Nanoengineered, Pd-doped Co@C nanoparticles as an effective electrocatalyst for OER in alkaline seawater electrolysis.

Water electrolysis is considered one of the major sources of green hydrogen as the fuel of the future. However, due to limited freshwater resources, more interest has been geared toward seawater electrolysis for hydrogen production. The development of effective and selective electrocatalysts from earth-abundant elements for oxygen evolution reaction (OER) as the bottleneck for seawater electrolysis is highly desirable. This work introduces novel Pd-doped Co nanoparticles encapsulated in graphite carbon shell electrode (Pd-doped CoNPs@C shell) as a highly active OER electrocatalyst towards alkaline seawater oxidation, which outperforms the state-of-the-art catalyst, RuO2. Significantly, Pd-doped CoNPs@C shell electrode exhibiting low OER overpotential of ≈213, ≈372, and ≈ 429 mV at 10, 50, and 100 mA/cm2, respectively together with a small Tafel slope of ≈ 120 mV/dec than pure Co@C and Pd@C electrode in alkaline seawater media. The high catalytic activity at the aforementioned current density reveals decent selectivity, thus obviating the evolution of chloride reaction (CER), i.e., ∼490 mV, as competitive to the OER. Results indicated that Pd-doped Co nanoparticles encapsulated in graphite carbon shell (Pd-doped CoNPs@C electrode) could be a very promising candidate for seawater electrolysis.

Strong-Proton-Adsorption Co-Based Electrocatalysts Achieve Active and Stable Neutral Seawater Splitting.

Direct electrolysis of pH-neutral seawater to generate hydrogen is an attractive approach for storing renewable energy. However, due to the anodic competition between the chlorine evolution and the oxygen evolution reaction (OER), direct seawater splitting suffers from a low current density and limited operating stability. Exploration of catalysts enabling an OER overpotential below the hypochlorite formation overpotential (≈490 mV) is critical to suppress the chloride evolution and facilitate seawater splitting. Here, a proton-adsorption-promoting strategy to increase the OER rate is reported, resulting in a promoted and more stable neutral seawater splitting. The best catalysts herein are strong-proton-adsorption (SPA) materials such as palladium-doped cobalt oxide (Co3- x Pdx O4 ) catalysts. These achieve an OER overpotential of 370 mV at 10 mA cm-2 in pH-neutral simulated seawater, outperforming Co3 O4 by a margin of 70 mV. Co3- x Pdx O4 catalysts provide stable catalytic performance for 450 h at 200 mA cm-2 and 20 h at 1 A cm-2 in neutral seawater. Experimental studies and theoretical calculations suggest that the incorporation of SPA cations accelerates the rate-determining water dissociation step in neutral OER pathway, and control studies rule out the provision of additional OER sites as a main factor herein.

Biomonitoring of a Nile Delta Lake using benthic foraminifera.

Lake Edku, one of the northern Nile Delta lakes, is a shallow brackish coastal lake subjected to domestic and agricultural effluents via two main drains, El-Khairy and Barsik, in addition to the discharge water of hundreds of fish farms. This study measures the responses of the benthic foraminiferal assemblage to the environmental stressors in Lake Edku. Grain size, organic carbon, and seven potentially toxic elements (Cu, Pb, Zn, Cd, Cr, Ni, and As) were determined in nine short cores (25-35 cm depth). The lake was characterized by vertical increase in mud, organic matter, and concentrations of all metals, particularly in the eastern basin at the vicinity of the drain discharges. This trend coincides with a general decrease in species diversity and increase in deformed specimens. The foraminiferal assemblage was dominated by Ammonia tepida (Cushman), a pollution-tolerant and euryhaline species. This study demonstrates that benthic foraminiferal assemblages provide a reliable pollution proxy in the brackish environments of Nile Delta that can be used in the periodical monitoring of the coastal lakes.

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.

Oxygen-Deficient Cobalt-Based Oxides for Electrocatalytic Water Splitting.

An apparent increased interest has been recently devoted towards the previously untrodden path for anionic point defect engineering of electrocatalytic surfaces. The role of vacancy engineering in improving photo- and electrocatalytic activities of transition metal oxides (TMOs) has been widely reported. In particular, oxygen vacancy modulation on electrocatalysts of cobalt-based TMOs has seen a fresh spike of research work due to the substantial improvements they have shown towards oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Oxygen vacancy engineering is an effective scheme to quintessentially tune the electronic structure and charge transport, generate secondary active surface phases, and modify the surface adsorption/desorption behavior of reaction intermediates during water splitting. Based on contemporary efforts for inducing oxygen vacancies in a variety of cobalt oxide types, this work addresses facile and environmentally benign synthesis strategies, characterization techniques, and detailed insight into the intrinsic mechanistic modulation of electrocatalysts. It is our foresight that appropriate utilization of the principles discussed herein will aid researchers in rationally designing novel materials that can outperform noble metal-based electrocatalysts. Ultimately, future electrocatalysis implementation for selective seawater splitting is believed to depend on regulating the surface chemistry of active and stable TMOs.