Carbon monoxide poisoning-resistant electrocatalyst for hydroxide reaction and preparation method of carbon monoxide poisoning-resistant electrocatalyst

Abstract

The invention belongs to the technical field of fuel cell electrocatalysts, and particularly relates to a carbon monoxide poisoning resistant electrocatalyst for a hydroxide reaction and a preparation method of the carbon monoxide poisoning resistant electrocatalyst. The preparation method comprises the following steps: impregnating and reducing noble metals (Pt, Pd, Ir, Rh, Ru and the like) on a transition metal-nitrogen-carbon (M-N-C, M = Fe, Co, Ni, Cu, Zn and the like) carrier by virtue of an impregnation and reduction method, and creatively synthesizing the M-N-C supported noble metal alloy electrocatalyst by virtue of a one-step pyrolysis method. The electrocatalyst prepared by the invention has excellent hydrogen oxidation activity, carbon monoxide poisoning resistance and durability, the preparation method is simple, clean and environment-friendly, the equipment investment is low, batch production is facilitated, and a new thought is provided for preparing the carbon monoxide poisoning resistance electrocatalyst for hydrogen oxidation reaction.

Description

Technical Field

[0001] The invention relates to a carbon monoxide poisoning resistant electrocatalyst for hydrogen oxidation reaction and a preparation method thereof, belonging to the field of fuel cell electrocatalyst materials. Background Art

[0002] Proton exchange membrane fuel cells (PEMFCs), as an efficient and environmentally friendly energy conversion device, are the cornerstone technology of the emerging green hydrogen economy. The hydrogen oxidation reaction (HOR) plays an important role in PEMFCs. Currently, Pt-based electrocatalysts provide the best intrinsic activity for HOR. However, Pt has very strong adsorption of carbon monoxide and is easily poisoned by trace CO impurities in hydrogen. Since most hydrogen is currently produced by steam methane reforming, large amounts of expensive hydrogen purification are required before it can be used in PEMFCs, which affects the economic viability of PEMFCs. Therefore, research and development of low-cost, efficient, stable, and CO-poisoning-resistant HOR electrocatalysts are urgently needed. Summary of the Invention

[0003] In order to reduce the cost of hydrogen used in PEMFCs, the present invention provides an electrocatalyst resistant to carbon monoxide poisoning for hydrogen oxidation reaction and a preparation method thereof. The CO tolerance of the electrocatalyst in HOR is synergistically improved through the alloying effect and the interaction between MNC and metal particles. The process is simple and the cost is low. The electrocatalyst prepared by this method has high activity and durability and is suitable for the anode hydrogen oxidation reaction of fuel cells.

[0004] The technical solution adopted in the present invention is as follows:

[0005] A method for preparing a carbon monoxide-poisoning-resistant electrocatalyst for hydrogen oxidation reaction comprises the following steps:

[0006] (1) Dispersing metal-nitrogen-carbon (MNC) powder in deionized water and sonicating for 10-15 min, referred to as solution D; dissolving a noble metal salt in deionized water and sonicating for 10-15 min, referred to as solution E; adding solution E to solution D and sonicating for 10-60 min to obtain a mixture, which was then stirred at room temperature for 2-6 h, and then rotary evaporated to dryness to obtain a black powder;

[0007] (2) heat-treating the black powder and grinding the resulting product to obtain the final product;

[0008] The concentration of metal-nitrogen-carbon powder in the D solution is 0.1-50 mg mL -1 , preferably 5-10 mg mL -1 ;

[0009] The concentration of the noble metal salt in the E solution is 0.1 to 50 mmol / L -1 , preferably 1 to 40 mmol / L -1 , more preferably 1 to 5 mmol / L -1 ;

[0010] The volume ratio of the D solution to the E solution is 1 to 20:1, preferably 1 to 10:1, more preferably 1 to 5:1.

[0011] Furthermore, the type of transition metal (M) in the M-N-C is one of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), cerium (Ce), magnesium (Mg), etc.

[0012] Furthermore, when the metal contains iron, the iron metal salt is one of iron acetylacetonate, hemin, and ferric chloride;

[0013] Furthermore, when the metal contains cobalt, the cobalt metal salt is one of cobalt acetylacetonate, cobalt acetate, and cobalt oxalate;

[0014] Furthermore, when the metal contains nickel, the nickel metal salt is one of nickel acetylacetonate, nickel chloride, and nickel acetate;

[0015] Furthermore, when the metal contains copper, the copper metal salt is one of copper acetylacetonate, copper oxalate, and copper chloride;

[0016] Furthermore, when the metal contains zinc, the zinc metal salt is one of zinc chloride, zinc iodide, and zinc formate;

[0017] Furthermore, when the metal contains cerium, the cerium metal salt is one of cerium chloride, cerium carbonate, and cerium oxalate;

[0018] Furthermore, when the metal contains magnesium, the magnesium metal salt is one of magnesium acetate, magnesium chloride, and magnesium bromide.

[0019] Furthermore, the types of noble metals in the noble metal salt include two or more of platinum (Pt), palladium (Pd), iridium (Ir), rhodium (Rh), ruthenium (Ru), etc.

