Brønsted acid sites on the oxide overlayers of metal–metal oxide 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 the functionalities of the constituent materials. Here we investigate the formation and the dynamics of Brønsted acid and redox sites on PtWO_x/C under working conditions. Density functional theory-based thermodynamic calculations and microkinetic modelling reveal a complex interplay between Brønsted acid and redox sites and potentially fast catalyst dynamics at comparable timescales to the Brønsted acid catalysed dehydration chemistry. Combining in situ characterization and probe chemistry, we demonstrate that the density of Brønsted acid sites on the PtWO_x/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-catalysed dehydration average reaction rate by periodic hydrogen pulsing.

金属-金属氧化物反相催化剂的氧化物覆盖层上的布朗斯台德酸位点通常被假设为驱动选择性 C-O 键活化。然而，由于组成材料的功能性，工作条件下的布朗斯台德酸位性质和动力学仍然知之甚少。在这里，我们研究了工作条件下PtWO _{x /C 上布朗斯台德酸和氧化还原位点的形成和动力学。}基于密度泛函理论的热力学计算和微动力学建模揭示了 Brønsted 酸和氧化还原位点之间的复杂相互作用，以及在与 Brønsted 酸催化的脱水化学相当的时间尺度上潜在的快速催化剂动力学。结合原位表征和探针化学，我们证明了 PtWO 上 Brønsted 酸位点的密度_x /C 逆催化剂可以通过改变反应参数和化学本身来调节多达两个数量级。我们通过周期性的氢脉冲使酸催化的脱水平均反应速率提高了一个数量级。