A Knowledge-Based Molecular Single-Source Precursor Approach to Nickel Chalcogenide Precatalysts for Electrocatalytic Water, Alcohol, and Aldehyde Oxidations.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 39626115.
- Also identified by DOI 10.1021/acsnano.4c08058 and PMC identifier 11656844.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
The development and comprehensive understanding of nickel chalcogenides are critical since they constitute a class of efficient electro(pre)catalysts for the oxygen evolution reaction (OER) and value-added organic oxidations. This study introduces a knowledge-based facile approach to analogous NiE (E = S, Se, Te) phases, originating from molecular β-diketiminato [Ni<sub>2</sub>E<sub>2</sub>] complexes and their application for OER and organic oxidations. The recorded activity trends for both target reactions follow the order NiSe > NiS > NiTe. Notably, NiSe displayed efficient performance for both OER and the selective oxidation of benzyl alcohol and 5-hydroxymethylfurfural, exhibiting stability in OER for 11 days under industrially pertinent conditions. Comprehensive analysis, including quasi <i>in situ</i> X-ray absorption and Raman spectroscopy, in combination with several <i>ex situ</i> techniques, revealed a material reconstruction process under alkaline OER conditions, involving chalcogen leaching. While NiS and NiSe experienced full chalcogen leaching and reconstruction into Ni<sup>III/IV</sup> oxyhydroxide active phases with intercalated potassium ions, the transformation of NiTe is incomplete. This study highlights the structure-activity relationship of a whole series of analogous nickel chalcogenides, directly linking material activity to the availability of active sites for catalysis. Such findings hold great promise for the development of efficient electrocatalysts for a wide range of applications, impacting various industrial processes and sustainable energy solutions.