[0020] Furthermore, when the noble metal contains platinum, the platinum metal salt includes one or a mixture of two or more of chloroplatinic acid, chloroplatinous acid, potassium chloroplatinate, potassium chloroplatinate, sodium chloroplatinate, sodium chloroplatinate, ammonium chloroplatinate, ammonium chloroplatinate, and platinum acetylacetonate.

[0021] Furthermore, when the noble metal contains palladium, the palladium metal salt includes one or a mixture of two or more of palladium chloride, palladium nitrate, palladium acetate, chloropalladic acid, palladium sulfate, and palladium acetylacetonate.

[0022] Further, when the noble metal contains iridium, the iridium metal salt includes one or a mixture of two or more of iridium chloride, iridic acid, iridium acetate, iridium tetrachloride, iridium chloride trihydrate, and iridium acetylacetonate.

[0023] Further, when the noble metal contains rhodium, the rhodium metal salt includes one or a mixture of two or more of rhodium chloride, ammonium chlororhodate, potassium hexachlororhodate, and rhodium acetylacetonate.

[0024] Further, when the noble metal contains ruthenium, the ruthenium metal salt includes one or a mixture of two or more of ruthenium trichloride, ruthenium trichloride hydrate, ruthenium acetate, hexammine ruthenium chloride, ammonium chlororuthenate, and ruthenium acetylacetonate.

[0025] Further, when the noble metal salts are platinum salt and ruthenium salt, the molar ratio of the platinum salt to the ruthenium salt is 1 to 5:1 to 5, such as 1:1 to 1.5; when the noble metal salts are iridium salt and ruthenium salt, the molar ratio of the iridium salt to the ruthenium salt is 1 to 5:1 to 5, such as 2:3; when the noble metal salts are iridium salt and rhodium salt, the molar ratio of the iridium salt to the rhodium salt is 1 to 5:1 to 5, such as 1:2; when the noble metal salts are platinum salt, palladium salt and ruthenium salt, the molar ratio of the platinum salt, the palladium salt to the ruthenium salt is 1 to 5:1 to 5:1 to 5, such as 1:2:2; when the noble metal salts are platinum salt, iridium salt, rhodium salt and ruthenium salt, the molar ratio of the platinum salt, the iridium salt, the rhodium salt to the ruthenium salt is 1 to 5:1 to 5:1 to 5:1 to 5, such as 1:2:1.6:2; when the noble metal salts are platinum salt, iridium salt, palladium salt, rhodium salt and ruthenium salt, the molar ratio of the platinum salt, the iridium salt, the palladium salt, the rhodium salt to the ruthenium salt is 1 to 5:1 to 5:1 to 5:1 to 5:1 to 5, such as 1:2:3:1.6:2.

[0026] Further, in step (1), the method for preparing the metal-nitrogen-carbon powder includes the following steps:

[0027] 1) Disperse 2-methylimidazole in deionized water and ultrasonicate for 10 to 15 min, denoted as solution A; disperse the metal salt in N,N-dimethylformamide or deionized water and ultrasonicate for 10 to 15 min, denoted as solution B; disperse zinc acetate and polyvinylpyrrolidone in deionized water and ultrasonicate for 15 to 30 min, denoted as solution C; add solution B to solution A and continue ultrasonication for 10 to 15 min, then add solution C, stir the mixture at room temperature for 2 to 6 h, then filter, wash, and dry to obtain a solid powder;

[0028] 2) Heat-treat the above solid powder, and after grinding the obtained product, obtain the metal-nitrogen-carbon powder.

[0029] The concentration of 2-methylimidazole in the solution A is 200 to 900 mg / mL -1 , preferably 300 to 800 mg / mL-1 , more preferably 500 - 700 mg / mL -1 ;

[0030] The concentration of the metal salt in the B solution is 1 - 100 mg / mL -1 , preferably 5 - 80 mg / mL -1 , more preferably 100 - 30 mg / mL -1 ;

[0031] The concentration of zinc acetate in the C solution is 20 - 200 mg / mL -1 , preferably 20 - 120 mg / mL -1 , more preferably 80 - 120 mg / mL -1 ;

[0032] The concentration of polyvinylpyrrolidone in the C solution is 1 - 200 mg / mL -1 , preferably 10 - 160 mg / mL -1 , more preferably 100 - 160 mg / mL -1 ;

[0033] The volume ratio of the A solution, B solution, and C solution is 1 - 10:1 - 10:1 - 10, preferably 1 - 5:1 - 5:1 - 5, more preferably 1 - 2:1 - 2:1 - 2.

[0034] Furthermore, N,N - dimethylformamide or deionized water is selected in the B solution according to the solubility of the metal salt.

[0035] Furthermore, in step 2), the heat treatment conditions are as follows: in an atmosphere of nitrogen, argon, or a 2 - 15 vol% hydrogen / argon mixture, the temperature is raised at a heating rate of 5 - 20 °C / min to 800 - 1000 °C, held for 1 - 4 h, and then cooled to room temperature with the furnace.

[0036] Furthermore, in step (1), the temperature of the rotary evaporation drying is 45 - 85 °C, and the rotation speed is 10 - 200 rpm.

