sucking 10-30 μ L of catalyst suspension (2.01 mg/mL) with a pipette gun, dropping the catalyst suspension onto a polished glassy carbon electrode (GC electrode: phi 5 mm) to serve as a working electrode, and sucking 5-20 μ L of 0.5% Nafion solution (C: (GC electrode))m/m) Coating on glassy carbon electrode to dry and fix catalyst. The electrochemical testing instrument is an AUTOLAB electrochemical workstation (PGSTAT12), and the testing temperature is room temperature (10-50 ℃). A standard three-electrode system is adopted, the counter electrode is a platinum sheet (1cm multiplied by 1cm) plated with platinum black, and the reference electrode is a Saturated Calomel Electrode (SCE). The pretreatment of the working electrode and the activation of the Nafion membrane are carried out in sodium hydroxide solution saturated by nitrogen (the concentration has no special requirement), the Nafion membrane is activated by adopting electrochemical cyclic voltammetry, and the scanning potential is-0.9V-0.5V (C)vsSCE), the scanning speed is 5-100 mV/s, and the number of scanning cycles is 20-100 cycles. Electrochemical gradient dealloying is carried out in sulfuric acid solution (concentration is not required) saturated by nitrogen, dealloying gradient test is carried out by adopting electrochemical cyclic voltammetry, and scanning potential is-0.2V-0.9V (V) ((vsSCE), the sweeping speed is 5-100 mV/s, the number of sweeping turns is 1-10 turns/time, and the step of carrying out gradient dealloying once every 1-10 turns in the sulfuric acid solution. Scanning for 8-100 circles in total, and detecting the gradient dealloying result through a methanol oxidation test and an oxygen reduction test.
More preferably, in the mixed reaction solution in the step (1), the concentration of the triblock copolymer P123 is 20 mg/mL, the concentration of cobalt chloride is 0.1 mmol/L, the concentration of sodium borohydride is 5 mg/mL, the concentration of potassium chloropalladate is 0.03 mmol/L, and the concentration of chloroauric acid is 0.03 mmol/L. Firstly dropwise adding sodium borohydride solution to synthesize Co seed crystal, and slowly adding the Co seed crystal dropwise through a constant-pressure funnel, wherein the dropping speed is controlled at 5 s/drop. After dropping for 30 min, the mixed solution of chloroauric acid and potassium chloropalladate is dropped by a constant pressure funnel, the dropping speed is controlled at 5 s/drop, and potential displacement reaction is carried out. After the reaction, in the centrifugal separation process, washing with secondary distilled water for 3 times and absolute ethyl alcohol for 3 times to ensure that the triblock copolymer P123 is completely removed from the surface of the catalyst.
In the step (2), the pretreatment of the working electrode and the activation of the Nafion membrane are carried out in 1.0M NaOH solution saturated by nitrogen, the Nafion membrane is activated by adopting an electrochemical cyclic voltammetry, and the scanning potential is-0.9V-0.5V (C: (2))vsSCE), the sweep rate is 100 mV/s, and the number of sweep turns is 20.
In the step (2), the electrochemical gradient dealloying is carried out at 0.1M H2SO4In solution, electrochemical cyclic voltammetry is adopted, and the scanning potential is-0.2V-0.9V ()vsSCE), the sweep rate is 100 mV/s, the number of sweep turns is 2 turns/time, and dealloying is carried out as a gradient in the sulfuric acid solution every 2 turns. Only a small amount of Co is dissolved in each dealloying process after 2 circles/time, and then the relation between the dealloying degree and the catalytic activity is explored through a methanol oxidation test, so that gradient dealloying is realized. A total of 8 scans was performed to achieve complete dealloying.
In step (2), methanol oxidation was tested in nitrogen saturated 1.0M NaOH + 1.0M CH3In OH solution, and adopting Cyclic Voltammetry (CV) and scanning potential of-0.8V-0.4V ((CV))vsSCE), the sweep rate is 50 mV/s, the number of scanning turns is 2 turns/time, and the relation between the dealloying degree and the catalytic activity is researched to realize gradient dealloying. The oxygen reduction test was performed in 0.1M KOH solution saturated with oxygen using Linear Sweep Voltammetry (LSV) at a sweep potential of-0.7V to 0.3V (V)vsSCE), the sweeping speed is 10 mV/s, and the rotating speed is 100-2500 rpm.
The fuel cell catalyst coaudd has two distinct three-dimensional self-assembled structures: novel three-dimensional multi-branched nano thorn structure and cluster structure of hollow nano frame.
The CoAuPd electrochemical active area (ECSA) of the fuel cell catalyst is 1-100 m2/gPd。
Co in the fuel cell catalyst CoAuPd: au: the atomic molar ratio of Pd is 1:1: 1.
The preparation method of the CoAuPd catalyst for the fuel cell and the electrochemical gradient dealloying method have the following remarkable characteristics:
(1) the preparation method is a continuous reduction method, utilizes sodium borohydride reduction and potential displacement reaction, is easy to synthesize a novel three-dimensional self-assembly structure and a hollow structure, and has the advantages of mild reaction conditions, simple flow and simple and convenient operation. The triblock copolymer P123 is used as a protective agent and sodium borohydride is used as a reducing agent, so that the environment-friendly effect is achieved.
