Highly Efficient Catalytic Oxidation of Glucose to Formic Acid over Mn-Mo Doped Carbon Nanotube

The production of formic acid (FA) from lignocellulose and its derived sugars represents a pivotal upgrading reaction in biorefinery. This work prepared a Mn-Mo doped carbon nanotube composite catalyst for the catalytic oxidation of glucose into FA in an O₂ atmosphere, under extremely low Mn (3.27%) and Mo (0.40%) loading conditions, displaying a comparable performance with the traditional vanadium-based catalyst suffering from toxicity issues. It was confirmed that the doping of Mo led to the formation of MnMoO_X and increased the contents of low-valence Mn species (Mn²⁺ + Mn³⁺), lattice oxygen (O_latt), and surface adsorbed oxygen (O_ads) based on various characterization methods, such as XRD, XPS, TEM and ICP, which were beneficial to improve the catalytic performance. The maximum FA yield of 58.8% could be achieved over Mn₉Mo₁O_X@MWCNT after reaction for 6 h at 140 °C, which was far more than that obtained with undoped MnO_X@MWCNT (14.5%) at the identical conditions. Glyoxylic acid and arabinose were identified as two main intermediates, suggesting that the transformation of glucose into FA over Mn₉Mo₁O_X@MWCNT involved two different paths. This work proved that manganese-based catalyst was a green alternative for upgrading lignocellulose via catalytic oxidation.