Atomically Dispersed Transition Metal-Nitrogen-Carbon Electrocatalysts: Design, Synthesis, Characterization, Reactivity and Durability

Abstract

Platinum group metal-free (PGM-free) catalysts have been targeted as possible Earth Abundant Elements solution to many electrochemical energy conversion technologies. Special attention has been given to PGM-free electrocatalysis with atomically dispersed (AD) transition metal moieties decorated over nitrogen-doped carbonaceous materials (a.k.a. M-N-C catalysts). Major applications for M-N-Cs are in cathode catalysts for oxygen reduction reaction (ORR). 1 These materials are employed across the pH-range: in proton exchange membrane fuel cells (PEMFC), biological (microbial) fuel cells (MFC) and alkaline, including anion/hydroxyl exchange membrane fuel cells (AFC, AEMFC/HEMFC). We have successfully introduced M-N-C catalysts synthesized by sacrificial support method (SSM) as a hard template approach based on high temperature pyrolysis. 2 In most cases a secondary pyrolysis is being performed to promote AD display of the transition metal. 3 This talk will address structure-to-property correlations for M-N-C catalysts in ORR based on electrochemical activity obtained in rotating ring-disk electrodes (RRDE) with those spectroscopic and microscopic observations and density functional theory (DFT) calculations of oxygen binding on AD transition metal. We will discuss the role of the AD transition metal, participation of the surface N-groups as co-catalysts/alternative active sites and the possible role of surface oxides as co-catalysts or hydrophilic/hydrophobic properties descriptor. M-N-C catalysts performance in single membrane electrode assembly (MEA) fuel cells will also be discussed in the context of its surface chemistry and materials structure/morphology. We will focus on local hydrophobicity of SSM-based M-N-C electrocatalystsand its impact on the MEA performance. A broad spectrum of AD transition metal decorated MNCs have been synthesized and evaluated for catalytic activity in ORR (and other processes). The use of such materials as “active supports” for highly dispersed platinum or platinum alloy nanoparticles will be discussed. New developments in synthesis protocols enabling “green chemistry” scalable solutions will be discussed. References: T. Asset and P. Atanassov, Joule , 2020, 4, 33. Y. Huang, Y. Chen, M. Xu, T. Asset, P. Tieu, A. Gili, D.S. Kulkarni, V. de Andrade, F. De Carlo, H.S. Barnard, A. Doran, D. Parkinson, X. Pan, P. Atanassov, and I.V. Zenyuk, Materials Today , 47 (2021) 53-68 Y. Chen, Y. Huang, M. Xu, T. Asset, X. Yan, K. Artyushkova, M. Kodali, E. Murphy, A. Ly, X. Pan, I.V. Zenyuk, and P. Atanassov, Materials Today , 53 (2022) 58-70