P-region metal introduced palladium-based intermetallic compound catalyst and preparation method and application thereof

Abstract

The invention discloses a p-region metal introduced palladium-based intermetallic compound catalyst and a preparation method and application thereof in the field of electrocatalysts, and the preparation method comprises the following steps: introducing a p-region metal element into metal palladium through a colloid synthesis method to prepare a palladium-based intermetallic compound precursor; and calcining the precursor in a reducing atmosphere to obtain the p-region metal-introduced palladium-based intermetallic compound, which shows significantly improved alkaline HOR performance. The introduction of the p-region metal in the catalyst promotes d-p orbital hybridization and electron interaction, and the catalyst can be used as an electrocatalyst in alkaline hydroxide reaction, and is beneficial to optimization of binding energy of catalytic surface reaction intermediates, so that the alkaline HOR activity is improved, the cost is reduced, and the catalyst variety is widened.

Description

Technical Field

[0001] The invention relates to the technical field of electrocatalyst preparation, and in particular to a preparation method and application of a palladium-based intermetallic compound catalyst introduced with a p-zone metal. Background Art

[0002] As a clean energy, hydrogen has extremely high energy density and only produces water as a byproduct during use, achieving true zero-carbon emissions, which is of great significance for mitigating global climate change and reducing greenhouse gas emissions. At the same time, hydrogen energy has a wide range of sources. These advantages together make hydrogen energy an important option to replace traditional fossil fuels and promote the transformation of energy structure. Hydrogen fuel cell technology makes it possible to achieve efficient conversion of hydrogen energy to electrical energy. Hydrogen fuel cell technology, especially proton exchange membrane fuel cells (PEMFC), has opened up a new path for efficient conversion of hydrogen energy to electrical energy. However, PEMFC has encountered a major challenge in practical applications: in an acidic electrolyte environment, the oxygen reduction reaction (ORR) at the cathode is highly dependent on a large amount of expensive platinum (Pt) catalysts. In recent years, alkaline exchange membrane fuel cells (AEMFC) have attracted much attention due to the breakthrough progress of alkaline exchange membranes and the use of transition metal-based electrocatalysts with platinum (Pt)-like activity, high efficiency and low cost under alkaline conditions. These advances provide new and more cost-effective solutions for cathode ORR. However, AEMFC also faces some challenges, especially in the kinetics of the anodic hydrogen oxidation reaction (HOR). In alkaline electrolytes, the kinetics of HOR are more than two orders of magnitude slower than in acidic electrolytes. Therefore, the development of efficient and stable anode catalysts has become the key to improving the performance of AEMFC. Researchers are constantly exploring new catalyst materials, such as intermetallic compounds, to achieve a significant improvement in HOR performance under alkaline conditions by optimizing their chemical composition and electronic structure.

[0003] Currently, Pt-based electrocatalysts have been recognized as the most advanced catalysts for the preparation of HOR. However, their high cost, resource scarcity, and relatively low stability have severely hindered their large-scale application. Meanwhile, palladium (Pd)-based electrocatalysts have become candidate catalysts for HOR in alkaline media. In order to significantly improve the performance of Pd-based electrocatalysts in HOR, researchers have continuously devoted themselves to adjusting the chemical composition and electronic structure of the catalysts. Although some remarkable progress has been made in this field, the HOR performance of existing Pd-based electrocatalysts is still far from the standards required for practical applications. It is worth noting that the ordered and periodic atomic arrangement of intermetallic compounds promotes dp orbital hybridization and electronic interactions, which is beneficial to optimize the adsorption behavior of reaction intermediates on the catalytic surface, and is expected to significantly enhance the alkaline HOR performance. Summary of the invention

[0004] In view of the deficiencies of the above-mentioned prior art, the purpose of the present invention is to provide a palladium-based intermetallic compound catalyst introduced with a p-zone metal, a preparation method and use thereof, wherein the catalyst is prepared using a Pt-free metal material to obtain an efficient alkaline HOR catalyst, thereby reducing the production cost, and the catalyst can be used in alkaline hydrogen oxidation reactions.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides a method for preparing a Pd-based intermetallic compound catalyst introduced with a p-zone metal, comprising the following steps: introducing a p-zone metal element into metal Pd by a colloidal synthesis method to prepare an intermetallic compound precursor, and calcining the precursor in a reducing atmosphere to obtain a Pd-based intermetallic compound introduced with a p-zone metal.

