Search for: All records

Abstract The electrochemical reduction of nitrates (NO₃⁻) enables a pathway for the carbon neutral synthesis of ammonia (NH₃), via the nitrate reduction reaction (NO₃RR), which has been demonstrated at high selectivity. However, to make NH₃synthesis cost‐competitive with current technologies, high NH₃partial current densities (j_NH3) must be achieved to reduce the levelized cost of NH₃. Here, the high NO₃RR activity of Fe‐based materials is leveraged to synthesize a novel active particle‐active support system with Fe₂O₃nanoparticles supported on atomically dispersed Fe–N–C. The optimized 3×Fe₂O₃/Fe–N–C catalyst demonstrates an ultrahigh NO₃RR activity, reaching a maximum j_NH3of 1.95 A cm⁻²at a Faradaic efficiency (FE) for NH₃of 100% and an NH₃yield rate over 9 mmol hr⁻¹cm⁻². Operando XANES and post‐mortem XPS reveal the importance of a pre‐reduction activation step, reducing the surface Fe₂O₃(Fe³⁺) to highly active Fe⁰sites, which are maintained during electrolysis. Durability studies demonstrate the robustness of both the Fe₂O₃particles and Fe–N_xsites at highly cathodic potentials, maintaining a current of −1.3 A cm⁻²over 24 hours. This work exhibits an effective and durable active particle‐active support system enhancing the performance of the NO₃RR, enabling industrially relevant current densities and near 100% selectivity. 

A microwave assisted method was used to synthesize RhAu nanoparticles (NPs). Characterization, based upon transmission electron microscopy (TEM), energy dispersive spectroscopy, and powder X-ray diffraction, provided the evidence of monomodal alloy NPs with a mean size distribution between 3 and 5 nm, depending upon the composition. Extended X-ray adsorption fine-structure spectroscopy (EXAFS) also showed evidence of alloying, but the coordination numbers of Rh and Au indicated significant segregation between the metals. More problematic were the low coordination numbers for Rh; values of ca. 9 indicate NPs smaller than 2 nm, significantly smaller than those observed with TEM. Additionally, no single-particle structural models were able to reproduce the experimental EXAFS data. Resolution of this discrepancy was achieved with high resolution aberration corrected scanning TEM imaging which showed the presence of ultra-small (<2 nm) pure Rh clusters and larger (∼3–5 nm) segregated particles with Au-rich cores and Rh-decorated shells. A heterogeneous model with a mixture of ultrasmall pure Rh clusters and larger segregated Rh/Au NPs was able to explain the experimental measurements of the NPs over the range of compositions measured. The combination of density functional theory, EXAFS, and TEM allowed us to quantify the heterogeneity in the RhAu NPs. It was only through this combination of theoretical and experimental techniques that resulted in a bimodal distribution of particle sizes that was able to explain all of the experimental characterization data.