Jin Fan, Zhao Zhichao
Department of Applied Chemistry, Yuncheng University Yuncheng 044000 China
Department of Science Technology and Industry, Yuncheng University Yuncheng 044000 China.
RSC Adv. 2022 Oct 4;12(43):28178-28184. doi: 10.1039/d2ra05058g. eCollection 2022 Sep 28.
The anatase (001) surface has attracted a lot of interest in surface science due to its excellent performance. However, its reactivity is under debate since it can undergo a (1 × 4) reconstruction. Herein, we applied the many-body Green's function theory to investigate the electronic properties and excitons as well as the water adsorption behavior of the (1 × 4) unreconstructed anatase (001) surface and two reconstructed patterns, namely ADM and AOM. Our results revealed that the high reactivity of the (001) surface is probably not relevant to the reconstructed shape. The unreconstructed (001) surface and reconstructed ADM surface were very reactive for dissociating HO molecules among three surfaces, but the lower-energy singlet exciton for ADM was completely confined within the inner atomic layers in TiO, which is unfavorable for hole transfer to the reactant on the surface. Also, the required photon energy for initiating photochemical reactions on the reconstructed ADM surface should be higher than for the unreconstructed (001) surface, implying it is more difficult for the reaction to happen on the former surface. The unreconstructed (001) surface exhibited the highest reactivity due to the smaller optical absorption edge and the photoholes distributed on surface sites.
锐钛矿型（001）表面因其优异的性能在表面科学领域引起了广泛关注。然而，由于其会发生（1×4）重构，其反应活性仍存在争议。在此，我们应用多体格林函数理论来研究（1×4）未重构的锐钛矿型（001）表面以及两种重构模式，即ADM和AOM的电子性质、激子以及水吸附行为。我们的结果表明，（001）表面的高反应活性可能与重构形状无关。在这三种表面中，未重构的（001）表面和重构的ADM表面对HO分子解离具有很高的反应活性，但ADM的低能单重态激子完全局限于TiO的内部原子层内，这不利于空穴转移到表面的反应物上。此外，在重构的ADM表面引发光化学反应所需的光子能量应高于未重构的（001）表面，这意味着在前一种表面上反应更难发生。未重构的（001）表面由于其较小的光吸收边缘和分布在表面位点上的光生空穴而表现出最高的反应活性。
