Anion exchange membrane fuel cell anode anti-poisoning catalyst and preparation method thereof

Abstract

The invention discloses an anion exchange membrane fuel cell anode anti-poisoning catalyst and a preparation method thereof.The anion exchange membrane fuel cell anode anti-poisoning catalyst is simple in preparation method, low in cost and good in reproducibility; and the prepared catalyst has efficient hydroxide performance and anti-poisoning effect, and especially shows excellent anti-poisoning ability in long-term operation, so that the fuel cell has great possibility of directly utilizing the industrially produced crude hydrogen as the anode fuel, the commercial cost of the fuel cell can be greatly reduced, and the fuel cell has wide application prospect. The method has great industrial significance.

Description

Technical Field

[0001] The present invention belongs to the field of batteries, and particularly relates to an anti-poisoning catalyst for the anode of an anion exchange membrane fuel cell and a preparation method thereof. Background Art

[0002] With the increasing consumption of fossil energy and the decreasing of its reserves, the development and utilization of new energy technologies are particularly important. Hydrogen energy has received extensive attention due to its advantages such as pollution-free and high energy density, and is regarded as the clean energy with the most development potential in the 21st century. A hydrogen fuel cell is a device that converts chemical energy into electrical energy and has always been considered as the ultimate solution to utilize hydrogen energy and solve the human energy crisis. Anion exchange membrane fuel cells (AEMFCs) have attracted extensive attention due to their low-cost advantages. However, the anode catalysts of AEMFCs have the following problems: (1) The kinetics of anodic hydrogen oxidation (HOR) is slow, which is more than two orders of magnitude lower than that of the anode of proton exchange membrane fuel cells (PEMFCs); (2) The anode catalyst is easily poisoned by trace carbon monoxide in hydrogen, resulting in a decrease in battery performance. The prior art promotes the kinetics of hydrogen oxidation by introducing a second component, including metals, metal oxides, etc., and regulating the hydrogen binding energy (HBE) or hydroxyl binding energy (OHBE) of the catalyst; at the same time, the adsorption of carbon monoxide by the catalyst is reduced to improve the carbon monoxide tolerance.

[0003] Yunbo Li et al. introduced iron, cobalt, nickel, and vanadium through the potassium bromide template method to regulate the d-band center of ruthenium and prepared RuM (M = Fe, Co, Ni, V) alloy catalysts, which exhibited ultra-high hydrogen oxidation and fuel cell performance. However, this catalyst does not have carbon monoxide tolerance, and the ruthenium salt used is relatively expensive, making it unsuitable for large-scale preparation (Yunbo Li, Chaoyi Yang, Chuangxin Ge, et al. Electronic Modulation of Ru Nanosheet by d–d Orbital Coupling for Enhanced Hydrogen Oxidation Reaction in Alkaline Electrolytes. Small 2022, 2202404). Liqing Wu et al. regulated the electronic structure of ruthenium by introducing tin. The Sn-Ru / C catalyst with d-p orbital hybridization can optimize the adsorption of water and hydrogen, thus greatly promoting the hydrogen oxidation kinetics. However, this catalyst does not have the ability to resist carbon monoxide poisoning (Liqing Wu, Lixin Su, Qing Liang. Boosting Hydrogen Oxidation Kinetics by Promoting Interfacial Water Adsorption on d-p Hybridized Ru Catalysts. ACS Catal. 2023, 13, 4127-4133). Zhilong Yang et al. synthesized ruthenium nanoparticles supported on defective carbon. By reducing the d-band center of ruthenium through carbon defects, the adsorption of hydrogen and carbon monoxide by the catalyst was weakened, achieving high-performance hydrogen oxidation and anti-poisoning. However, this catalyst cannot oxidize carbon monoxide, and the improvement of its anti-poisoning ability comes from the weaker adsorption of carbon monoxide (Zhilong Yang, Wenchuan Lai, Bingling He. Tailoring Interfacial Chemistry of Defective Carbon-Supported Ru Catalyst Toward Efficient and CO-Tolerant Alkaline Hydrogen Oxidation Reaction. Adv. Energy Mater. 2023, 2300881).Leigang Li et al. prepared molybdenum-modified ruthenium nanosheets by oleylamine reduction. The obtained ruthenium-based catalyst has high hydrogen oxidation performance. However, this catalyst does not have the ability to resist carbon monoxide poisoning, and the preparation process is relatively complex. The ruthenium salt used is relatively expensive, increasing the cost of the catalyst (Leigang Li, Shangheng Liu, Changhong Zhan, et al. Surface and Lattice Engineered Ruthenium Superstructures towards High-Performance Bifunctional Hydrogen Catalysis. Energy Environ. Sci., 2023, 16, 157–166). Xiaoyu (Baohua) Zhang et al. prepared Ru / RuO₂ catalyst by the potassium bromide template method. 2 The catalyst, the active interface of Ru and RuO₂ 2 optimizes the adsorption of hydrogen species and hydrogen hydroxide species, showing high hydrogen oxidation activity and stability. However, its carbon monoxide tolerance is poor, and the current rapidly decays in the presence of 1000 ppm CO (Xiaoyu (Baohua) Zhang, Lixue Xia, Guoqiang Zhao, et al. Fast and Durable Alkaline Hydrogen Oxidation Reaction at the Electron-Deficient Ruthenium–Ruthenium Oxide Interface. Adv. Mater. 2023, 35, 2208821).

