Dataset for C-O bond activation using ultra-low loading noble metal catalysts on moderately reducible oxides

Selective C-O activation of complex multifunctional molecules is an essential step for many important chemical processes. Although reducible metal oxides are active and selective towards reductive C-O bond scission via the reverse Mars-van Krevelen mechanism, the most active oxides undergo bulk reduction during reaction. Here, we report a strategy for C-O bonds activation by surface doping moderately reducible oxides with ultra-low loading of noble metals. We demonstrate the principle using highly dispersed Pt anchored onto TiO2 for furfuryl alcohol conversion to methyl furan. A combination of density functional theory calculations, catalyst characterization (STEM, EPR, FTIR and XAS), kinetic experiments, and microkinetic modelling expose significant C-O activation rate enhancement, without either bulk catalyst reduction or unselective ring hydrogenation. A methodology is introduced to quantify various types of sites, revealing that the cationic redox Pt on TiO2 surface is more active than metallic sites for C-O bond activation.

复杂多官能团分子的选择性C-O活化，是诸多重要化学过程的核心步骤。尽管可还原金属氧化物可通过逆马斯-范克莱维伦（Mars-van Krevelen）机理，在还原断裂C-O键的反应中表现出优异的活性与选择性，但活性最高的可还原金属氧化物在反应过程中会发生体相还原。本文报道了一种C-O键活化策略：通过在适度可还原氧化物表面掺杂超低负载量的贵金属，实现C-O键的高效活化。我们以锚定在二氧化钛（TiO₂）表面的高分散铂（Pt）为模型催化剂，应用于糠醇向甲基呋喃的转化反应，验证了该策略的原理。结合密度泛函理论（density functional theory, DFT）计算、催化剂表征（扫描透射电子显微镜（STEM）、电子顺磁共振（EPR）、傅里叶变换红外光谱（FTIR）与X射线吸收光谱（XAS））、动力学实验以及微动力学建模，我们证实该策略可显著提升C-O活化速率，且不会引发催化剂体相还原或非选择性环加氢副反应。我们还引入了一种量化各类活性位点的方法，结果显示，二氧化钛表面的阳离子氧化还原型铂位点，相较于金属铂位点，在C-O键活化反应中具有更优异的催化活性。