Dataset Information

Chiral electrocatalysts eclipse water splitting metrics through spin control.

ABSTRACT: Continual progress in technologies that rely on water splitting are often hampered by the slow kinetics associated with the oxygen evolution reaction (OER). Here, we show that the efficiency of top-performing catalysts can be improved, beyond typical thermodynamic considerations, through control over reaction intermediate spin alignment during electrolysis. Spin alignment is achieved using the chiral induced spin selectivity (CISS) effect and the improvement in OER manifests as an increase in Faradaic efficiency, decrease in reaction overpotential, and change in the rate determining step for chiral nanocatalysts over compositionally analogous achiral nanocatalysts. These studies illustrate that a defined spatial orientation of the nanocatalysts is not necessary to exhibit spin selectivity and therefore represent a viable platform for employing the transformative role of chirality in other reaction pathways and processes.

SUBMITTER: Vadakkayil A

PROVIDER: S-EPMC9958132 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Chiral electrocatalysts eclipse water splitting metrics through spin control.

Vadakkayil Aravind A Clever Caleb C Kunzler Karli N KN Tan Susheng S Bloom Brian P BP Waldeck David H DH

Nature communications 20230224 1

Continual progress in technologies that rely on water splitting are often hampered by the slow kinetics associated with the oxygen evolution reaction (OER). Here, we show that the efficiency of top-performing catalysts can be improved, beyond typical thermodynamic considerations, through control over reaction intermediate spin alignment during electrolysis. Spin alignment is achieved using the chiral induced spin selectivity (CISS) effect and the improvement in OER manifests as an increase in Fa ...[more]

PMID: 36828840

Similar Datasets

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

Chiral electrocatalysts eclipse water splitting metrics through spin control.

Publications

Chiral electrocatalysts eclipse water splitting metrics through spin control.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets