Quantifying interactions on interfaces between metal partic¬les and oxide supports in catalytic nanomaterials

Metal-support interactions can dramatically affect the properties of nanocomposite materials. Nevertheless, comprehensive studies of the interfaces between metal nanoparticles and oxide supports remain scarce due to challenges in experimental characterization. A significant understanding of the interactions at such interfaces can be obtained by combining state-of-the-art experiments with density functional calculations. In particular, this Perspective illustrates how theory and experiment can be combined to study interfacial charge transfer, the short- or long-range natures of nanoparticle-support interactions and the effects of oxide nanostructuring on the properties of supported metal particles. These studies aid our understanding of the role of metal-oxide interactions in industrially employed nanocomposites and the design of interfaces with unique properties for future applications

Effects of electron transfer in model catalyst composed of Pt nanoparticles on CeO2(111) surface

Interactions between transition metal nanoparticles and reducible oxide supports are thought to significantly affect the performance of many catalysts. Usually, several metal-support effects act together and cannot be separated from each other. Herein, by means of density-functional calculations we succeeded to single out and quantify effects of the metal-support electron transfer on the structure and electronic properties of important model Pt-ceria catalysts. Namely, we considered ∼1.5 nm large Pt95 and Pt122 particles supported on CeO2(1 1 1). We show that Pt-ceria interactions notably reconstruct Pt nanofacets forming the interface and shift valence d-states of the Pt particles. These effects are rather insensitive to the Pt-ceria electron transfer, at variance with the electronic structure of oxygen anions at the interface, which is significantly affected by the electron transfer. The findings of this work and the special modeling approach applied pave the way for deeper analysis of electronic metal-support interactions in catalysis

Accurate relativistic many-body calculations of van der Waals coefficients C_8 and C_10 for alkali-metal dimers

We consider long-range interactions between two alkali-metal atoms in their respective ground states. We extend the previous relativistic many-body calculations of C_6 dispersion coefficients [Phys.Rev. Lett. {\bf 82}, 3589 (1999)] to higher-multipole coefficients C_8 and C_10. A special attention is paid to usually omitted contribution of core-excited states. We calculate this contribution within relativistic random-phase approximation and demonstrate that for heavy atoms core excitations contribute as much as 10% to the dispersion coefficients. We tabulate results for both homonuclear and heteronuclear dimers and estimate theoretical uncertainties. The estimated uncertainties for C_8 coefficients range from 0.5% for Li_2 to 4% for Cs_2.Comment: 12 pages, submitted to Journal of Chemical Physic

Hyperfine quenching of the metastable 3P0,2^3P_{0,2} states in divalent atoms

Hyperfine quenching rates of the lowest-energy metastable $^3P_0$ and $^3P_2$ states of Mg, Ca, Sr, and Yb atoms are computed. The calculations are carried out using ab initio relativistic many-body methods. The computed lifetimes may be useful for designing novel ultra-precise optical clocks and trapping experiments with the $3P_2$ fermionic isotopes. The resulting natural widths of the $^3P_0 -> ^1S_0$ clock transition are 0.44 mHz for $^{25}$Mg, 2.2 mHz for $^{43}$Ca, 7.6 mHz for $^{87}$Sr, 43.5 mHz for $^{171}$Yb, and 38.5 mHz for $^{173}$Yb. Compared to the bosonic isotopes, the lifetime of the $3P_2$ states in fermionic isotopes is noticeably shortened by the hyperfine quenching but still remains long enough for trapping experiments.Comment: 10 pages, 1 figure, submitted to Phys. Rev.

Energetic stability of absorbed H in Pd and Pt nanoparticles in a more realistic environment

Absorbed hydrogen can dramatically increase hydrogenation activity of Pd nanoparticles and was predicted to do so also for Pt. This calls for investigations of the energetic stability of absorbed H in Pd and Pt using nanoparticle models as realistic as possible, i.e., (i) sufficiently large, (ii) supported, and (iii) precovered by hydrogen. Herein, hydrogen absorption is studied in MgO(100)-supported 1.6 nm large Pd and Pt nanoparticles with surfaces saturated by hydrogen. The effect of surface H on the stability of absorbed H is found to be significant and to exceed the effect of the support. H absorption is calculated to be endothermic in Pt, energy neutral in Pd(111) and bare Pd nanoparticles, and exothermic in H-covered Pd nanoparticles. Hence, we identify the abundance of surface H and the nanostructuring of Pd as prerequisites for facile absorption of hydrogen in Pd and for the concomitantly altered catalytic activity

