Hydrogen Adsorption on Gallium Nanoclusters

Henry, David J.

doi:10.1021/jp4074366

Cited by 10 publications

(6 citation statements)

References 33 publications

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“…Icosahedral endo-Ga 12 C has been found to be the most stable cluster that exhibits the most jellium-like orbital structure. Moreover, it has been observed that the hydrogen adsorption on these doped clusters is energetically favorable, but adsorption energies vary significantly with valence electron count and the adsorption site . The structures, stabilities, and electronic properties of lithium-doped gallium clusters, Ga n Li ( n = 1–13), have been investigated by means of the B3LYP/LANL2DZ level of theory as well as the dissociation energies, second-order energy differences, and HOMO–LUMO energy gaps .…”

Section: Main Group Metal Clustersmentioning

confidence: 99%

Quantum Mechanical Studies of Large Metal, Metal Oxide, and Metal Chalcogenide Nanoparticles and Clusters

et al. 2015

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Section: Main Group Metal Clustersmentioning

confidence: 99%

Quantum Mechanical Studies of Large Metal, Metal Oxide, and Metal Chalcogenide Nanoparticles and Clusters

et al. 2015

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“…The RDFT analysis also reveals similarities between the bonding in the Ga atoms of the equatorial region of the endo-Ga 12 X clusters and the ground state of the Ga 2 molecule. The calculated b ε bond indices and surface maps of electronic chemical potential provide understanding for the previously observed regioselectivity for hydrogen atom adsorption [20]. The significant deshielding around the surface atoms, caused by migration of charge towards the core, suggests that these clusters will interact strongly with nucleophiles and Lewis bases.…”

Section: Discussionmentioning

confidence: 80%

“…However, as shown previously [19] the Ga 2 subunits and axial bonds of these clusters are particularly sensitive to changes in the bonding environment within the cluster. In our recent study [20] we probed the reactivity of doped gallium nanoclusters and identified distinct regioselectivity for hydrogen adsorption.…”

Section: Introductionmentioning

confidence: 99%

Bonding in doped gallium nanoclusters: Insights from regional DFT

Henry

Ichikawa

Nozaki

et al. 2016

Computational Materials Science

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Abstract:The molecular nature (Ga 2 ) n of gallium makes this an interesting metal to investigate for the development of novel nano-materials. However, establishment of a targeted approach to manipulating the properties of gallium clusters requires a detailed understanding of how doping affects the bonding in these species. In this study, the bonding of gallium nanoclusters has been investigated using electron deformation densities and Regional Density Functional Theory (RDFT). Bonding throughout Ga 12 X clusters is generally intermediate between covalent and metallic. However, the presence of Ga 2 subunits is clearly identified in clusters with endohedral dopants (Ga 12 X, X = Al, Si, P, Ga, Ge, As).Although there is evidence of Ga 2 subunits in exohedral doped clusters, localized bonding to the dopant generally leads to significant disruption to the cluster framework. Maps of electronic chemical potential provide understanding for the observed differences in regioselectivity for hydrogen adsorption.

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“…Figures 2h,i shows how the resonances blueshift and damp in agreement with the experimental results (Figure 2e,f,h,i), as the electron density in the particle increases, because of the donor character of hydrogen (see Section S1, Supporting Information for details). This indicates that the electron density in the Ga NPs increases [ 36 ] consistently with the electron donor character of interstitial hydrogen, [ 37 ] as well as with the formation of metallic GaH 5 and/or GaH 3 phases. The liquid Ga accommodates reversible plastic distortion and the hydrogenation process maintains the metallic character of the NP.…”

Section: Resultsmentioning

confidence: 99%

Gallium Plasmonic Nanoantennas Unveiling Multiple Kinetics of Hydrogen Sensing, Storage, and Spillover

et al. 2021

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hydrogen sensing and storage new materials solutions are needed to reduce thermodynamic (process-temperatures limitations) and kinetic (process rate limitations) barriers and meet the challenges of sensing of a response time of less than 1 s, an operating temperature of −30 to 80 degrees Celsius, and a measurement of 0.1% to 10%, [1] as well as of hydrogen storage with low hydrogen refilling time and output power.The integration of plasmonics [2] with the recently introduced concept of novel catalytically-active liquid metal hydrides and hydrogen trapping mechanisms represents a breakthrough toward creating a new generation of plasmonic-enhanced photocatalytic nanosystems for enhancing both hydrogen sensing [3] and storage. [4] Surface-plasmon-resonance (SPR) induces electromagnetic field enhancement on common hydrogen-absorbing metals such as magnesium (Mg), palladium (Pd), titanium (Ti), and nickel (Ni) which may be exploitable in the microwave region for hydrogen storage. [5,6] Previous studies have reported SPR hydrogen sensing platforms based on Pd, [7,8] gold (Au), [9][10][11] aluminum (Al), [12] and Mg [13] nanoparticles (NPs). Considering the essential requirements for hydrogen storage, such as high storage capacity and fast hydrogen adsorption kinetics, requirements of hydrogen Hydrogen is the key element to accomplish a carbon-free based economy. Here, the first evidence of plasmonic gallium (Ga) nanoantennas is provided as nanoreactors supported on sapphire (α-Al 2 O 3 ) acting as direct plasmonenhanced photocatalyst for hydrogen sensing, storage, and spillover. The role of plasmon-catalyzed electron transfer between hydrogen and plasmonic Ga nanoparticle in the activation of those processes is highlighted, as opposed to conventional refractive index-change-based sensing. This study reveals that, while temperature selectively operates those various processes, longitudinal (LO-LSPR) and transverse (TO-LSPR) localized surface plasmon resonances of supported Ga nanoparticles open selectivity of localized reaction pathways at specific sites corresponding to the electromagnetic hot-spots. Specifically, the TO-LSPR couples light into the surface dissociative adsorption of hydrogen and formation of hydrides, whereas the LO-LSPR activates heterogeneous reactions at the interface with the support, that is, hydrogen spillover into α-Al 2 O 3 and reverse-oxygen spillover from α-Al 2 O 3. This Ga-based plasmon-catalytic platform expands the application of supported plasmoncatalysis to hydrogen technologies, including reversible fast hydrogen sensing in a timescale of a few seconds with a limit of detection as low as 5 ppm and in a broad temperature range from room-temperature up to 600 °C while remaining stable and reusable over an extended period of time.

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Hydrogen Adsorption on Gallium Nanoclusters

Cited by 10 publications

References 33 publications

Quantum Mechanical Studies of Large Metal, Metal Oxide, and Metal Chalcogenide Nanoparticles and Clusters

Quantum Mechanical Studies of Large Metal, Metal Oxide, and Metal Chalcogenide Nanoparticles and Clusters

Bonding in doped gallium nanoclusters: Insights from regional DFT

Gallium Plasmonic Nanoantennas Unveiling Multiple Kinetics of Hydrogen Sensing, Storage, and Spillover

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