Reaction-Induced Strong Metal–Support Interactions between Metals and Inert Boron Nitride Nanosheets

Abstract

Encapsulation of metal nanocatalysts by supportderived materials is well known as a classical strong metal−support interaction (SMSI) effect that occurs almost exclusively with active oxide supports and often blocks metal-catalyzed surface reactions. In the present work this classical SMSI process has been surprisingly observed between metal nanoparticles, e.g., Ni, Fe, Co, and Ru, and inert hexagonal boron nitride (h-BN) nanosheets. We find that weak oxidizing gases such as CO 2 and H 2 O induce the encapsulation of nickel (Ni) nanoparticles by ultrathin boron oxide (BO x ) overlayers derived from the h-BN support (Ni@BO x / h-BN) during the dry reforming of methane (DRM) reaction. Insitu surface characterization and theory calculations reveal that surface B−O and B−OH sites in the formed BO x encapsulation overlayers work synergistically with surface Ni sites to promote the DRM process rather than blocking the surface reactions.

Strong Metal–Support Interaction for 2D Materials: Application in Noble Metal/TiB2 Heterointerfaces and their Enhanced Catalytic Performance for Formic Acid Dehydrogenation

“…This overlayer serves as a continuous physical barrier hindering the sintering of metal nanoparticles. Besides the well‐known occurrences at metal/reducible oxide interfaces, recent studies have also reported SMSI on nonoxidic supports, such as hydroxyapatite, [ 8 ] boron nitride, [ 9 ] layered double hydroxides, [ 10 ] and carbides. [ 11 ] These new discoveries motivate the exploration of SMSI beyond the classical metal/oxide catalyst structure.…”

Boron Nanosheet-Supported Rh Catalysts for Hydrogen Evolution: A New Territory for the Strong Metal-Support Interaction Effect

“…It should be emphasized that the component at 188.5 eV may arise from the formation of a B–Rh bond due to the SMSI effect. Encapsulation of Rh NP anchored on BNS by a thin layer of support-derived boron oxide, which is a well-known characteristic of the classical SMSI effect observed in oxide-SMCs [ 10 , 37 ]. The Rh 3 d spectrum in Fig.…”

“…For SMCs, most supports not only play the single role of physical carriers, but also interact with the active metal. Among all the interactions, the so-called SMSI effect has been mainly applied in oxide-supported metal catalysts and opens a new era in the field of heterogeneous catalysis [ 10 , 11 ]. Nevertheless, due to the low coordination, metal atoms have extremely high surface free energy and tend to agglomerate during synthesis or under working conditions, being unable to achieve the theoretical atom utilization efficiency [ 12 , 13 ].…”

Coking-resistant dry reforming of methane over Ni/γ-Al2O3 catalysts by rationally steering metal-support interaction

“…For example, the acidic properties of g-Al 2 O 3 would contribute to the decomposition of CH 4 , giving rise to good DRM activity (Osaki et al, 1995;Shehu et al, 2019). However, Al 2 O 3 -supported Ni catalysts still severely suffered from carbon accumulation due to the CH 4 decomposition and CO disproportionation (Dong et al, 2020;Joo et al, 2020). To enhance its ability of anti-coking, researchers tried to control the size of Ni particles via using specific precursors (Dama et al, 2018;Song et al, 2018) or increase the basicity of the support by incorporating alkali or alkaline earth metals into the support (Mette et al, 2016;Wang et al, 2013).…”