(2) And metal Au is introduced, so that the use amount of noble metal Pd is reduced, an alloy is formed, the catalytic activity is improved by utilizing the alloy effect, and the structural stability is enhanced. And then non-noble metal Co is further introduced to reduce the use amount of noble metal, and a ternary CoAuPd alloy catalyst is formed, so that the catalytic performance is further improved.
(3) Due to the novel three-dimensional multi-branch self-assembled nano thorn structure and the cluster structure of the hollow nano framework, the two special three-dimensional self-assembled structures are formed by the ferromagnetism of Co and multi-stage self assembly and have a large number of reactive active sites and excellent stability.
(4) By utilizing the characteristic that non-noble metal Co is easy to dissolve in acid electrolyte, electrochemical gradient dealloying is carried out, so that the ternary CoAuPd alloy catalyst forms a CoAuPd @ AuPd core-shell structure and a rough AuPd alloy surface, reaction active sites are increased, and the catalytic activity is further enhanced.
(5) The prepared catalyst has greatly improved catalytic performance after dealloying, excellent catalytic oxidation alcohol performance and oxygen reduction performance, and has larger application and development prospect in direct alcohol fuel cells.
Compared with a binary Pd-based catalyst, the ternary Pd-based catalyst has larger operation space in the aspects of component selection, control synthesis, surface regulation and control and catalytic performance regulation, and is far superior to a corresponding binary alloy catalyst in the aspect of catalytic activity. By introducing Au, the catalyst has a cocatalyst effect by utilizing an alloy effect, so that the anti-poisoning performance of the catalyst is enhanced, and the catalytic activity and chemical stability of methanol are improved. On the basis, non-noble metals (Cu, Fe, Co, Ni and the like) are introduced to form a ternary alloy catalyst, so that the use amount of the noble metals is further reduced, and the catalytic activity is improved. Meanwhile, the characteristics that non-noble metal on the surface layer of the catalyst is easy to dissolve in acid electrolyte are utilized to carry out electrochemical dealloying to form a core-shell structure of a ternary alloy core and a rough binary alloy shell. The rough alloy surface and the alloying effect may further improve the catalytic activity.
Drawings
FIG. 1: a transmission electron microscope of three-dimensional nano thorns and nanocluster structures of the ternary coaudd catalyst for fuel cells prepared for example 1 is shown in fig. 1. Wherein, a is a three-dimensional self-assembled nano thorn structure, b is a three-dimensional self-assembled nano cluster structure, c is an enlarged three-dimensional self-assembled nano thorn structure, and d is an enlarged three-dimensional self-assembled nano cluster structure.
FIG. 2: a transmission electron microscope image 2 of the two-dimensional nano feather-like structure, the hollow structure and the solid structure of the ternary coaudd catalyst for fuel cells prepared in example 1. Wherein a is a two-dimensional self-assembled feather-like structure, b is a self-assembled hollow and solid structure, c is an enlarged two-dimensional self-assembled feather-like structure, and d is an enlarged hollow and solid structure.
FIG. 3: FIG. 3 is a high-power transmission electron microscope of one-dimensional nano filament structure, hollow structure and solid structure of the ternary CoAuPd catalyst for fuel cell prepared in example 1. Wherein, a is a one-dimensional nanometer filament structure, b is a high power transmission electron microscope image of a hollow structure and a solid structure, c is a high power transmission electron microscope image of a one-dimensional nanometer filament structure, and d is a high power transmission electron microscope image of a hollow structure and a solid structure.
FIG. 4: the cyclic voltammogram and methanol oxidation curve 4 were tested for electrochemical gradient de-alloying of the fuel cell catalyst, coaudd, prepared in example 1. Wherein a isThe cyclic voltammogram of the ternary CoAuPd alloy catalyst and pure Co in 1.0M NaOH before dealloying, and b is the cyclic voltammogram of the ternary CoAuPd alloy catalyst in 1.0M NaOH + 1.0M CH before dealloying3Cyclic voltammogram in OH, c is ternary CoAuPd alloy catalyst at 0.1M H2SO4The electrochemical gradient de-alloying in the ternary CoAuPd alloy catalyst, d is a detection result of the electrochemical gradient de-alloying of the ternary CoAuPd alloy catalyst in 1.0M NaOH and a cyclic voltammetry contrast chart before and after de-alloying, and e is a detection result of the electrochemical gradient de-alloying of the ternary CoAuPd alloy catalyst in 1.0M NaOH + 1.0M CH3OH detection results and a methanol catalytic oxidation comparison graph before and after dealloying.
FIG. 5: cyclic voltammograms of electrocatalytic methanol oxidation after de-alloying of the fuel cell catalyst coaudd prepared in example 1 and a comparison of commercial palladium black, palladium on carbon figure 5.
