高分散Co3O4对钙钛矿类LaCoO3低浓度甲烷催化燃烧性能的影响

Effect of highly dispersed Co3O4 on the catalytic performance of LaCoO3 perovskite in the combustion of lean methane

  • 摘要: 本研究采用溶胶凝胶法,通过调变镧钴比合成了一种纳米新型钙钛矿类催化剂。利用物理吸附、ICP、XRD、H2-TPR、O2-TPD和XPS等技术对催化剂进行了表征,并对其在乏风甲烷氧化燃烧中的催化性能进行了研究。结果表明,高分散性的Co3O4纳米颗粒有利于甲烷的低温活化,且催化剂中镧钴钙钛矿体相可提供大量的晶格氧,促进高温下甲烷的催化燃烧速率和催化剂的高温稳定性。通过调变镧钴比例,可有效调变催化剂中Co3O4纳米颗粒的分散状态,进而实现催化剂低温活性和高温稳定性的有效统一。当La/Co比为0.9时,在空速为30000 mL/(gcat·h)的条件下,La0.9CoO3钙钛矿催化剂的甲烷起燃温度为382 ℃;稳定运行72 h后,甲烷转化率保持在95%以上。这些结果为今后开发低成本、高活性和高稳定性的甲烷燃烧催化剂提供了参考。

     

    Abstract: In this work, a series of nano LaCoO3 perovskite catalysts were effectively synthesized by a sol-gel method through modulating the La/Co molar ratio. These catalysts were characterized by ICP, XRD, N2 sorption, H2-TPR, O2-TPD, and XPS, and their catalytic performance in the lean methane combustion were then investigated. The results indicate that highly dispersed Co3O4 nanoparticles on the LaCoO3 perovskite catalysts are beneficial to the activation of CH4 at a low temperature, while the La-Co-perovskite bulk phase can provide a large amount of lattice oxygen, which can enhance the reaction rate of methane combustion and the catalytic stability at a high temperature. Through altering the La/Co molar ratio, the dispersion of Co3O4 nanoparticles in the La-Co-perovskite catalyst can be effectively modulated, to achieve the concurrence of low-temperature activity and high-temperature stability in the lean methane combustion. In particular, the La0.9CoO3 perovskite catalyst with a La/Co molar ratio of 0.9 exhibits excellent performance in lean methane combustion, with a light-off temperature of 382 ℃ at a space velocity of 30000 mL/(gcat·h), the light-off temperature of methane is 382 ℃, and the methane conversion rate is still maintained above 95% after 72 h of stable operation, indicating that the highly dispersed Co3O4 nanoparticles were beneficial to the low-temperature activation of CH4, and the lanthanum-cobalt-perovskite bulk phase in the catalyst could provide a large amount of lattice oxygen, which promotes the catalytic combustion rate of CH4 and the high-temperature stability of the catalyst under high-temperature conditions. By modulating the lanthanum-cobalt ratio, the dispersion state of Co3O4 nanoparticles in the catalyst can be effectively modulated, and then the effective unification of low-temperature activity and high-temperature stability of the catalyst can be achieved, which guides the future development of low-cost, high-activity and high-stability catalysts for methane catalytic combustion.

     

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