Computational modelling of the reaction-induced surface evolution of nanoporous gold

在这个子项目中，我们将在原子尺度上进行量子化学建模，以研究纳米多孔金的表面形态，化学成分和表面应变如何影响这种材料对氧化反应的催化活性和选择性。我们将在CO、甲醇和丙烯氧化的背景下研究这些影响。该分项目将侧重于吸附物和反应引起的表面动力学。因此，理想化的完美清洁和刚性表面的图像将被一个表面所取代，该表面被吸附物覆盖，并且在催化转化过程中动态变化。这些见解将通过传统（静态）DFT计算和AIMD模拟之间的组合来实现。我们的建模研究将有助于更深入地了解所发挥的作用（一）表面形态，特别是低配位的网站，（二）晶格应变（三）浓度和分布的杂质金属，如银或铜，（四）表面人口的含氧物种，如O2，O，OH，OOH和H2O，纳米多孔金的催化功能。对关键反应中间体、其吸附几何形状、结合强度、振动频率以及动力学参数的理论预测将有助于分析和解释参与研究小组的实验数据。

Within this subproject we will perform quantum-chemical modelling at the atomic scale to investigate how surface morphology, chemical composition, and surface strain of nanoporous gold influence the catalytic activity and selectivity of this material toward oxidation reactions. We will study these effects in the context of CO, methanol, and propylene oxidation. The subproject will have a focus on the adsorbate- and reaction-induced surface dynamics. Hence, an idealized picture of a perfect clean and rigid surface will be replaced by a surface, which is covered by adsorbates and is dynamicallychanging during catalytic transformations. These insights will be achieved through a combination between traditional (static) DFT calculations and AIMD simulations. Our modelling studies will contribute to a more advanced understanding of the role played by (i) surface morphology and, in particular, low-coordinated sites, (ii) lattice strain (iii) concentration and distribution of an impurity metal, such as Ag or Cu, (iv) surface population of O containing species, e.g. O2, O, OH, OOH, and H2O, for the catalytic function of nanoporous gold. Theoretical prediction of the key reaction intermediates, their adsorption geometry, binding strengths, vibrational frequencies, as well as kinetic parameters will assist the analysis and interpretation of the experimental data of the participating research groups.