FIG. 6: the polarization curves before and after the coaudd de-alloying of the fuel cell catalyst prepared for example 1 are compared with fig. 6. Wherein, a is the polarization curve before the dealloying of the ternary CoAuPd alloy catalyst, b is the polarization curve after the dealloying of the ternary CoAuPd alloy catalyst, c is the comparison graph of the oxygen reduction polarization curves before and after the dealloying of the ternary CoAuPd alloy catalyst (under 1600 rpm), and d is the corresponding polarization curve of 0.4V (C)vsRHE) versus K-L curve.
FIG. 7: the polarization curve of the fuel cell catalyst prepared for example 1, after coaudd dealloying, is compared to that of commercial palladium black, palladium on carbon in fig. 7.
FIG. 8: a transmission electron microscope image 8 of a three-dimensional nano thorn structure of the ternary coaudd catalyst for fuel cell prepared for example 2. Wherein, a and b are three-dimensional self-assembly nano thorn structures, and c and d are enlarged three-dimensional self-assembly nano thorn structures.
FIG. 9: the element distribution diagram of the three-dimensional nano bramble structure of the ternary coaudd catalyst for fuel cells prepared in example 2 is shown in fig. 9. Wherein a is a three-dimensional self-assembly nano thorn structure, b is a distribution diagram of Co element, c is a distribution diagram of Au element, and d is a distribution diagram of Pd element; e-g is a two-by-two superposition diagram of three elements of Co, Au and Pd; h is an overlay of the three elements.
FIG. 10: transmission electron microscopy of three-dimensional nanocluster structure of ternary coaudd catalyst for fuel cell prepared for example 3 fig. 10. Wherein, a and b are three-dimensional self-assembly nano-cluster structures and hollow structures, and c and d are enlarged three-dimensional self-assembly nano-cluster structures and hollow structures.
FIG. 11: element distribution diagram 11 of three-dimensional nanocluster structure of ternary coaudd catalyst for fuel cell prepared in example 3. Wherein a is a three-dimensional self-assembly nano-cluster structure and a hollow structure, b is a distribution diagram of Co element, c is a distribution diagram of Au element, and d is a distribution diagram of Pd element; e-g is a two-by-two superposition diagram of three elements of Co, Au and Pd; h is an overlay of the three elements.
Detailed Description
The present invention is further described with reference to the accompanying drawings and detailed description, it is to be understood that these examples are intended in an illustrative rather than in a limiting sense, and that various equivalent modifications of the invention will become apparent to those skilled in the art upon reading the present disclosure and are intended to be included within the scope of the appended claims.
Example 1
(1) Taking 1.0 g of triblock copolymer P123, stirring and ultrasonically dissolving in 50 mL of secondary distilled water; then 20 mL of 1.1 mg/mL cobalt chloride solution was added, nitrogen was introduced to prevent Co oxidation and magnetic stirring was performed, the temperature was controlled at 30 ℃ and 20 mL of sodium borohydride solution (5.0 mg/mL) was added dropwise at a rate of 5 s/drop to the mixed solution of P123 and cobalt chloride.
(2) After the completion of the dropwise addition of sodium borohydride, after 30 minutes of reaction, 20 mL of a mixed solution of chloroauric acid (0.03 mmol/L) and potassium chloropalladate (0.03 mmol/L) was added dropwise to the reaction mixture at a rate of 5 s/drop until the mixed solution became black and a precipitate formed.
(3) After 4 hours of reaction, centrifugally separating the obtained black suspension at 10000 r/min, washing the black suspension for 3 times by using secondary distilled water, then using absolute ethyl alcohol for 3 times, and finally adding the product after being washed clean into the absolute ethyl alcohol for dispersion protection to obtain the ternary CoAuPd catalyst for the fuel cell.
Fig. 1, fig. 2 and fig. 3 are Transmission Electron Micrographs (TEM) of the ternary coaudd catalyst for a fuel cell prepared in this example, and as can be seen from fig. 1, the prepared catalyst has good dispersibility and comprises two three-dimensional self-assembled structures: novel multi-branched nano thorn structures and hollow nano frame cluster structures are formed through ferromagnetism of Co seed crystals and multi-stage self-assembly. The well-organized multi-branched structure and the hollow porous structure often have higher catalytic activity and excellent stability.
(4) The ternary coaudd catalyst prepared in this example was coated on a glassy carbon electrode as a working electrode, and subjected to electrochemical dealloying gradient test: the electrochemical testing apparatus is an AUTOLAB electrochemical workstation (PGSTAT12), and the testing temperature is room temperature (30 ℃). A standard three-electrode system is adopted, the counter electrode is a platinum sheet (1cm multiplied by 1cm) plated with platinum black, and the reference electrode is a Saturated Calomel Electrode (SCE). The pretreatment of the working electrode and the activation of the Nafion membrane are carried out in 1.0M NaOH solution saturated by nitrogen, the Nafion membrane is activated by adopting electrochemical cyclic voltammetry, and the scanning potential is-0.9V-0.5V ()vsSCE), the sweep rate is 100 mV/s, and the number of sweep turns is 20.
