Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, and College of Chemistry and Molecular Engineering , Peking University , Beijing 100871 , China.
Key Laboratory for Colloid and Interface Chemistry, Key Laboratory of Special Aggregated Materials, School of Chemistry and Chemical Engineering , Shandong University , Jinan 250100 , China.
ACS Appl Mater Interfaces. 2018 Oct 10;10(40):34172-34183. doi: 10.1021/acsami.8b10496. Epub 2018 Sep 25.
Exploring the state-of-the-art heterogeneous catalysts has been a general concern for sustainable and clean energy. Here, Pt-embedded CuO -CeO multicore-shell (Pt/CuO -CeO MS) composites are fabricated at room temperature via a one-pot and template-free procedure for catalyzing CO oxidation, a classical probe reaction, showing a volcano-shaped relationship between the composition and catalytic activity. We experimentally unravel that the Pt/CuO -CeO MS composites are derived from an interfacial autoredox process, where Pt nanoparticles (NPs) are in situ encapsulated by self-assembled ceria nanospheres with CuO clusters adhered through deposition/precipitation-calcination process. Only Cu-O and Pt-Pt coordination structures are determined for CuO clusters and Pt NPs in Pt/CuO -CeO MS, respectively. Importantly, the close vicinity between Pt and CeO benefits to more oxygen vacancies in CeO counterparts and results in thin oxide layers on Pt NPs. Meanwhile, the introduction of CuO clusters is crucial for triggering synergistic catalysis, which leads to high resistance to aggregation of Pt NPs and improvement of catalytic performance. In CO oxidation reaction, both Pt-CO and Cu-CO can act as active sites during CO adsorption and activation. Nonetheless, redundant content of Pt or Cu will induce a strongly bound Pt-O-Ce or Cu-[O ]-Ce structures in air-calcinated Pt/CuO -CeO MS composites, respectively, which are both deleterious to catalytic reactivity. As a result, the composition-dependent catalytic activity and superior durability of Pt/CuO -CeO MS composites toward CO oxidation reaction are achieved. This work should be instructive for fabricating desirable multicomponent catalysts composed of noble metal and bimetallic oxide composites for diverse heterogeneous catalysis.
探索先进的多相催化剂一直是可持续清洁能源的普遍关注点。在这里,通过一种室温下的一锅法和无模板方法,制备了 Pt 嵌入的 CuO-CeO 多核壳(Pt/CuO-CeO MS)复合材料,用于催化 CO 氧化,这是一个经典的探针反应,其组成和催化活性之间存在火山形关系。我们通过实验揭示,Pt/CuO-CeO MS 复合材料源自界面自氧化还原过程,其中 Pt 纳米颗粒(NPs)通过沉积/沉淀-煅烧过程原位被自组装的氧化铈纳米球包裹,同时 CuO 簇附着在上面。对于 Pt/CuO-CeO MS 中的 CuO 簇和 Pt NPs,分别确定了仅 Cu-O 和 Pt-Pt 配位结构。重要的是,Pt 和 CeO 的紧密接近有利于 CeO 中更多的氧空位,并导致 Pt NPs 上的氧化物层变薄。同时,CuO 簇的引入对于触发协同催化至关重要,这导致 Pt NPs 的聚集阻力增加,催化性能提高。在 CO 氧化反应中,Pt-CO 和 Cu-CO 都可以作为 CO 吸附和活化过程中的活性位点。然而,过多的 Pt 或 Cu 会导致空气煅烧的 Pt/CuO-CeO MS 复合材料中分别形成强结合的 Pt-O-Ce 或 Cu-[O]-Ce 结构,这都对催化反应性有害。结果,Pt/CuO-CeO MS 复合材料对 CO 氧化反应的组成依赖性催化活性和卓越的耐久性得到了实现。这项工作对于构建由贵金属和双金属氧化物复合材料组成的理想多组分催化剂,用于各种多相催化,具有指导意义。