Institute of Chemical Research of Catalonia (ICIQ), Avinguda Països Catalans, 16, 43007 Tarragona (Spain).
ChemSusChem. 2015 Jul 8;8(13):2231-9. doi: 10.1002/cssc.201500315. Epub 2015 Jun 17.
Methanol is oxidised to formaldehyde by the Formox process, in which molybdenum oxides, usually doped with iron, are the catalyst. The active phase of the catalysts and the reasons for the selectivity observed are still unknown. We present a density functional theory based study that indicates the unique character of Mo(VI)¢Mo(IV) pairs as the most active and selective sites and indicates the active sites on the surface, the controlling factors of selectivity, and the role of the dopant. Iron reduces the energy requirements of the redox Mo(VI)¢Mo(IV) pair by acting as an electron reservoir that sets in if required. Our present study paves the way towards a better understanding of the process.
甲醇通过 Formox 工艺氧化为甲醛，其中钼氧化物通常掺杂铁作为催化剂。催化剂的活性相和观察到的选择性的原因仍不清楚。我们提出了一项基于密度泛函理论的研究，表明 Mo(VI)¢Mo(IV) 对作为最活跃和选择性的位点的独特性质，并指出了表面上的活性位点、选择性的控制因素以及掺杂剂的作用。铁通过充当电子储库来降低氧化还原 Mo(VI)¢Mo(IV) 对的能量需求，如果需要的话。我们目前的研究为更好地理解该过程铺平了道路。