[0006] Optionally, the intermetallic compound is selected from Pd 2 Ga / C, Pd 2 Sn / C and Pd 3 Bi / C, preferably Pd 2 Ga / C.

[0007] Optionally, the colloidal synthesis method for preparing the intermetallic compound precursor comprises the following steps: dissolving palladium salt, carbon powder, p-block metal salt and amine hydrochloride in a solvent, heating and reacting at 200-300 ° C for 30-90 min; preferably, heating at 220 ℃ conditions for heating reaction for 60 minutes; further, the palladium salt is selected from palladium acetylacetonate, palladium chloride, palladium nitrate, palladium acetate, preferably, palladium acetylacetonate; further, the solvent is selected from pure oleylamine, a mixed solvent of oleylamine and one of octadecene, hexadecylamine, octylamine, and oleic acid, preferably, pure oleylamine; further, the carbon carrier is selected from the carbon carrier is XC-72 carbon, acetylene black, furnace black, activated carbon, graphene, reduced graphene oxide or carbon nanotubes, preferably, XC-72 carbon; further, the p-block metal salt is selected from chloride, acetylacetonate, acetate or nitrate, preferably, acetylacetonate; further, the amine hydrochloride is selected from methylamine hydrochloride, dimethylamine hydrochloride, ethylamine hydrochloride or trimethylamine hydrochloride, preferably, methylamine hydrochloride. Furthermore, the colloidal synthesis method for preparing an intermetallic compound precursor comprises the following steps: dissolving palladium salt, carbon powder, p-block metal salt and amine hydrochloride in a solvent, raising the solution temperature to 100-120°C, reacting in vacuum for 20-60 min, removing moisture and oxygen in the reaction system, and heating to 200-300°C in a nitrogen atmosphere for 60-120 min to obtain an intermetallic compound precursor.

[0008] Optionally, the reducing atmosphere includes: a hydrogen / nitrogen mixed reducing atmosphere or a hydrogen / argon mixed reducing atmosphere, preferably a hydrogen / nitrogen mixed reducing atmosphere; further, the volume ratio of nitrogen to hydrogen is 50:1, 40:1, 30:1, 20:1, 10:1, preferably 20:1.

[0009] Optionally, the calcination treatment in a reducing atmosphere is: calcination treatment is performed in a reducing atmosphere using a tubular furnace, and the calcination treatment conditions are calcination at 300-600° C. for 30-180 min, preferably, calcination at 400° C. for 60 min.

[0010] In order to achieve the above-mentioned object of the invention, the present invention provides a p-zone metal-introduced palladium-based intermetallic compound catalyst prepared by the above-mentioned preparation method of the p-zone metal-introduced palladium-based intermetallic compound catalyst.

[0011] Optionally, the palladium-based metal intermetallic compound catalyst introduced into the p-zone metal is Pd 2 Ga / C, Pd 2 Sn / C and Pd 3 Bi / C, preferably Pd 2 Ga / C intermetallic compound catalyst.

[0012] In order to achieve the above-mentioned purpose of the invention, the present invention applies the palladium-based intermetallic compound catalyst introduced with the p-zone metal to the alkaline hydrogen oxidation reaction, and uses it as an electrocatalyst for the alkaline hydrogen oxidation reaction.

[0013] Compared with the prior art, the present invention has the following beneficial effects: 1. The preparation method of the palladium-based intermetallic compound catalyst introduced with a p-zone metal provided by the present invention uses a Pt-free metal material to prepare an efficient alkaline HOR catalyst, which reduces the production cost, is suitable for commercial mass production, and broadens the types of catalysts.