[0004] In summary, the developed anode catalysts have the following problems: (1) The synthesis process of the catalyst is complex and cumbersome or the reaction conditions are harsh, with low reproducibility, and the drugs used are expensive; (2) The hydrogen oxidation performance of the catalyst is insufficient, affecting the performance expression of the fuel cell; (3) The developed catalysts can only improve the hydrogen oxidation activity, and do not have carbon monoxide tolerance or have poor carbon monoxide tolerance, which cannot meet the long-term operation of the fuel cell. Summary of the Invention

[0005] The purpose of this part is to outline some aspects of the embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this part, as well as in the abstract and title of the specification of this application, to avoid obscuring the purpose of this part, the abstract of the specification, and the title of the invention. However, such simplifications or omissions cannot be used to limit the scope of the present invention.

[0006] In view of the above problems and / or those existing in the prior art, the present invention is proposed.

[0007] Therefore, an object of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing an anti-poisoning catalyst for the anode of an anion exchange membrane fuel cell.

[0008] To solve the above technical problems, the present invention provides the following technical solution: A method for preparing an anti-poisoning catalyst for the anode of an anion exchange membrane fuel cell, comprising:

[0009] Disperse the carbon support in ultrapure water at room temperature, and ultrasonically disperse it evenly to obtain a first suspension;

[0010] Dissolve the ruthenium precursor in ultrapure water, and ultrasonically disperse it evenly to obtain an aqueous solution of the ruthenium precursor;

[0011] Dropwise add the obtained aqueous solution of the ruthenium precursor to the first suspension, adjust the pH, and stir evenly to obtain a second suspension;

[0012] Perform hydrothermal treatment on the second suspension to obtain a third suspension;

[0013] Centrifuge and separate the third suspension, and obtain a first composite solid after drying;

[0014] Place the first composite solid in a tube furnace for calcination, and obtain an anti-poisoning catalyst for the anode of an anion exchange membrane fuel cell after grinding.

[0015] As a preferred embodiment of the preparation method of the present invention, wherein: the specific surface area of the carbon support is 200 - 400 m 2 / g, the resistivity is greater than 18 MΩ·cm, including commercial carbon support XC-72 and commercial carbon support BP-2000; the resistivity of the ultrapure water is 18.25 MΩ·cm.

[0016] As a preferred embodiment of the preparation method of the present invention, wherein: in the first suspension, the ratio of the carbon support to the ultrapure water is 70 - 100 mg: 30 mL.

[0017] As a preferred embodiment of the preparation method of the present invention, wherein: the ruthenium precursor includes ruthenium trichloride hydrate RuCl 3 ·xH 2 O.

[0018] As a preferred embodiment of the preparation method of the present invention, wherein: when dissolving the ruthenium precursor in ultrapure water, the ratio of the ruthenium precursor to the ultrapure water is 30 - 50 mg: 10 mL.

[0019] As a preferred embodiment of the preparation method of the present invention, wherein: for the pH adjustment, the pH regulator is one or more of 1M KOH solution, 1M NaOH solution or ammonia water, and the pH adjustment range is 7-9.

[0020] As a preferred embodiment of the preparation method of the present invention, wherein: the obtained ruthenium precursor aqueous solution is added dropwise to the first suspension, wherein the ratio of the ruthenium precursor to the carbon support is 30-50 mg: 70-100 mg.

[0021] As a preferred embodiment of the preparation method of the present invention, wherein: the second suspension is subjected to hydrothermal treatment, wherein the hydrothermal treatment temperature is 100-120 °C and the hydrothermal treatment time is 6-8 h.

[0022] As a preferred embodiment of the preparation method of the present invention, wherein: the first composite solid is calcined in a tubular furnace, wherein the calcination atmosphere is argon, the calcination temperature is 350-450 °C, and the calcination time is 20-45 min.

[0023] Another object of the present invention is to overcome the deficiencies in the prior art and provide a product prepared by a preparation method of an anion exchange membrane fuel cell anode anti-poisoning catalyst.

[0024] Advantages of the present invention:

[0025] (1) The present invention constructs a ruthenium-ruthenium dioxide active interface by hydrothermal method, and improves the hydrogen oxidation activity by optimizing the adsorption of hydrogen species and hydroxyl species intermediates.

