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通过乙酸对 La0.5Sr0.5CoO3 钙钛矿催化剂进行表面调谐用于 NOx 的存储和还原。

Surface Tuning of La0.5Sr0.5CoO3 Perovskite Catalysts by Acetic Acid for NOx Storage and Reduction.

机构信息

State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University , Beijing 100084, People's Republic of China.

School of Civil and Environmental Engineering, Georgia Institute of Technology , Atlanta, Georgia 30332, United States.

出版信息

Environ Sci Technol. 2016 Jun 21;50(12):6442-8. doi: 10.1021/acs.est.6b00110. Epub 2016 Jun 3.

Abstract

Selective dissolution of perovskite A site (A of ABO3 structure) was performed on the La1 - xSrxCoO3 catalysts for the NOx storage and reduction (NSR) reaction. The surface area of the catalysts were enhanced using dilute HNO3 impregnation to dissolve Sr. Inactive SrCO3 was removed effectively within 6 h, and the catalyst preserved the perovskite framework after 24 h of treatment. The tuned catalysts exhibited higher NSR performance (both NOx storage and NO-to-NO2 oxidation) under lean-burn and fuel-rich cycles at 250 °C. Large amounts of NOx adsorption were due to the increase of nitrate/nitrite species bonding to the A site and the growth of newly formed monodentate nitrate species. Nitrate species were stored stably on the partial exposed Sr(2+) cations. These exposed Sr(2+) cations played an important role on the NOx reduction by C3H6. High NO-to-NO2 oxidation ability was due to the generation of oxygen defects and Co(2+)-Co(3+) redox couples, which resulted from B-site exsolution induced by A-site dissolution. Hence, our method is facile to modify the surface structures of perovskite catalysts and provides a new strategy to obtain highly active catalysts for the NSR reaction.

摘要

采用稀硝酸浸渍对钙钛矿 A 位(ABO3 结构中的 A)选择性溶解,以提高 La1-xSrxCoO3 催化剂的 NOx 存储还原(NSR)性能。该方法可以溶解 Sr,从而提高催化剂的比表面积。在 6 h 内可以有效去除无活性的 SrCO3,并且在处理 24 h 后催化剂仍能保持钙钛矿结构。调变后的催化剂在 250℃的贫燃和富燃循环条件下,具有更高的 NSR 性能(NOx 存储和 NO 到 NO2 的氧化)。大量的 NOx 吸附归因于硝酸盐/亚硝酸盐物种与 A 位的结合增加以及新形成的单齿硝酸盐物种的生长。硝酸盐物种稳定地储存在部分暴露的 Sr(2+)位上。这些暴露的 Sr(2+)位在 C3H6 还原 NOx 过程中起着重要作用。高的 NO 到 NO2 的氧化能力归因于氧空位和 Co(2+)-Co(3+)氧化还原对的产生,这是由于 A 位溶解引起的 B 位离溶所致。因此,我们的方法易于修饰钙钛矿催化剂的表面结构,并为获得 NSR 反应的高活性催化剂提供了一种新策略。

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