Institut für Physik and IRIS Adlershof, Humboldt-Universität zu Berlin, 12489 Berlin, Germany.
School of Chemistry and Chemical Engineering, Shandong University, 250100 Jinan, China.
Phys Rev Lett. 2019 Feb 1;122(4):046101. doi: 10.1103/PhysRevLett.122.046101.
Single-atom catalysts (SACs) combine the best of two worlds by bridging heterogeneous and homogeneous catalysis. The superior catalytic properties of SACs, however, can hardly be exploited without a suitable substrate. Here, we explore the possibility of using hybrid organic-inorganic perovskites as supporting materials for single transition-metal atoms. By means of first-principles calculations, we predict that single Pt atoms can be incorporated into methylammonium lead iodide surfaces by replacing the methylammonium groups at the outermost layer. The iodide anions at the surface provide potentially uniform anchoring sites for the Pt atoms and donate electrons, generating negatively charged Pt_{1}^{δ-} species that allow for preferential O_{2} adsorption in the presence of CO. Such Pt sites are able to catalyze CO oxidation and may also play a role in CO_{2} reduction. The fundamental understanding generated here will shed light on potential applications of hybrid perovskites in the field of (photo)catalysis.
单原子催化剂 (SACs) 通过连接多相和均相催化，结合了两者的优点。然而，如果没有合适的底物，SACs 的优越催化性能很难被利用。在这里，我们探索了将杂化有机-无机钙钛矿作为单过渡金属原子的支撑材料的可能性。通过第一性原理计算，我们预测单 Pt 原子可以通过取代最外层的甲基铵基团掺入碘化甲基铵铅表面。表面的碘阴离子为 Pt 原子提供潜在均匀的锚固位点，并提供电子，生成带负电荷的 Pt_{1}^{δ-}物种，从而允许在存在 CO 的情况下优先吸附 O_{2}。这种 Pt 位点能够催化 CO 氧化，也可能在 CO_{2}还原中发挥作用。这里得到的基本认识将为杂化钙钛矿在（光）催化领域的潜在应用提供启示。