[0014] 2. The introduction of p-zone metals in the p-zone metal-introduced palladium-based intermetallic compound catalyst provided by the present invention promotes dp orbital hybridization and electronic interaction, which is beneficial to the optimization of the binding energy of the catalytic surface reaction intermediates, thereby improving the catalytic activity of HOR, while reducing costs and broadening the types of catalysts. Specifically, in terms of alkaline HOR activity, the catalyst Pd 2 Ga / C, exchange current density normalized to metal mass ( j 0,m ) is 28.6 mA mg -1 , the exchange current density normalized to the electrochemical specific surface area ( j 0,s ) is 0.093 mA cm -2, which is four times higher than the comparison sample Pd / C and has excellent catalytic performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 The catalyst Pd prepared in Examples 1-3 of the present invention 2 Ga / C, Pd 2 Sn / C、Pd 3 X-ray diffraction curves of Bi / C and Pd / C catalyst prepared in Comparative Example 1.

[0016] Figure 2 The catalyst Pd / C (2a) prepared in Comparative Example 1 of the present invention and the catalyst Pd prepared in Examples 1-3 are 2 Sn / C(2b), Pd 3 Bi / C(2c) and Pd 2 Transmission electron microscopy image of Ga / C(2d).

[0017] Figure 3 The catalyst Pd / C (2a) prepared in Comparative Example 1 of the present invention and the catalyst Pd prepared in Examples 1-3 are 2 Sn / C(2b), Pd 3 Bi / C(2c) and Pd 2 Particle size analysis diagram of Ga / C(2d).

[0018] Figure 4 The catalyst Pd prepared in Examples 1-3 of the present invention 2 Ga / C, Pd 2 Sn / C and Pd 3 Bi / C and the Pd 3 d X-ray photoelectron spectrum of .

[0019] Figure 5 The catalyst Pd prepared in Example 1 of the present invention 2 Ga / C Ga 2 p and the catalyst Pd prepared in Example 2 2 Sn / C Sn3 d and the catalyst Pd prepared in Example 3 3 Bi / C Bi 4 f X-ray photoelectron spectrum of .

[0020] Figure 6 The catalyst Pd prepared in Examples 1-3 of the present invention 2 Ga / C, Pd 2 Sn / C and Pd 3 Bi / C and the catalyst Pd / C prepared in Comparative Example 1 in H 2Polarization curve of HOR in saturated 0.1 M KOH at a scan rate of 10 mV s -1 , the speed is 1600 rpm.

[0021] Figure 7 a is the catalyst Pd prepared in Example 1 of the present invention 2 Polarization curves of Ga / C in 0.1 M KOH saturated hydrogen solution at a scan rate of 10 mV s -1 , speed is 2500 to 625 rpm; Figure 7 b is Figure 7 a Koutecky–Levich plot obtained at an overpotential of 0.6 V.

[0022] Figure 8 The catalyst Pd prepared in Examples 1-3 of the present invention 2 Ga / C, Pd 2 Sn / C and Pd 3 Tafel plots of Bi / C and the catalyst Pd / C prepared in Comparative Example 1 were drawn using Butler-Volmer fitting.

[0023] Fig. 9 The catalyst Pd prepared in Examples 1-3 of the present invention 2 Ga / C, Pd 2 Sn / C and Pd 3 Linear curves of Bi / C and the catalyst Pd / C prepared in Comparative Example 1 were drawn using simplified Butler-Volmer fitting in a small polarization range. DETAILED DESCRIPTION

[0024] The preparation method and application of the palladium-based intermetallic compound catalyst introduced with a p-zone metal provided by the present invention are further described in detail below through specific examples. Example 1

[0025] Pd 2 Preparation method of Ga / C intermetallic compound: Oleylamine (5.0 mL), gallium acetylacetonate (18.4 mg), palladium acetylacetonate (30.5 mg), XC-72 carbon powder (30.0 mg) and methylamine hydrochloride (33.8 mg) were added to a two-necked flask and magnetically stirred. Subsequently, the solution temperature was raised to 100 °C and reacted in vacuum for 30 min to remove moisture and oxygen from the reaction system. After nitrogen was refilled, the temperature was further raised to 220 °C and maintained at this temperature for 60 min, and then naturally cooled to room temperature. The sample was then collected by centrifugation, washed with n-hexane and ethanol, and dried in vacuum at room temperature. Finally, the dried sample was placed in a quartz boat in the center of a tube furnace and calcined at 400 °C for 60 min in a reducing atmosphere with a volume ratio of nitrogen to hydrogen of 20:1 to obtain Pd 2 Ga / C. Example 2

