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溶解在SrTiCoO多晶钙钛矿薄膜上的单个Co颗粒的生长动力学

Growth Kinetics of Individual Co Particles Ex-solved on SrTiCoO Polycrystalline Perovskite Thin Films.

作者信息

Jo Yong-Ryun, Koo Bonjae, Seo Min-Ji, Kim Jun Kyu, Lee Siwon, Kim Kyeounghak, Han Jeong Woo, Jung WooChul, Kim Bong-Joong

机构信息

School of Materials Science and Engineering , Gwangju Institute of Science and Technology (GIST) , 123 Cheomdangwagi-ro , Buk-gu, Gwangju , Korea.

Department of Materials Science and Engineering , Korea Advanced Institute of Science and Technology (KAIST) , 291 Daehak-ro , Yuseong-gu, Daejeon , Korea.

出版信息

J Am Chem Soc. 2019 Apr 24;141(16):6690-6697. doi: 10.1021/jacs.9b01882. Epub 2019 Apr 15.

Abstract

A precise control of the size, density, and distribution of metal nanoparticles dispersed on functional oxide supports is critical for promoting catalytic activity and stability in renewable energy and catalysis devices. Here, we measure the growth kinetics of individual Co particles ex-solved on SrTiCoO polycrystalline thin films under a high vacuum, and at various temperatures and grain sizes using in situ transmission electron microscopy. The ex-solution preferentially occurs at grain boundaries and corners which appear essential for controlling particle density and distribution, and enabling low temperature ex-solution. The particle reaches a saturated size after a few minutes, and the size depends on temperature. Quantitative measurements with a kinetic model determine the rate limiting step, vacancy formation enthalpy, ex-solution enthalpy, and activation energy for particle growth. The ex-solved particles are tightly socketed, preventing interactions among them over 800 °C. Furthermore, we obtain the first direct clarification of the active reaction site for CO oxidation-the Co-oxide interface, agreeing well with density functional theory calculations.

摘要

精确控制分散在功能氧化物载体上的金属纳米颗粒的尺寸、密度和分布,对于提高可再生能源和催化装置中的催化活性及稳定性至关重要。在此,我们利用原位透射电子显微镜,在高真空、不同温度和晶粒尺寸条件下,测量了溶解在SrTiCoO多晶薄膜上的单个Co颗粒的生长动力学。析出优先发生在晶界和角落,这对于控制颗粒密度和分布以及实现低温析出似乎至关重要。颗粒在几分钟后达到饱和尺寸,且尺寸取决于温度。用动力学模型进行的定量测量确定了速率限制步骤、空位形成焓、析出焓以及颗粒生长的活化能。析出的颗粒紧密套接,在800℃以上可防止它们之间的相互作用。此外,我们首次直接阐明了CO氧化的活性反应位点——Co-氧化物界面,这与密度泛函理论计算结果吻合良好。

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