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CN-122025675-A - Hydrogen fuel cell catalyst for resisting carbon monoxide poisoning and preparation method thereof

CN122025675ACN 122025675 ACN122025675 ACN 122025675ACN-122025675-A

Abstract

The invention relates to a hydrogen fuel cell catalyst for resisting carbon monoxide poisoning and a preparation method thereof, belonging to the technical field of fuel cell catalysts. The catalyst consists of a modified carbon carrier, an active component and an auxiliary component, wherein the active component is Pt, the auxiliary component is Ti and Ru, and the catalyst has good dispersibility of the active component, good quality activity and good CO poisoning resistance. The method comprises the steps of adopting a ball milling method to finish the modification of the ruthenium and titanium composite oxide on the carbon carrier in one step, providing abundant Pt anchoring sites, and enhancing the structural stability of the carbon carrier and the CO poisoning resistance of the catalyst.

Inventors

  • CHENG YANHU
  • TANG WEIHUA
  • LI TONG
  • WANG TAO
  • LIU YANXIAO

Assignees

  • 中国船舶集团有限公司第七一八研究所
  • 中国船舶集团有限公司

Dates

Publication Date
20260512
Application Date
20251231

Claims (8)

  1. 1. A hydrogen fuel cell catalyst for resisting carbon monoxide poisoning is characterized by comprising a modified carbon carrier, an active component and an auxiliary component, wherein the active component is Pt, and the auxiliary component is Ti and Ru.
  2. 2. The catalyst for hydrogen fuel cells resistant to carbon monoxide poisoning according to claim 1, wherein the mass fraction of Pt is 20% -55% in terms of metal, the mass fraction of Ti is 0.5% -15% in terms of the oxide mass, and the mass fraction of Pt/Ru is 3% -0.5, based on 100% of the total mass of the catalyst.
  3. 3. A method for preparing the carbon monoxide poisoning resistant hydrogen fuel cell catalyst according to claim 1 or 2, characterized in that: (1) Preparing a carbon carrier powder into a solution, heating and refluxing the solution, filtering the solution to remove carbon carrier impurities, drying the solution at 70-95 ℃ for 2-6 h, adding the dried carbon carrier and a nitric acid solution with the mass fraction of 10-45% into a ball milling tank, and performing ball milling for 1-6 h to obtain a pretreated carbon carrier, wherein the liquid-solid ratio is 5 g/ml-25 g/ml; (2) Adding the solution A and the solution B into a ball milling tank respectively, adding citric acid and hydrogen peroxide as grinding aids, adding pretreated activated carbon after ball milling, continuing ball milling for 1h to 6h, drying, and roasting for 2h to 8h at 180-450 ℃ in nitrogen atmosphere to prepare a modified carbon carrier; (3) Adding a Pt precursor and a modified carbon carrier into a ball milling tank for ball milling, adding citric acid and hydrogen peroxide as milling aids, ball milling for 1 h-6 h, drying, heating to 120-350 ℃ at a heating rate of 2-10 ℃ per minute, and introducing hydrogen for reducing for 0.5-h-6 h to obtain the hydrogen fuel cell catalyst for resisting carbon monoxide poisoning.
  4. 4. The method for preparing the catalyst for the hydrogen fuel cell resistant to carbon monoxide poisoning according to claim 3, wherein the carbon carrier is XC-72 carbon black, MWCNTS, mesoporous carbon material CMK-1 or acetylene black; the Pt precursor is H 2 PtCl 6 、Pt(NO 3 ) 2 、H 2 Pt(OH) 6 or Na 6 Pt(SO 3 ) 4 ; the Ti source is titanium tetrachloride, butyl titanate, tetraethyl titanate or titanium isopropoxide; The Ru source is RuCl 3 、Ru(NO)(NO 3 ) 3 or Ru (OAC) x .
  5. 5. The method for preparing a catalyst for hydrogen fuel cells resistant to carbon monoxide poisoning according to claim 3, wherein in the step (2) and the step (3), when the mass fraction of the hydrogen peroxide is 25%, the mass ratio of the hydrogen peroxide to the citric acid to the modified carbon carrier is 0.05:0.1:1-0.5:0.1:1, and the hydrogen peroxide is dried at 110 ℃ to 1 h-6 h.
  6. 6. The method for preparing the carbon monoxide poisoning resistant hydrogen fuel cell catalyst according to any one of claims 3 to 5, wherein the hydrogen gas is introduced at a rate of 10 ml/min to 30 ml/min; the mass of Pt in the Pt precursor is 20% -55% of the mass of the catalyst; the mass ratio of the hydrogen peroxide to the citric acid to the modified carbon carrier is 0.1:0.1:1-0.3:0.1:1; the ball milling time is 1.5 h-4 h; 150. Introducing hydrogen at the temperature of between C and 300 ℃ to reduce the temperature by 2 h to 4 h.
  7. 7. The method of claim 1 or 2, wherein the hydrogen fuel cell catalyst is used for CO poisoning resistance test of electrocatalytic oxidation of H 2 .
  8. 8. The method for preparing a catalyst for hydrogen fuel cells with carbon monoxide poisoning resistance according to claim 7, wherein the method comprises the following steps: The substrate of the working electrode is a glassy carbon electrode with the diameter of 5mm, the glassy carbon electrode is ground to a mirror surface on metallographic sand paper and Al 2 O 3 powder, 10 mg of the catalyst is weighed, 2 ml of absolute ethyl alcohol is added for ultrasonic dispersion, 10 mu L of suspension liquid is taken to be dropped on the surface of the glassy carbon electrode, 60 ℃ is dried, then 8 mu L of 5% Nation solution is taken to be placed on the surface of the electrode, 60 ℃ is dried, the actual load of the catalyst on the electrode is calculated according to the concentration and the volume of the used ink, 0.1M HClO 4 solution is taken as an electrolyte, a platinum sheet is taken as a counter electrode, and a Saturated Calomel Electrode (SCE) is taken as a reference electrode, so that an electrolytic cell is formed; Before CV test, 15 min N 2 is introduced into electrolyte solution to remove dissolved O 2 , 50 mV/S scanning is carried out on the electrolyte solution at-0.2V-1.2V until current density is not increased, then CV test is carried out on the catalyst under the conditions of H 2 atmosphere and CO and H 2 mixed gas at a scanning speed of 100 mV/S at 0.6V-1.0V, and according to the mass specific activity I a 、I b of the catalyst subjected to H 2 reaction and CO and H 2 reaction and the change thereof, wherein the change is expressed as I b /I a , the electrochemical area change is that the electrochemical area S a after H 2 reaction and the electrochemical area S b after CO and H 2 mixed gas reaction are expressed as S b /S a , and the ratio of I b /I a to S b /S a is closer to 1, the catalyst is evaluated to have stronger CO poisoning resistance.