(5) Electrochemical gradient dealloying at 0.1M H saturated in nitrogen2SO4Performing dealloying gradient test in solution by electrochemical cyclic voltammetry at a scanning potential of-0.2V-0.9V (vsSCE) at a sweep rate of 100 mV/s and 2 cycles/sweep at 0.1M H2SO4Dealloying as a gradient once every 2 rounds of sweeping in the solution. The total scan was 8 cycles and the results of the gradient dealloying were examined by the methanol oxidation test and the oxygen reduction test. Methanol Oxidation test 1.0M NaOH + 1.0M CH saturated in Nitrogen3OH solution, and scanning in the range of-0.8V-0.4V (by cyclic voltammetry)vsSCE), the scanning speed is 50 mV/s, and the number of scanning turns is 2 turns/time; the oxygen reduction test was carried out under a rotating disk electrode manufactured by PINE corporation, USA, the geometric area of which is 0.196 cm2The test electrolyte is 0.1M KOH solution saturated with oxygen, and the scanning range is-0.7V-0.2V ((R))vsSCE), the scanning speed is 10 mV/s, the electrode rotating speed is 100, 400, 900, 1600 and 2500 rpm; linear scan 1 time at each speed.
FIG. 4 is a comparison graph of cyclic voltammetry curves of the ternary CoAuPd alloy catalyst for fuel cells prepared in this example in a nitrogen-saturated 1.0M NaOH solution before and after electrochemical gradient dealloying, with the scan range being-0.9V-0.5V ((V))vsSCE), the scanning speed is 100 mV/s; and 1.0M NaOH + 1.0M CH saturated with nitrogen3The contrast graph of the cyclic voltammogram in the OH solution has a scanning range of-0.8V-0.4V ((C))vsSCE), the scanning speed is 50 mV/s; and at 0.1M H2SO4The scanning range of the cyclic voltammetry curve for electrochemical gradient dealloying in the solution is-0.2V-0.9V ()vsSCE), scan rate of 100 mV/s, number of scan cycles of 8 cycles, 8 cycles being sufficient to completely dealloye. Fig. 5 is a graph comparing the methanol oxidation performance of the ternary coaudd alloy catalyst for fuel cells prepared in this example after electrochemical gradient de-alloying with commercial pd black and pd/carbon. Wherein the ECSA of the ternary CoAuPd alloy catalyst after being completely de-alloyed is 42.64 m through a carbon monoxide adsorption test2/gPd。
FIG. 6 shows the linear sweep voltammograms before and after the electrochemical gradient dealloying of the ternary CoAuPd catalyst for a fuel cell prepared in this example in an oxygen-saturated 0.1M KOH solution, over a sweep range of-0.7V-0.2V (vs SCE), at a sweep rate of 10 mV/s and at a rotating disk electrode speed of 100, 400, 900, 1600, 2500 rpm; and correspondingly at 0.4V: (vsRHE) versus K-L curve. Figure 7 is a graph comparing the oxygen reduction performance (at 1600 rpm) of the fuel cell prepared in this example after electrochemical gradient de-alloying with a ternary coaudd alloy catalyst with commercial palladium black, palladium on carbon.
As can be seen from fig. 4, the prepared ternary coaudd catalyst initially showed a peak of pure Co due to the surface enrichment of Co element. With the proceeding of electrochemical dealloying gradient test, the reduction peak of Pd appears gradually under the potential of-0.35V, after dealloying is completed, the peak shape of the ternary CoAuPd catalyst is very similar to that of the AuPd binary alloy, because the ternary CoAuPd alloy catalyst becomes a CoAuPd @ AuPd core-shell structure after dealloying. The methanol oxidation peak of the CoAuPd catalyst is gradually enhanced under the potential of 0V, particularly after 6-8 circles of acid sweeping, the current density reaches the maximum value and does not change any more, and the CoAuPd catalyst shows better methanol catalytic oxidation activity after de-alloying. After dealloying, a special CoAuPd @ AuPd core-shell structure is formed, the rough AuPd alloy surface is possessed, more reaction active sites and electrochemical active area are exposed, and the catalytic activity is greatly improved.
As can be seen from FIG. 5, the prepared ternary CoAuPd catalyst has the methanol catalysis area current density of 1.16 mA/cm after dealloying23.625 times that of the commercial palladium black catalyst and 2.367 times that of palladium/carbon. FIG. 6 shows that the oxygen reduction activity of the ternary CoAuPd catalyst is greatly improved after dealloying, and the limiting current density finally reaches 193.464 μ A cm-2. As shown in fig. 7, the limiting current density of the de-alloyed ternary coaudd alloy catalyst was 1.506 times that of commercial palladium black and 1.180 times that of palladium on carbon.
Example 2
(1) Taking 1.0 g of triblock copolymer P123, stirring and ultrasonically dissolving in 50 mL of secondary distilled water; then 20 mL of 1.1 mg/mL cobalt chloride solution was added, nitrogen was introduced to prevent Co oxidation and magnetic stirring was performed, the temperature was controlled at 30 ℃ and 20 mL of sodium borohydride solution (5.0 mg/mL) was added dropwise at a rate of 5 s/drop to the mixed solution of P123 and cobalt chloride.
