Molecular adsorption of H2 on small cationic nickel clusters

Swart, Ingmar; Gruene, Philipp; Fielicke, André; Meijer, Gerard; Weckhuysen, Bert M.; Groot, Frank M. F. de

doi:10.1039/b807313a

Cited by 25 publications

(35 citation statements)

References 23 publications

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“…The IR spectra of the few smaller sizes that do adsorb hydrogen, namely Al n V + with n= 2, 8, 9 (see Figure b), do not show any discernible IR bands, which could be due to insufficient oscillator strength of the vibrational resonances to desorb the hydrogen. Another explanation could be that the hydrogen for these sizes is mainly bound molecularly, in which case the characteristic vibrations are expected to lie outside our measurement range, that is, below 800 cm −1 (M−(H 2 ) stretch) and above 2100 cm −1 (H−H stretch).…”

Section: Figuresupporting

confidence: 91%

Hydrogen Chemisorption on Singly Vanadium‐Doped Aluminum Clusters

Vanbuel

Fernández

Ferrari

et al. 2017

Chemistry A European J

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The effect of vanadium doping on the hydrogen adsorption capacity of aluminum clusters (Al , n=2-18) is studied experimentally by mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy. We find that vanadium doping enhances the reactivity of the clusters towards hydrogen, albeit in a size-dependent way. IRMPD spectra, which provide a fingerprint of the hydrogen binding geometry, show that H dissociates upon adsorption. Density functional theory (DFT) calculations for the smaller Al V (n=2-8,10) clusters are in good agreement with the observed reactivity pattern and underline the importance of activation barriers in the chemisorption process. Orbital analysis shows that the activation barriers are due to an unfavorable overlap between cluster and hydrogen orbitals.

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Section: Figuresupporting

confidence: 91%

Hydrogen Chemisorption on Singly Vanadium‐Doped Aluminum Clusters

Vanbuel

Fernández

Ferrari

et al. 2017

Chemistry A European J

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“…The average desorption energies (Table 2) of the hydrides attribute that desorption may occur at higher condition (temperature, pressure) for the less adsorbed hydrogen and maximum captured hydrogen decompose at low temperature. Predicted hydrogen desoprtion energies (or decomposition energy) of MgH 2 and Mg 2 NiH 4 are 79.31 kJ/mol and 54.72 kJ/mol which is one of the important concerns for reversible hydrogenated materials and those are close to the calculated desorption energy value of 76 kJ/mol (for MgH 2 ) by Swart et al, [27]. Reaction electrophilicity values of hydrides are decreasing upon increasing number of hydrogen captured.…”

Section: Microstructure Analysis Using Dftsupporting

confidence: 77%

Hydrogenated Microstructure and Its Hydrogenation Properties: A Density Functional Theory Study

Salam

Abdullah

Sufian

2014

Journal of Nanomaterials

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The relationship between microstructure and hydrogenation properties of the mixed metals has been investigated via different spectroscopic techniques and the density functional theory (DFT). FESEM and TEM analyses demonstrated the nano-grains of Mg2NiH4and MgH2on the hydrogenated microstructure of the adsorbents that were confirmed by using XPS analysis technique. SAED pattern of hydrogenated metals attributed the polycrystalline nature of mixed metals and ensured the hydrogenation to Mg2NiH4and MgH2compounds. Flower-like rough surface of mixed metals showed high hydrogenation capacity. The density functional theory (DFT) predicted hydrogenation properties; enthalpy and entropy changes of hydrogenated microstructure of MgH2and Mg2NiH4are −62.90 kJ/mol, −158 J/mol·K and −52.78 kJ/mol, −166 J/mol·K, respectively. The investigation corresponds to the hydrogen adsorption feasibility, reversible range hydrogenation thermodynamics, and hydrogen desorption energy of 54.72 kJ/mol. DFT predicted IR band for MgH2and Mg2NiH4attributed hydrogen saturation on metal surfaces.

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“…These vibrational frequencies are similar to those observed for molecularly adsorbed hydrogen on transition metal (TM = V, Fe, Co, and Ni) clusters. 9,34 Bands in the range of 1700-1800 cm -1 correspond to the stretching vibrational modes of Rh-H bonds and those in the 1850- Figure 4 Comparisons of IRMPD spectra (top panels, the crosses are the original data points and the full lines correspond to six-point running averages) of Al2RhH4 + , Al7RhH4 + , and AlnRhH2 + (n = 3-10) with calculated harmonic IR spectra (bottom panels, without scaling) of the lowest energy structures obtained under PBE/Def2TZVP level. For AlnRhH2 + (n = 4, 6, and 7), the spectrum of a second isomer is included (blue lines).…”

Section: Comparisons Of the Irmpd Spectra With The Calculated Ir Spectramentioning

confidence: 99%

Size Dependent H₂ Adsorption on Al_nRh⁺ (n = 1–12) Clusters

et al. 2018

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The interaction of hydrogen with singly rhodium doped aluminum clusters AlnRh + (n = 1−12) is investigated experimentally by a combination of time-of-flight mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy. Density functional theory (DFT) is employed to optimize the geometric and electronic structures of bare and hydrogenated AlnRh + clusters and the obtained infrared spectra of hydrogenated clusters are compared with the corresponding IRMPD spectra. The reactivity of the AlnRh + clusters towards H2 is found to be strongly size-dependent, with n = 1−3, and 7 being the most reactive. Furthermore, it is favorable for H2 to adsorb molecularly on Al2Rh + and Al3Rh + , while it prefers dissociative adsorption on other sizes. The initial molecular adsorption of H2 is identified as the determining step for hydrogen interaction with the AlnRh + clusters, because the calculated molecular adsorption energies of H2 correlate well with the experimental abundances of the hydrogenated clusters. Natural charge populations and properties of the AlnRh + clusters are analyzed to interpret the observed size-dependent reactivity.

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Molecular adsorption of H2 on small cationic nickel clusters

Cited by 25 publications

References 23 publications

Hydrogen Chemisorption on Singly Vanadium‐Doped Aluminum Clusters

Hydrogen Chemisorption on Singly Vanadium‐Doped Aluminum Clusters

Hydrogenated Microstructure and Its Hydrogenation Properties: A Density Functional Theory Study

Size Dependent H₂ Adsorption on Al_nRh⁺ (n = 1–12) Clusters

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Molecular adsorption of H2 on small cationic nickel clusters

Cited by 25 publications

References 23 publications

Hydrogen Chemisorption on Singly Vanadium‐Doped Aluminum Clusters

Hydrogen Chemisorption on Singly Vanadium‐Doped Aluminum Clusters

Hydrogenated Microstructure and Its Hydrogenation Properties: A Density Functional Theory Study

Size Dependent H2 Adsorption on AlnRh+ (n = 1–12) Clusters

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Size Dependent H₂ Adsorption on Al_nRh⁺ (n = 1–12) Clusters