Hinuma Yoyo, Mine Shinya, Toyao Takashi, Shimizu Ken-Ichi
Department of Energy and Environment, National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31, Midorigaoka, Ikeda 563-8577, Japan.
Institute for Catalysis, Hokkaido University, N-21, W-10, 1-5, Sapporo 001-0021, Japan.
ACS Omega. 2022 May 24;7(22):18427-18433. doi: 10.1021/acsomega.2c00702. eCollection 2022 Jun 7.
Perovskite oxides comprise an important class of materials, and some of their applications depend on the surface reactivity characteristics. We calculated, using density functional theory, the surface O vacancy formation energy ( ) for perovskite-structure oxides, with a transition metal (Ti-Fe) as the B-site cation, to estimate the catalytic reactivity of perovskite oxides. The value correlated well with the band gap and bulk formation energy, which is a trend also found in other oxides. A low value, which is expected to result in higher catalytic activity via the Mars-van Krevelen mechanism, was found in metallic perovskites such as CaCoO, BaFeO, and SrFeO. On the other hand, titanates had high values, typically exceeding 4 eV/atom, suggesting that these materials are less reactive when O vacancy formation is involved in the reaction mechanism.
钙钛矿氧化物是一类重要的材料，它们的一些应用取决于表面反应特性。我们使用密度泛函理论计算了以过渡金属（Ti-Fe）作为B位阳离子的钙钛矿结构氧化物的表面氧空位形成能（ ），以评估钙钛矿氧化物的催化反应活性。该 值与带隙和体相形成能具有良好的相关性，这也是在其他氧化物中发现的一种趋势。在金属钙钛矿如CaCoO、BaFeO和SrFeO中发现了较低的 值，通过Mars-van Krevelen机理，该值有望导致更高的催化活性。另一方面，钛酸盐具有较高的 值，通常超过4 eV/原子，这表明当反应机理涉及氧空位形成时，这些材料的反应活性较低。
