The Chemistry of Bulk Hydrogen: Reaction of Hydrogen Embedded in Nickel with Adsorbed CH
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Johnson, Andrew; Daley, S. P.; Utz, A. L.; Ceyer, S. T.

doi:10.1126/science.257.5067.223

Cited by 188 publications

(145 citation statements)

References 12 publications

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“…Recently, there has been increased awareness of the role of subsurface solutes in bulk-like model catalysts (Pd, Cu, etc.) by recognizing, for example, that carbon in the bulk and the subsurface, usually considered ''frozen,'' actually changes the structure of the surface and even participates in heterogeneous catalysis [55][56][57][58]. Our findings suggest that similar effects may be even more pronounced in nanoparticles, capable of forming mixed metal-carbon structures that have no bulk equivalent and give rise to extremely high solute solubilities.…”

mentioning

confidence: 55%

Giant carbon solubility in Au nanoparticles

Sutter

2011

J Mater Sci

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Variable temperature transmission electron microscopy of individual 5 nm Au nanoparticles shows a striking increase in the particle size on raising the temperature from room temperature to 500°C in the presence of carbon from amorphous carbon support. Using the assembly of ordered graphene shells on the surface of individual nanoparticles at elevated temperatures-and the high pressures induced by such shells-as an experimental tool to study the origins of this swelling, we find that the volume increase is associated with the uptake of carbon to concentrations exceeding the bulk solubility by more than four orders of magnitude. The formation of stable metalcarbon nanostructures that have no bulk equivalent may have important implications on the functional properties of metal nanoparticles.The interaction of carbon with transition metals is key to processes for synthesizing the known sp 2 bonded carbon allotropes-fullerenes, nanotubes, and graphene-all of which are materials showing extraordinary properties and enormous potential for applications.Graphene, a planar two-dimensional honeycomb lattice of sp 2 bonded carbon atoms [1] Typically, transition metals catalytically dissociate hydrocarbons at their surfaces to set free carbon adatoms, which can be absorbed into the bulk at high temperature and segregate to the surface on subsequent cooling to form sp 2 -bonded structures. Planar graphene is synthesized by this process on bulk crystals or thin films of transition metals, such as Ru [16][17][18], Pt [19], Ir [20], and Ni [21], which can take up carbon into interstitial sites with solubilities up to a few atomic percent. Carbon nanostructures, such as fullerenes [22][23][24][25] are synthesized over transition metal (Fe, Ni, Co) nanoparticles, using the same steps of hydrocarbon dissociation, carbon intake into interstitial sites, and precipitation. It is generally assumed that the uptake of carbon in metal nanoparticles involves interstitial sites, similar to the bulk, but the stable concentrations (i.e., the carbon solubility) may be different at the nanoscale. The high surface-to-volume ratio of nanoparticles has been predicted to cause a significant increase of the solubility [26][27][28][29][30][31][32][33]. However, lattice relaxation in very small particles Electronic supplementary material The online version of this article

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mentioning

confidence: 55%

Giant carbon solubility in Au nanoparticles

Sutter

2011

J Mater Sci

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“…11,12 Subsurface and bulk H could act as spectators modifying the electronic structure of the metal surface and thus its catalytic activity, 31 or act as a direct reactant in the hydrogenation reaction. 7 Compared to surface H, subsurface H in the octahedral site (O h ) of Ni(111) -directly underneath a surface fcc site-is metastable, with a binding energy of -2.19 eV. This metastable subsurface H can be prepared at low temperatures by exposure of the surface to atomic hydrogen followed by collision-induced recombinative desorption to remove the surface bound H under UHV conditions.…”

Section: Methodsmentioning

confidence: 99%

“…Independently, Ni has been found to be a good catalyst for hydrogenation of hydrocarbons, whereby the presence of bulk and/or subsurface hydrogen played a special role in the observed reactivity. [7][8][9][10] In particular, it has been suggested that bulk and/or subsurface H exhibits unique reactivity in the heterogeneously catalyzed hydrogenation of hydrocarbons, such as methyl, ethylene and acetylene, on Ni(111). [7][8][9][10][11][12][13][14] For example, in seminal work by Ceyer et al, 7 it was unambiguously demonstrated that subsurface H is the reactant for hydrogenation of methyl radical to methane on Ni(111), whereas surface H is unreactive.…”

