Boosting Nitrate to Ammonia Electroconversion through Hydrogen Gas Evolution over Cu-foam@mesh Catalysts.

The hydrogen evolution reaction (HER) is often considered parasitic to numerous cathodic electro-transformations of high technological interest, including but not limited to metal plating (e.g., for semiconductor processing), the CO2 reduction reaction (CO2RR), the dinitrogen → ammonia conversion (N2RR), and the nitrate reduction reaction (NO3-RR). Herein, we introduce a porous Cu foam material electrodeposited onto a mesh support through the dynamic hydrogen bubble template method as an efficient catalyst for electrochemical nitrate → ammonia conversion. To take advantage of the intrinsically high surface area of this spongy foam material, effective mass transport of the nitrate reactants from the bulk electrolyte solution into its three-dimensional porous structure is critical. At high reaction rates, NO3-RR becomes, however, readily mass transport limited because of the slow nitrate diffusion into the three-dimensional porous catalyst. Herein, we demonstrate that the gas-evolving HER can mitigate the depletion of reactants inside the 3D foam catalyst through opening an additional convective nitrate mass transport pathway provided the NO3-RR becomes already mass transport limited prior to the HER onset. This pathway is achieved through the formation and release of hydrogen bubbles facilitating electrolyte replenishment inside the foam during water/nitrate co-electrolysis. This HER-mediated transport effect "boosts" the effective limiting current of nitrate reduction, as evidenced by potentiostatic electrolyses combined with an operando video inspection of the Cu-foam@mesh catalysts under operating NO3-RR conditions. Depending on the solution pH and the nitrate concentration, NO3-RR partial current densities beyond 1 A cm-2 were achieved.

Novel Ni foam catalysts for sustainable nitrate to ammonia electroreduction.

Electrochemical nitrate reduction (NO3-RR) is considered a promising approach to remove environmentally harmful nitrate from wastewater while simultaneously producing ammonia, a product with high value. An important consideration is the choice of catalyst, which is required not only to accelerate NO3-RR but also to direct the product selectivity of the electrolysis toward ammonia production. To this end, we demonstrate the fabrication of novel Ni foam catalysts produced through a dynamic hydrogen bubble template assisted electrodeposition process. The resulting foam morphology of the catalyst is demonstrated to crucially govern its overall electrocatalytic performance. More than 95% Faradaic efficiency of ammonia production was achieved in the low potential range from -0.1 to -0.3 V vs. RHE. Hydrogen was found to be the only by-product of the nitrate reduction. Intriguingly, no other nitrogen containing products (e.g., NO,N2O, or N2) formed during electrolysis, thus indicating a 100% selective (nitrate→ammonia) conversion. Therefore, this novel Ni foam catalyst is a highly promising candidate for truly selective (nitrate→ammonia) electroreduction and a promising alternative to mature copper-based NO3-RR benchmark catalysts. Excellent catalytic performance of the novel Ni foam catalyst was also observed in screening experiments under conditions mimicking those in wastewater treatment.

Development of vanadium-based polyanion positive electrode active materials for high-voltage sodium-based batteries.

Polyanion compounds offer a playground for designing prospective electrode active materials for sodium-ion storage due to their structural diversity and chemical variety. Here, by combining a NaVPO4F composition and KTiOPO4-type framework via a low-temperature (e.g., 190 °C) ion-exchange synthesis approach, we develop a high-capacity and high-voltage positive electrode active material. When tested in a coin cell configuration in combination with a Na metal negative electrode and a NaPF6-based non-aqueous electrolyte solution, this cathode active material enables a discharge capacity of 136 mAh g-1 at 14.3 mA g-1 with an average cell discharge voltage of about 4.0 V. Furthermore, a specific discharge capacity of 123 mAh g-1 at 5.7 A g-1 is also reported for the same cell configuration. Through ex situ and operando structural characterizations, we also demonstrate that the reversible Na-ion storage at the positive electrode occurs mostly via a solid-solution de/insertion mechanism.

The rapid microwave-assisted hydrothermal synthesis of NASICON-structured Na3V2O2x (PO4)2F3-2x (0 < x ≤ 1) cathode materials for Na-ion batteries.

NASICON-structured Na3V2O2x (PO4)2F3-2x (0 < x ≤ 1) solid solutions have been prepared using a microwave-assisted hydrothermal (MW-HT) technique. Well-crystallized phases were obtained for x = 1 and 0.4 by reacting V2O5, NH4H2PO4, and NaF precursors at temperatures as low as 180-200 °C for less than 15 min. Various available and inexpensive reducing agents were used to control the vanadium oxidation state and final product morphology. The vanadium oxidation state and O/F ratios were assessed using electron energy loss spectroscopy and infrared spectroscopy. According to electron diffraction and powder X-ray diffraction, the Na3V2O2x (PO4)2F3-2x solid solutions crystallized in a metastable disordered I4/mmm structure (a = 6.38643(4) Å, c = 10.62375(8) Å for Na3V2O2(PO4)2F and a = 6.39455(5) Å, c = 10.6988(2) Å for Na3V2O0.8(PO4)2F2.2). With respect to electrochemical Na+ (de)insertion as positive electrodes (cathodes) for Na-ion batteries, the as-synthesized materials displayed two sloping plateaus upon charge and discharge, centered near 3.5-3.6 V and 4.0-4.1 V vs. Na+/Na, respectively, with a reversible capacity of ∼110 mA h g-1. The application of a conducting carbon coating through the surface polymerization of dopamine with subsequent annealing at 500 °C improved both the rate capability (∼55 mA h g-1 at a discharge rate of 10C) and capacity retention (∼93% after 50 cycles at a discharge rate of C/2).