Dynamically driven rutile-based acidic oxygen evolution electrocatalysts beyond stationary efficiency (DaCapo)

“DaCapo”项目将研究和测试从动态共振理论（DRT）中得出的一个基本假设，该假设是关于在周期性驱动与固定操作制度下，时间平均催化性能优势的可行性。我们将利用基于金红石的模型和纳米结构氧化物催化剂在动态驱动电极电位下的电催化析氧反应（OER），从催化活性、稳定性和效率方面对DRT假设进行检验和机制分析。这种方法的关键原子思想是周期性地、优先地在阴极电位较高的表面填充活性中间体，然后在阳极电位较高的表面快速形成产物。因此，在特征共振条件下，当应用参数变化与本征催化时间尺度相匹配时，这两种机制之间的周期性切换可以提高总体的时间平均反应速率和效率。我们将在明确定义的催化模型表面和实际催化剂材料的活性位点和活性表面相的原子动力学见解和其动力学行为的多尺度模拟之间建立桥梁，以金红石基酸性OER催化剂（IrO2, RuO2，混合（Ru-Ir-Ti）O2）在强制振荡操作的影响下为例。我们将探索在酸性条件下OER中催化活性动态共振态的存在、机制和开发，使用三支组合i)超高真空和原位表面科学方法（光电，振动光谱）在单晶和薄膜模型电极（Hofmann）上阐明在动态电化学条件下表面物质的种群；ii)计算研究，包括密度泛函理论，动态动力学蒙特卡罗（DKMC）和耦合到电化学系统的数值模型（Hess），以预测DEC对OER活性的影响。利用Ab-initio分子动力学计算开关瞬态过程中表面中间体的光谱特征，以辅助实验光谱的分配；iii)采用实时差分电化学质谱法（dem）和操作电位x射线吸收光谱法对模型薄膜和更现实的纳米颗粒电极进行电催化研究，以监测和关联DEC下的产物形成速率、表面空穴电荷和法拉第产物效率（Strasser）。在DaCapo中获得的实验数据和模拟模型将与SPP2080中合作小组的宏观尺度建模相关联，目的是通过多尺度理解来理解和实现动态控制在OER电催化中的应用。

The project “DaCapo” will study and test a fundamental hypothesis derived from Dynamic Resonance Theory (DRT) as to the feasibility of time-averaged catalytic performance benefits in periodically driven versus stationary operation regimes. The DRT hypothesis will be tested and mechanistically analyzed in terms of catalytic reactivity, stability, and efficiency using the electrocatalytic oxygen evolution reaction (OER) on rutile-based model and nanostructured oxide catalysts under dynamically driven electrode potentials. The key atomistic idea of this approach is to periodically and preferentially populate the surface with reactive intermediates at more cathodic electrode potentials, followed by rapid product formation at more anodic electrode potentials. As a result, at characteristic resonance conditions, where applied parameter variations match intrinsic catalytic time scales, the periodic switching between these two regimes can enhance the overall time-averaged reaction rate and efficiency. We will form a bridge between atomic insights into the dynamics of active site and active surface phases of well-defined catalytic model surfaces and real catalyst materials and multiscale simulations of their dynamic behavior, exemplified by rutile based acidic OER catalyst (IrO2, RuO2, mixed (Ru-Ir-Ti)O2) under the influence of forced oscillatory operation. We will explore the existence, mechanisms, and exploitation of catalytically active dynamic resonant states in the OER under acidic conditions using a three-branched combination of i) ultrahigh vacuum-based and in situ surface science methods (photoemission, vibrational spectroscopies) on single crystal and thin film model electrodes (Hofmann) to elucidate the population of surface species under dynamic electrochemical conditions (DEC); ii) computational studies including density functional theory, dynamic kinetic Monte Carlo (DKMC) and coupling to a numerical model of the electrochemical system (Hess) to predict the influence of DEC on OER activity. Spectroscopic signatures of intermediates on the surface during switching transients will be computed with Ab-initio Molecular Dynamics to assist in the assignment of experimental spectra; iii) electrocatalytic studies on model thin-film and more realistic nanoparticle electrodes employing real-time Differential Electrochemical Mass Spectrometry (DEMS) and operando potentiodynamic X-ray absorption spectroscopy to monitor and correlate product formation rates, surface hole charge, and Faradaic product efficiencies under DEC (Strasser). The experimental data and simulation models obtained in DaCapo will be placed in relation to macroscale modelling of collaborating groups in the SPP2080 with the goal to understand and enable application of dynamic control in OER electrocatalysis through a multiscale understanding.