[0037] Furthermore, in step (2), the heat treatment conditions are as follows: in an atmosphere of nitrogen, argon, or a 2 - 15 vol% hydrogen / argon mixture, the temperature is raised at a heating rate of 5 - 20 °C / min to 800 - 1000 °C, held for 1 - 4 h, and then cooled to room temperature with the furnace.

[0038] Further, in step (2), the heat treatment conditions are as follows: in an atmosphere of nitrogen, argon, or a 2-15 vol% hydrogen / argon mixture, ammonium chloride powder is placed near the upper air inlet at the center of the tubular furnace, and the black powder obtained in step (1) is placed near the lower air inlet at the center. The temperature is raised to 800-1000 °C at a heating rate of 5-20 °C / min, held for 1-4 h, and then cooled to room temperature with the furnace. Preferably, the mass ratio of ammonium chloride powder to the black powder obtained in step (1) is 0-200:20-200, preferably 0-60:30-80; for example, the addition amount of ammonium chloride powder is 0-200 mg, preferably 0-60 mg, and the addition amount of black powder is 20-200 mg, preferably 30-80 mg.

[0039] The present invention also relates to protecting the electrocatalyst obtained by the above preparation method. The loading of the electrocatalyst is 10-60 wt%, preferably 2-10 wt%, and it has high electrocatalytic activity and durability.

[0040] The present invention also relates to protecting the application of the above electrocatalyst in the catalytic hydrogen oxidation reaction in high-purity hydrogen (≥99.999%) and H2 containing 10-1000 ppm CO.

[0041] In the present invention, noble metals are impregnated and reduced on a transition metal-nitrogen-carbon support by a simple impregnation reduction method, and a noble metal alloy electrocatalyst supported by M-N-C is creatively synthesized through a one-step pyrolysis method. The prepared electrocatalyst has excellent electrocatalytic activity and CO poisoning resistance performance, and has excellent durability, and is applicable to the hydrogen evolution reaction. And the preparation method is simple and convenient for batch production, providing a new idea for preparing an anti-carbon monoxide poisoning electrocatalyst for the hydrogen oxidation reaction. Compared with the reported anti-CO poisoning electrocatalysts, the present invention has the following advantages:

[0042] a) The electrocatalyst of the present invention is prepared by an impregnation reduction method and a one-step pyrolysis method. The method is simple to operate, clean and environmentally friendly, and has less equipment investment.

[0043] b) The electrocatalyst prepared in the present invention combines the alloying effect and the interaction effect between M-N-C and metal particles, effectively regulates the electronic energy level of platinum metal, and weakens the adsorption of platinum metal to carbon monoxide.

[0044] c) The M-N-C supported metal alloy electrocatalyst prepared in the present invention has excellent hydrogen oxidation activity and CO poisoning resistance performance.

[0045] d) The M-N-C supported metal alloy electrocatalyst prepared in the present invention has excellent durability in the hydrogen oxidation reaction. Description of the Drawings

[0046] Figure 1It is the transmission electron microscope image (a), high-angle annular dark-field scanning transmission electron microscope image (b) and statistical chart of metal particle size (c) of the electrocatalyst prepared in Example 1 of the present invention.

[0047] Figure 2 It is the hydrogen oxidation reaction (HOR) polarization curve of the electrocatalyst material in 0.5 M H2SO4 saturated with H2 or 1000 ppm CO / H2, where (a) is the commercial 20 wt% Pt / C electrocatalyst material, (b) is the commercial 30 wt% PtRu / C (Pt / Ru = 1 / 1) electrocatalyst material, and (c) is the electrocatalyst prepared in Example 1 of the present invention.

[0048] Figure 3 It is the polarization curve of the durability test of the electrocatalyst prepared in Example 1 of the present invention, commercial 20 wt% Pt / C and commercial 30 wt% PtRu / C (Pt / Ru = 1 / 1) electrocatalyst materials in 0.5 M H2SO4 saturated with 1000 ppm CO / H2.

[0049] Figure 4 It is the HOR polarization curve of the electrocatalyst prepared in Example 2 of the present invention in 0.5 M H2SO4 saturated with H2 or 1000 ppm CO / H2;

[0050] Figure 5 It is the HOR polarization curve of the electrocatalyst prepared in Comparative Example 1 of the present invention in acidic electrolyte saturated with H2 or 1000 ppm CO / H2. Detailed implementation manners

[0051] The following non-limiting examples can enable those of ordinary skill in the art to more comprehensively understand the present invention, but do not limit the present invention in any way.

[0052] Example 1

[0053] 1) Disperse 3.3 g of 2-methylimidazole in 5 ml of deionized water and sonicate for 15 min, denoted as solution A; disperse 0.1 g of hemin in 4.6 ml of N,N-dimethylformamide and sonicate for 15 min, denoted as solution B; disperse 0.5 g of zinc acetate and 0.8 g of polyvinylpyrrolidone in 5 ml of deionized water and sonicate for 30 min, denoted as solution C; add solution B to solution A and continue to sonicate for 15 min, then add solution C, stir the mixture at room temperature for 4 h, then filter, wash, and dry to obtain a solid powder;

[0054] 2) Heat-treat the above powder. Specifically, under an argon atmosphere, heat it to 900 °C at a heating rate of 5 °C / min, hold for 2 h, and then cool it to room temperature with the furnace to obtain the Fe-N-C support.

