Oxygen Functionalization of Hexagonal Boron Nitride on Ni(111)

Späth, Florian; Soni, Himadri R.; Steinhauer, Johann; Düll, Fabian; Bauer, Udo; Bachmann, Philipp; Hieringer, Wolfgang; Görling, Andreas; Steinrück, Hans‐Peter; Papp, Christian

doi:10.1002/chem.201901504

Cited by 13 publications

(34 citation statements)

References 69 publications

(187 reference statements)

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“…Unlike B-BNO, the porous BNO sample exhibited a prominent shoulder peak in the B 1s spectrum at 193.1 eV after exposure to water, related to boron oxide ( Supplementary Figure 9). [44,[68][69][70] This result is in agreement with the reaction observed and described in the literature, where boron nitride reacts with water to form boron oxide and ammonia. [44,46] Further evidence of the decomposition is shown in Figure 4d, not only by the increase in the oxygen content, but also by the relative percentage of nitrogen decreasing, which is in line with the formation of ammonia.…”

Section: Resultssupporting

confidence: 92%

Boron-Doped Boron Nitride Photocatalyst for Visible Light-Driven H2 Evolution and CO2 Photoreduction

Shankar¹,

Lubert-Perquel²,

Mistry³

et al. 2020

Preprint

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<p>Developing robust, multifunctional photocatalysts that can facilitate both hydrogen evolution via photoreforming of water and gas phase CO2 photoreduction is highly desirable with the long-term vision of integrated photocatalytic setups. Here, we present a new addition to the boron nitride (BN) photocatalyst material platform, boron-doped boron oxynitride (B-BNO), capable of fulfilling this goal. Detailed EPR studies revealed hyperfine interactions between free charges located on discrete OB3 sites, exhibiting an out-of-plane symmetry, and the nuclei of neighbouring boron atoms. This material resolves two long-standing bottlenecks associated to BN-based materials concomitantly: instability in water and lack of photo activity under visible light. We show that B-BNO maintains prolonged stability in water for at least three straight days and can facilitate both liquid phase H2 evolution and gas phase CO2 photoreduction, using UV-Vis and deep visible irradiation (λ > 550 nm), without any cocatalysts. The evolution rates, apparent quantum yields, and selectivities observed for both reactions with B-BNO exceed those of its porous BNO counterpart, P25 TiO2 and bulk g-C3N4. This work provides scope to expand the BN photocatalyst platform to a wider range of reactions.</p>

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Section: Resultssupporting

confidence: 92%

Boron-Doped Boron Nitride Photocatalyst for Visible Light-Driven H2 Evolution and CO2 Photoreduction

Shankar¹,

Lubert-Perquel²,

Mistry³

et al. 2020

Preprint

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“…For a kinetic energy of about 0.7 eV, we applied an O 2 :He ratio of 0.7 : 45 (referring to the mass flow in sccm) and a nozzle temperature of ca. 450 K. [27,28] For 0.5 eV and 0.3 eV we used O 2 : He = 0.7 : 45 at T nozzle = 320 K and O 2 : He = 0.7 : 6 at T nozzle = RT, respectively. The exposure of oxygen and hydrogen is given in Langmuir (L, 1.33 × 10 À 6 mbar s).…”

Section: Methodsmentioning

confidence: 99%

“…Since h-BN is chemically quite inert, this observation is in line with our expectations and fits the results obtained by Späth et al for larger oxygen exposures on h-BN/Ni(111). [27] We, thus, used our supersonic molecular beam (SSMB) for dosing molecular oxygen. The SSMB allows for tuning of the kinetic energy of gas molecules via heating of the nozzle and/or seeding with helium.…”

Section: Oxygen Functionalizationmentioning

confidence: 99%

“…Späth et al described oxygen functionalization of h-BN/Ni(111) in detail. [27] Using theoretical calculations, they found that the adsorbed oxygen species binds molecularly to boron in a bridged configuration with a charge state between superoxide (O 2 À ) and peroxide (O 2 2À ). From the very comparable behavior observed here, we propose the same bonding mechanism for the oxygen molecules in the pores of the h-BN/Rh(111) nanomesh.…”

Section: Oxygen Functionalizationmentioning

confidence: 99%

“…In previous studies, functionalization of Ni(111) supported h-BN with molecular oxygen and atomic hydrogen has been demonstrated. [26][27][28] In the case of the h-BN nanomesh on Rh(111), we hypothesize that the pores, which undergo a stronger interaction with the substrate, resemble h-BN/Ni(111) while the rather weakly bound wires are comparable to h-BN/ Pt(111). Considering this modulation in interaction strength, the pores and wires are likely to exhibit a different reactivity towards chemical modification.…”

Section: Introductionmentioning

confidence: 99%

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Selective Oxygen and Hydrogen Functionalization of the h‐BN/Rh(111) Nanomesh

Freiberger

Späth

Bauer

et al. 2021

Chemistry A European J

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We present detailed studies on the covalent adsorption of molecular oxygen and atomic hydrogen on the hexagonal boron nitride (h-BN) nanomesh on Rh(111). The functionalization of this two-dimensional (2D) material was investigated under ultra-high vacuum conditions using synchrotron radiation-based in situ high-resolution X-ray photoelectron spectroscopy, temperature-programmed X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. We are able to provide a deep insight into the adsorption behavior and thermal stability of oxygen and hydrogen on h-BN/Rh(111). Oxygen functionalization was achieved via a supersonic molecular beam while hydrogen functionalization was realized using an atomic hydrogen source. Adsorption of the respective species was observed to occur selectively in the pores of h-BN leading to spatially defined modification of the 2D layer. The adsorption of the observed molecular oxygen species was found to be an activated process that requires high-energy oxygen molecules. Upon heating to 700 K, oxygen functionalization was observed to be almost reversible except for small amounts of boron oxides evolving due to the reaction of oxygen with the 2D material. Hydrogen functionalization of h-BN/Rh(111) was fully reversed upon heating to about 640 K.

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Oxygen‐Induced Dissociation of a Single Water Molecule in Confined 2‐D Layers: A Semiempirical Study

Majumder

Tiwari

2022

ChemPhysChem

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Semiempirical quantum mechanical methods provide a middle ground to molecule-surface interactions between computationally demanding full ab initio quantum chemistry calculations and force-field calculations. In the present study, the PM7 semiempirical method is used to evaluate the adsorption energy values of X@h-BN monolayer [X = O, OH, and H 2 O], followed by a mechanistic study of oxygen-induced water dissociation on a free-standing h-BN monolayer. Based on oxygen adsorption configurations, two reaction pathways for water dissociation are studied that yield two distinct configurations of double OH-functionalized h-BN monolayer. The effect of a graphene cover layer on these proposed mechanistic pathways is then investigated by placing the graphene cover layer on the top of the h-BN monolayer and continuously tuning the separation (d Gr/h-BN ) between these two layers.

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Oxygen Functionalization of Hexagonal Boron Nitride on Ni(111)

Cited by 13 publications

References 69 publications

Boron-Doped Boron Nitride Photocatalyst for Visible Light-Driven H2 Evolution and CO2 Photoreduction

Boron-Doped Boron Nitride Photocatalyst for Visible Light-Driven H2 Evolution and CO2 Photoreduction

Selective Oxygen and Hydrogen Functionalization of the h‐BN/Rh(111) Nanomesh

Oxygen‐Induced Dissociation of a Single Water Molecule in Confined 2‐D Layers: A Semiempirical Study

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