The Nature of Interface Interactions Leading to High Ionic Conductivity in LiBH4/SiO2Nanocomposites

Complex metal hydride/oxide nanocomposites are a promising class of solid-state electrolytes. They exhibit high ionic conductivities due to an interaction of the metal hydride with the surface of the oxide. The exact nature of this interaction and composition of the hydride/oxide interface is not yet known. Using 1H, 7Li, 11B, and 29Si NMR spectroscopy and lithium borohydride confined in nanoporous silica as a model system, we now elucidate the chemistry and dynamics occurring at the interface between the scaffold and the complex metal hydride. We observed that the structure of the oxide scaffold has a significant effect on the ionic conductivity. A previously unknown silicon site was observed in the nanocomposites and correlated to the LiBH4 at the interface with silica. We provide a model for the origin of this silicon site which reveals that siloxane bonds are broken and highly dynamic silicon-hydride-borohydride and silicon-oxide-lithium bonds are formed at the interface between LiBH4 and silica. Additionally, we discovered a strong correlation between the thickness of the silica pore walls and the fraction of the LiBH4 that displays fast dynamics. Our findings provide insights on the role of the local scaffold structure and the chemistry of the interaction at the interface between complex metal hydrides and oxide hosts. These findings are relevant for other complex hydride/metal oxide systems where interface effects leads to a high ionic conductivity

The invisible force that shapes our world:insights into complex, dynamic social influence processes, a marketing perpespective

Sociale invloed heeft een belangrijke impact op consumentengedrag en mag om die reden niet genegeerd worden in klantenonderzoek, concludeert Peter van Eck in zijn proefschrift. Van Eck toont aan hoe complex sociale beïnvloedingsprocessen zijn. Hij introduceert instrumenten die een bijdrage kunnen leveren aan het wetenschappelijke en commerciële onderzoek naar deze processen. Van Eck maakt in zijn onderzoek nadrukkelijk onderscheid tussen informatieve invloed en normatieve invloed. Vaak richt onderzoek naar sociale beïnvloeding zich op informatieve invloed (mond-tot-mondreclame) of wordt uitgegaan van een positieve normatieve invloed (sociale aansteking). Van Eck toont aan dat het negeren van één van de twee invloeden zal leiden tot een verkeerde inschatting van de effecten ervan. Zo blijkt normatieve invloed in alle simulaties een negatief effect te hebben. Informatieve invloed blijkt vooral een rol te spelen bij het vergroten van de bekendheid van het nieuwe product, terwijl normatieve invloed vooral het adoptiepercentage beïnvloedt. Verrassend genoeg kan normatieve invloed de bekendheid van een nieuw product negatief beïnvloeden.

The Nature of Interface Interactions Leading to High Ionic Conductivity in LiBH4/SiO2Nanocomposites

Complex metal hydride/oxide nanocomposites are a promising class of solid-state electrolytes. They exhibit high ionic conductivities due to an interaction of the metal hydride with the surface of the oxide. The exact nature of this interaction and composition of the hydride/oxide interface is not yet known. Using 1H, 7Li, 11B, and 29Si NMR spectroscopy and lithium borohydride confined in nanoporous silica as a model system, we now elucidate the chemistry and dynamics occurring at the interface between the scaffold and the complex metal hydride. We observed that the structure of the oxide scaffold has a significant effect on the ionic conductivity. A previously unknown silicon site was observed in the nanocomposites and correlated to the LiBH4 at the interface with silica. We provide a model for the origin of this silicon site which reveals that siloxane bonds are broken and highly dynamic silicon-hydride-borohydride and silicon-oxide-lithium bonds are formed at the interface between LiBH4 and silica. Additionally, we discovered a strong correlation between the thickness of the silica pore walls and the fraction of the LiBH4 that displays fast dynamics. Our findings provide insights on the role of the local scaffold structure and the chemistry of the interaction at the interface between complex metal hydrides and oxide hosts. These findings are relevant for other complex hydride/metal oxide systems where interface effects leads to a high ionic conductivity

