Oxygen reduction reaction (ORR) in alkaline solution catalysed by an atomically precise catalyst based on a Pd(<sc>ii</sc>) complex supported on multi-walled carbon nanotubes (MWCNTs). Electrochemical and structural considerations

A new atomically precise, single-ion catalyst (MWCNT-LPd) for ORR (oxygen reduction reaction), consisting of a Pd(ii) complex of a tetraazacycloalkane anchored on multiwalled carbon nanotubes, has been prepared through a supramolecular approach ensuring a uniform distribution of catalytic centres on the support surface. A tetraazacycloalkane was chosen to saturate the four coordination sites of the typical square planar coordination geometry of Pd(ii) with the aim of ascertaining whether the metal ion must have free coordination sites to function effectively in the ORR or whether, as predicted by quantum mechanical calculations, the catalytic effect can be originated from an interaction of O-2 in the fifth coordinative position. The results clearly demonstrated that tetracoordination of Pd(ii) does not influence its catalytic capacity in the ORR. Electrodes based on this catalyst show ORR performance very close to that of commercial Pt electrodes, despite the low Pd(ii) content (1.72% by weight) in the catalyst. The onset potential (Eon) value and the half-wave potential (E-1/2) of the catalyst are, respectively, only 53 mV and 24 mV less positive than those observed for the Pt electrode and direct conversion of O2 to H2O reaches 85.0%, compared to 89% of the Pt electrode. Furthermore, a preliminary galvanostatic test (simulating a working fuel cell at a fixed potential) showed that the catalyst maintains its efficiency continuing to produce water throughout the process (the average number of electrons exchanged over time per O-2 molecule remains close to 4).