Palladium clusters, free and supported on surfaces, and their applications in hydrogen storage

Alonso, J. A.; López, M. J.

doi:10.1039/d1cp03524j

Cited by 14 publications

(17 citation statements)

References 158 publications

(314 reference statements)

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“…For comparison, Pd 6 anchored to a vacancy in graphene can adsorb nine molecules, three dissociated and six nondissociated. 12,15,29 Our proposed explanation is that Pd 6 fits better in the space of the triangular holes of GDY, as compared to the smaller graphene vacancies. The more efficient fitting results in a larger number of Pd−C bonds in GDY, so a part of the bonding capacity of the Pd atoms is exhausted, and consequently, the affinity of the Pd 6 cluster for hydrogen is lower.…”

Section: Hydrogen Adsorption In Pd-doped Gdymentioning

confidence: 89%

“…Free Pd 6 is an octahedron. 12 In order to simulate the results of a soft-landing experiment, 66 Pd 6 was placed on GDY at different locations and with different orientations of the cluster on the substrate, and all those configurations were optimized to find the structure with the lowest energy. This procedure is likely to deliver the structures achievable in soft-landing cluster deposition experiments at low or moderate temperatures.…”

Section: Pd 6 Deposited On Gdy and Bgdymentioning

confidence: 99%

“…The adsorption energy is substantially larger than the adsorption energy of Pd 6 on graphene and not far from the binding energy of Pd 6 to a graphene vacancy. 12 The dispersion contribution to the adsorption energy is 0.67 eV, which amounts to 15%.…”

Section: Pd 6 Deposited On Gdy and Bgdymentioning

confidence: 99%

“…Carbon materials in multiple forms, like porous carbons, activated carbon flakes, graphene, fullerenes, and carbon nanotubes, are outlined as candidates for storage . Doping these materials with metal atoms, clusters, and nanoparticles significantly improves their hydrogen storage capacity. − One proposal to explain this improvement has been to assume a mechanism of spillover, in which the hydrogen molecules first adsorb on the surface of the metallic nanoparticle and dissociate, and then, the hydrogen atoms migrate toward the carbon substrate . However, this mechanism has been analyzed in detail for the case of Pd nanoparticles supported on graphene by performing accurate atomistic dynamical simulations, and its validity has been questioned, because of the existence of large spillover barriers. , Sizable barriers have also been predicted from calculations for other supported transition metal clusters. − Palladium is, in fact, a promising metal for applications related to hydrogen storage because it can absorb large amounts of hydrogen in the form of palladium hydrides .…”

Section: Introductionmentioning

confidence: 99%

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Supported Metal Nanohydrides for Hydrogen Storage

et al. 2023

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Adsorption of hydrogen on graphdiyne (GDY) and boron-graphdiyne (BGDY) doped with palladium clusters has been investigated by performing density functional calculations. Pd6 fits well on the large holes of those porous layers, preserving its octahedral structure in GDY and changing it to a capped trigonal bipyramid structure in BGDY. Pd6GDY adsorbs up to five H2 molecules with sizable adsorption energies, two dissociated and three nondissociated. The dissociation barrier of H2 on the Pd6GDY cluster is 0.58 eV. Pd6BGDY can adsorb up to six molecules, three dissociated and three nondissociated, and the dissociation barrier of H2 on Pd6BGDY is 0.23 eV. In both cases, the dissociation barriers are substantially smaller than the corresponding dissociation barriers on undoped GDY and BGDY. The Pd clusters saturated with hydrogen can be viewed as nanohydrides. Spilling of the adsorbed hydrogen atoms toward the GDY and BGDY substrates is hindered by large activation barriers. We then propose using BGDY and GDY layers as support platforms for metal nanohydrides. The amount of stored hydrogen using Pd as the dopant is below the target of 6% of hydrogen in weight, but replacing Pd by a lighter metal with similar or higher affinity for hydrogen would substantially enhance the storage.

