Dataset for Modulating the Dynamics of Brønsted Acid Sites on PtWOx Inverse Catalyst

Brønsted acid sites on the oxide overlayers of metal-metal oxide (M-MO) inverse catalysts are often hypothesized to drive selective C-O bond activation. However, the Brønsted acid site nature and dynamics under working conditions remain poorly understood due to multiple materials functionalities. Here, we investigate the formation and the dynamics of Brønsted acid and redox sites on PtWOx/C under working conditions. DFT-based thermodynamic calculations and microkinetic modeling reveal a complex interplay between Brønsted acid and redox sites and potentially fast catalyst dynamics at comparable time scales to the Bronsted acid catalyzed dehydration chemistry. Combining in situ characterization and probe chemistry, we demonstrate that the density of Brønsted acid sites on the PtWOx/C inverse catalyst could be modulated by up to two orders of magnitude by altering the reaction parameters and by the chemistry itself. We elicit an order of magnitude increase in the acid-catalyzed dehydration average reaction rate by periodic hydrogen pulsing.

金属-金属氧化物（M-MO）反相催化剂的氧化物覆盖层上的布朗斯特酸位点（Brønsted acid site）常被假说为驱动选择性C-O键活化的核心因素。然而，受材料多重功能性的限制，工作条件下布朗斯特酸位点的本质与动态行为仍未被充分阐明。在此，我们针对PtWOx/C反相催化剂上布朗斯特酸位点与氧化还原位点的形成及动态过程展开研究。基于密度泛函理论（DFT）的热力学计算与微观动力学建模结果显示，布朗斯特酸位点与氧化还原位点之间存在复杂的相互作用，且催化剂的动态变化可能发生在与布朗斯特酸催化脱水反应相当的时间尺度上，过程速率极快。结合原位表征与探针化学实验，我们证实：通过调控反应参数以及反应自身的化学过程，PtWOx/C反相催化剂上的布朗斯特酸位点密度可被调控高达两个数量级。此外，我们发现通过周期性氢脉冲处理，酸催化脱水反应的平均反应速率可提升一个数量级。