Implications of Coordination Chemistry to Cationic Interactions in Honeycomb Layered Nickel Tellurates

Abstract

Honeycomb layered tellurates represent a burgeoning class of multi-functional materials with fascinating crystal-structural versatility and a rich composition space. Despite their multifold capabilities, their compositional diversity remains underexplored due to complexities in experimental design and syntheses. Thus, in a bid to expand this frontier and derive relevant insights into allowed metastable compositions, we employ a density functional theory ($\mathrm{DFT}$) approach to predict $in$ $silico$ the crystal structures of new honeycomb layered tellurates embodied by the composition, $A{}_2\mathrm{N}{\mathrm{i}}_2\mathrm{Te}{\mathrm{O}}_6$ ($A$ = alkali, hydrogen or coinage-metal cations). Here, alkali-metal atoms with vastly larger radii than $\mathrm{K}$ ($\mathrm{Rb}$ and $\mathrm{Cs}$) are found to engender a prismatic coordination with the oxygen atoms from the honeycomb slabs whilst coinage-metal atoms ($\mathrm{Ag}$, $\mathrm{Au}$ and $\mathrm{Cu}$) display a propensity for linear coordination. Further, ${\mathrm{H}}_2\mathrm{N}{\mathrm{i}}_2\mathrm{Te}{\mathrm{O}}_6$ is found to also render a linear coordination wherein the hydrogen atom preferentially establishes a stronger coordination with one of the oxygen atoms to form hydroxyl groups. All $A$ cations in the studied $A{}_2\mathrm{N}{\mathrm{i}}_2\mathrm{Te}{\mathrm{O}}_6$ compositions form a honeycomb lattice. Conclusions on the possibility of a monolayer-bilayer phase transition in coinage metal atom tellurates can be drawn by considering the implications of conformal symmetry of the cation honeycomb lattice and metallophilicity. This work not only propounds new honeycomb layered tellurate compositions but also provides novel insight into the rational design of multifunctional materials for applications ranging from energy storage, catalysis and optics to analogue condensed matter systems of gravity.

49 pages, 10 figures, 1 cover picture, 6 supplementary tables, 13 supplementary figures

References in corpus (9)

• Sulfonylamide-Based Ionic Liquids for High-Voltage Potassium-Ion Batteries with Honeycomb Layered Cathode Oxides
• Sodium layer chiral distribution and spin structure of Na${}_2$Ni${}_2$TeO${}_6$ with a honeycomb network
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• Topological Defects and Unique Stacking Disorders in Honeycomb Layered Oxide ${\mathrm{K}}_2\mathrm{N}{\mathrm{i}}_2\mathrm{Te}{\mathrm{O}}_6$ Nanomaterials: Implications for Rechargeable Batteries
• Honeycomb Layered Oxides With Silver Atom Bilayers and Emergence of Non-Abelian SU(2) Interactions
• Cationic vacancies as defects in honeycomb lattices with modular symmetries
• Advances in honeycomb layered oxides: Part II -- Theoretical advances in the characterisation of honeycomb layered oxides with optimised lattices of cations

Cited by in corpus (5)

• Honeycomb Layered Oxides With Silver Atom Bilayers and Emergence of Non-Abelian SU(2) Interactions
• Cationic vacancies as defects in honeycomb lattices with modular symmetries
• Advances in honeycomb layered oxides: Part I -- Syntheses and Characterisations of Pnictogen- and Chalcogen-Based Honeycomb Layered Oxides
• Honeycomb Layered Frameworks with Metallophilic Bilayers
• Pseudo-spin model of argentophilicity in honeycomb bilayered materials