Back to Search
Start Over
New Compounds and Phase Selection of Nickel Sulfides via Oxidation State Control in Molten Hydroxides.
- Source :
-
Journal of the American Chemical Society [J Am Chem Soc] 2021 Sep 01; Vol. 143 (34), pp. 13646-13654. Date of Electronic Publication: 2021 Aug 19. - Publication Year :
- 2021
-
Abstract
- Molten salts are promising reaction media candidates for the discovery of novel materials; however, they offer little control over oxidation state compared to aqueous solutions. Here, we demonstrated that when two hydroxides are mixed, their melts become fluxes with tunable solubility, which are surprisingly powerful solvents for ternary chalcogenides and offer effective paths for crystal growth to new compounds. We report that precise control of the oxidation state of Ni is achievable in mixed molten LiOH/KOH to grow single crystals of all known ternary K-Ni-S compounds. It is also possible to access several new phases, including a new polytope of β-K <subscript>2</subscript> Ni <subscript>3</subscript> S <subscript>4</subscript> , as well as low-valence KNi <subscript>4</subscript> S <subscript>2</subscript> and K <subscript>4</subscript> Ni <subscript>9</subscript> S <subscript>11</subscript> . KNi <subscript>4</subscript> S <subscript>2</subscript> is a two-dimensional low-valence nickel-rich sulfide, and β-K <subscript>2</subscript> Ni <subscript>3</subscript> S <subscript>4</subscript> has a hexagonal lattice. Moreover, using KNi <subscript>4</subscript> S <subscript>2</subscript> as a template, we obtained a new layered binary Ni <subscript>2</subscript> S by topotactic deintercalation of K. The new binary Ni <subscript>2</subscript> S has a van der Waals gap and can function as a new host layer for intercalation chemistry, as demonstrated by the intercalation of LiOH between its layers. The oxidation states of low-valence KNi <subscript>4</subscript> S <subscript>2</subscript> and Ni <subscript>2</subscript> S were studied using X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. Density functional theory calculations showed large antibonding interactions at the Fermi level for both KNi <subscript>4</subscript> S <subscript>2</subscript> and Ni <subscript>2</subscript> S, corresponding to the flat-bands with large Ni-d <subscript> x <superscript>2</superscript> - y <superscript>2</superscript> </subscript> character.
Details
- Language :
- English
- ISSN :
- 1520-5126
- Volume :
- 143
- Issue :
- 34
- Database :
- MEDLINE
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Academic Journal
- Accession number :
- 34410691
- Full Text :
- https://doi.org/10.1021/jacs.1c05107