Metal-Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO2 Electroreduction to CO and Hydrocarbons.

This study explores the kinetics, mechanism, and active sites of the CO2 electroreduction reaction (CO2RR) to syngas and hydrocarbons on a class of functionalized solid carbon-based catalysts. Commercial carbon blacks were functionalized with nitrogen and Fe and/or Mn ions using pyrolysis and acid leaching. The resulting solid powder catalysts were found to be active and highly CO selective electrocatalysts in the electroreduction of CO2 to CO/H2 mixtures outperforming a low-area polycrystalline gold benchmark. Unspecific with respect to the nature of the metal, CO production is believed to occur on nitrogen functionalities in competition with hydrogen evolution. Evidence is provided that sufficiently strong interaction between CO and the metal enables the protonation of CO and the formation of hydrocarbons. Our results highlight a promising new class of low-cost, abundant electrocatalysts for synthetic fuel production from CO2 .

Surface site density and utilization of platinum group metal (PGM)-free Fe-NC and FeNi-NC electrocatalysts for the oxygen reduction reaction.

Pyrolyzed iron-based platinum group metal (PGM)-free nitrogen-doped single site carbon catalysts (Fe-NC) are possible alternatives to platinum-based carbon catalysts for the oxygen reduction reaction (ORR). Bimetallic PGM-free M1M2-NC catalysts and their active sites, however, have been poorly studied to date. The present study explores the active accessible sites of mono- and bimetallic Fe-NC and FeNi-NC catalysts. Combining CO cryo chemisorption, X-ray absorption and 57Fe Mössbauer spectroscopy, we evaluate the number and chemical state of metal sites at the surface of the catalysts along with an estimate of their dispersion and utilization. Fe L3,2-edge X-ray adsorption spectra, Mössbauer spectra and CO desorption all suggested an essentially identical nature of Fe sites in both monometallic Fe-NC and bimetallic FeNi-NC; however, Ni blocks the formation of active sites during the pyrolysis and thus causes a sharp reduction in the accessible metal site density, while with only a minor direct participation as a catalytic site in the final catalyst. We also use the site density utilization factor, ϕ SDsurface/bulk , as a measure of the metal site dispersion in PGM-free ORR catalysts. ϕ SDsurface/bulk enables a quantitative evaluation and comparison of distinct catalyst synthesis routes in terms of their ratio of accessible metal sites. It gives guidance for further optimization of the accessible site density of M-NC catalysts.

The chemical identity, state and structure of catalytically active centers during the electrochemical CO2 reduction on porous Fe-nitrogen-carbon (Fe-N-C) materials.

We report novel structure-activity relationships and explore the chemical state and structure of catalytically active sites under operando conditions during the electrochemical CO2 reduction reaction (CO2RR) catalyzed by a series of porous iron-nitrogen-carbon (FeNC) catalysts. The FeNC catalysts were synthesized from different nitrogen precursors and, as a result of this, exhibited quite distinct physical properties, such as BET surface areas and distinct chemical N-functionalities in varying ratios. The chemical diversity of the FeNC catalysts was harnessed to set up correlations between the catalytic CO2RR activity and their chemical nitrogen-functionalities, which provided a deeper understanding between catalyst chemistry and function. XPS measurements revealed a dominant role of porphyrin-like Fe-N x motifs and pyridinic nitrogen species in catalyzing the overall reaction process. Operando EXAFS measurements revealed an unexpected change in the Fe oxidation state and associated coordination from Fe2+ to Fe1+. This redox change coincides with the onset of catalytic CH4 production around -0.9 VRHE. The ability of the solid state coordinative Fe1+-N x moiety to form hydrocarbons from CO2 is remarkable, as it represents the solid-state analogue to molecular Fe1+ coordination compounds with the same catalytic capability under homogeneous catalytic environments. This finding highlights a conceptual bridge between heterogeneous and homogenous catalysis and contributes significantly to our fundamental understanding of the FeNC catalyst function in the CO2RR.

Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts.

Carbon materials doped with transition metal and nitrogen are highly active, non-precious metal catalysts for the electrochemical conversion of molecular oxygen in fuel cells, metal air batteries, and electrolytic processes. However, accurate measurement of their intrinsic turn-over frequency and active-site density based on metal centres in bulk and surface has remained difficult to date, which has hampered a more rational catalyst design. Here we report a successful quantification of bulk and surface-based active-site density and associated turn-over frequency values of mono- and bimetallic Fe/N-doped carbons using a combination of chemisorption, desorption and (57)Fe Mössbauer spectroscopy techniques. Our general approach yields an experimental descriptor for the intrinsic activity and the active-site utilization, aiding in the catalyst development process and enabling a previously unachieved level of understanding of reactivity trends owing to a deconvolution of site density and intrinsic activity.