In this report, the preparation of Fe-carbon nitride (CN)-based electrocatalysts (ECs) with a “core-shell” morphology for the oxygen reduction reaction (ORR) is described. The ECs consist of spherical XC-72R carbon nanoparticles, the “cores”, that are covered by a CN matrix, the “shell”, that embeds Fe species in “coordination nests”. The latter consist of hollow cavities in the CN matrix, whose internal surface is covered by N- and C-ligands able to stabilize alloy nanoparticles or active sites. Two families of CN-based ECs are prepared, which are grouped on the basis of the concentration of N atoms in the CN “shell”. Each group comprises of both a “pristine” and an “activated” EC; the latter is obtained from the “pristine” EC by a suitable series of treatments (A) devised to improve the ORR performance. The chemical composition of the CN-based ECs is determined by Inductively-Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and microanalysis. The thermal stability under both inert and oxidizing atmospheres is gauged by High-Resolution Thermogravimetric Analysis (HR-TGA). The structure is probed by powder X-ray diffraction, and the morphology is inspected by Scanning Electron Microscopy (SEM) and High-Resolution Transmission Electron Microscopy (HR-TEM). The surface area of the CN-based ECs is determined by nitrogen physisorption techniques, and the surface composition is probed by X-ray Photoelectron Spectroscopy (XPS). The electrochemical performance and reaction mechanism of the CN-based ECs in the ORR is investigated in both acid and alkaline environments by cyclic voltammetry with the Thin-Film Rotating Ring-Disk Electrode setup (CV-TF-RRDE). The influence of the preparation parameters and of the treatments on the physicochemical properties, the ORR performance, and reaction mechanism is studied in detail. In the alkaline environment the FeFe2-CNl900/CA“core-shell” EC shows a remarkable ORR onset potential of 0.908 V vs. RHE which, with respect to the value of 0.946 V vs. RHE of the Pt/C ref., classifies the proposed materials as very promising “Platinum Group Metal-free” ECs for the ORR

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We report on the development of two new Pt-free electrocatalysts (ECs) for the oxygen reduction reaction (ORR) based on graphene nanoplatelets (GNPs). We designed the ECs with a core-shell morphology, where a GNP core support is covered by a carbon nitride (CN) shell. The proposed ECs present ORR active sites that are not associated to nanoparticles of metal/alloy/oxide, but are instead based on Fe and Sn sub-nanometric clusters bound in coordination nests formed by carbon and nitrogen ligands of the CN shell. The performance and reaction mechanism of the ECs in the ORR are evaluated in an alkaline medium by cyclic voltammetry with the thin-film rotating ring-disk approach and confirmed by measurements on gas-diffusion electrodes. The proposed GNP-supported ECs present an ORR overpotential of only ca. 70 mV higher with respect to a conventional Pt/C reference EC including a XC-72R carbon black support. These results make the reported ECs very promising for application in anion-exchange membrane fuel cells. Moreover, our methodology provides an example of a general synthesis protocol for the development of new Pt-free ECs for the ORR having ample room for further performance improvement beyond the state of the art.

The ethanol oxidation reaction (EOR) was investigated by potentiodynamic techniques on Pt/C, Rh/C, Pt-Rh/C, Pt-SnO2/C and Pt-Rh-SnO2/C by differential electrochemical mass spectrometry (DEMS) in a flow cell system. Prior to the cyclic voltammetries, adsorption of H- and OH-species was carried out by chronoamperometry at Ead = 0.05 and 1 V vs. RHE, respectively, in order to examine their influence on the EOR on the different electrocatalysts. For the sake of comparison, another adsorption potential was chosen at Ead = 0.3 V vs. RHE, in the double layer region (i.e. in the absence of such adsorbates). For this study, 20 wt% electrocatalysts were synthesized using a modified polyol method and were physically characterized by inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray diffraction (XRD) and transmission electron microscopy (TEM). When comparing the first and second cycles of the cyclic voltammograms (CVs) on Pt/C and Pt-SnO2/C, the presence of Had on the electrocatalyst surface seems to hinder the initiation of the ethanol electrooxidation, whereas the reaction onset potential is shifted negatively with the presence of OH-adsorbates. In contrast to them, the EOR on Rh/C is enhanced when the electrocatalyst surface is covered with Had and is inhibited after adsorption at Ead = 0.3 and 1 V vs. RHE. Finally, on Pt-Rh/C and Pt-Rh-SnO2/C, neither the H- nor OH-adsorbates do impact the EOR initiation. The lowest EOR onset was recorded on Pt-SnO2/C and Pt-Rh-SnO2/C electrocatalysts. The CO2 currency efficiency (CCE) was also determined for each electrocatalyst and demonstrated higher values on Pt-Rh-SnO2/C.

The electrocatalytic activity of Pt/C and Pt-Rh/C electrocatalysts for the ethanol oxidation reaction (EOR) was investigated by potentiostatic and potentiodynamic techniques by differential electrochemistry mass spectrometry (DEMS) in a flow cell system. The 10 wt% electrocatalysts were synthesized by a modified polyol method and physically characterized by different techniques including X-Ray Diffraction (XRD) and Transmission Electron Microscopy (TEM). The chronoamperometry study shows that, although the ethanol oxidation starts at lower potential on Pt-Rh/C, the kinetics of the reaction is faster on Pt/C. Differential Electrochemical Mass Spectrometry (DEMS) allowed the detection of volatile intermediates/products of the EOR. At low potential, the ionic current corresponding to the signal m/z = 15 increases, conversely to the signal m/z = 44; this points out the production of adsorbed CH x species and thus possibly of adsorbed CO either during the negative scan or the previous positive scan of the cyclic voltammetry. The CO 2 current efficiency (CCE) was also determined on both electrocatalysts after calibration of the m/z = 22 signal: the CCE value can reach up to 25% on Pt-Rh/C at room temperature, compared to ca. 5% on Pt/C.

This study aims to provide further understanding of the influence of different parameters that control mass-transport (the revolution rate of the rotating disk electrode and the potential scan rate) on the ethanol oxidation reaction (EOR). The experiments were conducted on a home-made carbon-supported 20 wt% Pt/C electrocatalyst, synthesized using a modified polyol method, and characterized in terms of physicochemical properties by thermogravimetric analysis (TGA), powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). The EOR at the thin active layer of this electrocatalyst was characterized using both differential electrochemical mass spectrometry (DEMS) in a flow cell configuration and the rotating disc electrode (RDE). The results demonstrate that operating under stationary conditions (low scan rate and high RDE speed) hinders complete ethanol electrooxidation into CO and favors the poisoning of the electrocatalyst surface by hydroxide and strong ethanol adsorbates. As such, the EOR appears to be more efficient and faster under dynamic conditions than in near steady-state.

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