[0026] (2) The present invention effectively improves the carbon monoxide oxidation ability of the catalyst by regulating the adsorption of ruthenium on hydroxyl species by ruthenium dioxide.

[0027] (3) Compared with the prior art, the anion exchange membrane fuel cell anode anti-poisoning catalyst proposed by the present invention not only has a simple preparation method, low cost and good reproducibility, but also the prepared catalyst has both high hydrogen oxidation performance and anti-poisoning effect. Especially, it shows excellent anti-poisoning ability during long-term operation, which makes it highly possible for the fuel cell to directly use the crude hydrogen produced by industrial production as the anode fuel, which can greatly reduce the commercial cost of the fuel cell and has great industrial significance. Description of the Drawings

[0028] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts. Among them:

[0029] Figure 1 It is the X-ray diffraction (XRD) pattern of the sample in Embodiment 1 of the present invention;

[0030] Figure 2 It is the transmission electron microscope (TEM) image of the sample in Embodiment 1 of the present invention;

[0031] Figure 3 It is the high-resolution transmission electron microscope (HRTEM) image of the sample in Embodiment 1 of the present invention;

[0032] Figure 4 It is the schematic diagram of the hydrogenation activity of the samples prepared from the samples in Embodiments 1-11 of the present invention and Comparative Experiment A;

[0033] Figure 5 It is the schematic diagram of the carbon monoxide oxidation activity of the sample in Embodiment 1 of the present invention and Comparative Experiment B;

[0034] Figure 6 It is the schematic diagram of the carbon monoxide anti-poisoning performance of the sample in Embodiment 1 of the present invention and Comparative Experiment C;

[0035] Figure 7 It is the schematic diagram of the hydrogenation activity of the samples prepared from the sample in Embodiment 1 of the present invention and Comparative Experiments D and E. Detailed implementation manners

[0036] To make the above objects, features and advantages of the present invention more obvious and understandable, the following will describe the detailed implementation manners of the present invention in conjunction with the embodiments of the specification.

[0037] In the following description, many specific details are set forth to fully understand the present invention. However, the present invention can also be implemented in other ways different from those described herein. Those skilled in the art can make similar extensions without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

[0038] Secondly, the so-called "one embodiment" or "embodiment" herein refers to a specific feature, structure or characteristic that can be included in at least one implementation manner of the present invention. The "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment that is mutually exclusive with other embodiments.

[0039] The main principle of the technology of the present invention is as follows:

[0040] Using the hydrothermal method, ruthenium nanoclusters and ruthenium dioxide clusters with a size of about 2 nm were loaded on the XC-72 carbon support, and a rich ruthenium-ruthenium dioxide heterojunction was formed. Ruthenium dioxide can regulate the d-band center of ruthenium, thereby reducing the adsorption of ruthenium to hydrogen species; moreover, ruthenium dioxide can adjust the adsorption strength of ruthenium to hydrogen and oxygen species through the competitive adsorption pathway. By optimizing the adsorption of ruthenium to hydrogen and hydrogen and oxygen species, the hydrogen oxidation activity of the catalyst was improved; secondly, by optimizing the adsorption strength of ruthenium to hydrogen and oxygen species, the carbon monoxide oxidation performance of the catalyst can be greatly improved, achieving excellent anti-poisoning ability.

[0041] In the examples of the present invention, the XC-72 carbon support was purchased from Cabot Corporation; RuCl 3 ·xH 2 O was purchased from Aladdin (Shanghai) Chemical Technology Co., Ltd., CAS: 10049-08-8.

[0042] Example 1

[0043] (1) At room temperature, 90 mg of the XC-72 carbon support was dispersed in 30 mL of ultrapure water, and after ultrasonic dispersion for 10 min, a first suspension was obtained;

[0044] (2) Weigh 40 mg of RuCl 3 ·xH 2 O and dissolve it in 10 mL of ultrapure water, and disperse it evenly by ultrasonic treatment for 10 min; the ruthenium chloride aqueous solution was added dropwise to the first suspension, and 1 M NaOH solution was added to adjust the pH to 7, and stirred for 30 min to obtain a second suspension;

[0045] (3) The second suspension was hydrothermally treated under hydrothermal conditions of 120 °C for 6 h to obtain a third suspension;

[0046] (4) The above third suspension was centrifuged at a speed of 11,000 rpm and dried at 60 °C for 12 h to obtain a first composite solid;

[0047] (5) The first composite solid was calcined at 400 °C in an argon atmosphere for 30 min, and after grinding, an anion exchange membrane fuel cell anode anti-poisoning catalyst was obtained.

[0048] X-ray analysis was performed on the anion exchange membrane fuel cell anode anti-poisoning catalyst obtained in Example 1, and the results were as Figure 1 shown. The obtained catalyst contained diffraction peaks of metallic ruthenium and ruthenium dioxide, indicating the coexistence state of ruthenium and ruthenium dioxide.