Reduced ceria nanofilms from structure prediction

Experimentally, Ce2O3 films are used to study cerium oxide in its fully or partially reduced state, as present in many applications. We have explored the space of low energy Ce2O3 nanofilms using structure prediction and density functional calculations, yielding more than 30 distinct nanofilm structures. First, our results help to rationalize the roles of thermodynamics and kinetics in the preparation of reduced ceria nanofilms with different bulk crystalline structures (e.g. A-type or bixbyite) depending on the support used. Second, we predict a novel, as yet experimentally unresolved, nanofilm which has a structure that does not correspond to any previously reported bulk A2B3 phase and which has an energetic stability between that of A-type and bixbyite. To assist identification and fabrication of this new Ce2O3 nanofilm we calculate some observable properties and propose supports for its epitaxial growth

Surface composition changes of CuNi-ZrO2 during methane decomposition: An operando NAP-XPS and density functional study

AbstractBimetallic CuNi nanoparticles of various nominal compositions (1:3, 1:1, 3:1) supported on ZrO2 were employed for operando spectroscopy and theoretical studies of stable surface compositions under reaction conditions of catalytic methane decomposition up to 500°C. The addition of Cu was intended to increase the coke resistance of the catalyst. After synthesis and (in situ) reduction the CuNi nanoparticles were characterized by HR-TEM/EDX, XRD, FTIR (using CO as probe molecule) and NAP-XPS, all indicating a Cu rich surface, even when the overall nanoparticle composition was rich in Ni. Density functional (DF) theory modelling, applying a recently developed computational protocol based on the construction of topological energy expressions, confirmed that in any studied composition Cu segregation on surface positions is an energetically favourable process, with Cu preferentially occupying corner and edge sites. Ni is present on terraces only when not enough Cu atoms are available to occupy all surface sites.When the catalysts were applied for methane decomposition they were inactive at low temperature but became active above 425°C. Synchrotron-based operando NAP-XPS indicated segregation of Ni on the nanoparticle surface when reactivity set in for CuNi-ZrO2. Under these conditions C 1s core level spectra revealed the presence of various carbonaceous species at the surface. DF calculations indicated that both the increase in temperature and especially the adsorption of CHx groups (x=0-3) induce the segregation of Ni atoms on the surface, with CH3 providing the lowest and C the highest driving force.Combined operando and theoretical studies clearly indicate that, independent of the initial surface composition after synthesis and reduction, the CuNi-ZrO2 catalyst adopts a specific Ni rich surface under reaction conditions. Based on these findings we provide an explanation why Cu rich bimetallic systems show improved coke resistance

Versatile optimization of chemical ordering in bimetallic nanoparticles

Chemical ordering in bimetallic nanocrystallites can now be efficiently determined by density-functional calculations with the help of topological energy expressions. Herein, we deal with extending the usage of that computational scheme. We show that it enables one to structurally characterize bimetallic nanoparticles of less regular shapes than previously studied magic-type particles. In fcc Pd-Au particles of different shapes (cuboctahedral Pd58Au58, C3v Pd61Au61, cubic Pd68Au67, and truncated octahedral Pd70Au70), we identify the surface segregation of gold as the driving force to the lowest-energy chemical ordering. We applied the calculated descriptor values quantifying the segregation propensity of Au and energies of Pd-Au bonds in these ∼1.5 nm large particles to optimize and analyze the chemical ordering in 3.7-6 nm large Pd-Au particles. We also discuss how to predict the chemical ordering in nanoalloys at elevated temperatures. The present study paves the way to advanced structural investigations of nanoalloys to substantially accelerate their knowledge-driven engineering and manufacturing

Possibility of an ultra-precise optical clock using the 61S0→63P0o6 ^1S_0 \to 6 ^3P^o_0 transition in 171,173^{171, 173}Yb atoms held in an optical lattice

We report calculations designed to assess the ultimate precision of an atomic clock based on the 578 nm $6 ^1S_0 --> 6 ^3P^o_0$ transition in Yb atoms confined in an optical lattice trap. We find that this transition has a natural linewidth less than 10 mHz in the odd Yb isotopes, caused by hyperfine coupling. The shift in this transition due to the trapping light acting through the lowest order AC polarizability is found to become zero at the magic trap wavelength of about 752 nm. The effects of Rayleigh scattering, higher-order polarizabilities, vector polarizability, and hyperfine induced electronic magnetic moments can all be held below a mHz (about a part in 10^{18}), except in the case of the hyperpolarizability larger shifts due to nearly resonant terms cannot be ruled out without an accurate measurement of the magic wavelength.Comment: 4 pages, 1 figur

Novel Biomarkers for Coronary Restenosis Occurrence After Drug-Eluting Stent Implantation in Patients With Diabetes Having Stable Coronary Artery Disease

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