The catalytic properties of 1 wt % Ru catalysts with the same mean Ru cluster size of 1.4–1.5 nm supported on herringbone‐type carbon nanofibers with different N contents were compared for H2 production from formic acid decomposition. The Ru catalyst on the support with 6.8 wt % N gave a 1.5–2 times higher activity for the dehydrogenation reaction (CO2, H2) than the catalyst on the undoped support. The activity in the dehydration reaction (CO, H2O) was the same. As a result, the selectivity to H2 increased significantly from 83 to 92 % with N‐doping, and the activation energies for both reactions were close (55–58 kJ mol−1). The improvement could be explained by the presence of Ru clusters stabilized by pyridinic N located on the open edges of the external surface of the carbon nanofibers. This N may activate formic acid by the formation of an adduct (>NH+HCOO−) followed by its dehydrogenation on the adjacent Ru clusters.

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The selectivity of Fe-MFI catalysts to partial peroxide oxidation of methane to methanol and formic acid was studied depending on their topology (Nanocrystals, Microcrystals, and bulk Commercial) and activation with oxalic acid. The catalysts were characterized by XRD, ICP-OES, SEM, UV-vis DR, NH 3-TPD, N 2 adsorption. TOF of methane oxidation increased in the series: Nanocrystals < Microcrystals << Commercial. The selectivity to methanol depended mainly on the crystallite size and increased in the same series. The increase in TOF and selectivity to formic acid, as well as a sharp decrease in the selectivity to CO 2 over all the activated catalysts were accounted for by an increase in the total acidity of the catalysts and the number of oligomeric Fe oxo-clusters. Different pathways to the formation of methanol/CO 2 (via free radical mechanism) and formic acid (via heterogeneous route) over Fe-MFI catalysts were suggested.