[0055] 3) Place 50 mg of Fe-N-C powder in a 50-ml conical flask, add 10 ml of deionized water, and ultrasonicate for 15 min to obtain a well-dispersed black suspension, denoted as D. Separately, place potassium chloroplatinate and ruthenium chloride in a 10-ml vial, add 5 ml of deionized water to dissolve, and ultrasonicate for 15 min. The concentrations of platinum salt and ruthenium salt in the aqueous solution are both 1 mmol / L -1 , denoted as E; add E to D, ultrasonicate for 30 min to obtain a mixture, then vigorously stir the mixture at room temperature for 4 h, and subsequently rotary evaporate and dry the mixture at 65 °C with a rotation speed of 70 rpm to obtain a black powder.

[0056] 4) Heat-treat the black powder. Specifically, place 50 mg of ammonium chloride powder near the upper air inlet in the center of a tubular furnace under an argon atmosphere, and place the black powder obtained in step 3) near the lower air inlet in the center. Heat it at a heating rate of 20 °C / min to 900 °C, hold for 1 h, and then cool it to room temperature with the furnace to obtain the Pt1Ru1-Fe / N / C electrocatalyst.

[0057] As Figure 1 (a), the transmission electron microscopy results show that the metal particles in the electrocatalyst prepared in this example are evenly distributed on the carrier; as Figure 1 (b), it can be analyzed from the high-angle annular dark-field scanning transmission electron microscopy image that the lattice spacing of the metal is As Figure 1 (c), through statistical analysis, it can be known that the average particle size of the metal particles of the prepared catalyst is about 2.2 nm.

[0058] As Figure 2 (a), the current densities of the commercial 20 wt% Pt / C electrocatalyst in 0.5 M H2SO4 saturated with H2 and in 0.5 M H2SO4 saturated with 1000 ppm CO / H2 can reach 2.52 mA / cm -2 and 2.22 mA / cm -2 ; as Figure 2 (b), the current densities of the commercial 30 wt% PtRu / C electrocatalyst in 0.5 M H2SO4 saturated with H2 and in 0.5 M H2SO4 saturated with 1000 ppm CO / H2 can reach 2.53 mA / cm -2 and 3.29 mA / cm -2 ; as Figure 2 (c), the current densities of the electrocatalyst prepared in this example in 0.5 M H2SO4 saturated with H2 and in 0.5 M H2SO4 saturated with 1000 ppm CO / H2 can reach 3.21 mA / cm -2 and 3 mA / cm -2 , having excellent HOR performance and being higher than that of commercial catalysts.

[0059] As Figure 3 , the electrocatalyst prepared in this example has better durability than commercial catalysts in 0.5 M H2SO4 saturated with 1000 ppm CO / H2.

[0060] Example 2

[0061] 1) Disperse 3.3 g of 2-methylimidazole in 5 ml of deionized water and sonicate for 15 min, denoted as solution A; disperse 0.1 g of hemin in 4.6 ml of N,N-dimethylformamide and sonicate for 15 min, denoted as solution B; disperse 0.5 g of zinc acetate and 0.8 g of polyvinylpyrrolidone in 5 ml of deionized water and sonicate for 30 min, denoted as solution C; add solution B to solution A and continue to sonicate for 15 min, then add solution C, stir the mixture at room temperature for 4 h, then filter, wash, and dry to obtain a solid powder;

[0062] 2) Heat-treat the above powder. Specifically, under an argon atmosphere, heat it to 900 °C at a heating rate of 5 °C / min, hold for 2 h, and then cool it to room temperature with the furnace to obtain an Fe-N-C support.

[0063] 3) Take 50 mg of Fe-N-C powder and place it in a 50 ml conical flask, add 10 ml of deionized water, and sonicate for 15 min to obtain a well-dispersed black suspension, denoted as D. Take potassium chloroplatinate and ruthenium chloride in a 10 ml vial, add 5 ml of deionized water to dissolve, and sonicate for 1 -1 5 min. The concentration of platinum salt in the aqueous solution is 1 mmol / L -1 , and the concentration of ruthenium salt in the aqueous solution is 1.5 mmol / L

[0064] , denoted as E; add E to D, sonicate for 30 min to obtain a mixture, then stir the mixture vigorously at room temperature for 4 h, and then rotary evaporate and dry the mixture at 65 °C at a rotation speed of 70 rpm to obtain a black powder. 1.5 -Fe / N / C electrocatalyst.

[0065] As Figure 4 , the current densities of the electrocatalyst prepared in this Example 2 in 0.5 M H2SO4 saturated with H2 and in 0.5 M H2SO4 saturated with 1000 ppm CO / H2 can reach 3.11 mA / cm -2 and 2.42 mA / cm -2 .