(2) After completion of the dropwise addition of sodium borohydride, after 10 minutes of reaction, 20 mL of a mixed solution of chloroauric acid (0.03 mmol/L) and potassium chloropalladate (0.03 mmol/L) was added dropwise to the reaction mixture at a rate of 5 s/drop until the mixed solution became black and a precipitate formed.
(3) After 4 hours of reaction, centrifugally separating the obtained black suspension at 10000 r/min, washing the black suspension for 3 times by using secondary distilled water, then using absolute ethyl alcohol for 3 times, and finally adding the product after being washed clean into the absolute ethyl alcohol for dispersion protection to obtain the ternary CoAuPd catalyst for the fuel cell.
Fig. 8 is a Transmission Electron Micrograph (TEM) of the ternary coaudd catalyst for a fuel cell prepared in this example, and it can be seen from fig. 8 that the catalyst prepared has good dispersibility and comprises a novel three-dimensional self-assembled structure: novel multi-branched nano thorn structure formed by ferromagnetism of Co seed crystal and multi-stage self-assembly. The well-organized multi-branched structure and the hollow porous structure often have higher catalytic activity and excellent stability. Fig. 9 shows an element distribution diagram (EDS Mapping) of the ternary coaudd catalyst for a fuel cell prepared in this example, and it can be seen from fig. 9 that the three elements of the novel multi-branched nano thorn structure are uniformly distributed and uniformly dispersed throughout the nano thorn structure, so that the ternary coaudd catalyst has an alloy structure with the three elements uniformly distributed. The homogeneous ternary CoAuPd alloy structure can form a special CoAuPd @ AuPd core-shell structure and a rough binary AuPd alloy surface after electrochemical de-alloying, and can further improve the catalytic performance of the ternary CoAuPd alloy catalyst.
Example 3
(1) Taking 1.0 g of triblock copolymer P123, stirring and ultrasonically dissolving in 50 mL of secondary distilled water; then 20 mL of 1.1 mg/mL cobalt chloride solution was added, nitrogen was introduced to prevent Co oxidation and magnetic stirring was performed, the temperature was controlled at 30 ℃ and 20 mL of sodium borohydride solution (10.0 mg/mL) was added dropwise at a rate of 5 s/drop to the mixed solution of P123 and cobalt chloride.
(2) After the completion of the dropwise addition of sodium borohydride, after 50 minutes of reaction, 20 mL of a mixed solution of chloroauric acid (0.03 mmol/L) and potassium chloropalladate (0.03 mmol/L) was added dropwise to the reaction mixture at a rate of 5 s/drop until the mixed solution became black and a precipitate formed.
(3) After 4 hours of reaction, centrifugally separating the obtained black suspension at 10000 r/min, washing the black suspension for 3 times by using secondary distilled water, then using absolute ethyl alcohol for 3 times, and finally adding the product after being washed clean into the absolute ethyl alcohol for dispersion protection to obtain the ternary CoAuPd catalyst for the fuel cell.
Fig. 10 is a Transmission Electron Micrograph (TEM) of the ternary coaudd catalyst for fuel cells prepared in this example, and it can be seen from fig. 10 that the prepared catalyst has good dispersibility, comprises novel three-dimensional self-assembled nanocluster structures and hollow structures, and is formed by ferromagnetism of Co seed crystals, multistage self-assembly, and a potential displacement reaction (GRR). The self-assembled cluster structure and the hollow structure with good structure usually have higher catalytic activity and excellent stability, and the hollow structure has two surfaces, namely an inner surface and an outer surface, and the inner surface and the outer surface of the hollow structure can be subjected to catalytic action, so that the performance of the hollow structure catalyst is far superior to that of a common solid structure catalyst. Fig. 11 is an element distribution diagram (EDS Mapping) of the ternary coaudd catalyst for a fuel cell prepared in this example, and it can be seen from fig. 11 that the three elements of the resulting nanocluster structure and hollow structure are uniformly distributed and uniformly dispersed throughout the nanocluster structure and hollow structure, so that the ternary coaudd catalyst has an alloy structure in which the three elements are uniformly distributed. The homogeneous ternary CoAuPd alloy structure can form a special CoAuPd @ AuPd core-shell structure and a rough binary AuPd alloy surface after electrochemical dealloying, particularly, the ternary CoAuPd alloy hollow structure can form a novel hollow porous CoAuPd @ AuPd core-shell structure and two rough internal and external binary AuPd alloy surfaces after electrochemical dealloying, and the catalytic performance of the ternary CoAuPd alloy catalyst can be greatly improved.
Example 4
(1) Taking 1.0 g of triblock copolymer P123, stirring and ultrasonically dissolving in 50 mL of secondary distilled water; then 20 mL of 1.1 mg/mL cobalt chloride solution was added, nitrogen was introduced to prevent Co oxidation and magnetic stirring was performed, the temperature was controlled at 30 ℃ and 20 mL of sodium borohydride solution (5.0 mg/mL) was added dropwise at a rate of 5 s/drop to the mixed solution of P123 and cobalt chloride.
