Establishing reactivity descriptors for platinum group metal (PGM)-free Fe–N–C catalysts for PEM fuel cells

TL;DR: In this article, the authors report a comprehensive analysis of the catalytic oxygen reduction reaction (ORR) reactivity of four of today's most active benchmark platinum group metal-free (PGM-free) iron/nitrogen doped carbon electrocatalysts (Fe-N-Cs) in PEMFC.

Abstract: We report a comprehensive analysis of the catalytic oxygen reduction reaction (ORR) reactivity of four of today's most active benchmark platinum group metal-free (PGM-free) iron/nitrogen doped carbon electrocatalysts (Fe-N-Cs) Our analysis reaches far beyond previous such attempts in linking kinetic performance metrics, such as electrocatalytic mass-based and surface area-based catalytic activity with previously elusive kinetic metrics such as the active metal site density (SD) and the catalytic turnover frequency (TOF) Kinetic ORR activities, SD and TOF values were evaluated using in situ electrochemical NO 2 A reduction as well as an ex situ gaseous CO cryo chemisorption Experimental ex situ and in situ Fe surface site densities displayed remarkable quantitative congruence Plots of SD versus TOF (''reactivity maps'') are utilized as new analytical tools to deconvolute ORR reactivities and thus enabling rational catalyst developments A microporous catalyst showed large SD values paired with low TOF, while mesoporous catalysts displayed the opposite Trends in Fe surface site density were linked to molecular nitrogen and Fe moieties (D1 and D2 from 57 Fe Mossbauer spectroscopy), from which pore locations of catalytically active D1 and D2 sites were established This cross-laboratory analysis, its employed experimental practices and analytical methodologies are expected to serve as a widely accepted reference for future, knowledge-based research into improved PGM-free fuel cell cathode catalysts Broader context Polymer electrolyte membrane fuel cells (PEMFC) have reached the commercial stage and ever wider deployment is imminent To further reduce the loading of platinum group metal (PGM) catalysts in PEMFC electrodes, PGM-free, iron and nitrogen-doped carbon oxygen reduction (ORR) electrocatalysts (Fe-N-C) were developed over past decades Recent advances in activity and stability of Fe-N-C are impressive, yet methods to evaluate the number of catalytic active Fe sites at the surface and intrinsic turn over frequency remained elusive This changed with the advent of CO cryo-sorption and in situ nitrite stripping techniques that yielded these intrinsic reactivity descriptors Never before, however, have these two complementary specific adsorption/stripping techniques been compared and combined with other chemical and spectroscopic analytics for an in-depth analysis of catalytic reactivity of Fe-N-C ORR electrocatalysts The present study addresses this issue and presents a comprehensive analysis of the reactivity of the four state-of-the-art Fe-N-C PEMFC electrocatalysts The study provides a deeper understanding of the origin and difference in catalytic performance through the combination of a host of different surface sensitive and bulk analysis methods The methodologies and analyses of this benchmark catalyst study will benefit future developments in Fe-N-C catalysis