Defect Enriched Tungsten Oxide Phosphate with Strategic Sulfur Doping for Effective Seawater Oxidation.

The intrinsic ability of defects within the electrocatalysts can be judiciously utilized in designing robust electrocatalysts for efficient seawater oxidation. Herein, we have fabricated a novel tungsten oxide phosphate (W12PO38.5) with optimized sulfur doping triggering the insertion of a large number of defect sites. This allows for boosted OER performance in alkaline freshwater as well as seawater, avoiding the unwanted chlorine evolution reaction. The optimized electrocatalyst achieved high current densities of 500 mA cm-2 at an overpotential of just 387 mV in fresh water and 100 mA cm-2 at 380 mV in alkaline seawater for OER. Besides the excellent catalytic performances, the developed electrocatalyst appeared to be a durable catalyst as well. An interesting electrocatalytic activation caused by the generous electronic redistribution led the electrocatalyst to achieve great stability over 100 h at a 100 mA cm-2 current density in alkaline real seawater.

Transition Metal Non-Oxides as Electrocatalysts: Advantages and Challenges.

The identification of hydrogen as green fuel in the near future has stirred global realization toward a sustainable outlook and thus boosted extensive research in the field of water electrolysis focusing on the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). A huge class of compounds consisting of transition metal-based nitrides, carbides, chalcogenides, phosphides, and borides, which can be collectively termed transition metal non-oxides (TMNOs), has emerged recently as an efficient class of electrocatalysts in terms of performance and longevity when compared to transition metal oxides (TMOs). Moreover, the superiority of TMNOs over TMOs to effectively catalyze not only OERs but also HERs and ORRs renders bifunctionality and even trifunctionality in some cases and therefore can replace conventional noble metal electrocatalysts. In this review, the crystal structure and phases of different classes of nanostructured TMNOs are extensively discussed, focusing on recent advances in design strategies by various regulatory synthetic routes, and hence diversified properties of TMNOs are identified to serve as next-generation bi/trifunctional electrocatalysts. The challenges and future perspectives of materials in the field of energy conversion and storage aiding toward a better hydrogen economy are also discussed in this review.

New age chloride shielding strategies for corrosion resistant direct seawater splitting.

Electrocatalytic direct seawater splitting is considered to be one of the most desirable and necessary approach to produce substantial amount of green hydrogen to meet the energy demand. However, practical seawater splitting remains far-fetched due to the electrochemical interference of multiple elements present in seawater, among which chlorine chemistry is the most aggravating one, causing severe damages to electrodes. To overcome such limitations, apart from robust electrocatalyst design, electrolyte engineering along with in depth corrosion engineering are essential aspects, which needs to be thoroughly judged and explored. Indeed, extensive studies and various approaches including smart electrolyzer design have been attempted in the last couple of years on this matter. The present review offers a comprehensive discussion on various strategies to achieve effective and sustainable direct seawater splitting, avoiding chlorine electrochemistry to achieve industry-level performances.

Cobalt and iron phosphates with modulated compositions and phases as efficient electrocatalysts for alkaline seawater oxidation.

An electrocatalyst which is suitable for use in both fresh water and real seawater electrolysis is very uncommon. In this work, we have developed a series of iron-tuned cobalt phosphates and cobalt-tuned iron phosphate solid solutions as electrocatalysts exhibiting excellent OER activities not only in freshwater but also in alkaline real seawater with a faradaic efficiency of 95%.