Facile solid-phase synthesis of the diammoniate of diborane and its thermal decomposition behavior

Abstract

The recent mechanistic finding of the hydrogen release pathways from ammonia borane (AB) has sparked new interest in the chemistry and properties of the diammoniate of diborane (DADB), an ionic isomer of AB. We herein report a facile one-step solid-phase synthesis route of DADB using inexpensive starting materials. Our study found that mechanically milling a 1 : 1 NaBH₄/NH₄F powder mixture causes the formation of crystalline DADBvia a NH₄BH₄ intermediate. The produced DADB can be readily separated from the sodium fluoride (NaF) by-product by a purification procedure using liquid ammonia at −78 °C. The thermal decomposition behavior of DADB was studied using synchronous thermal analyses, particularly in comparison with AB. It was found that the decomposition steps and products of DADB are similar to those of AB. But meanwhile, DADB exhibits a series of advantages over AB that merit its potential hydrogen storage application, such as lower dehydrogenation temperature, free of foaming and lack of an induction period in the thermal decomposition process. Our study further found that the volatile non-hydrogen products from DADB can be effectively suppressed by milling with MgH₂.