A molecular cross-linking approach for hybrid metal oxides

Abstract

There is significant interest in the development of methods to create hybrid materials that transform capabilities, in particular for Earth-abundant metal oxides, such as TiO, to give improved or new properties relevant to a broad spectrum of applications. Here we introduce an approach we refer to as 'molecular cross-linking', whereby a hybrid molecular boron oxide material is formed from polyhedral boron-cluster precursors of the type [B(OH)]. This new approach is enabled by the inherent robustness of the boron-cluster molecular building block, which is compatible with the harsh thermal and oxidizing conditions that are necessary for the synthesis of many metal oxides. In this work, using a battery of experimental techniques and materials simulation, we show how this material can be interfaced successfully with TiO and other metal oxides to give boron-rich hybrid materials with intriguing photophysical and electrochemical properties.

Ethanol- and Methanol-Coordinated and Solvent-Free Dodecahydro closo-Dodecaborates of 3d Transition Metals and of Magnesium

“…Dodecahydro closo-dodecaborates of transition metals (TM) have attracted interest for various applications [1,2], and have been studied in the framework of boron chemistry. As most of the compounds have been crystallized from solution they are very often prepared in solvated state [3][4][5][6][7][8][9][10][11][12].…”

Easy conversion process of titanium surface covered with passive film into functional surface

“…However, in order to consolidate the functionality of titanium metal, further modification and functionalization of the surface of titanium have been performed continuously. 13,14 Here, we have addressed the issue by establishing an inexpensive and easily applicable process for creating tetrahedral-anatase-TiO 2 on the surface of titanium by performing a simple oxidation in air. Regarding the abovementioned functionalization of titanium, anatase-TiO 2 formation is very attractive for achieving excellent biocompatibility, photocatalytic activity, and so forth.…”

“…[8][9][10][11][12] It is because titanium thermodynamically forms only octahedral-rutile-TiO 2 on the surface by a simple oxidation in air according to the changes in the Gibb's free energy of oxidation in the entire temperature region, while chemical synthesis using precursors can easily produce tetrahedral-anatase-TiO 2 at 600°C or less ( Figure 1). 13,14 Here, we have addressed the issue by establishing an inexpensive and easily applicable process for creating tetrahedral-anatase-TiO 2 on the surface of titanium by performing a simple oxidation in air. Our simple process is based on the | 1709…”

Cross-linking dots on metal oxides

“…3b). 16 The product featured a unique structure composed of boron-rich clusters covalently cross-linked to TiO 2 nanocrystals (Fig. 4).…”

“…Furthermore, this new material exhibited dramatically altered light absorption properties and electrochemical behavior that was superior to pristine TiO 2 merely via the introduction of the molecular boron cross-linker. 16 The work by Jung et al posed an important question: can the introduction of a cross-linking agent do more than just enrich the existing properties of a metal oxide? In this particular case, it was speculated that the molecular cross-linking enabled a wide range of charge transfer excitations between boron clusters in different valence states and between the clusters and the boron/titanium oxides.…”