Development of Novel Non-Pt Group Metal Electrocatalysts for PEM Fuel Cell Applications (2016)

The objective of this multi-institutional effort was to comprehensively pursue the goal of eliminating noble metal (Pt group metals, PGM) from the cathodic oxygen reduction reaction (ORR) electrode thereby providing a quantum leap in lowering the overall PGM loading in a polymer electrolyte fuel cell (PEMFC). The overall project scope encompassed (a) comprehensive materials discovery effort, (b) a concomitant effort to scale up these materials with very high ( ±5%) reproducibility, both intra and inter, (c) understanding mass transport in porous medium both in gas diffusion and micro-porous layers for enhanced areal activity, (d) understanding mechanistic aspects of active site structure and ORR electrocatalytic pathway. Overall project milestones and metrics were (a) first phase effort based on performance in oxygen where the project’s Go/No-Go decision point milestone of 100 mA/cm2 at 0.8 V (internal resistance-free, iR-free) at 80°C, pure H2/O2, with 1.5 bar total pressure was met. Subsequently, the principle objectives were to (a) transition the project from H2/O2 to H2/Air with slated target of exceeding 30 mA/cm2 @ 0.8 V, 2.5 bar total pressure and an end of the project target of 1 A/cm2 @ 0.4 V (same total pressure), both under 100% relative humidity. The target for catalyst material scale up was to achieve 100 g batch size at the end of the program. This scale up target had a quality control milestone of less than 5% variation of activity measured with H2/Air (2.5 bar total pressure) at 0.8 V. In addition, the project also aimed at arriving at a unified understanding of the nature of active sites in these catalysts as well as some preliminary understanding of the mechanistic pathway. Also addressed is the development of an integrated method for determination of mass transport parameters using a combination of Helox experiments and modeling of the gas diffusion media, especially the micro-porous layer on the gas diffusion electrode (GDE). Detailed aspects of technical metrics and milestones are provided in Table 1 of the final report. Besides the success in meeting the DOE milestones in areal activities for oxygen and air described above one of the key successes of this effort was in understanding the nature of the active site(s) and aspects of the ORR pathway. In this it should be noted that the materials discovery effort provided for use of unconventional approaches, some of which led to very active catalysts. This aspect is described in detail in the final report. From a mechanistic perspective, a combination spectroscopic techniques confirmed that the high activity observed for most pyrolyzed Fe-based catalysts, irrespective of the precursors materials (macrocycles or individual Fe, N, and C precursors), the synthesis method (wet chemical impregnation or SSM), and final Fe-species (with or without inorganic iron species), can mainly be attributed to a single active site: non-planar Fe-N4 moiety embedded in distorted carbon matrix characterized by a high potential for the Fe2+/3+ redox transition in acidic electrolyte/environment, which is likely formed via the covalent incorporation of distorted Fe-N4 moieties in the defective centers on the carbon basal plane or in armchair edges of two adjacent graphene layers. This Fe2+-N4 active site at 0.3 V undergoes redox transition to a pentacoordinate HO₋Fe3+₋N4 at 0.90 V, and the adsorption of the *OH trigged by the Fe2+/Fe3+ redox transition poisons the active sites, thereby providing experimental evidence of the redox mechanism. Moreover, a highly active MOF-based catalyst devoid of any Fe-N moieties was also developed, and the active sites were identified as nitrogen-doped carbon fibers with embedded iron particles that are not directly involved in the oxygen reduction pathway. The high ORR activity and durability of catalysts involving this site in fuel cells are attributed to the high density of active sites and the elimination or reduction of Fenton-type processes. The latter are initiated by hydrogen peroxide but are known to be accelerated by iron ions exposed to the surface, resulting in the formation of damaging free-radicals. We expect that the comprehensive understanding of the synthesis-products correlations, nature of active sites, and the reaction mechanisms acquired here by systematically studying a broad variety of M-N-C materials under in situ conditions will provide guidelines to rational design of this type of non-PGM catalysts.