[0026] Pd 2 Preparation method of Sn / C catalyst: Oleylamine (5.0 mL), tin acetate (12.0 mg), palladium acetylacetonate (30.5 mg), XC-72 carbon powder (30.0 mg) and methylamine hydrochloride (33.8 mg) were added to a two-necked flask and stirred magnetically. Subsequently, the solution temperature was raised to 100 °C and reacted in vacuum for 30 min to remove moisture and oxygen from the reaction system. After nitrogen was refilled, the temperature was further raised to 220 °C and maintained at this temperature for 60 min, and then naturally cooled to room temperature. The sample was then collected by centrifugation, washed with n-hexane and ethanol, and dried in vacuum at room temperature. Finally, the dried sample was placed in a quartz boat in the center of a tube furnace and calcined at 400 °C for 60 min in a reducing atmosphere with a volume ratio of nitrogen to hydrogen of 20:1 to obtain Pd 2 Sn / C. Example 3

[0027] Pd 3 Preparation method of Bi / C catalyst: Oleylamine (5.0 mL), bismuth acetate (12.9 mg), palladium acetylacetonate (30.5 mg), XC-72 carbon powder (30.0 mg) and methylamine hydrochloride (33.8 mg) were added to a two-necked flask and stirred magnetically. Subsequently, the solution temperature was raised to 100 °C and reacted in vacuum for 30 min to remove moisture and oxygen from the reaction system. After nitrogen was refilled, the temperature was further raised to 220 °C and maintained at this temperature for 60 min, and then naturally cooled to room temperature. The sample was then collected by centrifugation, washed with n-hexane and ethanol, and dried in vacuum at room temperature. Finally, the dried sample was placed in a quartz boat in the center of a tube furnace and calcined at 400 °C for 60 min in a reducing atmosphere with a volume ratio of nitrogen to hydrogen of 20:1 to obtain Pd3 Bi / C.

[0028] Comparative Example 1 Preparation method of Pd / C catalyst: Oleylamine (5.0 mL), palladium acetylacetonate (30.5 mg) and XC-72 carbon powder (40.0 mg) were added to a two-necked flask and stirred magnetically. Subsequently, the solution temperature was raised to 100 °C and reacted in vacuum for 30 min to remove moisture and oxygen from the reaction system. After nitrogen was refilled, the temperature was further raised to 220 °C and maintained at this temperature for 60 min, and then cooled naturally to room temperature. The sample was then collected by centrifugation, washed with n-hexane and ethanol, and dried in vacuum at room temperature. Finally, the dried sample was placed in a quartz boat in the center of a tube furnace and calcined at 500 °C for 60 min in a reducing atmosphere with a volume ratio of nitrogen to hydrogen of 20:1 to obtain Pd / C.

[0029] 1. Physical and chemical performance analysis of the catalysts prepared in Examples 1-3 and Comparative Example 1: Related results such as Figure 1 As shown. Figure 1 The X-ray powder diffraction (XRD) curve showed that Pd 2 Ga / C(PDF#65-7607), Pd 2 Sn / C(PDF#65-1293), Pd 3 Successful formation of Bi / C (PDF#65-8737).

[0030] from Figure 2 The transmission electron microscopy (TEM) images show that the morphology of these samples is in the form of nanoparticles.

[0031] from Figure 3 The particle size analysis chart shows that the particle size of these samples is 6-7 nm.

[0032] like Figure 4 As shown in the X-ray photoelectron spectroscopy (XPS), the Pd prepared in Examples 1-3 2 Ga / C, Pd 2 Sn / C、Pd 3 The Bi / C catalyst was compared with the Pd / C catalyst prepared in Comparative Example 1, and it was found that the peak of the Pd species shifted positively, which further verified that the Pd 2 Electron transfer in Ga / C electrocatalysts.