[0066] Example 3

[0067] 1) Disperse 2.8 g of 2-methylimidazole in 6 ml of deionized water and ultrasonicate for 15 min, denoted as solution A; disperse 0.02 g of copper chloride in 6 ml of deionized water and ultrasonicate for 10 min, denoted as solution B; disperse 0.6 g of zinc acetate and 0.2 g of polyvinylpyrrolidone in 6 ml of deionized water and ultrasonicate for 20 min, denoted as solution C; add solution B to solution A and continue ultrasonication for 10 min, then add solution C, stir the mixture at room temperature for 6 h, then filter, wash, and dry to obtain a solid powder;

[0068] 2) Heat-treat the above powder. Specifically, under an argon atmosphere, heat it to 800 °C at a heating rate of 10 °C / min, hold for 2 h, and then cool it to room temperature with the furnace to obtain a Cu-N-C support.

[0069] 3) Take 60 mg of Cu-N-C powder and place it in a 50-ml conical flask, add 10 ml of deionized water, and ultrasonicate for 15 min to obtain a well-dispersed black suspension, denoted as D. Take iridium acetate and ammonium chlororuthenate in a 10-ml vial, add 5 ml of deionized water to dissolve, and ultrasonicate for 15 min. The concentration of iridium salt in the aqueous solution is 2 mmol / L -1 , and the concentration of ruthenium salt in the aqueous solution is 3 mmol / L -1 , denoted as E; add E to D, ultrasonicate for 30 min to obtain a mixture, then stir the mixture vigorously at room temperature for 4 h, and then rotary evaporate and dry the mixture at 65 °C with a rotation speed of 70 rpm to obtain a black powder.

[0070] 4) Heat-treat the black powder. Specifically, under an argon atmosphere, place 10 mg of ammonium chloride powder near the upper air inlet in the center of the tubular furnace, place the black powder obtained in step 3) near the lower air inlet in the center, heat it to 900 °C at a heating rate of 5 °C / min, hold for 1 h, and then cool it to room temperature with the furnace to obtain an IrRu-Cu / N / C electrocatalyst.

[0071] Example 4

[0072] 1) Disperse 3.1 g of 2-methylimidazole in 8 ml of deionized water and ultrasonicate for 12 min, denoted as solution A; disperse 0.03 g of magnesium chloride in 6 ml of deionized water and ultrasonicate for 15 min, denoted as solution B; disperse 0.3 g of zinc acetate and 0.2 g of polyvinylpyrrolidone in 8 ml of deionized water and ultrasonicate for 20 min, denoted as solution C; add solution B to solution A and continue ultrasonication for 15 min, then add solution C, stir the mixture at room temperature for 5 h, then filter, wash, and dry to obtain a solid powder;

[0073] 2) Heat-treat the above powder. Specifically, under an argon atmosphere, heat it to 850 °C at a heating rate of 8 °C / min, hold for 2 h, and then cool it to room temperature with the furnace to obtain the Mg-N-C support.

[0074] 3) Take 40 mg of Mg-N-C powder and place it in a 50 ml conical flask. Add 10 ml of deionized water and sonicate for 15 min to obtain a well-dispersed black suspension, denoted as D. Take iridium acetate and ammonium chlororhodate in a 10 ml vial, add 5 ml of deionized water to dissolve, and sonicate for 15 min. The concentration of iridium salt in the aqueous solution is 5 mmol L -1 , and the concentration of rhodium salt in the aqueous solution is 10 mmol L -1 , denoted as E; Add E to D, sonicate for 40 min to obtain a mixture, then stir the mixture vigorously at room temperature for 6 h, and then rotary evaporate and dry the mixture at 50 °C with a rotation speed of 60 rpm to obtain a black powder.

[0075] 4) Heat-treat the black powder. Specifically, under an argon atmosphere, place the black powder obtained in step 3) in a tubular furnace, heat it to 800 °C at a heating rate of 10 °C / min, hold for 1 h, and then cool it to room temperature with the furnace to obtain the IrRh-Mg / N / C electrocatalyst.

[0076] Example 5

[0077] 1) Disperse 3.0 g of 2-methylimidazole in 10 ml of deionized water and sonicate for 15 min, denoted as solution A; Disperse 0.02 g of nickel chloride in 5 ml of deionized water and sonicate for 10 min, denoted as solution B; Disperse 0.2 g of zinc acetate and 0.1 g of polyvinylpyrrolidone in 10 ml of deionized water and sonicate for 20 min, denoted as solution C; Add solution B to solution A and continue to sonicate for 10 min, then add solution C, stir the mixture at room temperature for 6 h, and then filter, wash, and dry to obtain a solid powder;

[0078] 2) Heat-treat the above powder. Specifically, under an argon atmosphere, heat it to 850 °C at a heating rate of 8 °C / min, hold for 2 h, and then cool it to room temperature with the furnace to obtain the Ni-N-C support.

[0079] 3) Take 70 mg of Ni-N-C powder and place it in a 50 ml conical flask. Add 10 ml of deionized water and sonicate for 15 min to obtain a well-dispersed black suspension, denoted as D. Take potassium chloroplatinate, palladium chloride, and ruthenium trichloride in a 10 ml vial, add 5 ml of deionized water to dissolve, and sonicate for 15 min. The concentration of platinum salt in the aqueous solution is 5 mmol L -1 , and the concentration of palladium salt in the aqueous solution is 10 mmol L -1 , and the concentration of ruthenium salt in the aqueous solution is 10 mmol L-1 Denoted as E; Add E to D, and after ultrasonic treatment for 30 min, a mixture is obtained. Then, it is vigorously stirred at room temperature for 4 h. Subsequently, the mixture is rotary evaporated and dried at 75 °C with a rotation speed of 80 rpm to obtain a black powder.

