Molecular orbital calculations of hydrogen storage in carbon and boron nitride clusters

Koi, Naruhiro; Oku, Takeo

doi:10.1016/j.stam.2004.02.024

Cited by 22 publications

(15 citation statements)

References 12 publications

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“…[15][16][17][18][19][20][21][22] One of the most basic arguments in these theoretical works is whether BN nanomaterials have site selectivity on adsorption of atomic hydrogen. Some reports mentioned that atomic hydrogen is adsorbed on B or N sites selectively.…”

Section: Introductionmentioning

confidence: 99%

“…Some reports mentioned that atomic hydrogen is adsorbed on B or N sites selectively. [15][16][17][18][19] Mårlid et al 15 reported an adsorption energy difference of atomic hydrogen between B and N sites of hexagonal BN (h-BN). They applied DFT calculations to model structures of h-BN and found that adsorption at N sites is even more unstable than adsorption at B sites.…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, Margulis et al 18 performed calculations based on the semi-empirical Austin Model 1 (AM1) method and reported that atomic hydrogen prefers to be adsorbed on N sites. Koi et al 19 considered chemisorptions of hydrogen on BN clusters, showing that hydrogen adsorption on N atoms is more stable than that on B atoms.…”

Section: Introductionmentioning

confidence: 99%

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Selective adsorption of atomic hydrogen on a h-BN thin film

Koswattage

Shimoyama

Baba

et al. 2011

The Journal of Chemical Physics

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The adsorption of atomic hydrogen on hexagonal boron nitride (h-BN) is studied using two element-specific spectroscopies, i.e., near-edge x-ray absorption fine structure (NEXAFS) spectroscopy and x-ray photoelectron spectroscopy (XPS). B K-edge NEXAFS spectra show a clear change in the energy region of the π* band before and after reaction with atomic deuterium. On the other hand, N K-edge NEXAFS spectra show only a little change. B 1s XPS spectra show a distinct component at the low binding energy side of a main component, while N 1s XPS spectra show peak broadening at the high binding energy side. These experimental results are analyzed by the discrete variational Xα method with a core-hole effect and are explained by a model in which hydrogen atoms are preferentially adsorbed on the B sites of h-BN. Based on the experimental and theoretical results, we propose a site-selective property of BN material on adsorption of atomic hydrogen.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Selective adsorption of atomic hydrogen on a h-BN thin film

Koswattage

Shimoyama

Baba

et al. 2011

The Journal of Chemical Physics

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“…Spinpolarized NBO analysis of alkali encapsulated B 24 N 24 through DFT method also reported [21]. Many other investigations have been performed on B 24 N 24 nanocage to probe its chemical and physical properties [22][23][24][25]. Chemical concepts, reactivity indices and rules [26,27], stemming from density functional theory (DFT), such as frontier orbitals (HOMO/LUMO), electronegativity (chemical potential), global and local hardness and softness, Fukui function, electrophilicity index, hard and soft acid and base (HSAB), maximum hardness principle (MHP), etc., have attracted considerable interests in the literature in the last few decades.…”

Section: Introductionmentioning

confidence: 87%

DFT based insights into reactivity descriptors of encapsulated B24N24 nanocages

2011

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The purpose of this study is to probe the DFT based chemical reactivity parameter, electrophilicity index as a possible molecular engineering of endohedral BN-nanocages. The structure and electronic properties of endohedral boron nitride nanocages have been investigated as a function of alkali atom inside the nanocage using density functional theory. We have calculated and analyzed basic characteristic related to the reactive behavior, such as HOMO-LUMO band gap, chemical hardness, chemical potential, vertical electron affinity, and vertical ionization potential, as well as the global electrophilicity index, x(I, A) of the encapsulated B 24 N 24 nanocages. We also investigated the MQZVP basis set effect on total electronic energy of the clusters.

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“…For the chemisorption site of atomic hydrogen on h-BN, however, a couple of theoretical results are presented, which are apparently contradictory to each other. While some researchers claim that hydrogen atoms are site-selectively chemisorbed on electron-deficient boron atoms, [17][18][19] others claim N site-selectivity, 20 no site-selectivity, 21,22 or H cluster formation after B-H bond formation. 23 For experimental results, it is claimed that high energy plasma treatment or accelerated ion irradiation results in both B-H and N-H formation, 24,25 while the selective formation of the B-H bond was claimed by Koswattage et al upon atomic hydrogen exposure.…”

Section: Introductionmentioning

confidence: 99%

Direct observation of site-selective hydrogenation and spin-polarization in hydrogenated hexagonal boron nitride on Ni(111)

et al. 2017

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We report the structural analysis and spin-dependent band structure of hydrogenated boron nitride adsorbed on Ni(111). The atomic displacement studied by using the normal incidence X-ray standing wave (NIXSW) technique supports the H-B(fcc):N(top) model, in which hydrogen atoms are site-selectively chemisorbed on boron atoms and N atoms remain on top of Ni atoms. The distance between the Ni plane and nitrogen plane did not change after hydrogenation, which implies that the interaction between Ni and N is 3d-π orbital mixing (donation and back-donation) even after hydrogenation of boron. The remaining π* peaks in near-edge X-ray absorption fine structure (NEXAFS) spectra are a manifestation of the rehybridization of sp into sp states, which is consistent with the N-B-N bonding angle derived from NIXSW measurement. The SPMDS measurement revealed the spin asymmetry appearing on hydrogenated h-BN, which was originated from a π related orbital with back donation from the Ni 3d state. Even though the atomic displacement is reproduced by the density functional theory (DFT) calculation with the H-B(fcc):N(top) model, the experimental spin-dependent band structure was not reproduced by DFT possibly due to the self-interaction error (SIE). These results reinforce the site-selective hydrogenation of boron and pave the way for efficient design of BN nanomaterials for hydrogen storage.

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Molecular orbital calculations of hydrogen storage in carbon and boron nitride clusters

Cited by 22 publications

References 12 publications

Selective adsorption of atomic hydrogen on a h-BN thin film

Selective adsorption of atomic hydrogen on a h-BN thin film

DFT based insights into reactivity descriptors of encapsulated B24N24 nanocages

Direct observation of site-selective hydrogenation and spin-polarization in hydrogenated hexagonal boron nitride on Ni(111)

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