[0049] The anodic anti-poisoning catalyst obtained in Example 1 was dispersed in absolute ethanol (1 mg of catalyst was dispersed in 20 mL of absolute ethanol), and then dropped onto a copper grid for transmission electron microscopy characterization. The results are as Figure 2 shown. Metal particles are uniformly dispersed on the carbon support, and the particle size is about 2 nm;

[0050] Figure 3 For the high-resolution transmission electron microscopy, it shows that the dispersed particles are ruthenium nanoparticles and ruthenium dioxide nanoparticles, and there is an obvious ruthenium-ruthenium dioxide heterointerface.

[0051] (6) The anodic anti-poisoning catalyst obtained in Example 1 was made into an ink. The composition of the ink was 5 mg of catalyst, 50 μL of 0.5% Nafion solution, and 950 μL of absolute ethanol. The ink was ultrasonically dispersed for 30 min until it was in a uniformly dispersed state.

[0052] 8 μL of the ink obtained in Example 1 was uniformly dispersed on a 5 mm glassy carbon electrode and placed in a 0.1 M KOH solution for hydrogen oxidation experiment testing under alkaline conditions (the specific testing conditions were that hydrogen was continuously passed into the 0.1 M KOH solution until saturation for 20 min, and the hydrogen flow rate was 100 mL / min). The reference electrode was a saturated calomel electrode, the counter electrode was a carbon rod, and the testing atmosphere was pure hydrogen. Figure 4 is the hydrogen oxidation polarization curve of the catalyst, showing hydrogen oxidation performance superior to that of commercial Pt / C.

[0053] 8 μL of the ink obtained in Example 1 was uniformly dispersed on a 5 mm glassy carbon electrode and placed in a 0.1 M KOH solution for carbon monoxide oxidation performance testing under alkaline conditions (the specific testing conditions were that carbon monoxide was continuously passed into the 0.1 M KOH solution until saturation for 20 min, and the carbon monoxide flow rate was 100 mL / min). The reference electrode was a saturated calomel electrode, the counter electrode was a carbon rod, and the testing atmosphere was pure carbon monoxide. Figure 5 is the carbon monoxide oxidation polarization curve of the catalyst, showing carbon monoxide oxidation performance superior to that of commercial Pt / C.

[0054] 8 μL of the ink obtained in the example was uniformly dispersed on a 5 mm glassy carbon electrode and placed in a 0.1 M KOH solution for a potentiostatic chronoamperometry curve under alkaline conditions. The potentiostatic value was 0.1 V. The reference electrode was a saturated calomel electrode, the counter electrode was a carbon rod, and the testing atmosphere was a 1000 ppm CO / H 2 mixed atmosphere to evaluate the anti-poisoning ability of the catalyst. As Figure 6 shown, the catalyst shows excellent anti-poisoning performance superior to that of commercial Pt / C.

[0055] Example 2

[0056] At room temperature, 90 mg of XC-72 carbon support was dispersed in 30 mL of ultrapure water, and the first suspension was obtained after ultrasonic dispersion for 10 min;

[0057] Weighed 40 mg of RuCl 3 ·xH 2 O was dissolved in 10 mL of ultrapure water and dispersed evenly by ultrasonic treatment for 10 min; the obtained ruthenium chloride aqueous solution was added dropwise to the first suspension, and ammonia water was added to adjust the pH to 7, and stirred for 30 min to obtain the second suspension;

[0058] The second suspension was hydrothermally treated under hydrothermal conditions of 120 °C for 6 h to obtain the third suspension;

[0059] The above-mentioned third suspension was centrifuged at a speed of 11000 rpm and dried at 60 °C for 12 h to obtain the first composite solid;

[0060] The first composite solid was calcined at 400 °C in an argon atmosphere for 30 min, and ground to obtain the anionic exchange membrane fuel cell anode anti-poisoning catalyst. Figure 4 The hydrogen oxidation polarization curve of the catalyst shows better hydrogen oxidation performance than commercial Pt / C.

[0061] Example 3

[0062] At room temperature, 90 mg of XC-72 carbon support was dispersed in 30 mL of ultrapure water, and the first suspension was obtained after ultrasonic dispersion for 10 min;

[0063] Weighed 40 mg of RuCl 3 ·xH 2 O was dissolved in 10 mL of ultrapure water and dispersed evenly by ultrasonic treatment for 10 min; the obtained ruthenium chloride aqueous solution was added dropwise to the first suspension, and 1 M KOH solution was added to adjust the pH to 7, and stirred for 30 min to obtain the second suspension;

[0064] The second suspension was hydrothermally treated under hydrothermal conditions of 120 °C for 6 h to obtain the third suspension;

[0065] The above-mentioned third suspension was centrifuged at a speed of 11000 rpm and dried at 60 °C for 12 h to obtain the first composite solid;

[0066] The first composite solid was calcined at 400 °C in an argon atmosphere for 30 min, and ground to obtain the anionic exchange membrane fuel cell anode anti-poisoning catalyst. Figure 4 The hydrogen oxidation polarization curve of the catalyst shows better hydrogen oxidation performance than commercial Pt / C.