(2) After the completion of the dropwise addition of sodium borohydride, after 30 minutes of reaction, 20 mL of a mixed solution of chloroauric acid (0.03 mmol/L) and potassium chloropalladate (0.03 mmol/L) was added dropwise to the reaction mixture at a rate of 5 s/drop until the mixed solution became black and a precipitate formed.
(3) After 4 hours of reaction, centrifugally separating the obtained black suspension at 10000 r/min, washing the black suspension for 3 times by using secondary distilled water, then using absolute ethyl alcohol for 3 times, and finally adding the product after being washed clean into the absolute ethyl alcohol for dispersion protection to obtain the ternary CoAuPd catalyst for the fuel cell.
Example 5
(1) Taking 1.0 g of triblock copolymer P123, stirring and ultrasonically dissolving in 50 mL of secondary distilled water; then 20 mL of 1.1 mg/mL cobalt chloride solution was added, nitrogen was introduced to prevent Co oxidation and magnetic stirring was performed, the temperature was controlled at 10 ℃ and 20 mL of sodium borohydride solution (5.0 mg/mL) was added dropwise at a rate of 5 s/drop to the mixed solution of P123 and cobalt chloride.
(2) After the completion of the dropwise addition of sodium borohydride, after 30 minutes of reaction, 20 mL of a mixed solution of chloroauric acid (0.03 mmol/L) and potassium chloropalladate (0.03 mmol/L) was added dropwise to the reaction mixture at a rate of 5 s/drop until the mixed solution became black and a precipitate formed.
(3) After 4 hours of reaction, centrifugally separating the obtained black suspension at 10000 r/min, washing the black suspension for 3 times by using secondary distilled water, then using absolute ethyl alcohol for 3 times, and finally adding the product after being washed clean into the absolute ethyl alcohol for dispersion protection to obtain the ternary CoAuPd catalyst for the fuel cell.
Example 6
(1) Taking 1.0 g of triblock copolymer P123, stirring and ultrasonically dissolving in 50 mL of secondary distilled water; then 20 mL of 1.1 mg/mL cobalt chloride solution was added, nitrogen was introduced to prevent Co oxidation and magnetic stirring was performed, the temperature was controlled at 100 ℃ and 20 mL of sodium borohydride solution (5.0 mg/mL) was added dropwise at a rate of 5 s/drop to the mixed solution of P123 and cobalt chloride.
(2) After the completion of the dropwise addition of sodium borohydride, after 30 minutes of reaction, 20 mL of a mixed solution of chloroauric acid (0.03 mmol/L) and potassium chloropalladate (0.03 mmol/L) was added dropwise to the reaction mixture at a rate of 5 s/drop until the mixed solution became black and a precipitate formed.
(3) After 4 hours of reaction, centrifugally separating the obtained black suspension at 10000 r/min, washing the black suspension for 3 times by using secondary distilled water, then using absolute ethyl alcohol for 3 times, and finally adding the product after being washed clean into the absolute ethyl alcohol for dispersion protection to obtain the ternary CoAuPd catalyst for the fuel cell.
Example 7
(1) Taking 1.0 g of triblock copolymer P123, stirring and ultrasonically dissolving in 50 mL of secondary distilled water; then 20 mL of 1.1 mg/mL cobalt chloride solution was added, nitrogen was introduced to prevent Co oxidation and magnetic stirring was performed, the temperature was controlled at 30 ℃ and 20 mL of sodium borohydride solution (5.0 mg/mL) was added dropwise at a rate of 5 s/drop to the mixed solution of P123 and cobalt chloride.
(2) After the completion of the dropwise addition of sodium borohydride, after 30 minutes of reaction, 20 mL of a mixed solution of chloroauric acid (0.03 mmol/L) and potassium chloropalladate (0.03 mmol/L) was added dropwise to the reaction mixture at a rate of 5 s/drop until the mixed solution became black and a precipitate formed.
(3) After 4 hours of reaction, centrifugally separating the obtained black suspension at 10000 r/min, washing the black suspension for 3 times by using secondary distilled water, then using absolute ethyl alcohol for 3 times, and finally adding the product after being washed clean into the absolute ethyl alcohol for dispersion protection to obtain the ternary CoAuPd catalyst for the fuel cell.
(4) The ternary coaudd catalyst prepared in this example was coated on a glassy carbon electrode as a working electrode, and subjected to electrochemical dealloying gradient test: the electrochemical testing apparatus is an AUTOLAB electrochemical workstation (PGSTAT12), and the testing temperature is room temperature (30 ℃). A standard three-electrode system is adopted, the counter electrode is a platinum sheet (1cm multiplied by 1cm) plated with platinum black, and the reference electrode is a Saturated Calomel Electrode (SCE). The pretreatment of the working electrode and the activation of the Nafion membrane are carried out in 1.0M NaOH solution saturated by nitrogen, the Nafion membrane is activated by adopting electrochemical cyclic voltammetry, and the scanning potential is-0.9V-0.5V ()vsSCE), the sweep rate is 100 mV/s, and the number of sweep turns is 20.