[0080] 4) Heat-treat the black powder. Specifically, in an argon atmosphere, 80 mg of ammonium chloride powder is placed near the upper air inlet at the center of a tubular furnace, and the black powder obtained in step (3) is placed near the lower air inlet at the center. It is heated to 850 °C at a heating rate of 20 °C / min, held for 2 h, and then cooled to room temperature with the furnace to obtain the PtPdRu-Ni / N / C electrocatalyst.

[0081] Example 6

[0082] 1) Disperse 2.5 g of 2-methylimidazole in 8 ml of deionized water and ultrasonicate for 10 min, denoted as solution A; Disperse 0.02 g of zinc chloride in 4.6 ml of deionized water and ultrasonicate for 15 min, denoted as solution B; Disperse 0.6 g of zinc acetate and 0.7 g of polyvinylpyrrolidone in 5 ml of deionized water and ultrasonicate for 30 min, denoted as solution C; Add solution B to solution A and continue ultrasonication for 10 min, then add solution C. Stir the mixture at room temperature for 5 h, and then filter, wash, and dry to obtain a solid powder.

[0083] 2) Heat-treat the above powder. Specifically, in an argon atmosphere, heat it to 1000 °C at a heating rate of 15 °C / min, hold for 2 h, and then cool to room temperature with the furnace to obtain the Zn-N-C support.

[0084] 3) Take 50 mg of Zn-N-C powder and place it in a 50 ml conical flask, add 10 ml of deionized water, and ultrasonicate for 15 min to obtain a well-dispersed black suspension, denoted as D. Separately, take potassium chloroplatinate, iridium acetate, rhodium acetylacetonate, and ruthenium chloride in a 10 ml vial, add 5 ml of deionized water to dissolve, and ultrasonicate for 15 min. The concentration of platinum salt in the aqueous solution is 5 mmol L -1 , the concentration of iridium salt in the aqueous solution is 10 mmol L -1 , the concentration of rhodium salt in the aqueous solution is 8 mmol L -1 , the concentration of ruthenium salt in the aqueous solution is 10 mmol L -1 , denoted as E; Add E to D, and after ultrasonic treatment for 50 min, a mixture is obtained. Then, it is vigorously stirred at room temperature for 4 h. Subsequently, the mixture is rotary evaporated and dried at 85 °C with a rotation speed of 100 rpm to obtain a black powder.

[0085] 4) Heat-treat the black powder. Specifically, place 70 mg of ammonium chloride powder near the upper air inlet at the center of a tubular furnace under an argon atmosphere, and place the black powder obtained in step 3) near the lower air inlet at the center. Heat it at a heating rate of 20 °C / min to 1000 °C, hold for 1 h, and then cool it to room temperature with the furnace to obtain the PtIrRhRu-Zn / N / C electrocatalyst.

[0086] Example 7

[0087] 1) Disperse 2.6 g of 2-methylimidazole in 12 ml of deionized water and sonicate for 15 min, denoted as solution A; disperse 0.06 g of cerium chloride in 4.6 ml of deionized water and sonicate for 15 min, denoted as solution B; disperse 0.4 g of zinc acetate and 0.6 g of polyvinylpyrrolidone in 6 ml of deionized water and sonicate for 18 min, denoted as solution C; add solution B to solution A and continue to sonicate for 10 min, then add solution C. Stir the mixture at room temperature for 4 h, then filter, wash, and dry to obtain a solid powder.

[0088] 2) Heat-treat the above powder. Specifically, under an argon atmosphere, heat it at a heating rate of 12 °C / min to 950 °C, hold for 2 h, and then cool it to room temperature with the furnace to obtain the Ce-N-C support.

[0089] 3) Take 60 mg of Ce-N-C powder and place it in a 50 ml conical flask, add 10 ml of deionized water, and sonicate for 10 min to obtain a well-dispersed black suspension, denoted as D. Take potassium chloroplatinate, iridium chloride, palladium chloride, rhodium chloride, and ruthenium chloride in a 10 ml vial, add 5 ml of deionized water to dissolve, and sonicate for 15 min. The concentration of platinum salt in the aqueous solution is 5 mmol L -1 , the concentration of iridium salt in the aqueous solution is 10 mmol L -1 , the concentration of palladium salt in the aqueous solution is 15 mmol L -1 , the concentration of rhodium salt in the aqueous solution is 8 mmol L -1 , the concentration of ruthenium salt in the aqueous solution is 10 mmol L -1 , denoted as E; add E to D, sonicate for 30 min to obtain a mixture, then stir the mixture vigorously at room temperature for 5 h, and then rotary evaporate and dry the mixture at 75 °C at a rotation speed of 90 rpm to obtain a black powder.

[0090] 4) Heat-treat the black powder. Specifically, under an argon atmosphere, place 60 mg of ammonium chloride powder near the upper air inlet at the center of a tubular furnace, and place the black powder obtained in step 3) near the lower air inlet at the center. Heat it at a heating rate of 20 °C / min to 950 °C, hold for 2 h, and then cool it to room temperature with the furnace to obtain the PtPdIrRhRu-Ce / N / C electrocatalyst.

