(Keynote) Mechanistic Understanding of the Activity of Atomically Dispersed Transition Metal-Nitrogen-Carbon Catalysts in Oxygen, Carbon Dioxide or Nitrogen Electro-Reduction (2022)

Over the last two decades, platinum group metal-free (PGM-free) catalysts are attracting increasing attention and finding applications in several important process across many electrochemical energy technologies. Among those PGM-free materials, atomically dispersed (AD) transition metal-nitrogen-carbon (M-N-C) catalysts are gaining exceptional popularity as they demonstrate very high (for this class of materials) activity in oxygen reduction reaction (ORR) 1 and are the only cathode catalysts suitable for both proton exchange membrane fuel cells (PEMFC) and alkaline, including anion/hydroxyl exchange membrane fuel cells (AFC, AEMFC/HEMFC). Over the last few years, M-N-C catalysts have shown promising activity in carbon dioxide reduction reaction (CO 2 RR). 2 In this case, varying the transition metal in M-N-Cs opens routes for controlling the selectivity towards a list of C 1 and C 2 products. There are recent reports on catalytic activity of AD M-N-C materials in direct electro-reduction of molecular nitrogen (N 2 RR) or reactions of reduction of nitrates, nitrites or various nitrogen oxides (NO x ). We have systematically investigated all these processes having as a base the M-N-C catalysts synthesized by sacrificial support method (SSM) – a hard template approach with transition metal salt and charge-transfer organic salt ( nicarbazin ) mixed by ball-milling, pyrolyzed at high temperature in inert atmosphere and then etched in HF after cooling. In most cases a secondary (similar) pyrolysis was performed to refine the material and ensure its AD character. The makeup and structure of the active site/sites of the AD M-N0C electrocatalysts, including geometry (coordination) and chemistry (composition and oxidation state) remain contentious to this day. There is an emerging agreement however, that the transition metal (at least for the 2 nd row transitions meals) is immediately associated with (liganded by) the nitrogen functionalities, displayed on the surface if the carbonaceous substrate. It is almost universally accepted that N-coordinated AD transition metal ions, either as in-plane or edge-type defect in “graphene” sheet, are the main/principal active sites. This is often combined with a broadly accepted hypothesis that micro-porous surface area plays a critical role forming edge-type, intercalational active sites while meso-porous interface is most-likely associated with the in-plane, substitutional AD metal sites. Candidate structures participating in reativity towards O 2 , CO 2 or nitrogen species include a list of nitrogen-containg and oxygen-containng moeties in the carbonaceous matrix. The carbon itself displays various degrees of graphitization, depending on the transition metal used in M-N-C synthesis. Additional complexity in this calss of caralysts study comes from the fact that many samples are not strictly AD materials. They often contain incorporated metal nano-particles, corresponding (native) oxides and/or carbides and nitrides (oxocabides and oxonitrides have been observed as well).These “unrefined” M-N-C materials are often used in practice and the corresponding nano-particle components of the de-facto nanocomposites do alter substantially the reactivity and selectivity of the catalysts in all these electro-reduction reactions. This talk discusses the mechanistic aspects of M-N-C catalysts in ORR, CO 2 RR, N 2 RR and electroreduction of nitrogen-containing oxo-species, obtained when cross-referencing electrochemical activity results obtained in rotating disk and rotating ring-disk electrodes setting (RDE/RRDE) with those observed in near-ambient pressure X-ray photo-electron spectroscopy (NAP-XPS) and supported by density functional theory calculations of the reagents adsorption on AD transition metal or nitrogen- or oxygen-containing moieties from the carbonaceous matrix of the M-N-Cs. The later are of particular importance as significant reactivity has been observed for most of those processes when metal-free, nitrogen-doped carbon (N-C) catalysts are used. 3 We will present a case that outlines the reactivity of M-N-C in those important electro-reduction reactions in terms of (i) role of the AD transition metal, (ii) role of the surface N-groups as co-catalysts/alternative sites (iii) role of surface oxides as co-catalysts or hydrophilic/hydrophobic properties descriptor, the last being also critically dependent on morphology. 4 References: T. Asset and P. Atanassov, Joule , 2020, 4, 33. T. Asset, S.T. Garcia, S. Herrera, N. Andersen, Y. Chen, E.J. Peterson, I. Matanovic, K.Artyushkova, J. Lee, S.D. Minteer,S. Dai, X. Pan, K. Chavan, S. Calabrese Bartonand P. Atanassov, ACS Catalysis , 2019, 9, 7668 D . Hursán , A . Samu,K. Artyushkova,T . Asset, P . Atanassov and C . Janáky , Joule, 2019, 3 1719 Y. Huang, Y. Chen, M. Xu, T. Asset, P. Tieu, A. Gili, D. Kulkarni, V. de Andrade, F. de Carlo, H. S. Barnard, A. Doran, D. Y. Parkinson, X. Pan, P. Atanassov, and I. Zenyuk, Materials Today , 2021, 47, 53.