[0067] Example 4

[0068] At room temperature, 90 mg of XC-72 carbon support and 40 mg of RuCl 3 ·xH 2 O were dispersed in 40 mL of ultrapure water and sonicated for 10 min to obtain a uniform first suspension;

[0069] 1 M NaOH solution was added to adjust the pH to 7 and stirred for 30 min to obtain a second suspension;

[0070] The second suspension was hydrothermally treated under hydrothermal conditions of 120 °C for 6 h to obtain a third suspension;

[0071] The above third suspension was centrifuged at a speed of 11,000 rpm and dried at 60 °C for 12 h to obtain a first composite solid;

[0072] The first composite solid was calcined at 400 °C in an argon atmosphere for 30 min and ground to obtain an anion exchange membrane fuel cell anode anti-poisoning catalyst. Figure 4 The hydrogen oxidation polarization curve of the catalyst shows better hydrogen oxidation performance than commercial Pt / C.

[0073] Example 5

[0074] At room temperature, 90 mg of XC-72 carbon support was dispersed in 30 mL of ultrapure water and sonicated for 10 min to obtain a first suspension;

[0075] Weighed 40 mg of RuCl 3 ·xH 2 O was dissolved in 10 mL of ultrapure water and sonicated for 10 min to be uniformly dispersed;

[0076] The ruthenium chloride aqueous solution was added dropwise to the first suspension, and 1 M NaOH solution was added to adjust the pH to 7 and stirred for 30 min to obtain a second suspension;

[0077] The second suspension was hydrothermally treated under hydrothermal conditions of 120 °C for 6 h to obtain a third suspension;

[0078] The above third suspension was filtered by suction, washed three times with ultrapure water, the filter cake was collected and dried at 60 °C for 12 h to obtain a first composite solid;

[0079] The first composite solid was calcined at 400 °C in an argon atmosphere for 30 min and ground to obtain an anion exchange membrane fuel cell anode anti-poisoning catalyst. Figure 4 The hydrogen oxidation polarization curve of the catalyst shows better hydrogen oxidation performance than commercial Pt / C.

[0080] Example 6

[0081] At room temperature, 90 mg of XC-72 carbon support was dispersed in 30 mL of ultrapure water. After ultrasonic dispersion for 10 min, the first suspension was obtained;

[0082] Weighed 40 mg of RuCl 3 ·xH 2 O was dissolved in 10 mL of ultrapure water and dispersed evenly by ultrasonic treatment for 10 min;

[0083] The ruthenium chloride aqueous solution was added dropwise to the first suspension, and 1 M NaOH solution was added to adjust the pH to 7. After stirring for 30 min, the second suspension was obtained;

[0084] The second suspension was hydrothermally treated under hydrothermal conditions of 120 °C for 6 h to obtain the third suspension;

[0085] The above-mentioned third suspension was filtered by suction, washed three times with ultrapure water, the filter cake was collected, and after drying at 60 °C for 12 h, the first composite solid was obtained;

[0086] The first composite solid was calcined at 300 °C in an argon atmosphere for 60 min, and after grinding, the anodic anti-poisoning catalyst for anion exchange membrane fuel cells was obtained. Figure 4 The hydrogen oxidation polarization curve of the catalyst shows better hydrogen oxidation performance than commercial Pt / C.

[0087] Example 7

[0088] At room temperature, 90 mg of XC-72 carbon support was dispersed in 30 mL of ultrapure water. After ultrasonic dispersion for 10 min, the first suspension was obtained;

[0089] Weighed 40 mg of RuCl 3 ·xH 2 O was dissolved in 10 mL of ultrapure water and dispersed evenly by ultrasonic treatment for 10 min;

[0090] The ruthenium chloride aqueous solution was added dropwise to the first suspension, and 1 M NaOH solution was added to adjust the pH to 7. After stirring for 30 min, the second suspension was obtained;

[0091] The second suspension was hydrothermally treated under hydrothermal conditions of 120 °C for 6 h to obtain the third suspension;

[0092] The above-mentioned third suspension was filtered by suction, washed three times with ultrapure water, the filter cake was collected, and after drying at 60 °C for 12 h, the first composite solid was obtained;

[0093] The first composite solid was calcined at 350 °C in an argon atmosphere for 45 min, and after grinding, the anodic anti-poisoning catalyst for anion exchange membrane fuel cells was obtained. Figure 4 The hydrogen oxidation polarization curve of the catalyst shows better hydrogen oxidation performance than commercial Pt / C.

