水相中负载型金属催化剂催化醛基加氢的动态机理研究

生物质的利用近年来已成为绿色催化领域极具前景的方向，醛基（RCHO）加氢是其中重要的反应。目前，大量生物质催化实验是在水相环境中利用氧化物负载的金属催化剂实现的。然而，由于水相环境下表征的困难，其反应机制仍不明确，因此相关理论模拟研究显得尤为重要。本文结合密度泛函理论计算和从头算分子动力学模拟，研究了在水相中二氧化钛负载的铂催化剂（Pt/TiO₂）催化醛基加氢的模型反应。研究结果表明，催化剂载体上的氧空位和水相中的溶剂水分子都可以向Pt团簇提供电荷，其中氧空位起主导作用，能够将Pt团簇带电性质由正还原为负。在甲醛氢化过程中，水分子通过酸碱交换作用可以自发地质子化醛基中的氧，并进一步通过长程质子转移在金属-载体界面生成吸附态的OH*中间体。通过对比符合化学计量的二氧化钛（TiO₂）表面和因存在氧空位而被还原的二氧化钛（TiO_2-x）表面，发现OH*进一步氢化过程对TiO₂载体上的带正电荷的Pt团簇来说比较困难。相比之下，TiO_2-x载体上带负电荷的Pt团簇使得OH*氢化的基元步骤不仅在热力学上能够自发进行，而且在动力学上更加容易。这说明二氧化钛表面氧空位可以防止OH*对催化剂的毒化，有利于水分子的质子转移过程，从而协同地促进醛基加氢。本工作中研究结果显示，在水相环境中即使是如此简单的甲醛加氢模型反应，其机理可以与体系中所有的催化组分（金属团簇、氧化物载体和水溶剂环境）直接相关联。考虑到可还原性氧化物载体表面广泛存在的氧空位和常见的水相反应条件，该协同效应可能不仅限于Pt/TiO₂催化剂，还对其他生物质转化中负载型金属催化剂的理性设计和实验条件的高效选择非常关键

The utilization of biomass is a promising way in the development of green catalysis in recent years, with hydrogenation of aldehydes (RCHO) being an important reaction. For now, many biomass catalytical experiments have been carried out in aqueous phase using metal catalysts supported by oxide. However, given the difficulty of characterizing reactions in aqueous phase, the reaction mechanism is still unclear, making related theoretical simulation research particularly needed. In this study, a model reaction of aldehyde hydrogenation was investigated using a platinum catalyst supported on titanium dioxide (Pt/TiO₂) in aqueous phase, combining density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. The results show that both the oxygen vacancy on the catalyst support and the solvent water molecules in the aqueous phase can donate electrons to the Pt cluster, with the oxygen vacancy playing a dominant role in reducing the Pt cluster from positively charged to negatively charged. During the formaldehyde hydrogenation process, water molecules can spontaneously protonate the oxygen in the aldehyde group through acid-base exchange, and further generate adsorbed OH* intermediates at the metal-support interface through a long-range proton transfer. By comparing the stoichiometric titanium dioxide surface (TiO₂) and the reduced titanium dioxide surface (TiO_2-x) due to the existence of oxygen vacancy, it was found that the further hydrogenation process of OH* on the TiO₂ support is more difficult for the positively charged Pt cluster. However, the negatively charged Pt cluster on the TiO_2-x support make this elementary reaction not only thermodynamically spontaneous, but also more kinetically favorable. This suggests that oxygen vacancy on the titanium dioxide surface can prevent poisoning of the catalyst by OH* and have a synergistic promoting effect on aldehyde hydrogenation with water molecules. The results of this study show that even for such a simple model reaction of formaldehyde hydrogenation in an aqueous phase, the mechanism may directly relate to all the catalytic components (metal clusters, oxide supports, and water solvent environment). Considering the widespread existence of oxygen vacancies in reducible oxide supports and common aqueous reaction conditions, this synergistic effect may not only be limited to Pt/TiO₂ but also be crucial for the rational design of supported metal catalysts and the efficient selection of experimental conditions in biomass conversion.

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