[0091] Comparative Example 1

[0092] 1) Disperse 3.3 g of 2-methylimidazole in 5 ml of deionized water and ultrasonicate for 15 min, denoted as solution A; disperse 0.1 g of hemin in 4.6 ml of N,N-dimethylformamide and ultrasonicate for 15 min, denoted as solution B; disperse 0.5 g of zinc acetate and 0.8 g of polyvinylpyrrolidone in 5 ml of deionized water and ultrasonicate for 30 min, denoted as solution C; add solution B to solution A and continue ultrasonication for 15 min, then add solution C, stir the mixture at room temperature for 4 h, then filter, wash, and dry to obtain a solid powder;

[0093] 2) Heat-treat the above powder. Specifically, under an argon atmosphere, heat it to 900 °C at a heating rate of 5 °C / min, hold for 2 h, and then cool it to room temperature with the furnace to obtain an Fe-N-C support.

[0094] 3) Take 50 mg of Fe-N-C powder and place it in a 50 ml conical flask, add 10 ml of deionized water, and ultrasonicate for 15 min to obtain a well-dispersed black suspension, denoted as D. Take potassium chloroplatinate in a 10 ml vial, add 5 ml of deionized water to dissolve it, and ultrasonicate for 15 min. The concentration of platinum salt in the aqueous solution is 2 mmol L -1 , denoted as E; add E to D, ultrasonicate for 30 min to obtain a mixture, then stir the mixture vigorously at room temperature for 4 h, and then rotary evaporate and dry the mixture at 65 °C with a rotation speed of 70 rpm to obtain a black powder.

[0095] 4) Heat-treat the black powder. Specifically, place 50 mg of ammonium chloride powder near the upper air inlet in the center of a tubular furnace under an argon atmosphere, place the black powder obtained in step 3) near the lower air inlet in the center, heat it to 900 °C at a heating rate of 20 °C / min, hold for 1 h, and then cool it to room temperature with the furnace to obtain a Pt-Fe / N / C electrocatalyst.

[0096] As Figure 5 , the current densities of the electrocatalyst prepared in this Comparative Example 1 in 0.5 M H2SO4 saturated with H2 and in 0.5 M H2SO4 saturated with 1000 ppm CO / H2 can reach 3.15 mAcm -2 and 1.26 mAcm -2 , respectively.

[0097] Comparative Example 2

[0098] 1) Disperse 3.3 g of 2-methylimidazole in 5 ml of deionized water and ultrasonicate for 15 min, denoted as solution A; disperse 0.1 g of hemin in 4.6 ml of N,N-dimethylformamide and ultrasonicate for 15 min, denoted as solution B; disperse 0.5 g of zinc acetate and 0.8 g of polyvinylpyrrolidone in 5 ml of deionized water and ultrasonicate for 30 min, denoted as solution C; add solution B to solution A and continue to ultrasonicate for 15 min, then add solution C, stir the mixture at room temperature for 4 h, then filter, wash, and dry to obtain a solid powder;

[0099] 2) Heat-treat the above powder. Specifically, under an argon atmosphere, heat it to 900 °C at a heating rate of 5 °C / min, hold for 2 h, and then cool it to room temperature with the furnace to obtain the Fe-N-C support.

[0100] 3) Take 50 mg of Fe-N-C powder and place it in a 50 ml conical flask, add 10 ml of deionized water, and ultrasonicate for 15 min to obtain a well-dispersed black suspension, denoted as D. Take ruthenium chloride in a 10 ml vial, add 5 ml of deionized water to dissolve it, and ultrasonicate for 15 min. The concentration of ruthenium salt in the aqueous solution is 2 mmol L -1 , denoted as E; add E to D, ultrasonicate for 30 min to obtain a mixture, then stir the mixture vigorously at room temperature for 4 h, and then rotary evaporate and dry the mixture at 65 °C at a rotation speed of 70 rpm to obtain a black powder.

[0101] 4) Heat-treat the black powder. Specifically, under an argon atmosphere, place 50 mg of ammonium chloride powder near the upper air inlet at the center of the tubular furnace, and place the black powder obtained in step 3) near the lower air inlet at the center. Heat it to 900 °C at a heating rate of 20 °C / min, hold for 1 h, and then cool it to room temperature with the furnace to obtain the Ru-Fe / N / C electrocatalyst.

Claims

1. A preparation method of a carbon monoxide poisoning resistant electrocatalyst for hydrogen oxidation reaction, characterized in that, It includes the following steps: (1) Disperse the metal-nitrogen-carbon powder in deionized water and ultrasonicate for 10 - 15 min, denoted as solution D; dissolve the noble metal salt in deionized water and ultrasonicate for 10 - 15 min, denoted as solution E; add solution E to solution D, ultrasonicate for 10 - 60 min to obtain a mixture, then stir at room temperature for 2 - 6 h, and subsequently rotary evaporate and dry the mixture to obtain a black powder; (2) Heat-treat the black powder, and after grinding the obtained product, obtain the final product; The concentration of the metal-nitrogen-carbon powder in the described D solution is 0.1 to 50 mg / mL -1 ; The concentration of the precious metal salt in the E solution is 0.1 to 50 mmol / L -1 ; The volume ratio of the said solution D to solution E is 1 - 20:

1.

