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Insights on the Electrocatalytic Seawater Splitting at Heterogeneous Nickel-Cobalt Based Electrocatalysts Engineered from Oxidative Aniline Polymerization and Calcination.

ABSTRACT: Given the limited access to freshwater compared to seawater, a growing interest surrounds the direct seawater electrolysis to produce hydrogen. However, we currently lack efficient electrocatalysts to selectively perform the oxygen evolution reaction (OER) over the oxidation of the chloride ions that are the main components of seawater. In this contribution, we report an engineering strategy to synthesize heterogeneous electrocatalysts by the simultaneous formation of separate chalcogenides of nickel (NiS_x, x = 0, 2/3, 8/9, and 4/3) and cobalt (CoS_x, x = 0 and 8/9) onto a carbon-nitrogen-sulfur nanostructured network. Specifically, the oxidative aniline polymerization in the presence of metallic cations was combined with the calcination to regulate the separate formation of various self-supported phases in order to target the multifunctional applicability as both hydrogen evolution reaction (HER) and OER in a simulated alkaline seawater. The OER's metric current densities of 10 and 100 mA cm^-2 were achieved at the bimetallic for only 1.60 and 1.63 V_RHE, respectively. This high-performance was maintained in the electrolysis with a starting voltage of 1.6 V and satisfactory stability at 100 mA over 17 h. Our findings validate a high selectivity for OER of ~100%, which outperforms the previously reported data of 87-95%.

SUBMITTER: Hajjar P

PROVIDER: S-EPMC8512141 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The rational design of efficient electrocatalysts for industrial water splitting is essential to generate sustainable hydrogen fuel. However, a comprehensive understanding of the complex catalytic mechanisms under harsh reaction conditions remains a major challenge. We apply a self-templated strategy to introduce hierarchically nanostructured "all-surface" Fe-doped cobalt phosphide nanoboxes (Co@CoFe-P NBs) as alternative electrocatalysts for industrial-scale applications. Operando Raman spectroscopy and X-ray absorption spectroscopy (XAS) experiments were carried out to track the dynamics of their structural reconstruction and the real catalytically active intermediates during water splitting. Our operando analyses reveal that partial Fe substitution in cobalt phosphides promotes a structural reconstruction into P-Co-O-Fe-P configurations with low-valence metal centers (M0/M+) during the hydrogen evolution reaction (HER). Results from density functional theory (DFT) demonstrate that these in situ reconstructed configurations significantly enhance the HER performance by lowering the energy barrier for water dissociation and by facilitating the adsorption/desorption of HER intermediates (H*). The competitive activity in the oxygen evolution reaction (OER) arises from the transformation of the reconstructed P-Co-O-Fe-P configurations into oxygen-bridged, high-valence CoIV-O-FeIV moieties as true active intermediates. In sharp contrast, the formation of such CoIII/IV-O-FeIII/IV moieties in Co-FeOOH is hindered under the same conditions, which outlines the key advantages of phosphide-based electrocatalysts. Ex situ studies of the as-synthesized reference cobalt sulfides (Co-S), Fe doped cobalt selenides (Co@CoFe-Se), and Fe doped cobalt tellurides (Co@CoFe-Te) further corroborate the observed structural transformations. These insights are vital to systematically exploit the intrinsic catalytic mechanisms of non-oxide, low-cost, and robust overall water splitting electrocatalysts for future energy conversion and storage.

Dataset Information

Insights on the Electrocatalytic Seawater Splitting at Heterogeneous Nickel-Cobalt Based Electrocatalysts Engineered from Oxidative Aniline Polymerization and Calcination.

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