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Section: Hydrogen Adsorption In Pd-doped Gdymentioning

confidence: 89%

Section: Pd 6 Deposited On Gdy and Bgdymentioning

confidence: 99%

Section: Pd 6 Deposited On Gdy and Bgdymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Supported Metal Nanohydrides for Hydrogen Storage

et al. 2023

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“…This increasing binding energy with increasing particle size is commonly found in DFT calculations as well, wherein, for the binding energy (per Pd atom) of Pd to unsupported Pd clusters and Pd clusters on a carbon support nearly doubles from Pd 3 to Pd 13 . 49 When the Pd particles grow large enough, the heat of adsorption approaches the heat of sublimation (ΔH sub ) of 377 kJ/mol, which corresponds to making six Pd−Pd bonds in a simple pairwise bond-additivity model.…”

Section: Heat Of Adsorption Of Pd On Single-layer Graphene On Ni(111)mentioning

confidence: 99%

Size-Dependent Energy and Adhesion of Pd Nanoparticles on Graphene on Ni(111) by Pd Vapor Adsorption Calorimetry

et al. 2023

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Carbon-supported late transition-metal nanoparticles are promising catalysts and electrocatalysts for wide-ranging applications. However, experimental investigations of the bonding energetics of metal nanoparticles on carbon supports are very limited. Here, we report heats of adsorption of Pd vapor deposited onto single-layer graphene(0001) supported on Ni(111) at 100 and 300 K as Pd grows particles of well-defined size in the range from three atom clusters to 6 nm diameter. Sizes were determined from He + low-energy ion scattering (LEIS). In this size range, the differential heat of Pd adsorption increases from 228 kJ/mol to within 10 kJ/mol of the heat of sublimation of bulk Pd (377 kJ/mol). The chemical potential of metal atoms in these nanoparticles as a function of average particle size was determined from these results. The adhesion energy at the Pd/graphene(0001)/Ni(111) interface was extracted from these data and found to be 3.5 J/m 2 for the largest Pd particles. For the three metal elements that have now been studied (Pd, Ni, and Ag), we found an increase in metal/graphene(0001)/Ni(111) adhesion energy with metal carbophilicity, which we defined here as the heat of C atom adsorption on that metal's (111) surface estimated from published density functional theory calculations.

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Probing Basal and Prismatic Planes of Graphitic Materials for Metal Single Atom and Subnanometer Cluster Stabilization

Vidal,

Pandey,

Navarro‐Ruiz

et al. 2024

Chemistry A European J

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Supported metal single atom catalysis is a dynamic research area in catalysis science combining the advantages of homogeneous and heterogeneous catalysis. Understanding the interactions between metal single atoms and the support constitutes a challenge facing the development of such catalysts, since these interactions are essential in optimizing the catalytic performance. For conventional carbon supports, two types of surfaces can contribute to single atom stabilization: the basal planes and the prismatic surface; both of which can be decorated by defects and surface oxygen groups. To date, most studies on carbon‐supported single atom catalysts focused on nitrogen‐doped carbons, which, unlike classic carbon materials, have a fairly well‐defined chemical environment. Herein we report the synthesis, characterization and modeling of rhodium single atom catalysts supported on carbon materials presenting distinct concentrations of surface oxygen groups and basal/prismatic surface area. The influence of these parameters on the speciation of the Rh species, their coordination and ultimately on their catalytic performance in hydrogenation and hydroformylation reactions is analyzed. The results obtained show that catalysis itself is an interesting tool for the fine characterization of these materials, for which the detection of small quantities of metal clusters remains a challenge, even when combining several cutting‐edge analytical methods.

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Palladium clusters, free and supported on surfaces, and their applications in hydrogen storage

Abstract: Palladium is a late transition metal element in the 4d row of the periodic table. Palladium nanoparticles show an efficient catalytic activity and selectivity in a number of chemical reactions....

Cited by 14 publications

References 158 publications

Supported Metal Nanohydrides for Hydrogen Storage

Supported Metal Nanohydrides for Hydrogen Storage

Size-Dependent Energy and Adhesion of Pd Nanoparticles on Graphene on Ni(111) by Pd Vapor Adsorption Calorimetry

Probing Basal and Prismatic Planes of Graphitic Materials for Metal Single Atom and Subnanometer Cluster Stabilization

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