Photo-thermo catalytic selective oxidation of cyclohexane by In-situ prepared nonstoichiometric Molybdenum oxide and Silver-palladium alloy composite.

The highly selective oxidation of cyclohexane to cyclohexanone and cyclohexanol (KA oil) is one of the most challenging issues in the chemical industry. However, the difficulty in attaining high selectivity and high conversion rate in parallel for the existing catalysts limits its practical application. In this paper, a novel photo-thermo synergistic catalyst was reported for the aerobic oxidation of cyclohexane. The uniform blue MoO nanowires with small diameter stabilized by polyvinyl pyrrolidone (PVP) were synthesized by a hydrothermal method, and a series of MoO-AgPd composite materials of different proportions were prepared by an in-situ reduction process. The morphology, crystalline structure, surface chemical bonding, photoelectrochemical properties of MoO-AgPd composites are thoroughly characterized. The MoO-AgPd composites present significantly increased catalytic performance than MoO nanowires in the photo-thermo synergistic catalytic oxidation of cyclohexane under dry air. The high conversion rate of 11.3% with the KA oil selectivity of 99.0% was achieved by the MoO-AgPd composites under photo-thermo catalytic process at 120 ℃, which is 1.5 times of that by MoO nanowires. Under photo-thermo catalytic process, a high cyclohexane conversion rate similar to that of higher temperature thermal catalysis can be obtained at lower reaction temperature, and more cyclohexanol can be produced with a ketone to alcohol (K/A) ratio of 0.254. The significantly enhanced catalytic activity can be attributed to the effective charge transfer in the AgPd alloy nanoparticles, the optimized band gap structure, the suppressed charge recombination, and the promoted photo-thermo synergetic catalytic effect. This work provides a new reference scheme for the design and preparation of high-efficiency photo-thermo catalysts for the selective oxidation of cyclohexane.