[0094] Example 8

[0095] At room temperature, 90 mg of XC-72 carbon support was dispersed in 30 mL of ultrapure water, and the first suspension was obtained after ultrasonic dispersion for 10 min;

[0096] Weigh 40 mg of RuCl 3 ·xH 2 O was dissolved in 10 mL of ultrapure water and dispersed evenly by ultrasonic treatment for 10 min;

[0097] The ruthenium chloride aqueous solution was added dropwise to the first suspension, and 1 M NaOH solution was added to adjust the pH to 7, and stirred for 30 min to obtain the second suspension;

[0098] The second suspension was hydrothermally treated under hydrothermal conditions of 120 °C for 6 h to obtain the third suspension;

[0099] The above third suspension was filtered by suction, washed three times with ultrapure water, the filter cake was collected, and after drying at 60 °C for 12 h, the first composite solid was obtained;

[0100] The first composite solid was calcined at 450 °C in an argon atmosphere for 20 min, and after grinding, an anionic exchange membrane fuel cell anode anti-poisoning catalyst was obtained. Figure 4 The hydrogen oxidation polarization curve of the catalyst shows hydrogen oxidation performance superior to that of commercial Pt / C.

[0101] Example 9

[0102] At room temperature, 80 mg of XC-72 carbon support was dispersed in 30 mL of ultrapure water, and the first suspension was obtained after ultrasonic dispersion for 10 min;

[0103] Weigh 40 mg of RuCl 3 ·xH 2 O was dissolved in 10 mL of ultrapure water and dispersed evenly by ultrasonic treatment for 10 min;

[0104] The ruthenium chloride aqueous solution was added dropwise to the first suspension, and 1 M NaOH solution was added to adjust the pH to 7, and stirred for 30 min to obtain the second suspension;

[0105] The second suspension was hydrothermally treated under hydrothermal conditions of 120 °C for 6 h to obtain the third suspension;

[0106] The above third suspension was filtered by suction, washed three times with ultrapure water, the filter cake was collected, and after drying at 60 °C for 12 h, the first composite solid was obtained;

[0107] The first composite solid was calcined at 400 °C in an argon atmosphere for 30 min, and after grinding, an anionic exchange membrane fuel cell anode anti-poisoning catalyst was obtained. Figure 4The hydrogen oxidation polarization curve of the catalyst shows hydrogen oxidation performance superior to that of commercial Pt / C.

[0108] Example 10

[0109] At room temperature, 180 mg of XC-72 carbon support was dispersed in 50 mL of ultrapure water. After ultrasonic dispersion for 10 min, a first suspension was obtained.

[0110] Weighed 80 mg of RuCl 3 ·xH 2 O was dissolved in 10 mL of ultrapure water and dispersed evenly by ultrasonic for 10 min.

[0111] The ruthenium chloride aqueous solution was added dropwise to the first suspension, and 1 M NaOH solution was added to adjust the pH to 7. After stirring for 30 min, a second suspension was obtained.

[0112] The second suspension was hydrothermally treated under hydrothermal conditions of 120 °C for 6 h to obtain a third suspension.

[0113] The above-mentioned third suspension was filtered by suction, washed three times with ultrapure water, the filter cake was collected, and after drying at 60 °C for 12 h, a first composite solid was obtained.

[0114] The first composite solid was calcined at 400 °C in an argon atmosphere for 30 min and ground to obtain an anion exchange membrane fuel cell anode anti-poisoning catalyst. Figure 4 The hydrogen oxidation polarization curve of the catalyst shows hydrogen oxidation performance superior to that of commercial Pt / C.

[0115] Example 11

[0116] At room temperature, 90 mg of XC-72 carbon support was dispersed in 30 mL of ultrapure water. After ultrasonic dispersion for 10 min, a first suspension was obtained.

[0117] Weighed 40 mg of RuCl 3 ·xH 2 O was dissolved in 10 mL of ultrapure water and dispersed evenly by ultrasonic for 10 min. The ruthenium chloride aqueous solution was added dropwise to the first suspension, and 1 M NaOH solution was added to adjust the pH to 8. After stirring for 30 min, a second suspension was obtained.

[0118] The second suspension was hydrothermally treated under hydrothermal conditions of 120 °C for 6 h to obtain a third suspension.

[0119] The above-mentioned third suspension was centrifuged at a speed of 11,000 rpm, and after drying at 60 °C for 12 h, a first composite solid was obtained.

[0120] The first composite solid was calcined at 400 °C in an argon atmosphere for 30 min, and after grinding, an anionic exchange membrane fuel cell anode anti-poisoning catalyst was obtained. Figure 4 The hydrogen oxidation polarization curve of the catalyst shows better hydrogen oxidation performance than commercial Pt / C.

