We recently reported the synthesis of a new quaternary hydride in the lithium−boron−nitrogen−hydrogen quaternary phase diagram with the approximate composition LiB0.33N0.67H2.67 having a theoretical hydrogen content of 11.9 wt %. This new compound forms by the reaction of appropriate amounts of lithium amide (LiNH2) and lithium borohydride (LiBH4) and releases greater than 10 wt % hydrogen when heated. A small amount of ammonia, 2−3 mol % of the generated gas, is also released. We now report a study of hydrogen and ammonia release from the series of reactant mixtures (LiNH2)x(LiBH4)1-x, where x = 0.667 corresponds to the composition LiB0.33N0.67H2.67. We measured hydrogen and ammonia release amounts as a function of composition and found that maximum hydrogen and minimum ammonia release do occur for x = 0.667. We also present evidence for an additional new quaternary phase and for two possibly metastable phases in this system.

Hydrogen release from mixtures of lithium borohydride and lithium amide: a phase diagram study.

High- and low-temperature phases of lithium boron nitride, Li3BN2: Preparation, phase relation, crystal structure, and ionic conductivity

Unter den Nichtmetallnitriden sind vor allem die polymer aufgebauten binaren Verbindungen BN und Si3N4 fur die Entwicklung von Werkstoffen fur Hochleistungsanwendungen von Interesse. Herausragende Merkmale beider Substanzen sind ihre thermische, mechanische und chemische Bestandigkeit bei gleichzeitig geringer Dichte. Aufgrund ihrer besonderen Reaktionstragheit wurden Bor- und Siliciumnitrid in der praparativen Chemie kaum als Ausgangssubstanzen zur Darstellung ternarer oder hoherer Nitride eingesetzt, sondern in erster Linie als Tiegel-, Gefas- oder Isolationsmaterialien. Die Chemie ternarer und hoherer Nichtmetallnitride, die elektropositive Elemente enthalten und somit analog zu Oxoverbindungen wie Boraten, Silicaten, Phosphaten oder Sulfaten sind, wurde hingegen lange Zeit vernachlassigt. Ausgehend von dem kurzlich erstmals rein dargestellten P3N5, einem weiteren binaren Nichtmetallnitrid, welches sowohl strukturell als auch bezuglich seiner Eigenschaften Analogien zu Si3N4 aufweist, wird in diesem Ubersichtsartikel die Festkorperchemie von ternaren und hoheren Phosphor(v)-nitriden beschrieben, Struktur-Eigenschafts-Beziehungen diskutiert sowie Anwendungsmoglichkeiten vorgestellt. Aus der Sicht der praparativen Festkorperchemie werden ferner Synthesen, Strukturen und Eigenschaften der binaren Nichtmetallnitride BN, Si3N4 und P3N5 einander gegenubergestellt. Ahnlich wie die Kombination Phosphor-Stickstoff zur umfangreichen Chemie von Phosphor(v)-nitriden fuhrt, so lassen auch andere Nichtmetalle wie Bor, Silicium, Schwefel oder Kohlenstoff eine umfangreiche Nitridochemie erwarten, wofur es bereits erste Anhaltspunkte gibt.

Festkörperchemie mit Nichtmetallnitriden

The isoelectronic analogs of the title molecules are screened for possible unknown species using ab initio HF or MP2 6-31G ∗ calculations. Some candidates are the bent cations OCNCO + and OCPCO + , the linear anions OBCBO 2− and OBNBO − , and the bent NBNBN 3− and NBOBN 2− . The known NC-NNN is predicted to have a CN 4 ( D 2d ) di(diazirine) isomer, only 2.7 eV above the cyanogen azide at HF level. The analogous BN 4 − is also found to have a local minimum. The predicted neutral species include the linear OCNBO and ONNBN and the bent OCPCN, rather resembling the experimentally known NCPCN − anion.

Ab initio studies of bonding trends: Part 9. The dicyanamide-carbon suboxide-dicyanoether-cyanogen azide isoelectronic series ABCDE1

The implementation of a future economy based on hydrogen-related energy needs an urgent development of efficient, safe, and economic solid-state hydrogen-storage materials. During the search process for novel materials for storing hydrogen, research interests in the past few decades have been intensively focused on light metal borohydrides and amides as two representative chemical complex hydrides with high hydrogen capacities. Recently, a large number of studies have reported new borohydride/amide combined systems that expand the scope of hydrogen-storage materials. Here, we review the interaction between light metal borohydrides and amides for storing hydrogen, with a special emphasis on the synthetic strategies and structural, physical, and chemical properties, which reveal a correlation between the composition, structure, and dehydrogenation properties and also provide general principles to the design of new combined systems with tailored functionality. This review also demonstrates the current progress on the dehydrogenation kinetic improvement of borohydride/amide combined systems.

Light metal borohydrides/amides combined hydrogen storage systems: composition, structure and properties

By heating mixtures of lithium nitride, calcium nitride, and barium amide with boron nitride to 700 to 1000 deg C, ternary nitrides of these metals with boron were prepared. The compositions Li/sub 3/BN/sub 2/, Cs/sub 3/B/sub 2/ N/sub 4/ and Ba/sub 3/B/su b 2/N/sub 4/ could be controlled by varying the proportions in the mixtures. The compounds formed were identified by changes in color, by their good solubility in water or cold dilute hydrochloric acid, and by Debye-Scherrer photographs. Infrared spectra support the assumption of the ion (N = B = N)/sup 3-/, but in the calcium compound a polymeric ion is perhaps present besides the monomer. Similar experiments with potassium amide and the nitrides of magnesium, gallium, and lanthanum have shown no results. (auth)

Über ternäre Metall‐Bornitride

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Über ternäre Metall‐Bornitride