Understanding Hydrogenation Chemistry at MgB2 Reactive Edges from Ab Initio Molecular Dynamics
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Solid-state hydrogen storage materials often operate via transient, multistep chemical reactions at complex interfaces that are difficult to capture. Here, we use direct ab initio molecular dynamics simulations at accelerated temperatures and hydrogen pressures to probe the hydrogenation chemistry of the candidate material MgB2 without a priori assumption of reaction pathways. Focusing on highly reactive ($$10\overline{1}0$$) edge planes where initial hydrogen attack is likely to occur, we track mechanistic steps toward the formation of hydrogen-saturated BH4– units and key chemical intermediates, involving H2 dissociation, generation of functionalities and molecular complexes containing BH2 and BH3 motifs, and B–B bond breaking. Further, the genesis of higher-order boron clustering is also observed. Different charge states and chemical environments at the B-rich and Mg-rich edge planes are found to produce different chemical pathways and preferred speciation, with implications for overall hydrogenation kinetics. The reaction processes rely on B–H bond polarization and fluctuations between ionic and covalent character, which are critically enabled by the presence of Mg2+ cations in the nearby interphase region. Our results provide guidance for devising kinetic improvement strategies for MgB2-based hydrogen storage materials, while also providing a template for exploring chemical pathways in other solid-state energy storage reactions.
- Research Organization:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Sponsoring Organization:
- USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- Grant/Contract Number:
- AC52-07NA27344; NA0003525
- OSTI ID:
- 1880957
- Report Number(s):
- LLNL-JRNL-829744; 1045742; TRN: US2307791
- Journal Information:
- ACS Applied Materials and Interfaces, Vol. 14, Issue 18; ISSN 1944-8244
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
36 MATERIALS SCIENCE
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
25 ENERGY STORAGE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ab initio molecular dynamics
hydrogen storage
hydrogen
solid-state reaction
energy storage
density functional theory
interphase
interface