[0121] Example 12

[0122] At room temperature, 90 mg of XC-72 carbon support was dispersed in 30 mL of ultrapure water, and after ultrasonic dispersion for 10 min, a first suspension was obtained;

[0123] Weighed 40 mg of RuCl 3 ·xH 2 O was dissolved in 10 mL of ultrapure water and ultrasonically dispersed for 10 min to be evenly dispersed;

[0124] The ruthenium chloride aqueous solution was added dropwise to the first suspension, and 1 M NaOH solution was added to adjust the pH to 9, and stirred for 30 min to obtain a second suspension;

[0125] The second suspension was hydrothermally treated under hydrothermal conditions of 120 °C for 6 h to obtain a third suspension;

[0126] The above third suspension was centrifuged at a speed of 11,000 rpm and dried at 60 °C for 12 h to obtain a first composite solid;

[0127] The first composite solid was calcined at 400 °C in an argon atmosphere for 30 min, and after grinding, an anionic exchange membrane fuel cell anode anti-poisoning catalyst was obtained. Figure 4 The hydrogen oxidation polarization curve of the catalyst shows better hydrogen oxidation performance than commercial Pt / C.

[0128] Comparative Example 1

[0129] Comparative experiment A: The purchased Johnson Matthey 20% Pt / C catalyst was formulated into an ink for testing the electrochemical hydrogen oxidation performance.

[0130] The ink formulation was 1 mg of catalyst, 50 μL of 5% Nafion solution, and 950 μL of absolute ethanol, and the ink was ultrasonically treated for 30 min until it was in a uniformly dispersed state.

[0131] 20 μL of the catalyst ink was evenly dropped on a 5 mm glassy carbon electrode and placed in a 0.1 M KOH solution for hydrogen oxidation experiment testing under alkaline conditions. The reference electrode was a saturated calomel electrode, the counter electrode was a carbon rod, and the test atmosphere was pure hydrogen, as Figure 4 shown in the comparison.

[0132] Comparative Example 2

[0133] Comparative Experiment B: The purchased Johnson Matthey 20% Pt / C catalyst was formulated into an ink for testing the electrochemistry performance of carbon monoxide oxidation.

[0134] The formulation of the ink was 1 mg catalyst, 50 μL of 5% Nafion solution, and 950 μL of absolute ethanol. The ink was sonicated for 30 min until it was in a homogeneous dispersion state.

[0135] 20 μL of the catalyst ink was evenly dropped onto a 5 mm glassy carbon electrode and placed in a 0.1 M KOH solution for testing the carbon monoxide oxidation experiment under alkaline conditions. The reference electrode was a saturated calomel electrode, the counter electrode was a carbon rod, and the test atmosphere was pure carbon monoxide, as Figure 5 shown in the comparison.

[0136] Comparative Example 3

[0137] Comparative Experiment C: The purchased Johnson Matthey 20% Pt / C catalyst was formulated into an ink for electrochemistry testing.

[0138] The formulation of the ink was 1 mg catalyst, 50 μL of 5% Nafion solution, and 950 μL of absolute ethanol. The ink was sonicated for 30 min until it was in a homogeneous dispersion state.

[0139] 20 μL of the catalyst ink was evenly dropped onto a 5 mm glassy carbon electrode and placed in a 0.1 M KOH solution for a potentiostatic chronoamperometry test. The constant potential was set at 0.1 V. The reference electrode was a saturated calomel electrode, the counter electrode was a carbon rod, and the test atmosphere was a 1000 ppm CO / H 2 mixed gas, as Figure 6 shown in the comparison.

[0140] Comparative Example 4

[0141] Comparative Experiment D: At room temperature, 90 mg of XC-72 carbon support was dispersed in 30 mL of ultrapure water, and the first suspension was obtained after sonication for 10 min;

[0142] Weighed 20 mg of RuCl 3 ·xH 2 O was dissolved in 10 mL of ultrapure water and sonicated for 10 min to be evenly dispersed; the obtained ruthenium chloride aqueous solution was gradually added dropwise to the first suspension, and 1 M NaOH solution was added to adjust the pH to 7, and stirred for 30 min to obtain the second suspension;

[0143] The second suspension was hydrothermally treated under hydrothermal conditions of 120 °C for 6 h to obtain the third suspension;

[0144] The above-mentioned third suspension was centrifuged at a speed of 11000 rpm and dried at 60 °C for 12 h to obtain the first composite solid;

[0145] The first composite solid was calcined at 400 °C for 30 min under an argon atmosphere, and after grinding, an anionic exchange membrane fuel cell anodic anti-poisoning catalyst was obtained.

[0146] The anionic exchange membrane fuel cell anodic anti-poisoning catalyst obtained in Comparative Example 4 was formulated into an ink. The composition of the ink was 5 mg of the catalyst, 50 μL of a 0.5% Nafion solution, and 950 μL of absolute ethanol. The ink was ultrasonically dispersed for 30 min until it was in a uniformly dispersed state.

[0147] 8 μL of the ink obtained in Comparative Example 4 was uniformly dispersed on a 5 mm glassy carbon electrode, and placed in a 0.1 M KOH solution for an experimental test of hydrogen oxidation under alkaline conditions. The reference electrode was a saturated calomel electrode, the counter electrode was a carbon rod, and the test atmosphere was pure hydrogen. Figure 7 This is the hydrogen oxidation polarization curve of the catalyst prepared in this comparative example. It can be seen that its performance has decreased.