[0033] like Figure 5 As shown in the X-ray photoelectron spectroscopy (XPS), Figure 5 (a) Pd 2 High-resolution Ga 2p The XPS spectrum can be divided into two pairs of peaks at 1116.3 and 1143.1 eV, and 1118.1 and 1145.1 eV, corresponding to the 2 p 3 / 2 and 2 p 1 / 2 , 2-GaO p 3 / 2 and 2 p 1 / 2 . Figure 5 (b) shows the Pd 2 High resolution Sn 3 on Sn / C d The XPS spectrum can be divided into two pairs of peaks at 485.1 and 493.5 eV, and 486.5 and 495.0 eV, corresponding to the 3 d 5 / 2 and 3 d 3 / 2 , Sn 3 d 5 / 2 and 3 d 3 / 2 . Figure 5 (c) Pd 3 High resolution Bi 4 on Bi / C f The XPS spectrum can be divided into two pairs of peaks at 157.7 and 162.9 eV, and 158.6 and 164 eV, corresponding to the 4 f 7 / 2 and 4 f 5 / 2 、Bi oxide 4 f 7 / 2 and 4 f 5 / 2 .

[0034] 2. HOR performance test and analysis of the catalysts prepared in Examples 1-3 and Comparative Example 1: First, prepare the working electrode: 4 mg of the catalyst Pd prepared in Example 1-3 2 Ga / C, Pd 3 Bi / C and Pd 2 Sn / C and Pd / C catalysts of Comparative Example 1 were added with 2 mL of isopropanol solvent containing 0.05 wt% perfluorosulfonic acid, mixed, and ultrasonicated for 30 min to form a uniform black solution. The glassy carbon electrode with a diameter of 5 mm was polished with 0.05 mm γ-alumina powder, and then cleaned with ultrapure water and ethanol to make the electrode surface smooth. After natural air drying, 5.0 μL of the black solution was dripped on the electrode surface and electrochemical measurements were performed after air drying in the air.

[0035] The electrochemical tests were carried out on a CHI 760E electrochemical workstation. The electrocatalyst-modified glassy carbon electrode was used as the working electrode, the graphite rod was used as the counter electrode, and the 0.1 M KOH saturated calomel electrode was used as the reference electrode. In this study, all operations were carried out at a constant temperature of 303 (± 0.1) K, and all measured potentials refer to the reversible hydrogen electrode (RHE) potential with iR compensation. 2 The catalyst was pretreated by cyclic voltammetry (CV) under 0.1 M KOH. 2 Ga / C, Pd 2 Sn / C、Pd 3 The voltammetric curves of Bi / C and Pd / C samples are stable in the range of ~ 0.02 to ~ 0.92 V. The fresh electrolyte is 2 After saturation, the scan rate was 10 mV s −1 , RDE speed 1600 rpm for Pd 2 Ga / C, Pd 2 Sn / C、Pd 3 Polarization curves of Bi / C and Pd / C samples were tested from −0.08 to 0.92 V.

[0036] The electrochemically active surface area (ECSA) was calculated based on the charge transfer at 50 mV s in the range of 0.02 to 1.22 V. −1 The reduction peak of PdO in the CV was recorded at a scan rate of 2.

[0037] The results of the HOR test are as follows: Catalyst Pd prepared in Example 1-3 2 Ga / C, Pd 2 Sn / C and Pd 3 Bi / C and Pd / C of Comparative Example 1 were prepared by rotating disk electrodes in H 2 The rotation speed was 1600 rpm and 10 mV s in saturated 0.1 M KOH electrolyte. -1 The polarization curve of the catalyst was recorded at a scan rate of Figure 6 As shown, Pd 2 The Ga / C sample has the most significant apparent reactivity among the four electrocatalysts.

[0038] In order to exclude H 2 The interference of mass transfer, the kinetic current density ( j k ). Generally, the Pd prepared in Example 1 2 The polarization curves of Ga / C measured at different rotation speeds from 2500 to 625 rpm are shown in Figure 2. Figure 7 As shown in a. Figure 7 As shown in b, Figure 7 When the overpotential of a is 0.6 V, the corresponding Koutecky-Levich plot is constructed, and its slope (1 / Bc 0 ) is 12.9 cm 2 mA - 1 rpm 1 / 2 Then, using the Koutecky-Levich equation, we get j k At the same time, the Pd prepared in Examples 1-3 and Comparative Example 1 was determined by inductively coupled plasma atomic emission spectroscopy. 2 Ga / C, Pd 2 Sn / C、Pd 3 The mass fractions of Bi / C and Pd / C. Based on this, their Pd contents were calculated to be 2.411, 2.106, 2.099, and 1.879 μg, respectively. On this basis, after Pd mass normalization, Pd 2 Ga / C, Pd 2 Sn / C、Pd 3 Bi / C and Pd / C at 50 mV j k,m 57.94, 52.67, 16.56 and 25.1 mAmg respectively -1 .