(5) Electrochemical gradient dealloying 0.1M HClO saturated in nitrogen4Performing dealloying gradient test in solution by electrochemical cyclic voltammetry at a scanning potential of-0.2V-0.9V (vsSCE) at a sweep rate of 100 mV/s and 2 cycles/sweep at 0.1M HClO4Dealloying as a gradient once every 2 rounds of sweeping in the solution. The total scan was 8 cycles and the results of the gradient dealloying were examined by the methanol oxidation test and the oxygen reduction test. Methanol oxidation test 1.0M NaOH + 1.0M C saturated in nitrogen2H5Performing in OH solution by cyclic voltammetry, wherein the scanning range is-0.8V-0.4V (vs SCE), the scanning rate is 50 mV/s, and the number of scanning cycles is 2 circles/time; the oxygen reduction test was carried out under a rotating disk electrode manufactured by PINE corporation, USA, the geometric area of which is 0.196 cm2The test electrolyte was a 0.1M NaOH solution saturated with oxygen and scanned over a range of-0.7V-0.2V (vsSCE), the scanning speed is 10 mV/s, the electrode rotating speed is 100, 400, 900, 1600 and 2500 rpm; linear scan 1 time at each speed.
Example 8
(1) Taking 1.0 g of triblock copolymer P123, stirring and ultrasonically dissolving in 50 mL of secondary distilled water; then 20 mL of 1.1 mg/mL cobalt chloride solution was added, nitrogen was introduced to prevent Co oxidation and magnetic stirring was performed, the temperature was controlled at 30 ℃ and 20 mL of sodium borohydride solution (5.0 mg/mL) was added dropwise at a rate of 5 s/drop to the mixed solution of P123 and cobalt chloride.
(2) After the completion of the dropwise addition of sodium borohydride, after 30 minutes of reaction, 20 mL of a mixed solution of chloroauric acid (0.03 mmol/L) and potassium chloropalladate (0.03 mmol/L) was added dropwise to the reaction mixture at a rate of 5 s/drop until the mixed solution became black and a precipitate formed.
(3) After 4 hours of reaction, centrifugally separating the obtained black suspension at 10000 r/min, washing the black suspension for 3 times by using secondary distilled water, then using absolute ethyl alcohol for 3 times, and finally adding the product after being washed clean into the absolute ethyl alcohol for dispersion protection to obtain the ternary CoAuPd catalyst for the fuel cell.
(4) The ternary coaudd catalyst prepared in this example was coated on a glassy carbon electrode as a working electrode, and subjected to electrochemical dealloying gradient test: the electrochemical testing apparatus is an AUTOLAB electrochemical workstation (PGSTAT12), and the testing temperature is room temperature (30 ℃). A standard three-electrode system is adopted, the counter electrode is a platinum sheet (1cm multiplied by 1cm) plated with platinum black, and the reference electrode is a Saturated Calomel Electrode (SCE). The pretreatment of the working electrode and the activation of the Nafion membrane are carried out in 1.0M NaOH solution saturated by nitrogen, the Nafion membrane is activated by adopting electrochemical cyclic voltammetry, and the scanning potential is-0.9V-0.5V ()vsSCE), the sweep rate is 100 mV/s, and the number of sweep turns is 20.
(5) Electrochemical gradient dealloying is carried out in 0.1M HCl solution saturated by nitrogen, dealloying gradient test is carried out by adopting electrochemical cyclic voltammetry, and scanning potential is-0.2V-0.9V ()vsSCE), sweep rate of 100 mV/s, number of sweeps of 2 cycles/time, dealloying as a gradient once per 2 sweeps in 0.1M HCl solution. Scanning for 8 circles in total, and obtaining results of gradient dealloyingThe methanol oxidation test and the oxygen reduction test. Methanol oxidation test 1.0M NaOH + 1.0M C saturated in nitrogen2H5Performing in OH solution by cyclic voltammetry, wherein the scanning range is-0.8V-0.4V (vs SCE), the scanning rate is 50 mV/s, and the number of scanning cycles is 2 circles/time; the oxygen reduction test was carried out under a rotating disk electrode manufactured by PINE corporation, USA, the geometric area of which is 0.196 cm2The electrolyte is tested to be 1.0M NaOH solution saturated by oxygen, and the scanning range is-0.7V-0.2V ()vsSCE), the scanning speed is 10 mV/s, the electrode rotating speed is 100, 400, 900, 1600 and 2500 rpm; linear scan 1 time at each speed.

