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原子尺度下观察双金属 Au-CuO 纳米粒子及其界面对 CO 分子的活化作用。

Atomic-Scale Observation of Bimetallic Au-CuO Nanoparticles and Their Interfaces for Activation of CO Molecules.

机构信息

State Key Laboratory of Fine Chemicals and Laboratory of Advanced Materials & Catalytic Engineering (AMCE), School of Chemical Engineering , Dalian University of Technology, Panjin Campus , Panjin 124221 , China.

Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics , Chinese Academy of Sciences , 457 Zhongshan Road , Dalian 116023 , China.

出版信息

ACS Appl Mater Interfaces. 2019 Sep 25;11(38):35468-35478. doi: 10.1021/acsami.9b12017. Epub 2019 Sep 13.

Abstract

Supported gold nanoparticles with sizes below 5 nm display attractive catalytic activities for heterogeneous reactions, particularly those promoted by secondary metal (e.g., Cu) because of the well-defined synergy between metal compositions. However, the specific atomic structure at interfaces is less interpreted systematically. In this work, various bimetallic Au-CuO catalysts with specific surface structures were synthesized and explored by aberration-corrected scanning transmission electron microscopy (AC-STEM), temperature-programmed experiments and in situ DRIFT experiments. Results suggest that the atomic structure and interfaces between gold and CuO are determined by the nucleation behaviors of the nanoparticles and result in subsequently the distinctive ability for CO activation. Bimetallic CuO*/Au sample formatted by gold particles surrounded with CuO nanoclusters have rough surface with prominently exposed low-coordinated Au step defects. Whereas the bimetallic Au@CuO sample formatted by copper precursor in the presence of gold nanoparticles have core-shell structure with relatively smooth surface. The former structure of CuO*/Au displays much accelerated properties for CO adsorption and activation with 90% CO converted to CO at 90 °C and nice stability with time on stream. The results clearly determine from atomic scale the significance of exposed gold step sites and intrinsic formation of defected surface by different nucleation. The above properties are directly responsible for the induced variation in chemical composition and the catalytic activity.

摘要

尺寸小于 5nm 的负载型金纳米粒子在多相反应中表现出优异的催化活性,特别是在次级金属(例如 Cu)的促进下,这是由于金属成分之间具有明确的协同作用。然而,界面处的特定原子结构还没有得到系统的解释。在这项工作中,通过球差校正扫描透射电子显微镜(AC-STEM)、程序升温实验和原位 DRIFT 实验,合成并研究了具有特定表面结构的各种双金属 Au-CuO 催化剂。结果表明,金和 CuO 之间的原子结构和界面取决于纳米粒子的成核行为,并由此导致对 CO 活化的独特能力。由金纳米粒子包围的 CuO 纳米团簇形成的双金属 CuO*/Au 样品具有粗糙的表面,明显暴露了低配位的 Au 台阶缺陷。而在金纳米粒子存在的情况下由铜前驱体制备的双金属 Au@CuO 样品具有核壳结构,表面相对光滑。CuO*/Au 的前一种结构对 CO 的吸附和活化具有更快的特性,在 90°C 时 90%的 CO 转化为 CO,并且具有良好的稳定性。结果从原子尺度上清楚地确定了暴露的金台阶位和不同成核引起的固有缺陷表面形成的重要性。上述性质直接导致了化学组成的变化和催化活性的变化。

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