Fe-doped mayenite electride composite with 2D reduced Graphene Oxide: As a non-platinum based, highly durable electrocatalyst for Oxygen Reduction Reaction

Abstract

Abstract Since the last decades, non-precious metal catalysts (NPMC), especially iron based electrocatalysts show sufficient activity, potentially applicant in oxygen reduction reaction (ORR), however they only withstand considerable current densities at low operating potentials. On the other hand iron based electrocatalysts are not stable at elevated cathode potentials, which is essential for high energy competence, and its remains difficult to deal. Therefore, via this research a simple approach is demonstrated that allows synthesis of nanosize Fe-doped mayenite electride, [Ca24Al28O64]4+·(e−)4 (can also write as, C12A7−xFex:e−, where doping level, x = 1) (thereafter, Fe-doped C12A7:e−), consist of abundantly available elements with gram level powder material production, based on simple citrate sol-gel method. The maximum achieved conductivity of this first time synthesized Fe-doped C12A7:e− composite materials was 249 S/cm. Consequently, Fe-doped C12A7:e− composite is cost-effective, more active and highly durable precious-metal free electrocatalyst, with 1.03 V onset potential, 0.89 V (RHE) half-wave potential, and ~5.9 mA/cm2 current density, which is higher than benchmark 20% Pt/C (5.65 mA/cm2, and 0.84 V). The Fe-doped C12A7:e− has also higher selectivity for desired 4e− pathway, and more stable than 20 wt% Pt/C electrode with higher immunity towards methanol poisoning. Fe-doped C12A7:e− loses was almost zero of its original activity after passing 11 h compared to the absence of methanol case, indicates that to introduce methanol has almost negligible consequence for ORR performance, which makes it highly desirable, precious-metal free electrocatalyst in ORR. This is primarily described due to coexistence of Fe-doped C12A7:e− related active sites with reduced graphene oxide (rGO) with pyridinic-nitrogen, and their strong coupling consequence along their porous morphology textures. These textures assist rapid diffusion of molecules to catalyst active sites quickly. In real system maximum power densities reached to 243 and 275 mW/cm2 for Pt/C and Fe-doped C12A7:e− composite, respectively.