New Transition Metal-CN ORR Electrocatalysts with a ' Core-Shell ' Structure
Authors: Di Noto Vito , Negro Enrico , Vezzù Keti , Nawn Graeme , Bertasi Federico , Serov Alexey , Artyushkova Kateryna , Atanassov Plamen 
Published: February 2020

The oxygen reduction reaction (ORR) plays a crucial role in the operation of a number of advanced energy conversion devices, including fuel cells and metal-air batteries. In general, the ORR kinetics is very sluggish, giving rise to very large losses; suitable electrocatalysts are needed to achieve a performance level compatible with applications [1]. Thus, the development of improved ORR electrocatalysts is a major objective of the research. Very recently, new families of energy conversion devices were developed adopting alkaline electrolytes. Typical examples of such systems include anion-exchange membrane fuel cells (AEMFCs) and lithium-air batteries. All these devices have a considerable potential to achieve a high performance level even without the application of ORR electrocatalysts based on platinum-group metals (PGMs), which are very expensive and prone to give rise to supply bottlenecks [2]. Indeed, in an alkaline medium, “outer shell” processes are heavily involved in the ORR mechanism; consequently, the direct adsorption of oxygen on active sites based on PGMs is not necessary [3]. As a result, in an alkaline medium the ORR can be effectively promoted by active sites based on non-noble, first-row transition metals including Fe, Co, Mn and Ni [3, 4].
In this work, a new family of ORR electrocatalysts meant for the alkaline environment is devised, taking advantage of an innovative preparation protocol [5]. The electrocatalysts consist of a carbon nitride matrix coordinating active sites based on first-row transition metals; the carbon nitride matrix further coats graphite nanoparticles characterized by a good electron conductivity, which act as the support and improve the dispersion of the active sites giving so rise to a “core-shell” morphology [6]. The chemical composition of the electrocatalysts is investigated by inductively-coupled plasma atomic emission spectroscopy (ICP-AES) and microanalysis; the morphology is characterized by high-resolution scanning electron microscopy (HR-SEM) and high-resolution transmission electron microscopy (HR-TEM); the surface structure and surface chemical composition is elucidated by nitrogen physisorption techniques and X-ray photoelectron spectroscopy, respectively. The structure of the electrocatalysts is studied by powder X-ray diffraction and vibrational spectroscopies. Finally, the performance of the electrocatalysts in the ORR and the reaction mechanism are determined by cyclic voltammetry with the thin-film rotating ring-disk electrode (CV-TF-RRDE) technique (see Figure 1).

References

[1] A. Morozan A, B. Jousselme, S. Palacin, Energy Environ. Sci.
4, 1238 (2011).
[2] JRC Scientific and Policy Reports “Critical Metals in the Path towards the Decarbonisation of the EU Energy Sector”, (2013).
[3] N. Ramaswamy, S. Mukerjee, Adv. Phys. Chem.#491604 (2012) doi:10.1155/2012/491604
[4] R. B. Valim, M. C. Santos, M. R. V. Lanza et al., Electrochim. Acta 85, 423 (2012).
[5] V. Di Noto, E. Negro, F. Bertasi et al., patent pending.
[6] V. Di Noto, E. Negro, S. Polizzi et al., ChemSusChem.
5, 2451 (2012).

Figure 1