[0039] like Figure 8 As shown, according to the Butler-Volmer equation, j k The Tafel plot of potential and exchange current density ( j 0 ).after, j 0 It can be further normalized by the metal mass to obtain the mass activity ( j 0,m ), Pd 2 Ga / C j 0,m (28.6 mA mg -1 ) than Pd 2 Sn / C (26.615 mA mg -1 ), Pd 3 Bi / C(11.7 mA mg -1 ) and Pd / C (13.15 mA mg -1 )high.

[0040] like Fig. 9 As shown, calculation j 0Another method is to perform linear fitting based on the approximate Butler-Volmer formula. 2 Ga / C has excellent HOR performance, which is close to the nonlinear fitting results.

[0041] In summary, the present invention provides a palladium-based intermetallic compound catalyst introduced with a p-zone metal. A palladium-based intermetallic compound precursor introducing a p-zone metal element into metallic palladium is obtained by a colloidal synthesis method, and the reaction precursor is calcined in a reducing atmosphere to obtain a palladium-based intermetallic compound anode catalyst introduced with a p-zone metal. The catalyst is a Pt-free metal material, and the introduction of a p-zone metal element reduces production costs and broadens the types of catalysts. In addition, the intermetallic compound catalyst reduces the d-band center of the catalyst, weakens the adsorption of H, and thus improves the catalytic activity of HOR. Specifically, the present invention uses acetylacetonate palladium as a palladium source, oleylamine as a reaction solvent, acetylacetonate gallium as a metal source, XC-72 as a carbon carrier, and methylamine hydrochloride as a stabilizer to prepare an intermetallic compound catalyst Pd 2 In alkaline HOR, the catalyst has an exchange current density normalized to the metal mass ( j 0,m ) is 28.6 mA mg -1 , the exchange current density normalized to the electrochemical specific surface area ( j 0,s ) is 0.093 mA cm -2 , four times higher than the comparison sample Pd / C, and has excellent HOR catalytic performance.

[0042] It should be noted that those skilled in the art should understand that the p-zone metal source can also be one of germanium or indium, which is not exhaustively listed in the embodiments of the present invention. The preparation method provided by the present invention can successfully prepare an intermetallic compound catalyst, such as Pd 2 Ge / C or Pd 2 One of In / C, and both showed high catalytic activity.

[0043] In the present invention, the intermetallic compound introduced by the p-zone metal is selected from Pd 2 Ga / C, Pd 2 Sn / C or Pd 3 Bi / C, preferably Pd 2 Ga / C.

[0044] The preparation method of the metal sulfide precursor introduced with the p-zone metal comprises: dissolving palladium salt, carbon powder, solvent, p-zone metal salt and amine hydrochloride together, heating and reacting at 200-300° C. for 60-120 min; preferably, heating at 220° C. The reaction is heated under the conditions for 60 minutes; further, the palladium salt is selected from palladium acetylacetonate, palladium chloride, palladium nitrate, palladium acetate, preferably palladium acetylacetonate; further, the solvent is selected from pure oleylamine, oleylamine and octadecene, oleylamine and dodecylamine, oleylamine and oleic acid, preferably pure oleylamine; further, the carbon carrier is selected from the carbon carrier is XC-72 carbon, activated carbon, graphene, reduced graphene oxide, acetylene black, carbon nanotubes, preferably XC-72 carbon; further, the p-block metal salt is selected from chloride, acetylacetonate, acetate or nitrate, preferably acetylacetonate; further, the amine hydrochloride is selected from methylamine hydrochloride, dimethylamine hydrochloride, ethylamine hydrochloride, trimethylamine hydrochloride, preferably methylamine hydrochloride.

