Abstract: Hexagonal boron nitride (hBN) has long been considered chemically inert due to its wide bandgap and robust covalent bonds. Its inertness hinders hBN from functionalization for energy conversion applications. A question arising is whether it is possible to make hBN chemically reactive. Here, we report cryomilling in liquid N2, as an effective strategy to activate the chemical reactivity of hBN by engineering different vacancies to produce defective-BN (d-BN). The local reactivity of the vacancies is probed by photoluminescence (PL) emissions and electron spin resonance spectroscopy (ESR). Density functional theory calculations reveal that the formation of different vacancies with/without oxygen cause the creation of mid-gap states that are responsible for the PL emissions in the visible region. These vacancies also generate localized free radicals which are both theoretically and experimentally confirmed by spin density calculations and ESR. Due to the vacancy induced free radicals and Fermi level shifts, d-BN can be controllably functionalized with single metal atoms by the spontaneous reduction of metal cations; mono-metallic or bi-metallic clusters can also be effectively reduced. As a proof of concept, the surface-bound metal nanostructures, especially substrate confined single metal atoms, exhibit improved hydrogen evolution catalytic performance, and can be further used for sensing, and quantum information.

Low temperature activation of inert hexagonal boron nitride for metal deposition and single atom catalysis
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DOI: 10.1016/j.mattod.2021.09.017