Hydrothermic reduction of rutile-ilmenite mineral producing an oxyhydride η-Ti<sub>2</sub>FeO<sub>0.2</sub>H<sub>2.8</sub>: Towards in-situ hydrogen production and storage

Abstract

As an alternative to the physical storage of hydrogen as compressed gas or liquid hydrogen requiring high-pressure tanks and cryogenic temperatures, the material-based storage of hydrogen in solids involves hydrogen uptake and release from the surface of adsorbents or within interstitials of hydrides. We report a hydrothermic reduction of rutile-ilmenite mineral into hydrogen-rich fibrous products, η-Ti2FeO0.2H2.8, in an ethanol-water system at 120°C for 4 hrs. As part of a project to generate hydrogen from water-ethanol system using advanced catalysts containing graphene oxide (GO) as carbon source, a system of 62.5 μg graphene oxide per g of rutile-ilmenite mineral was employed in a concentration of 50 mg/mL of ethanol-water solution. As well as in the original mineral, XRD of thermal annealed mineral between 500 and 800°C showed no hydride or phase change in rutile-ilmenite. With hydrothermal treatment of GO/rutile-ilmenite (50 mg/mL) in ethanol-water (1:1 v/v) at 120°C, a hydrogen-rich ferrotitanium hydride phase was formed, and there was a change in morphology from plate-like and granular particles into fibrous structures. Like the release of hydrogen by its ‘carriers’ (e.g., CaH2, NH4BH4, NaBH4, NH3, formic acid), it is anticipated that hydrogen was generated from the ethanol-water system in-situ, which reduced the rutile-ilmenite mineral into a hydride. EDX results showed that the reduction affected specifically the oxides of Fe and aluminosilicates in the mineral. The study demonstrated a possibility of in-situ hydrogen generation and storage via low-temperature graphene oxide hydrothermic reduction of rutile-ilmenite mineral in an ethanol-water system.