Rizzi Valerio, Polino Daniela, Sicilia Emilia, Russo Nino, Parrinello Michele
Department of Chemistry and Applied Biosciences, ETH Zurich, Switzerland.
Facoltà di Informatica, Istituto di Scienze Computazionali, Università della Svizzera Italiana, Via G. Buffi 13, 6900, Lugano, Switzerland.
Angew Chem Int Ed Engl. 2019 Mar 18;58(12):3976-3980. doi: 10.1002/anie.201900134. Epub 2019 Feb 18.
The discovery of effective hydrogen storage materials is fundamental for the progress of a clean energy economy. Ammonia borane (H BNH , AB) has attracted great interest as a promising candidate but the reaction path that leads from its solid phase to hydrogen release is not yet fully understood. To address the need for insights in the atomistic details of such a complex solid state process, in this work we use ab-initio molecular dynamics and metadynamics to study the early stages of AB dehydrogenation. We show that the formation of ammonia diborane (H NBH (μ-H)BH ) leads to the release of NH , which in turn triggers an autocatalytic H production cycle. Our calculations provide a model for how complex solid state reactions can be theoretically investigated and rely upon the presence of multiple ammonia borane molecules, as substantiated by standard quantum-mechanical simulations on a cluster.
发现有效的储氢材料是清洁能源经济发展的基础。氨硼烷（H₃BNH₃，AB）作为一种有前景的候选材料引起了极大的关注，但从其固相到氢释放的反应路径尚未完全了解。为了满足对这种复杂固态过程原子细节深入了解的需求，在这项工作中，我们使用从头算分子动力学和元动力学来研究AB脱氢的早期阶段。我们表明，二氨硼烷（H₂NBH₂(μ-H)BH₂）的形成导致NH₃的释放，这反过来又触发了一个自催化产氢循环。我们的计算提供了一个如何从理论上研究复杂固态反应的模型，并且依赖于多个氨硼烷分子的存在，这一点在对一个团簇的标准量子力学模拟中得到了证实。
