Selective growth of metal oxides on metal via atomic layer deposition (ALD) has attracted great interest due to their potential applications in the semiconductor industry, as well as energy and environment fields. In this work, the influence of an oxidizing coreactant and the reaction temperature on the selective growth of FeO_x on the facets of Pt nanoparticles and low coordination edge sites are studied via in situ Fourier transform infrared spectroscopy (FTIR) and first-principles calculations combined with microkinetic methods. It is found that selective deposition on the low coordination edge sites of Pt nanoparticles is realized when using O₃ as the coreactant at low temperature (150 °C), while the ALD reaction takes place only above 250 °C without selectivity when using O₂ as the coreactant. Based on density functional theory calculations, the edge-selective growth of FeO_x on Pt is attributed to energy barrier differences for ALD reactions taking place at the Pt(111), Pt(100), and edge sites. Moreover, reaction rate analysis indicates that the selectivity of FeO_x ALD on Pt nanoparticles is temperature dependent and that a high temperature suppresses the selectivity between different sites, which is also confirmed by the FTIR results.

中文翻译：

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FeOxon Pt纳米粒子固有的选择性原子层沉积对共反应物和温度的依赖性

由于其在半导体工业以及能源和环境领域的潜在应用，通过原子层沉积（ALD）在金属上选择性生长金属氧化物引起了极大的兴趣。在这项工作中，通过原位傅里叶变换红外光谱（FTIR）和第一性原理计算，研究了氧化共反应剂和反应温度对Pt纳米颗粒表面和低配位边缘位点上FeO _x选择性生长的影响。用微动力学方法。发现使用O ₃可以实现Pt纳米颗粒低配位边缘部位的选择性沉积。低温（150°C）时，ALD反应用作共反应剂，而使用O ₂作为共反应剂时，ALD反应仅在250°C以上发生而没有选择性。根据密度泛函理论计算，Pt上FeO _x的边缘选择性生长归因于在Pt（111），Pt（100）和边缘部位发生的ALD反应的能垒差。此外，反应速率分析表明，FeO _x ALD对Pt纳米颗粒的选择性取决于温度，并且高温抑制了不同位点之间的选择性，这也由FTIR结果证实。