[0148] Comparative Example 5

[0149] Comparative experiment E: At room temperature, 90 mg of XC-72 carbon support was dispersed in 30 mL of ultrapure water, and after ultrasonic dispersion for 10 min, a first suspension was obtained;

[0150] Weigh 60 mg of RuCl 3 ·xH 2 O was dissolved in 10 mL of ultrapure water and ultrasonically dispersed for 10 min until evenly dispersed; the obtained ruthenium chloride aqueous solution was added dropwise to the first suspension, and 1 M NaOH solution was added to adjust the pH to 7, and stirred for 30 min to obtain a second suspension;

[0151] The second suspension was hydrothermally treated under hydrothermal conditions of 120 °C for 6 h to obtain a third suspension;

[0152] The above third suspension was centrifuged at a speed of 11,000 rpm and dried at 60 °C for 12 h to obtain a first composite solid;

[0153] The first composite solid was calcined at 400 °C for 30 min under an argon atmosphere, and after grinding, an anionic exchange membrane fuel cell anodic anti-poisoning catalyst was obtained.

[0154] The anionic exchange membrane fuel cell anodic anti-poisoning catalyst obtained in Comparative Example 5 was formulated into an ink. The composition of the ink was 5 mg of the catalyst, 50 μL of a 0.5% Nafion solution, and 950 μL of absolute ethanol. The ink was ultrasonically dispersed for 30 min until it was in a uniformly dispersed state.

[0155] 8 μL of the ink obtained in Comparative Example 5 was evenly dispersed on a 5-mm glassy carbon electrode and placed in a 0.1 M KOH solution for the hydrogen oxidation experiment test under alkaline conditions. The reference electrode was a saturated calomel electrode, the counter electrode was a carbon rod, and the test atmosphere was pure hydrogen. Figure 7 This is the hydrogen oxidation polarization curve of the catalyst prepared in this comparative example. It can be seen that its performance has decreased.

[0156] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered within the scope of the present invention.

Claims

1. A method for preparing an anion exchange membrane fuel cell anode anti-poisoning catalyst, characterized in that: include, Dispersing the carbon carrier in ultrapure water at room temperature, and uniformly dispersing by ultrasonication to obtain a first suspension; Dissolving a ruthenium precursor in ultrapure water and uniformly dispersing the ruthenium precursor by ultrasonication to obtain a ruthenium precursor aqueous solution; Adding the obtained ruthenium precursor aqueous solution dropwise into the first suspension, adjusting the pH, and stirring evenly to obtain a second suspension; The second suspension is subjected to hydrothermal treatment to obtain a third suspension; The third suspension is centrifuged and dried to obtain a first composite solid; The first composite solid is placed in a tubular furnace for calcination, and after grinding, an anion exchange membrane fuel cell anode anti-poisoning catalyst is obtained.

2. The preparation method according to claim 1, characterized in that: The specific surface area of ​​the carbon carrier is 200 to 400 m 2 / g, with a resistivity greater than 18 MΩ·cm, including commercial carbon carrier XC-72 and commercial carbon carrier BP-2000; the resistivity of the ultrapure water is 18.25 MΩ·cm.

3. The preparation method according to claim 1 or 2, characterized in that: In the first suspension, the ratio of the carbon carrier to ultrapure water is 70-100 mg:30 mL.

4. The preparation method according to claim 1, characterized in that: The ruthenium precursor includes ruthenium trichloride hydrate RuCl3·xH2O.

5. The preparation method according to claim 1 or 4, characterized in that: The ruthenium precursor is dissolved in ultrapure water, wherein the ratio of the ruthenium precursor to the ultrapure water is 30-50 mg:10 mL.

6. The preparation method according to claim 1, characterized in that: The pH is adjusted, wherein the pH adjuster is one or more of 1M KOH solution, 1M NaOH solution or ammonia water, and the pH adjustment range is 7-9.

7. The preparation method according to claim 1, characterized in that: The obtained ruthenium precursor aqueous solution is added dropwise into the first suspension, wherein the ratio of the ruthenium precursor to the carbon carrier is 30-50 mg:70-100 mg.

8. The preparation method according to claim 1, characterized in that: The second suspension is subjected to hydrothermal treatment, wherein the hydrothermal treatment temperature is 100-120° C. and the hydrothermal treatment time is 6-8 hours.

9. The preparation method according to claim 1, characterized in that: The first composite solid is placed in a tubular furnace for calcination, wherein the calcination atmosphere is argon, the calcination temperature is 350-450° C., and the calcination time is 20-45 minutes.

10. Anion exchange membrane fuel cell anode anti-poisoning catalyst prepared by the preparation method according to any one of claims 1 to 9.

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