N-doped carbon xerogels from urea-resorcinol-formaldehyde as carbon matrix for Fe-N-C catalysts for oxygen reduction in fuel cells

9 figures, 5 tables. Supplementary material available.
Platinum group metal-free catalysts have been intensively investigated in the last decades as an alternative to platinum with the aim of lowering the cost of polymer electrolyte fuel cells. In particular, iron-nitrogen-carbon (Fe-N-C) has proved to be the most active towards the oxygen reduction reaction. For practical application, a hierarchical pore structure is required, with micropores favouring the creation of active sites and larger pores (meso- and macropores) facilitating the mass transport. In this work, carbon xerogels are investigated to hosting iron and nitrogen species obtained by a template-free method. The introduction of nitrogen in a one-step polymerization of urea with resorcinol and formaldehyde is investigated for the first time in this field by varying the relative content of reactants. The urea/resorcinol ratio greatly influences the pore structure of the Fe-N-C catalyst and the ORR electrocatalytic activity thereof. The ORR activity is favored for a balanced urea/resorcinol ratio where porosity is well developed and relatively high iron and nitrogen contents are incorporated to the carbon xerogel. In acid (0.5 M H2SO4), the onset potential is 0.82 V vs. RHE, with a number of exchanged electrons very close to 4 (i.e. full conversion to water) and low Tafel slope of 71 mV dec−1, for the most active catalyst of the series, possessing the best compromise of iron and nitrogen active sites. Fuel cell tests corroborate that the catalyst with the most developed porous structure shows the best performance.
The authors wish to acknowledge the grant PID2020-115848RB-C21 funded by MCIN/AEI/10.13039/501100011033. Authors also acknowledge Gobierno de Aragón (DGA) for the financial support to Grupo de Conversión de Combustibles (T06_20R). L. Álvarez acknowledges also DGA for her pre-doctoral contract.