Section: Introductionmentioning

confidence: 99%

CO₂ Hydrogenation to Formic Acid on Ni(111)

et al. 2012

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Periodic, self-consistent, density functional theory (DFT) calculations are employed to study CO 2 hydrogenation on Ni(111). CO 2 hydrogenation with H adsorbed on the surface and with H absorbed in the subsurface is investigated systematically and the respective microscopic reaction mechanisms are elucidated. We show that on Ni(111), CO 2 hydrogenation to formate intermediate is more favorable than to carboxyl intermediate. The hydrogenation to formate goes through the unidentate structure that rapidly transforms into the bidentate structure. Further hydrogenation from formate to formic acid is energetically more difficult than formate formation. Formation of adsorbed formic acid from adsorbed CO 2 and surface hydrogen is an endothermic reaction. Because subsurface H in Ni(111) is substantially less stable compared to surface H, its reaction with adsorbed CO 2 to adsorbed formic acid is an exothermic one. Our results may have significant implications for the synthesis of liquid fuels from CO 2 and for catalytic hydrogenation reactions in general.2

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“…For a Ni(111) surface it was previously shown by Johnson et al that recombinative desorption of adsorbed methyl groups occurs exclusively with hydrogen atoms present in the bulk of the Ni crystal. 24 Bulk D-atoms were prepared by exposing the Ni(111) surface to a flux of D-atoms and subsequent bombardment of the surface with Xe-atoms. This causes recombinative desorption of surface bound D-atoms but leaves the subsurface D-atoms in place.…”

Section: Bond Selectivity In Gas-surface Reactionsmentioning

confidence: 99%

Quantum state resolved gas–surface reaction dynamics experiments: a tutorial review

Chadwick

Beck

2016

Chem. Soc. Rev.

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We present a tutorial review of our quantum state resolved experiments designed to study gas-surface reaction dynamics. The combination of a molecular beam, state specific reactant preparation by infrared laser pumping, and ultrahigh vacuum surface analysis techniques make it possible to study chemical reactivity at the gas-surface interface in unprecedented detail. We describe the experimental techniques used for state specific reactant preparation and for detection of surface bound reaction products developed in our laboratory. Using the example of the reaction of methane on Ni and Pt surfaces, we show how state resolved experiments uncovered clear evidence for vibrational mode specificity and bond selectivity, as well as steric effects in chemisorption reactions. The state resolved experimental data provides valuable benchmarks for comparison with theoretical models for gas-surface reactivity aiding in the development of a detailed microscopic understanding of chemical reactivity at the gas-surface interface. Key learning points(1) How to prepare beams of quantum state selected molecules through rapid adiabatic passage. (2) Physisorption vs. chemisorption. (3) What is state and mode specificity? (4) What is vibrational bond selectivity? (5) Orientation vs. alignment and alignment dependent reactivity.

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The Chemistry of Bulk Hydrogen: Reaction of Hydrogen Embedded in Nickel with Adsorbed CH ₃

Cited by 188 publications

References 12 publications

Giant carbon solubility in Au nanoparticles

Giant carbon solubility in Au nanoparticles

CO₂ Hydrogenation to Formic Acid on Ni(111)

Quantum state resolved gas–surface reaction dynamics experiments: a tutorial review

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The Chemistry of Bulk Hydrogen: Reaction of Hydrogen Embedded in Nickel with Adsorbed CH 3

Cited by 188 publications

References 12 publications

Giant carbon solubility in Au nanoparticles

Giant carbon solubility in Au nanoparticles

CO2 Hydrogenation to Formic Acid on Ni(111)

Quantum state resolved gas–surface reaction dynamics experiments: a tutorial review

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Product

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The Chemistry of Bulk Hydrogen: Reaction of Hydrogen Embedded in Nickel with Adsorbed CH ₃

CO₂ Hydrogenation to Formic Acid on Ni(111)