Electrocatalytic reduction of waste nitrates (NO₃⁻) enables the synthesis of ammonia (NH₃) in a carbon neutral and decentralized manner. Atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts demonstrate a high catalytic activity and uniquely favor mono-nitrogen products. However, the reaction fundamentals remain largely underexplored. Herein, we report a set of 14; 3d-, 4d-, 5d- and f-block M-N-C catalysts. The selectivity and activity of NO₃⁻ reduction to NH₃ in neutral media, with a specific focus on deciphering the role of the NO₂⁻ intermediate in the reaction cascade, reveals strong correlations (R=0.9) between the NO₂⁻ reduction activity and NO₃⁻ reduction selectivity for NH₃. Moreover, theoretical computations reveal the associative/dissociative adsorption pathways for NO₂⁻ evolution, over the normal M-N₄ sites and their oxo-form (O-M-N₄) for oxyphilic metals. This work provides a platform for designing multi-element NO₃RR cascades with single-atom sites or their hybridization with extended catalytic surfaces.

There is a need to understand the water dynamics of alkaline membrane fuel cells under various operating conditions to create electrodes that enable high performance and stable, long-term operation. Here we show, via operando neutron imaging and operando micro X-ray computed tomography, visualizations of the spatial and temporal distribution of liquid water in operating cells. We provide direct evidence for liquid water accumulation at the anode, which causes severe ionomer swelling and performance loss, as well as cell dryout from undesirably low water content in the cathode. We observe that the operating conditions leading to the highest power density during polarization are not generally the conditions that allow for long-term stable operation. This observation leads to new catalyst layer designs and gas diffusion layers. This study reports alkaline membrane fuel cells that can be operated continuously for over 1000 h at 600 mA cm⁻² with voltage decay rate of only 32-μV h⁻¹ – the best-reported durability to date.

Ionic liquids (ILs) have shown to be promising additives to the catalyst layer to enhance oxygen reduction reaction in polymer electrolyte fuel cells. However, fundamental understanding of their role in complex catalyst layers in practically relevant membrane electrode assembly environment is needed for rational design of highly durable and active platinum-based catalysts. Here we explore three imidazolium-derived ionic liquids, selected for their high proton conductivity and oxygen solubility, and incorporate them into high surface area carbon black support. Further, we establish a correlation between the physical properties and electrochemical performance of the ionic liquid-modified catalysts by providing direct evidence of ionic liquids role in altering hydrophilic/hydrophobic interactions within the catalyst layer interface. The resulting catalyst with optimized interface design achieved a high mass activity of 347 A g⁻¹_Pt at 0.9 V under H₂/O₂, power density of 0.909 W cm⁻² under H₂/air and 1.5 bar, and had only 0.11 V potential decrease at 0.8 A cm⁻² after 30 k accelerated stress test cycles. This performance stems from substantial enhancement in Pt utilization, which is buried inside the mesopores and is now accessible due to ILs addition.

X-ray computed tomography (CT) is a nondestructive three-dimensional (3D) imaging technique used for studying morphological properties of porous and nonporous materials. In the field of electrocatalysis, X-ray CT is mainly used to quantify the morphology of electrodes and extract information such as porosity, tortuosity, pore-size distribution, and other relevant properties. For electrochemical systems such as fuel cells, electrolyzers, and redox flow batteries, X-ray CT gives the ability to study evolution of critical features of interest in ex situ, in situ, and operando environments. These include catalyst degradation, interface evolution under real conditions, formation of new phases (water and oxygen), and dynamics of transport processes. These studies enable more efficient device and electrode designs that will ultimately contribute to widespread decarbonization efforts.