Reduction properties of Ce in CeO_x/Pt/Al₂O₃ catalysts

A controlled surface reaction (CSR) technique has been successfully employed to prepare a series of CeOx modified Pt/Al2O3 catalysts, offering a unique system to specifically probe the relationship between Ce and Pt without any bulk CeO2 present. Ce L3 edge X-ray absorption near edge structure (XANES) analysis was used to ascertain the oxidation state of the Ce in the catalyst materials in atmospheres of air, H2 (g), and CO (g) at room temperature. The XANES data showed that the Ce was present as both Ce3+ and Ce4+ oxidation states in an atmosphere of air, becoming predominantly present as Ce3+ in H2 and CO. The results indicate the role of Pt in the process, and show that with the absence of bulk CeO2, changes in Ce oxidation state can be observed at non-elevated temperatures. The CeOx/Pt/Al2O3 catalysts were tested for their performance toward the water gas shift (WGS) reaction and showed improved performance compared to the unmodified Pt/Al2O3, even at very low concentrations of Ce (∼0.35 wt-%)

The structure, thermal properties and phase transformations of the cubic polymorph of magnesium tetrahydroborate

The structure of the cubic polymorph of magnesium tetrahydroborate (γ-Mg(BH(4))(2)) has been determined in space group Ia3d from a structural database of the isoelectronic compound SiO(2); this has been corroborated by DFT calculations. The structure is found to concur with that recently determined by Filinchuk et al. (Y. Filinchuk, B. Richter, T. R. Jensen, V. Dmitriev, D. Chernyshov and H. Hagemann, Angew. Chem. Int. Ed., 2011, DOI: 10.1002/anie.201100675). The phase transformations and subsequent decomposition of γ-Mg(BH(4))(2) on heating have been ascertained from variable-temperature synchrotron X-ray diffraction data combined with thermogravimetric and mass spectrometry measurements. At ~160 °C, conversion to a disordered variant of the β-Mg(BH(4))(2) phase (denoted as β') is observed along with a further unidentified polymorph. There is evidence of amorphous phases during decomposition but there is no direct crystallographic indication of the existence of Mg(B(12)H(12)) or other intermediate Mg-B-H compounds. MgH(2) and finally Mg are observed in the X-ray diffraction data after decomposition

A multidisciplinary combinatorial approach for tuning promising hydrogen storage materials towards automotive applications

HyStorM is a multidisciplinary hydrogen-storage project aiming to synthesise and tune materials hydrogen storage properties for automotive applications. Firstly, unique high-throughput combinatorial thin-film technologies are used to screen materials' hydrogen storage properties. Then promising thin-film candidate compositions are synthesised and examined in the bulk. In this paper, we report on our results within the ternary compositions Mg-Ti-B and Ca-Ti-B. Primary screening of the Mg-Ti-B ternary identified a high capacity hotspot corresponding to Mg0.36Ti0.06B0.58, with 10.6 wt% H2 capacity. Partial reversibility has been observed for this material in the thin-film. Bulk Ti-doped Mg(BH4)2 composites show rehydrogenation to MgH2 under the conditions used. The synthesised thin-film Ca-Ti-B ternary showed only low hydrogen storage capacities. In the bulk, Ti-doping experiments on Ca(BH4)2 demonstrated reversible storage capacities up to 5.9 wt% H2. Further characterisation experiments are required to decipher the role of the Ti-dopant in these systems in both films and in the bulk