A microwave assisted ionic liquid route to prepare bivalent Mn₅O₈ nanoplates for 5-hydroxymethylfurfural oxidation

In order to develop highly active non-precious metal catalysts for the selective oxidation of the platform compound 5-hydroxymethylfurfural (HMF) to the value-added bio-chemical 2,5-diformylfuran (DFF), we prepared high purity bivalent Mn₅O₈ nanoplates by a microwave-assisted ionic liquid route. The precursor of bivalent Mn₅O₈ nanoplates was formed through π-π stacking between imidazolium rings of the ionic liquid 1-butyl-3-methyl-imidazolium chloride and extending hydrogen bonds between Cl anions and hydrohausmannite. An oriented aggregation growth occurred on the basis of the Ostwald ripening under microwave heating. The high purity bivalent Mn₅O₈ nanoplates obtained through calcination at 550 °C for 2 h exhibited high HMF conversion (51%) and DFF selectivity (94%) at 5 bar of oxygen pressure in 2 h. The high concentration of Mn⁴⁺ on the exterior surfaces of Mn₅O₈ nanoplates as active sites coupled with good crystallinity played key roles for desirable mass and heat transfer, and for fast desorption avoiding over-oxidation. The reaction process over the Mn₅O₈ nanoplates was proposed based on the understanding of Mn⁴⁺ active centers and lattice oxygen via a Mn⁴⁺/Mn²⁺ two-electron cycle to enhance their catalytic performance. Furthermore, the Mn₅O₈ nanoplates could be readily recovered and reused without loss of catalytic activity. Thus, the high purity Mn₅O₈ nanoplates with good catalytic performance raises the prospect of using the type of sole metal oxide for practical applications.