[0045] Furthermore, the reducing atmosphere includes: a hydrogen / nitrogen mixed reducing atmosphere or a hydrogen / argon mixed reducing atmosphere, preferably a hydrogen / nitrogen mixed reducing atmosphere; further, the volume ratio of nitrogen to hydrogen is 50:1, 40:1, 30:1, 20:1, 10:1, preferably 20:1.

[0046] Furthermore, the calcination treatment in a reducing atmosphere is: calcination treatment is performed in a reducing atmosphere using a tubular furnace, and the calcination treatment conditions are calcination at 300-600° C. for 30-180 min, preferably, calcination at 400° C. for 60 min.

[0047] The present invention applies the palladium-based intermetallic compound catalyst introduced with the p-zone metal to the alkaline hydrogen oxidation reaction as an electrocatalyst for the alkaline hydrogen oxidation reaction. 2 The exchange current density normalized to the metal mass for Ga / C in alkaline HOR ( j 0,m ) is 28.6 mA mg -1 , the exchange current density normalized to the electrochemical specific surface area ( j 0,s ) is 0.093 mA cm -2 , which is four times higher than the comparison sample Pd / C and has excellent catalytic performance.

[0048] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a palladium-based intermetallic compound catalyst introduced with a p-zone metal, characterized in that: The method comprises the following steps: introducing a p-zone metal element into metal palladium by a colloidal synthesis method to prepare an intermetallic compound precursor, and calcining the precursor in a reducing atmosphere to obtain a palladium-based intermetallic compound introduced with a p-zone metal.

2. The method for preparing the p-zone metal-introduced palladium-based intermetallic compound according to claim 1, characterized in that: The p-region metal element is Ga, Sn or Bi.

3. The method for preparing the palladium-based intermetallic compound catalyst introduced with a p-block metal as claimed in claim 1, characterized in that: The colloidal synthesis method for preparing the intermetallic compound precursor comprises the following steps: dissolving palladium salt, carbon powder, p-zone metal salt and amine hydrochloride in a solvent, and heating the mixture at 200-300° C. for reaction for 30-90 min to obtain the precursor.

4. The method for preparing the p-zone metal-introduced palladium-based intermetallic compound catalyst according to claim 3, characterized in that: The palladium salt is palladium acetylacetonate, palladium chloride, palladium nitrate, or palladium acetate; the solvent is pure oleylamine, or a mixed solvent consisting of oleylamine and one of octadecene, hexadecylamine, octylamine, and oleic acid; the carbon carrier is XC-72 carbon, acetylene black, furnace black, activated carbon, graphene, reduced graphene oxide, or carbon nanotubes; the p-zone metal salt is chloride, acetylacetonate, acetate, or nitrate; and the amine hydrochloride is methylamine hydrochloride, dimethylamine hydrochloride, ethylamine hydrochloride, or trimethylamine hydrochloride.

5. The method for preparing the palladium-based intermetallic compound catalyst introduced with a p-zone metal as claimed in claim 1, characterized in that: The reducing atmosphere includes: a hydrogen / nitrogen mixed reducing atmosphere or a hydrogen / argon mixed reducing atmosphere.

6. The method for preparing the p-block metal-introduced palladium-based intermetallic compound catalyst according to claim 1, characterized in that: The calcination treatment in a reducing atmosphere is to use a tubular furnace to carry out the calcination treatment in a reducing atmosphere, the calcination treatment temperature condition is 300-600° C., and the calcination time is 30-180 min.

7. A palladium-based intermetallic compound catalyst introduced with a p-zone metal, characterized in that: The compound is prepared by the method for preparing a palladium-based intermetallic compound introduced with a p-block metal as described in any one of claims 1 to 6.

8. The p-zone metal-introduced palladium-based intermetallic compound catalyst as claimed in claim 7, characterized in that: The catalyst is a Pd2Ga / C, Pd2Sn / C or Pd3Bi / C intermetallic compound.

9. The p-zone metal-introduced palladium-based intermetallic compound catalyst of claim 7, characterized in that It is used in alkaline hydrogen oxidation reaction as an electrocatalyst for alkaline hydrogen oxidation reaction.

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