Fe/N/C Catalyst Production by Collinear CO₂ Laser Pyrolysis: Toward a Specific Mass-Weighted Energy-Deposited (J.g⁻¹) Parameter Opening Discussion on FeN_x Site Formation

We report the synthesis of Fe/N/C ORR electrocatalysts by an original collinear CO₂ laser pyrolysis of liquid aerosol droplets in various configurations and compared them to a catalyst synthesized in the classical perpendicular one. While the precursors were always injected at the bottom side of the reactor, two collinear configurations of the laser entry into the reactor are considered: by the Top Side (T.S.) or by the Bottom Side (B.S.). The two corresponding catalysts sets show significant different ORR performances. An in-depth XPS analysis and fitting of the N1s spectra allowed for drawing the ORR performance as a function of FeN_x sites components. An original approach considering the energy delivered to a quantity of precursors in J.g⁻¹, linked to the flame temperature feature, evidenced very different conditions for perpendicular CO₂ laser pyrolysis and each of the two collinear configurations. This mass-weighted energy delivered in the classical perpendicular configuration is too low to allow for the formation of FeN_x sites and the resulting ORR performance is extremely poor, suggesting a marginal role of nitrogen species without interaction with iron atoms. In contrast, the delivered mass-weighted energies are sufficient in both collinear configurations to produce FeN_x sites. The ORR performance for catalysts produced in these both configurations is positively correlated with the amount of energy deposited on the precursors. The ORR performance in the T.S. laser configuration is positively correlated to the amount of FeN_x sites. The best performing catalysts obtained in the B.S. configuration show an opposite variation. These trends, and the ORR performance degradation of B.S. catalysts under prolonged chronoamperometry are discussed in light of the effect of temperature on the formation of the various kind of FeN_x sites. A tentative explanation is given, considering that N1s XPS fitting with a single FeN_x component may hinder the fact that Pyridinic sites components may contain a part of FeN_x sites, as suggested by theoretical calculation from the literature. The best catalysts obtained in this work by collinear configuration show similar performances to those obtained by double stage perpendicular pyrolysis previously reported with an ORR onset potential of ~860 mV.