Ammonia borane thermolytic decomposition in the presence of metal (II) chlorides

• Published in: International journal of hydrogen energy 2012-04, Vol.37 (8), p.6749-6755
• Main Authors: Toche, F., Chiriac, R., Demirci, U.B., Miele, P.
• Format: Article
• Language: English
• Subjects: Alternative fuels. Production and utilization; Ammonia; Ammonia borane; Applied sciences; Chemical hydrogen storage; Chemical Sciences; Energy; Exact sciences and technology; Fuels; Hydrogen; Hydrogen release; Metal chlorides; Thermolysis
• ISSN: 0360-3199; 1879-3487
• DOI: 10.1016/j.ijhydene.2012.01.037

In the present work, we studied the effect of metal chlorides, MCl2, on the thermal decomposition of ammonia borane NH3BH3 (AB). Some metals from row n=4 of the periodic table were chosen and used as MCl2: namely, FeCl2, CoCl2, NiCl2, CuCl2, and ZnCl2. In addition, three metals from column VIII of the periodic table were considered: NiCl2, PdCl2 and PtCl2. The AB decomposition was followed by TGA and DSC; the decomposition gases analyzed by μGC/MSD coupling, and the solid by-products identified by XRD, IR and XPS. We observed that the presence of CuCl2 in AB is beneficial, making the decomposition occur in much milder conditions than for pristine AB; for example, the dehydrogenation of CuCl2-doped AB started at 25°C, with the sample losing about 14 wt% at 85°C. However, MCl2 does not hinder the evolution of the undesired borazine; it only contributes to a decrease in its content compared to pristine AB. To rationalize the better performance of CuCl2, we propose that Cu offers an optimal doping activity with intermediate binding energies for the intermediates: i.e. with H not too strongly bonded but optimally bonded to the N of AB. The germ Cu⋯NH2–BH2, then formed, acts as a Lewis acid through B and has an optimized reactivity towards a new AB molecule (head-to-tail dehydrocoupling). This is discussed herein. ► The effect of metal chlorides MCl2 on thermolysis of ammonia borane was studied. ► The presence of MCl2 reduces the induction period and the BZ release. ► CuCl2 is the most efficient doping agent, enabling a H2 release from 25°C. ► Cu0 offers the best electronic environment to destabilize AB (electronic effects). ► This is justified by intermediate binding energies for the different intermediates.