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Abstract:
In this study, we demonstrate the tuning of the oxygen reduction reaction (ORR) by iron/iron oxide nanoparticle grafted laser-patterned nitrogen-doped carbon (LP-NC) electrodes. Depending on the preparation route, i.e. addition of a molecular Fe(NO3)2 precursor before (route 1) or after pre-carbonization (route 2) of the citric acid / urea precursors, either the 4e- or the 2e- pathway in the ORR is facilitated leading to either H2O or H2O2 as a reaction product, respectively. The kinetic reaction conditions afford mixed valence metal oxide nanoparticles embedded in LP-NC in the form of either Fe2O3/Fe or Fe2O3/FeO/Fe, respectively, facilitated by an in situ carbothermal reduction during the laser-induced carbonization. In HR(S)TEM analysis we found evidence for the occurrence of Fe2O3 in the η- or α- phase, depending on the preparation route. Reciprocally, the graphitization is also affected by the preparation route leading to either homogeneous graphitization or locally a graphitized shell structures around the nanoparticles. In the 4e- mediated ORR facilitated by η-Fe2O3/Fe@LP-NC onset potentials as low as 0.70 V (vs. RHE) with a H2O2 production efficiency 4% and 10 % in alkaline and neutral electrolyte, respectively, were determined. On the other hand, α-Fe2O3/FeO/Fe@LP-NC present onset potentials for the 2e- mediated ORR is as low as 0.77 with a H2O2 production efficiency of nearly 80%.