Solution Combustion Synthesis of Novel S,B-Codoped CoFe Oxyhydroxides for the Oxygen Evolution Reaction in Saline Water.

Green hydrogen presents itself as a clean energy vector, which can be produced by electrolysis of water by utilizing renewable energy such as solar or wind. While current technologies are sufficient to support commercial deployment of fresh water electrolyzers, there remain a few well-defined challenges in the path of commercializing direct seawater electrolyzers, predominantly related to the sluggish oxygen evolution reaction (OER) kinetics and the competing chlorine evolution reaction (CER) at the anode. Herein, we report the facile and swift fabrication of an S,B-codoped CoFe oxyhydroxide via solution combustion synthesis for the OER with apparent CER suppression abilities. The as-prepared S,B-(CoFe)OOH-H attained ultralow overpotentials of 161 and 278 mV for achieving current densities of 10 and 1000 mA cm-2, respectively, in an alkaline saline (1 M KOH + 0.5 M NaCl) electrolyte, with a low Tafel slope of 46.7 mV dec-1. Chronoamperometry testing of the codoped bimetallic oxyhydroxides showed very stable behavior in harsh alkaline saline and in neutral pH saline environments. S,B-(CoFe)OOH-H oxyhydroxide showed a notable decrease in CER production in comparison to the other S,B-codoped counterparts. Selectivity measurements through online FE calculations showed high OER selectivity in alkaline (FE ∼ 97%) and neutral (FE ∼ 91%) pH saline conditions under standard 10 mA cm-2 operation. Moreover, systematic testing in electrolytes at pH values of 14 to 7 yielded promising results, thus bringing direct seawater electrolysis at near-neutral pH conditions closer to realization.

Early Transition-Metal-Based Binary Oxide/Nitride for Efficient Electrocatalytic Hydrogen Evolution from Saline Water in Different pH Environments.

Using abundant seawater can reduce reliance on freshwater resources for hydrogen production from electrocatalytic water splitting. However, seawater has detrimental effects on the stability and activity of the hydrogen evolution reaction (HER) electrocatalysts under different pH conditions. In this work, we report the synthesis of binary metallic core-sheath nitride@oxynitride electrocatalysts [Ni(ETM)]δ+-[O-N]δ-, where ETM is an early transition metal V or Cr. Using NiVN on a nickel foam (NF) substrate, we demonstrate an HER overpotential as low as 32 mV at -10 mA cm-2 in saline water (0.6 M NaCl). The results represent an advancement in saline water HER performance of earth-abundant electrocatalysts, especially under near-neutral pH range (i.e., pH 6-8). Doping ETMs in nickel oxynitrides accelerates the typically rate-determining H2O dissociation step for HER and suppresses chloride deactivation of the catalyst in neutral-pH saline water. Heterointerface synergism occurs through H2O adsorption and dissociation at interfacial oxide character, while adsorbed H* proceeds via Heyrovsky or Tafel step on the nitride character. This electrocatalyst showed stable performance under a constant current density of -50 mA cm-2 for 50 h followed by additional 50 h at -100 mA cm-2 in a neutral saline electrolyte (1 M PB + 0.6 M NaCl). Contrarily, under the same conditions, Pt/C@NF exhibited significantly low performance after a mere 4 h at -50 mA cm-2. The low Tafel slope of 25 mV dec-1 indicated that the reaction is Tafel limited, unlike commercial Pt/C, which is Heyrovsky limited. We close by discussing general principles concerning surface charge delocalization for the design of HER electrocatalysts in pH saline environments.

Spontaneous shape transition of Mn x Ge1- x islands to long nanowires.

We report experimental evidence for a spontaneous shape transition, from regular islands to elongated nanowires, upon high-temperature annealing of a thin Mn wetting layer evaporated on Ge(111). We demonstrate that 4.5 monolayers is the critical thickness of the Mn layer, governing the shape transition to wires. A small change around this value modulates the geometry of the nanostructures. The Mn-Ge alloy nanowires are single-crystalline structures with homogeneous composition and uniform width along their length. The shape evolution towards nanowires occurs for islands with a mean size of ≃170 nm. The wires, up to ≃1.1 µm long, asymptotically tend to ≃80 nm of width. We found that tuning the annealing process allows one to extend the wire length up to ≃1.5 µm with a minor rise of the lateral size to ≃100 nm. The elongation process of the nanostructures is in agreement with a strain-driven shape transition mechanism proposed in the literature for other heteroepitaxial systems. Our study gives experimental evidence for the spontaneous formation of spatially uniform and compositionally homogeneous Mn-rich GeMn nanowires on Ge(111). The reliable and simple synthesis approach allows one to exploit the room-temperature ferromagnetic properties of the Mn-Ge alloy to design and fabricate novel nanodevices.