Description

Hydrogen fuel cell catalyst for resisting carbon monoxide poisoning and preparation method thereof Technical Field The invention relates to a hydrogen fuel cell catalyst for resisting carbon monoxide poisoning and a preparation method thereof, belonging to the technical field of fuel cell catalysts. Background Hydrogen fuel cells are key devices for hydrogen energy applications, as an energy conversion device, to directly convert chemical energy in fuel into electrical energy, and catalysts are the core materials of hydrogen fuel cells, most commonly platinum-carbon (Pt/C) catalysts. Studies have shown that ppm carbon monoxide (CO) causes a dramatic drop in catalyst activity. The current large-scale production of hydrogen (H 2) is mainly realized by reforming reaction of petroleum and natural gas and incomplete combustion reaction and shift reaction of coal, wherein a certain amount of CO is contained in the hydrogen, in addition, the carbon carrier used by the Pt/C catalyst is generally a porous carbon carrier with high specific surface area, and a large amount of unsaturated bonds and defects exist on the surface of the carbon carrier, so that electrochemical oxidation corrosion is easy to generate CO, thereby causing Pt poisoning. Therefore, solving the CO poisoning problem of Pt-based catalysts is critical to hydrogen fuel cell development. A great deal of research proves that the adoption of Pt and other metals to form nano alloy can improve the CO poisoning resistance of the nano alloy. At present, the most promising catalyst with high activity and strong CO poisoning resistance is a binary alloy catalyst composed of any one of Mo, W, os, ru and Pt, and particularly the best Pt-Ru binary alloy catalyst. It is generally thought that Ru readily forms an active oxygen-containing species with water, which promotes oxidation of the Pt surface, thereby improving the activity and poisoning resistance of the catalyst, and that addition of Ru modulates the d-electron state of Pt, thereby reducing the interaction between Pt and CO, and thereby improving the poisoning resistance of the catalyst. In the prior report PtRu/C catalyst, the total loading of metal components is generally more than or equal to 20 wt%, so that good dispersion and performance of the loaded components are realized, and the preparation process requirement is high. Compared with the colloid method, the microemulsion method, the ion exchange method and other processes, the dipping reduction method is simple in operation and easy to scale up. In addition, the water and ionic radius of the Pt and Ru precursors are larger, the difficulty of entering the pore canal of the carrier is large, so that the dispersibility of the Pt and Ru of the obtained catalyst is difficult to control, the component distribution is uneven, and the high-quality alloying catalyst is difficult to obtain, and the dispersion effect of Pt and the second component metal such as Pd and Ru is improved by adopting a microwave-assisted drying method in the Chinese patent with the publication number of CN101912778A, but the low-temperature dry leaching adsorption step involved in the step is required to be carried out at 24 h-36 h under the condition of low temperature as low as-5 ℃, and the required time is longer, and the difficulty of realizing the condition by conventional amplifying equipment is larger. Disclosure of Invention In order to overcome the defects in the prior art, the invention aims to provide a hydrogen fuel cell catalyst for resisting carbon monoxide poisoning and a preparation method thereof. The catalyst has good dispersibility of active components, good quality activity, good CO poisoning resistance, small waste liquid amount and environmental protection. In order to achieve the purpose of the invention, the following technical scheme is provided. A hydrogen fuel cell catalyst for resisting carbon monoxide poisoning comprises a modified carbon carrier, an active component and an auxiliary component, wherein the active component is platinum (Pt), and the auxiliary component is titanium (Ti) and ruthenium (Ru); Further, based on the total mass of the catalyst being 100%, the mass fraction of Pt is 20% -55% based on metal, the mass fraction of Ti is 0.5% -15% based on the oxide mass, and the mass fraction of Pt/Ru is 3% -0.5. The preparation method of the hydrogen fuel cell catalyst for resisting carbon monoxide poisoning comprises the following steps: (1) Pretreatment of carbon support Preparing a solution from carbon carrier powder, heating and refluxing, filtering to remove carbon carrier impurities, and drying at 70-95 ℃ for 2-6 h. Then adding the dried carbon carrier and nitric acid solution with the mass fraction of 10% -45% into a ball milling tank, wherein the liquid-solid ratio is5 g/ml-25 g/ml, and ball milling is carried out for 1 h-6 h, so as to obtain a pretreated carbon carrier; the carbon carrier is a conventional carbon carrier in the field,