Phase behavior and ion dynamics of nanoconfined LiBH4 in Silica

The increasing demand for high capacity yet safe storage of renewable energy calls for the development of all-solid-state batteries. A major hurdle in this development is the identification of new suitable types of solid-state electrolytes. Nanoconfined lithium borohydride is a solid-state electrolyte candidate due to its high lithium-ion mobility at ambient temperatures. The origin of the high lithium-ion mobility is not fully understood, however. We studied nanocomposites of lithium borohydride and nanoporous silica Santa Barbara Amorphous-15 (SBA-15) with different pore sizes, using 1H, 6,7Li, and 11B solid-state NMR at various temperatures, to get in-depth insights into the phase behavior and ion dynamics of lithium borohydride in the silica pores. The results allow us to formulate a detailed dynamic model for lithium borohydride confined in SBA-15; bulklike LiBH4 is separated from the pore walls by an amorphous, highly dynamic LiBH4 fraction displaying both Li+ and BH4 - diffusion even at ambient temperatures. As shown by 11B temperature-jump exchange NMR, this dynamic fraction increases as a function of temperature. Li+ exchange between the bulklike and "dynamic" LiBH4 fraction is slow at ambient temperatures, but at elevated temperatures (≥90 °C), above the phase transition of the bulklike fraction, lithium ions rapidly diffuse through both LiBH4 fractions and exchange between these confined fractions at rates approaching the megahertz time scale

Phase behavior and ion dynamics of nanoconfined LiBH4 in Silica

The increasing demand for high capacity yet safe storage of renewable energy calls for the development of all-solid-state batteries. A major hurdle in this development is the identification of new suitable types of solid-state electrolytes. Nanoconfined lithium borohydride is a solid-state electrolyte candidate due to its high lithium-ion mobility at ambient temperatures. The origin of the high lithium-ion mobility is not fully understood, however. We studied nanocomposites of lithium borohydride and nanoporous silica Santa Barbara Amorphous-15 (SBA-15) with different pore sizes, using 1H, 6,7Li, and 11B solid-state NMR at various temperatures, to get in-depth insights into the phase behavior and ion dynamics of lithium borohydride in the silica pores. The results allow us to formulate a detailed dynamic model for lithium borohydride confined in SBA-15; bulklike LiBH4 is separated from the pore walls by an amorphous, highly dynamic LiBH4 fraction displaying both Li+ and BH4 - diffusion even at ambient temperatures. As shown by 11B temperature-jump exchange NMR, this dynamic fraction increases as a function of temperature. Li+ exchange between the bulklike and "dynamic" LiBH4 fraction is slow at ambient temperatures, but at elevated temperatures (≥90 °C), above the phase transition of the bulklike fraction, lithium ions rapidly diffuse through both LiBH4 fractions and exchange between these confined fractions at rates approaching the megahertz time scale

The tomato genome sequence provides insights into fleshy fruit evolution

Tomato (Solanum lycopersicum) is a major crop plant and a model system for fruit development. Solanum is one of the largest angiosperm genera1 and includes annual and perennial plants from diverse habitats. Here we present a high-quality genome sequence of domesticated tomato, a draft sequence of its closest wild relative, Solanum pimpinellifolium2, and compare them to each other and to the potato genome (Solanum tuberosum). The two tomato genomes show only 0.6% nucleotide divergence and signs of recent admixture, but show more than 8% divergence from potato, with nine large and several smaller inversions. In contrast to Arabidopsis, but similar to soybean, tomato and potato small RNAs map predominantly to gene-rich chromosomal regions, including gene promoters. The Solanum lineage has experienced two consecutive genome triplications: one that is ancient and shared with rosids, and a more recent one. These triplications set the stage for the neofunctionalization of genes controlling fruit characteristics, such as colour and fleshiness