Designed functions of oxide/hydroxide nanosheets via elemental replacement/doping

Abstract

Partial replacement of one structural element in a solid with another of a similar size was conducted to impart functionality to the solids and modify their properties. This phenomenon is found in nature in coloured gemstones and clay minerals and is used in materials chemistry and physics, endowing materials with useful properties that can be controlled by incorporated heteroelements and their amounts. Depending on the area of research (or expected functions), the replacement is referred to as “isomorphous substitution”, “doping”, etc. Herein, elemental replacement in two-dimensional (2D) oxides and hydroxides (nanosheets or layered materials) is summarised with emphasis on the uniqueness of their preparation, characterisation and application compared with those of the corresponding bulk materials. Among the 2D materials (graphene, metallenes, transition metal chalcogenides, metal phosphate/phosphonates, MXenes, etc.), 2D oxides and hydroxides are characterised by their presence in nature, facile synthesis and storage under ambient conditions, and possible structural variation from atomic-level nanosheets to thicker nanosheets composed of multilayered structures. The heteroelements to be doped were selected depending on the target application objectively; however, there are structural and synthetic limitations in the doping of heteroelements. In the case of layered double hydroxides (single layer) and layered alkali silicates (from single layer to multiple layers), including layered clay minerals (2 : 1 layer), the replacement (commonly called isomorphous substitution) is discussed to understand/design characteristics such as catalytic, adsorptive (including ion exchange), and swelling properties. Due to the variation in their main components, the design of layered transition metal oxide/hydroxide materials via isomorphous substitution is more versatile; in this case, tuning their band structure, doping both holes and electrons, and creating impurity levels are examined by the elemental replacement of the main components. As typical examples, material design for the photocatalytic function of an ion-exchangeable layered titanate (lepidocrocite-type titanate) and a perovskite niobate (KCa₂Nb₃O₁₀) is discussed, where elemental replacement is effective in designing their multiple functions.