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

“DaCapo”项目将研究和检验从动态共振理论中得出的一个基本假设，即在周期性驱动与静止运行状态下时间平均催化性能效益的可行性。DRT假设将进行测试和机械分析的催化反应性，稳定性和效率，使用电催化析氧反应（OER）的金红石为基础的模型和纳米结构的氧化物催化剂在动态驱动的电极电位。这种方法的关键原子思想是周期性地和优先地填充表面与活性中间体在更多的阴极电极电位，然后快速的产品形成在更多的阳极电极电位。因此，在特征共振条件下，其中所施加的参数变化与固有催化时间尺度相匹配，这两种制度之间的周期性切换可以提高整体时间平均反应速率和效率。我们将形成一个桥梁之间的原子洞察到活性位点和活性表面相的动力学定义良好的催化模型表面和真实的催化剂材料和多尺度模拟其动态行为，例如金红石型酸性OER催化剂（IrO 2，RuO 2，混合（Ru-Ir-Ti）O2）的影响下，强制振荡操作。我们将探索存在，机制，并利用催化活性的动态共振态的OER在酸性条件下使用三个分支的组合i）在真空为基础的和原位表面科学的方法（光电发射、振动光谱）在单晶和薄膜模型电极上（霍夫曼），以阐明在动态电化学条件下（DEC）表面物种的群体; 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（赫斯）预测DEC对OER活性的影响。转换瞬变过程中表面上中间体的光谱特征将用从头算分子动力学计算，以协助实验光谱的分配; iii）对模型薄膜和更现实的纳米颗粒电极的电催化研究，采用实时差分电化学质谱（DEMS）和操作电位动态X射线吸收光谱来监测和关联产物形成速率，表面空穴电荷，和在DEC（Strasser）下的法拉第产品效率。在DaCapo获得的实验数据和模拟模型将与SPP 2080中合作小组的宏观建模相关，目的是通过多尺度理解理解OER电催化中的动态控制并使其应用成为可能。

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.