A series of Co1+xFe2–xO4 (0≤x≤2) spinel nanowires was synthesized by nanocasting using SBA‐15 silica as hard template, which was characterized by X‐ray powder diffraction, X‐ray photoelectron spectroscopy, and transmission electron microscopy. The Co1+xFe2–xO4 spinels were applied in the aerobic oxidation of aqueous 2‐propanol solutions to systematically study the influence of exposed Co and Fe cations on the catalytic properties. The activity of the catalysts was found to depend strongly on the Co content, showing an exponential increase of the reaction rate with increasing Co content. Ensembles of Co3+cus (coordinatively unsaturated) sites were identified as the active sites for selective 2‐propanol oxidation, which are assumed to consist of more than six Co ions. In addition, gas‐phase oxidation with and without water vapor co‐feeding was performed to achieve a comparison with liquid‐phase oxidation kinetics. An apparent activation energy of 94 kJ mol−1 was determined for 2‐propanol oxidation over Co3O4 in the liquid phase, which is in good agreement with the gas‐phase oxidation in the presence of water vapor. In contrast to gas‐phase conditions, the catalysts showed high stability and reusability in the aqueous phase with constant conversion in three consecutive runs.

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Selective oxidation of higher alcohols using heterogeneous catalysts is an important reaction in the synthesis of fine chemicals with added value. Though the process for primary alcohol oxidation is industrially established, there is still a lack of fundamental understanding considering the complexity of the catalysts and their dynamics under reaction conditions, especially when higher alcohols and liquid-phase reaction media are involved. Additionally, new materials should be developed offering higher activity, selectivity, and stability. This can be achieved by unraveling the structure-performance correlations of these catalysts under reaction conditions. In this regard, researchers are encouraged to develop more advanced characterization techniques to address the complex interplay between the solid surface, the dissolved reactants, and the solvent. In this mini-review, we report some of the most important approaches taken in the field and give a perspective on how to tackle the complex challenges for different approaches in alcohol oxidation while providing insight into the remaining challenges.

Due to the variability of the cation occupancy of octahedral and tetrahedral sites, spinel ferrites and cobaltites are particularly interesting to investigate activity trends in oxidation catalysis. Yet, the preparation of the respective catalyst series remains challenging. We employed pulsed laser defect engineering of CoFe2O4 nanoparticles in water to gradually alter the cation occupancy of octahedral and tetrahedral sites by single laser pulses and study its effect on cinnamyl alcohol oxidation. Three CoFe2O4 catalysts from different synthesis methods resembling different initial site occupancy were chosen as starting materials. The laser‐induced randomization of the cation occupancy was verified by Mössbauer spectroscopy and linearly correlated with the conversion of cinnamyl alcohol while the size and Co : Fe ratio was maintained during laser processing. The study solidifies the importance of octahedral Co3+‐sites and the feasibility of pulsed laser processing for altering the cation occupancy and related crystallographic defect density in oxidation catalysis.

A series of spray-flame made LaCo_1−xFe_xO₃ nanoparticles showed promising activity for liquid-phase cyclohexene oxidation. Various oxidizing agents, i.e., O₂, H₂O₂ and tert-butyl hydroperoxide, led to different product selectivities.