Endogenous Nanoparticles Strain Perovskite Host Lattice Providing Oxygen Capacity and Driving Oxygen Exchange and CH 4 Conversion to Syngas
Endogenous Nanoparticles Strain Perovskite Host Lattice Providing Oxygen Capacity and Driving Oxygen Exchange and CH 4 Conversion to Syngas
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内源纳米颗粒应变钙钛矿主体晶格提供氧容量并驱动氧交换和 CH 4 转化为合成气
DOI：
10.1002/ange.201915140
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发表时间：
2020
影响因子：
--
通讯作者：
Kousi K
中科院分区：
文献类型：
--
作者：
Kousi K
分散在氧化物载体表面的颗粒在电催化、电催化和多相催化中有着广泛的应用。然而，将纳米颗粒分散在大量氧化物中更具挑战性，因此较少探索，但可以开辟新的维度来控制类似于晶格中离子的替代掺杂的材料特性。在这里，我们展示了这样一个概念，允许广泛的，可控的金属纳米颗粒的生长，在纳米级的接近，在钙钛矿氧化物晶格以及其表面上。通过采用操作技术，我们表明，在新兴的纳米结构中，内源性纳米颗粒和钙钛矿晶格变得应变和无缝连接，从而增强氧交换。此外，即使是深度嵌入的纳米颗粒也可以与甲烷流可逆地交换氧气，从而在表面颗粒存在的情况下以显著的选择性和长期循环性驱动其氧化还原转化为合成气。这些结果不仅证明了创造具有增强的氧传输和储存能力的广泛的自应变纳米结构的方法，而且还证明了深埋的氧化还原活性纳米颗粒可以完全进入反应环境，驱动氧化还原转化，从而为设计支撑几种能量转换技术的材料提供了有趣的新替代方案。
Particles dispersed on the surface of oxide supports have enabled a wealth of applications in electrocatalysis, photocatalysis, and heterogeneous catalysis. Dispersing nanoparticles within the bulk of oxides is, however, synthetically much more challenging and therefore less explored, but could open new dimensions to control material properties analogous to substitutional doping of ions in crystal lattices. Here we demonstrate such a concept allowing extensive, controlled growth of metallic nanoparticles, at nanoscale proximity, within a perovskite oxide lattice as well as on its surface. By employing operando techniques, we show that in the emergent nanostructure, the endogenous nanoparticles and the perovskite lattice become reciprocally strained and seamlessly connected, enabling enhanced oxygen exchange. Additionally, even deeply embedded nanoparticles can reversibly exchange oxygen with a methane stream, driving its redox conversion to syngas with remarkable selectivity and long term cyclability while surface particles are present. These results not only exemplify the means to create extensive, self‐strained nanoarchitectures with enhanced oxygen transport and storage capabilities, but also demonstrate that deeply submerged, redox‐active nanoparticles could be entirely accessible to reaction environments, driving redox transformations and thus offering intriguing new alternatives to design materials underpinning several energy conversion technologies.