Claims (4)

1. A preparation method of a CoAuPd @ AuPd core-shell structure oxygen reduction catalyst for a fuel cell is characterized by comprising the following steps:
(1) dissolving a triblock copolymer P123 in secondary distilled water by ultrasonic waves; adding a cobalt chloride solution to the P123 solution; controlling the temperature to be 10-100 ℃, introducing nitrogen into the solution, and magnetically stirring, wherein the concentration of the triblock copolymer P123 is 10-100 mg/mL, and the concentration of cobalt chloride is 1.1 mg/L;
(2) dropwise adding a sodium borohydride solution into the solution obtained in the step (1), reacting for 30-60 minutes, dropwise adding a mixed solution of chloroauric acid and potassium chloropalladate into the mixed reaction solution, continuing to react for 120-480 minutes after dropwise adding, and finally changing the reaction solution into a black suspension, wherein the concentration of sodium borohydride is 5-10 mg/mL; the concentration of potassium chloropalladate is 0.01-0.1 mmol/L, and the concentration of chloroauric acid is 0.01-0.1 mmol/L; the dropping speed of the sodium borohydride solution is controlled to be 5-10 seconds per drop, and the dropping time is controlled to be 10-30 min; the dropping speed of the mixed solution of the chloroauric acid and the potassium chloropalladate is controlled to be 3-10 seconds per drop, and the dropping time is controlled to be 10-30 min;
(3) centrifuging and separating the black suspension at 1000-10000 r/min, and washing with water and absolute ethyl alcohol for 3-5 times to obtain a ternary CoAuPd alloy catalyst for the fuel cell, wherein the ternary CoAuPd alloy catalyst for the fuel cell is a three-dimensional self-assembly structure multi-branch nano thorn structure and a hollow nano framework cluster structure, or a three-dimensional self-assembly nano cluster structure and a hollow structure;
(4) the ternary CoAuPd alloy catalyst suspension liquid for the fuel cell is dropped on a glassy carbon electrode to be used as a working electrode, under the conditions of alkaline electrolyte and the temperature of 10-50 ℃, the scanning potential is-0.9V-0.5V, the scanning speed is 5-100 mV/s, the number of scanning cycles is 20-50 cycles, activation is carried out, and the activated working electrode coated with the catalyst is moved to acid electrolyte to carry out electrochemical dealloying gradient test; and (3) scanning potential range of the cyclic voltammetry is-0.2V-1.2V, scanning speed is 5-100 mV/s, dealloying gradient is 1-10 circles/time, and the CoAuPd @ AuPd core-shell structure for the fuel cell is obtained.
2. The method for preparing a CoAuPd @ AuPd core-shell structure oxygen reduction catalyst for a fuel cell according to claim 1,
in the mixed reaction liquid in the step (1), the concentration of the triblock copolymer P123 is 20 mg/mL;
in the step (2), the concentration of sodium borohydride is 5 mg/mL; the concentration of potassium chloropalladate is 0.03 mmol/L, and the concentration of chloroauric acid is 0.03 mmol/L;
the dropping speed of the sodium borohydride is controlled to be 5 seconds per drop, the dropping time is controlled to be 30 min, the dropping speed of the mixed solution of the chloroauric acid and the potassium chloropalladate is controlled to be 5 seconds per drop, and the dropping time is controlled to be 30 min.
3. The method for preparing the oxygen reduction catalyst with the CoAuPd @ AuPd core-shell structure for the fuel cell according to claim 1, wherein the alkaline electrolyte comprises a sodium hydroxide solution or a potassium hydroxide solution; the acid electrolyte comprises a sulfuric acid solution, a perchloric acid solution and a hydrochloric acid solution.
4. The method for preparing the oxygen reduction catalyst with the CoAuPd @ AuPd core-shell structure for the fuel cell according to claim 1, wherein the electrochemical test temperature is 30 ℃, the pretreatment and the activation of the working electrode are carried out in a 1.0M NaOH solution, the scanning potential is-0.9V-0.5V, the scanning rate is 100 mV/s, and the number of scanning cycles is 20; the electrochemical dealloying gradient test adopts cyclic voltammetry to dealloyeThe electrolyte used was 0.1M H2SO4The scanning potential range of the solution is-0.2V-1.2V, the scanning speed is 10 mV/s, the dealloying gradient is 2 circles/time, and the total scanning is 8-20 circles.
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* Cited by examiner, † Cited by third party
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106058277A (en) * 2016-08-13 2016-10-26 三峡大学 PdAu electrocatalyst for fuel cell and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Carbon supported trimetallic nickelepalladiumegold hollow nanoparticles with superior catalytic activity for methanol electrooxidation";Changshuai Shang，et al.;《Journal of Power Sources》;20150314;第12-15页 *
"Gold-promoted structurally ordered intermetallic palladium cobalt nanoparticles for the oxygen reduction reaction";Kurian A. Kuttiyiel，et al.;《NATURE COMMUNICATIONS》;20141106;文献号:5185 *
"PdAuCu Nanobranch as Self-Repairing Electrocatalyst for Oxygen Reduction Reaction";Hongyu Gong，et al.;《ChemSusChem》;20170302;第1469-1474页 *
"Studies on the synthesis, dealloying, and electrocatalytic properties of CoPd nanocatalysts";Ya-Li Gan，et al.;《J Solid State Electrochem》;20150321;第1799-1805页 *

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