Confinement Effects for Lithium Borohydride: Comparing Silica and Carbon Scaffolds.

LiBH4 is a promising material for hydrogen storage and as a solid-state electrolyte for Li ion batteries. Confining LiBH4 in porous scaffolds improves its hydrogen desorption kinetics, reversibility, and Li+ conductivity, but little is known about the influence of the chemical nature of the scaffold. Here, quasielastic neutron scattering and calorimetric measurements were used to study support effects for LiBH4 confined in nanoporous silica and carbon scaffolds. Pore radii were varied from 8 Å to 20 nm, with increasing confinement effects observed with decreasing pore size. For similar pore sizes, the confinement effects were more pronounced for silica than for carbon scaffolds. The shift in the solid-solid phase transition temperature is much larger in silica than in carbon scaffolds with similar pore sizes. A LiBH4 layer near the pore walls shows profoundly different phase behavior than crystalline LiBH4. This layer thickness was 1.94 ± 0.13 nm for the silica and 1.41 ± 0.16 nm for the carbon scaffolds. Quasi-elastic neutron scattering confirmed that the fraction of LiBH4 with high hydrogen mobility is larger for the silica than for the carbon nanoscaffold. These results clearly show that in addition to the pore size the chemical nature of the scaffold also plays a significant role in determining the hydrogen mobility and interfacial layer thickness in nanoconfined metal hydrides.

Melt infiltration: an emerging technique for the preparation of novel functional nanostructured materials.

The rapidly expanding toolbox for design and preparation is a major driving force for the advances in nanomaterials science and technology. Melt infiltration originates from the field of ceramic nanomaterials and is based on the infiltration of porous matrices with the melt of an active phase or precursor. In recent years, it has become a technique for the preparation of advanced materials: nanocomposites, pore-confined nanoparticles, ordered mesoporous and nanostructured materials. Although certain restrictions apply, mostly related to the melting behavior of the infiltrate and its interaction with the matrix, this review illustrates that it is applicable to a wide range of materials, including metals, polymers, ceramics, and metal hydrides and oxides. Melt infiltration provides an alternative to classical gas-phase and solution-based preparation methods, facilitating in several cases extended control over the nanostructure of the materials. This review starts with a concise discussion on the physical and chemical principles for melt infiltration, and the practical aspects. In the second part of this contribution, specific examples are discussed of nanostructured functional materials with applications in energy storage and conversion, catalysis, and as optical and structural materials and emerging materials with interesting new physical and chemical properties. Melt infiltration is a useful preparation route for material scientists from different fields, and we hope this review may inspire the search and discovery of novel nanostructured materials.

Fundamentals of melt infiltration for the preparation of supported metal catalysts. The case of Co/SiO2 for Fischer-Tropsch synthesis.

We explored melt infiltration of mesoporous silica supports to prepare supported metal catalysts with high loadings and controllable particle sizes. Melting of Co(NO(3))(2)·6H(2)O in the presence of silica supports was studied in situ with differential scanning calorimetry. The melting point depression of the intraporous phase was used to quantify the degree of pore loading after infiltration. Maximum pore-fillings corresponded to 70-80% of filled pore volume, if the intraporous phase was considered to be crystalline Co(NO(3))(2)·6H(2)O. However, diffraction was absent in XRD both from the ordered mesopores at low scattering angles and from crystalline cobalt nitrate phases at high angles. Hence, an amorphous, lower density, intraporous Co(NO(3))(2)·6H(2)O phase was proposed to fill the pores completely. Equilibration at 60 °C in a closed vessel was essential for successful melt infiltration. In an open crucible, dehydration of the precursor prior to infiltration inhibited homogeneous filling of support particles. The dispersion and distribution of Co(3)O(4) after calcination could be controlled using the same toolbox as for preparation via solution impregnation: confinement and the calcination gas atmosphere. Using ordered mesoporous silica supports as well as an industrial silica gel support, catalysts with Co metal loadings in the range of 10-22 wt % were prepared. The Co(3)O(4) crystallite sizes ranged from 4 to 10 nm and scaled with the support pore diameters. By calcination in N(2), pluglike nanoparticles were obtained that formed aggregates over several pore widths, while calcination in 1% NO/N(2) led to the formation of smaller individual nanoparticles. After reduction, the Co/SiO(2) catalysts showed high activity for the Fischer-Tropsch synthesis, illustrating the applicability of melt infiltration for supported catalyst preparation.