Strong Oxidation Resistance of Atomically Thin Boron Nitride Nanosheets

Li, Lu Hua; Červenka, Jiří; Watanabe, Kenji; Taniguchi, Takashi; Chen, Ying

doi:10.1021/nn500059s

Cited by 657 publications

(540 citation statements)

References 31 publications

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“…Despite ultrathin thickness, the 2D material sheets are quite stable under harsh conditions, e.g., there is no oxidation of graphene at 400°C (50) and oxidation resistance of h-BN up to 850°C in O 2 (51). When exposed to gaseous or liquid environments, molecules or solutions can diffuse underneath the 2D covers via an intercalation process, confirming that 2D material/solid interfaces act as stable and practical nanoreactors (see references in ref.…”

Section: Discussionmentioning

confidence: 76%

Confined catalysis under two-dimensional materials

Xiao

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

223

189

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Confined microenvironments formed in heterogeneous catalysts have recently been recognized as equally important as catalytically active sites. Understanding the fundamentals of confined catalysis has become an important topic in heterogeneous catalysis. Well-defined 2D space between a catalyst surface and a 2D material overlayer provides an ideal microenvironment to explore the confined catalysis experimentally and theoretically. Using density functional theory calculations, we reveal that adsorption of atoms and molecules on a Pt(111) surface always has been weakened under monolayer graphene, which is attributed to the geometric constraint and confinement field in the 2D space between the graphene overlayer and the Pt(111) surface. A similar result has been found on Pt(110) and Pt(100) surfaces covered with graphene. The microenvironment created by coating a catalyst surface with 2D material overlayer can be used to modulate surface reactivity, which has been illustrated by optimizing oxygen reduction reaction activity on Pt(111) covered by various 2D materials. We demonstrate a concept of confined catalysis under 2D cover based on a weak van der Waals interaction between 2D material overlayers and underlying catalyst surfaces.confined catalysis | two-dimensional materials | density functional theory | oxygen reduction reaction | graphene I n heterogeneous catalysis, active sites have long been regarded as one of the most important concepts (1-3), and, recently, the heterogeneous catalysis community has started to recognize that microenvironment around the active site is equally important (4-9). The confined microenvironment on a heterogeneous catalyst can help to stabilize active sites and modulate chemistry at the sites, which has a significant effect on catalytic performance, similar to the role of spheroproteins in an enzyme (10). Hence, understanding fundamentals of confined catalysis has become an important topic in heterogeneous catalysis (11,12).Reactions in zero-dimensional (0D) nanocavities of microporous and mesoporous materials such as zeolites and metal−organic frameworks (MOFs) have shown enhanced catalytic performance (6,9,(13)(14)(15). Theoretical investigations reveal that the spatially confined environment increases the molecular orbital energy and changes activity of the confined molecules, which have been recognized as the nest effect and quantum confinement effect (15, 16). In past decades, some experimental studies have demonstrated that carbon nanotubes (CNTs) strongly affect catalytic reactions occurring inside the nanotubes (7,17,18), and confined catalysis in 1D nanocavities has been theoretically addressed by studying molecule adsorption on metal clusters encapsulated in CNTs (19). As illustrated in Fig. 1, both 0D nanocavities in zeolites and 1D nanocavities in CNTs are spatially confined in three dimensions and two dimensions, respectively, in which simple and well-defined model systems are not feasible for both theoretical and experimental studies. Moreover, structural and composit...

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Section: Discussionmentioning

confidence: 76%

Confined catalysis under two-dimensional materials

Xiao

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

223

189

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“…Although BN has a much lower Raman yield than graphite, high-quality BN monolayers can still produce a sharp G band. [18,32] So the Raman results imply that the BN nanosheet is not of high quality. To gain a better understanding on the spatial variation in the quality of the BN nanosheet, we turned to conductive atomic force microscope (AFM).…”

Section: Resultsmentioning

confidence: 99%

“…This is very different from highquality CVD-grown graphene, in which defects are mainly located at grain boundaries and edges. [3] It can be seen from the SEM image of the BN+Cu foil heated for 2 h (Figure 5b have occurred at these low-quality regions where the BN nanosheet could be torn up by the growth of the copper oxide particles and then oxidized, because BN nanosheets are found to be resistant to oxidation below 850 °C [18] and the heating of the transferred BN nanosheet on SiO 2 /Si causes no morphology change (see Supporting Information, Figure S6). In contrast, the part covered by the BN nanosheet of a relatively good quality effectively blocks oxygen diffusion so that the underlying Cu is only slightly oxidized after heating for 100 h. These results suggest that the protection provided by BN nanosheets can depend on crystal quality.…”

Section: Resultsmentioning

confidence: 99%

“…[11][12][13][14][15][16][17] In addition, BN nanosheets are more transparent to visible light due to their wide bandgap and have greater chemical and thermal stability. [18] Most importantly, BN nanosheets are electrically insulating [19] and do not enhance galvanic corrosion of the underlying metal. BN nanosheets of relatively large sizes can be produced by chemical vapor deposition (CVD).…”

Section: Introductionmentioning

confidence: 99%

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Boron Nitride Nanosheets for Metal Protection

Tan

Chen

et al. 2014

Adv Materials Inter

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154

121

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Although the high impermeability of graphene makes it an excellent barrier to inhibit metal oxidation and corrosion, graphene can form a galvanic cell with the underlying metal that promotes corrosion of the metal in the long term. Boron nitride (BN) nanosheets which have a similar impermeability could be a better choice as protective barrier, because they are more thermally and chemically stable than graphene and, more importantly, do not cause galvanic corrosion due to their electrical insulation. In this study, the performance of commercially

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“…[29] 'the oxidation resistance of h-BN nanosheets makes them more preferable for high-temperature applications than graphene'.…”

Section: Introductionmentioning

confidence: 99%

A study on Si and P doped h-BN sheets: DFT calculations

Kökten¹,

Erkoç²

2014

Turk J Phys

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Structural properties and energetics of silicon and phosphorus doped hexagonal boron nitride sheets were investigated by performing density functional theory calculations. The dopant atoms were substituted in a neutral charge state at either the B or the N site in the system as an impurity. All the systems under consideration were fully optimized.A systematic study was performed to see the effect of cell size on the calculated quantities, such as bond length, charge transfer, and defect formation energies. It was found that both silicon and phosphorus atom substitutions cause the bond lengths to increase with respect to the pristine sheets. Si atom replaced on the N site yields relatively large charge transfer from Si to the lattice. Substitutions of Si at the B site and of P at the N site are exothermic processes, while for the other cases the processes are endothermic.

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Strong Oxidation Resistance of Atomically Thin Boron Nitride Nanosheets

Cited by 657 publications

References 31 publications

Confined catalysis under two-dimensional materials

Confined catalysis under two-dimensional materials

Boron Nitride Nanosheets for Metal Protection

A study on Si and P doped h-BN sheets: DFT calculations

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