Density functional theory study of the interaction of H2O, CO2 and Co with the ZrO2 (111), Ni/ZrO2 (111), YSZ (111) and Ni/YSZ (111) surfaces
Density functional theory study of the interaction of H2O, CO2 and Co with the ZrO2 (111), Ni/ZrO2 (111), YSZ (111) and Ni/YSZ (111) surfaces
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DOI：
10.1016/j.susc.2016.06.008
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发表时间：
2016-11-01
期刊：
影响因子：
1.9
通讯作者：
de Leeuw, Nora H.
中科院分区：
文献类型：
--
作者：
Cadi-Essadek, Abdelaziz;Roldan, Alberto;de Leeuw, Nora H.
三相边界（TPB），其中气相，Ni颗粒和氧化钇稳定的氧化锆（YSZ）表面相遇，在固体氧化物燃料电池（SOFC）的性能中起着重要的作用。事实上，关键的反应发生在TPB，在那里分子如H2O，CO2和CO相互作用和反应。本文系统地研究了H_2O、CO_2和CO与固体氧化物燃料电池（SOFC）相关的四种材料，即ZrO_2（111）、Ni/ZrO_2（111）、YSZ（111）和9%Y_2O_3稳定的立方相ZrO_2的Ni/YSZ（111）的主要表面的相互作用。该研究采用自旋极化密度泛函理论（DFT），考虑到长程色散力。我们已经调查了五个初始吸附位点的三个分子，并确定了最稳定的吸附构型的几何形状和电子结构。我们还分析了这三种分子在气相中的振动模式，并与吸附分子进行了比较。观察到三种吸附分子的振动模式的波数减少，证实了表面对分子的分子内键的影响。这些结果符合Ni在该体系中的重要作用，特别是对于CO的吸附和活化。(C)2016作者由Elsevier B. V.发布，这是CC BY许可下的开放获取文章。
The triple phase boundary (TPB), where the gas phase, Ni particles and the yttria-stabilised zirconia (YSZ) surface meet, plays a significant role in the performance of solid oxide fuel cells (SOFC). Indeed, the key reactions take place at the TPB, where molecules such as H2O, CO2 and CO interact and react. We have systematically studied the interaction of H2O, CO2 and CO with the dominant surfaces of four materials that are relevant to SOFC, i.e. ZrO2( 111), Ni/ZrO2(111), YSZ(111) and Ni/YSZ(111) of cubic ZrO2 stabilized with 9% of yttria (Y2O3). The study employed spin polarized density functional theory (DFT), taking into account the long-range dispersion forces. We have investigated up to five initial adsorption sites for the three molecules and have identified the geometries and electronic structures of the most stable adsorption configurations. We have also analysed the vibrational modes of the three molecules in the gas phase and compared them with the adsorbed molecules. A decrease of the wavenumbers of the vibrational modes for the three adsorbed molecules was observed, confirming the influence of the surface on the molecules' intra-molecular bonds. These results are in line with the important role of Ni in this system, in particular for the CO adsorption and activation. (C) 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license.