Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods.

Mononuclear Fe ions ligated by nitrogen (FeNx) dispersed on nitrogen-doped carbon (Fe-N-C) serve as active centers for electrocatalytic O2 reduction and thermocatalytic aerobic oxidations. Despite their promise as replacements for precious metals in a variety of practical applications, such as fuel cells, the discovery of new Fe-N-C catalysts has relied primarily on empirical approaches. In this context, the development of quantitative structure-reactivity relationships and benchmarking of catalysts prepared by different synthetic routes and by different laboratories would be facilitated by the broader adoption of methods to quantify atomically dispersed FeNx active centers. In this study, we develop a kinetic probe reaction method that uses the aerobic oxidation of a model hydroquinone substrate to quantify the density of FeNx centers in Fe-N-C catalysts. The kinetic method is compared with low-temperature Mössbauer spectroscopy, CO pulse chemisorption, and electrochemical reductive stripping of NO derived from NO2- on a suite of Fe-N-C catalysts prepared by diverse routes and featuring either the exclusive presence of Fe as FeNx sites or the coexistence of aggregated Fe species in addition to FeNx. The FeNx site densities derived from the kinetic method correlate well with those obtained from CO pulse chemisorption and Mössbauer spectroscopy. The broad survey of Fe-N-C materials also reveals the presence of outliers and challenges associated with each site quantification approach. The kinetic method developed here does not require pretreatments that may alter active-site distributions or specialized equipment beyond reaction vessels and standard analytical instrumentation.

Structural and Reactivity Effects of Secondary Metal Doping into Iron-Nitrogen-Carbon Catalysts for Oxygen Electroreduction.

While improved activity was recently reported for bimetallic iron-metal-nitrogen-carbon (FeMNC) catalysts for the oxygen reduction reaction (ORR) in acid medium, the nature of active sites and interactions between the two metals are poorly understood. Here, FeSnNC and FeCoNC catalysts were structurally and catalytically compared to their parent FeNC and SnNC catalysts. While CO cryo-chemisorption revealed a twice lower site density of M-Nx sites for FeSnNC and FeCoNC relative to FeNC and SnNC, the mass activity of both bimetallic catalysts is 50-100% higher than that of FeNC due to a larger turnover frequency in the bimetallic catalysts. Electron microscopy and X-ray absorption spectroscopy identified the coexistence of Fe-Nx and Sn-Nx or Co-Nx sites, while no evidence was found for binuclear Fe-M-Nx sites. 57Fe Mössbauer spectroscopy revealed that the bimetallic catalysts feature a higher D1/D2 ratio of the spectral signatures assigned to two distinct Fe-Nx sites, relative to the FeNC parent catalyst. Thus, the addition of the secondary metal favored the formation of D1 sites, associated with the higher turnover frequency.

Kinetic Diagnostics and Synthetic Design of Platinum Group Metal-Free Electrocatalysts for the Oxygen Reduction Reaction Using Reactivity Maps and Site Utilization Descriptors.

The experimental development of catalytically ever-more active platinum group metal (PGM)-free materials for the oxygen reduction reaction (ORR) at fuel cell cathodes has been until recently a rather empirical iteration of synthesis and testing. Here, we present how kinetic reactivity maps based on kinetic descriptors of PGM-free single-metal-site ORR electrocatalysts can help to better understand the origin of catalytic reactivity and help to derive rational synthetic guidelines toward improved catalysts. Key in our analysis are the catalytic surface site density (SD) and the catalytic turnover frequency (TOF) in their role as controlling kinetic parameters for the ORR reactivity of PGM-free nitrogen-coordinated single-metal M-site carbon (MNC) catalysts. SD-TOF plots establish two-dimensional reactivity maps. We also consider the ratio between SD and the total number of single-metal sites in the bulk, referred to as the site utilization factor, which we propose as another guiding parameter for optimizing the synthesis of MNC catalysts. Exemplified by two sets of FeNC, CoNC, and SnNC catalysts prepared using two distinctly different N- and C-precursor material classes (Zn-based zeolitic imidazolate frameworks and covalent polyaniline), we comparatively diagnose the intrinsic kinetic ORR parameters as well as structural, morphological, and chemical properties. From there, we derive and discuss possible synthetic guidelines for further improvements. Our approach can be extended to other families of catalysts and may involve kinetic performance data of idealized liquid-electrolyte cells as well as gas diffusion layer-type flow cells.