2. The preparation method according to claim 1, characterized in that, The transition metal type in the said metal-nitrogen-carbon is one of iron, cobalt, nickel, copper, zinc, cerium, and magnesium.

3. The preparation method according to claim 1 or 2, characterized in that, When the said metal is iron, the iron metal salt is one of iron acetylacetonate, hemin, and ferric chloride; When the said metal is cobalt, the cobalt metal salt is one of cobalt acetylacetonate, cobalt acetate, and cobalt oxalate; When the said metal is nickel, the nickel metal salt is one of nickel acetylacetonate, nickel chloride, and nickel acetate; When the said metal is copper, the copper metal salt is one of copper acetylacetonate, copper oxalate, and copper chloride; When the said metal is zinc, the zinc metal salt is one of zinc chloride, zinc iodide, and zinc formate; When the said metal is cerium, the cerium metal salt is one of cerium chloride, cerium carbonate, and cerium oxalate; When the said metal is magnesium, the magnesium metal salt is one of magnesium acetate, magnesium chloride, and magnesium bromide.

4. The preparation method according to claim 1, wherein The noble metals in the said noble metal salt include two or more of platinum, palladium, iridium, rhodium, and ruthenium.

5. The preparation method according to claim 1 or 4, characterized in that, When the said noble metal contains platinum, the platinum metal salt includes one or a mixture of two or more of chloroplatinic acid, chloroplatinous acid, potassium chloroplatinate, potassium chloroplatinate, sodium chloroplatinate, sodium chloroplatinate, ammonium chloroplatinate, ammonium chloroplatinate, and platinum acetylacetonate; When the said noble metal contains palladium, the palladium metal salt includes one or a mixture of two or more of palladium chloride, palladium nitrate, palladium acetate, chloropalladic acid, palladium sulfate, and palladium acetylacetonate; When the said noble metal contains iridium, the iridium metal salt includes one or a mixture of two or more of iridium chloride, chloroiridic acid, iridium acetate, iridium tetrachloride, iridium chloride trihydrate, and iridium acetylacetonate; When the said noble metal contains rhodium, the rhodium metal salt includes one or a mixture of two or more of rhodium chloride, ammonium chlororhodate, potassium hexachlororhodate, and rhodium acetylacetonate; When the said noble metal contains ruthenium, the ruthenium metal salt includes one or a mixture of two or more of ruthenium trichloride, ruthenium trichloride hydrate, ruthenium acetate, hexaammine ruthenium chloride, ammonium chlororuthenate, and ruthenium acetylacetonate.

6. The method according to claim 1, characterized in that: In step (1), the preparation method of the said metal-nitrogen-carbon powder includes the following steps: 1) Disperse 2-methylimidazole in deionized water and ultrasonicate for 10 - 15 min, denoted as solution A; disperse the metal salt in N,N-dimethylformamide or deionized water and ultrasonicate for 10 - 15 min, denoted as solution B; disperse zinc acetate and polyvinylpyrrolidone in deionized water and ultrasonicate for 15 - 30 min, denoted as solution C; Add solution B to solution A and continue ultrasonication for 10 - 15 min, then add solution C, stir the mixture at room temperature for 2 - 6 h, and subsequently filter, wash, and dry to obtain a solid powder; 2) Heat-treat the above solid powder, and after grinding the obtained product, a metal-nitrogen-carbon powder is obtained. The concentration of 2-methylimidazole in the described A solution is 200 - 900 mg / mL -1 ; The concentration of metal salt in the described Solution B is 1 to 100 mg / mL -1 ; The concentration of zinc acetate in the described C solution is 20 to 200 mg / mL -1 ; The concentration of polyvinylpyrrolidone in the C solution described is 1 to 200 mg / mL -1 ; The volume ratio of the A solution, B solution, and C solution described above is 1-10:1-10:1-10.

7. The method according to claim 1 or 6, characterized in that: In steps (2) and 2), the heat treatment conditions are as follows: under an atmosphere of nitrogen, argon, or a 2-15 vol% hydrogen / argon mixed gas, heat up to 800-1000 °C at a heating rate of 5-20 °C / min, hold for 1-4 h, and then cool to room temperature with the furnace.

8. The method according to claim 1 or 7, characterized in that: In step (1), the temperature of the rotary evaporation drying is 45-85 °C, and the rotation speed is 10-200 rpm; In step (2), in the heat treatment conditions, ammonium chloride powder is placed near the upper air outlet at the center of the tubular furnace, and the black powder obtained in step (1) is placed near the lower air outlet at the center; the mass ratio of the ammonium chloride powder to the black powder obtained in step (1) is 0-200:20-200.

9. The anti-carbon monoxide poisoning electrocatalyst for hydrogenation reaction obtained by the preparation method according to any one of claims 1-8, characterized in that, The loading of the electrocatalyst is 5-60 wt%.

10. Use of the electrocatalyst according to claim 9 in the catalytic hydrogen oxidation reaction in pure hydrogen and hydrogen containing CO.

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