Effect of the interfacial electric field on the HER on Pt(111)modified with iron adatoms in alkaline media

The study of the hydrogen evolution reaction(HER)aimed to reach a deeper understanding of the parameters that control the rate of this reaction is of great importance given the technical relevance of hydrogen production as an energy vector in the so-called hydrogen economy.In previous works,laser-induced temperature jump(LITJ)experiments on Pt(111)modified with Ni(OH)_(2)in alkaline media have revealed the importance of the interfacial electric field in the rate of the HER.It was hypothesised that small amounts of Ni(OH)_(2)cause a decrease of the electric field because of a negative shift of the pzfc toward the onset of the hydrogen evolution.In this work,to test the validity of this hypothesis,the study has been extended to Pt(111)surfaces modified with Fe(OH)_(2).The modified surfaces have been studied voltammetrically,and the voltammetric charges have been analysed.The voltammograms show a peak in the hydrogen evolution region that suggest the transformation in the adlayer from Fe(II)to Fe(0).In agreement with the coulometric analysis,the voltammetric features in the OH adsorption region would be related with the oxidation to the+3 valence state.The results obtained with LITJ method reflect the existence of a strong interaction of the Fe oxophilic species with the water molecules,shifting the potential of maximum entropy away from the onset of the HER.Hence,the most catalytic surface is the one with the lowest Fe coverage.

Adsorptions of metal adatoms on graphene-like BC3 and their rich electronic properties： A first-principles study

Density functional calculations have been performed to investigate the adsorption of twenty two different kinds of metal adatoms on graphene-like BC3. In contrast to the graphene adsorbed with adatoms, the BC3 with adatoms shows many interesting properties.（1） The interaction between the metal adatoms and the BC3 sheet is remarkably strong. The Li, Na, K, and Ca possess the binding energies larger than the cohesive energies of their corresponding bulk metals.（2）The Li, Na, and K adatoms form approximately ideal ionic bonds with BC3, while the Be, Mg, and Ca adatoms form ionic bonds with BC3 with slight hybridization of covalent bonds. The Al, Ga, In, Sn, and all transition metal adatoms form covalent bonds with BC3.（3） For all the structures studied, there exhibit metal, half-metal, semiconducting, and spin-semiconducting behaviors. Especially, the BC3 with Co adatom shows a quantum anomalous Hall（QAH） phase with a Chern number of -1 based on local density approximation calculations.（4） For Li, Na, K, Ca, Ga, In, Sn, Ti, V, Cr,Ni, Pd, and Pt, there exists a trend that the adatom species with lower ionization potential have lower work function. Our results indicate the potential applications of functionalization of BC3 with metal adatoms.

Molecular dynamics simulation of nanoscale surface diffusion of heterogeneous adatoms clusters

Molecular dynamics simulation employing the embedded atom method potential is utilized to investigate nanoscale surface diffusion mechanisms of binary heterogeneous adatoms clusters at 300 K, 500 K, and 700 K. Surface diffusion of heterogeneous adatoms clusters can be vital for the binary island growth on the surface and can be useful for the formation of alloy-based thin film surface through atomic exchange process. The results of the diffusion process show that at 300 K, the diffusion of small adatoms clusters shows hopping, sliding, and shear motion; whereas for large adatoms clusters（hexamer and above）, the diffusion is negligible. At 500 K, small adatoms clusters, i.e., dimer, show almost all possible diffusion mechanisms including the atomic exchange process; however no such exchange is observed for adatoms clusters greater than dimer. At 700 K, the exchange mechanism dominates for all types of clusters, where Zr adatoms show maximum tendency and Ag adatoms show minimum or no tendency toward the exchange process. Separation and recombination of one or more adatoms are also observed at 500 K and 700 K. The Ag adatoms also occupy pop-up positions over the adatoms clusters for short intervals. At 700 K, the vacancies are also generated in the vicinity of the adatoms cluster,vacancy formation, filling, and shifting can be observed from the results.

Pits and adatoms at the interface of 1-ML C_(84)/Ag(111)

We prepare a well-defined C84 monolayer on the surface of Ag （111） and study the geometric structure by scanning tunneling microscopy （STM）. The C84 molecules form a nearly close-packed incommensurate R30° lattice. The lattice is long-distance ordered with numerous local disorders. The monolayer exhibits complex bright/dim contrast; the largest height difference between the molecules can be greater than 0.4 nm. Annealing the monolayer at 380 ℃ can desorb part of the molecules, but more than sixty percent molecules stay on the Ag （111） surface even after the sample has been annealed at 650 ℃. Our analyses reveal that the 7-atom pits form beneath many molecules. Some other molecules sit at the 1-atom pits. Ag adatoms （those removed substrate atoms, accompanying the pit formation） play a very important role in this system. The adatoms can either stabilize or destabilize the monolayer, depending on the distribution manner of the adatoms at the interface. The distribution manner is determined by the co-play of the following factors： the dimension of the interstitial regions of the C84 overlayer, the number of the adatoms, and the long-distance migration of part adatoms.

Oxygen adatoms and vacancies on the (110) surface of CeO2

The behavior of oxygen on ceria surfaces is closely related with the applications of ceria as a catalyst and oxygen conductor in solid-oxide fuel cells. Here, the atomic configurations of oxygen adatoms and vacancies on the(110) surface of CeO_2 have been studied combining aberration-corrected transmission electron microscopy and first-principles calculations. The oxygen adatoms were estimated to be located on top of Ce atoms with 50% coverage, forming a c(2×2) reconstruction. The oxygen vacancies can form stable configuration, with the Ce atoms partly reduced.

Tailoring the Self-assembly of Melamine on Au（111） via Doping with Cu Atoms

The doping effect of Cu on the self-assembly film of melamine on an Au（111） surface has been investigated with scanning tunneling microscopy （STM）. The evaporated Cu adatoms occupy the positions underneath the amino groups and change the hydrogen bonding pat- tern between the melamine molecules. Accordingly, the self-assembly structure has changed stepwise from a well-defined honeycomb into a track-like and then a triangular structure depending on the amount of Cu adatoms. The interaction between Cu adatom and melamine is moderate thus the Cu adatoms can be released upon mild heating to around 100 ℃. These findings are different from previous observations of either the coordination assembly or the physically trapped metal adatoms.

Simple statistical model for predicting thermal atom diffusion on crystal surfaces

A simple model based on the statistics of single atoms is developed to predict the diffusion rate of thermal atoms in （or on） bulk materials without empirical parameters. Compared with vast classical molecular-dynamics simulations for predicting the self-diffusion rate of Pt, Cu, and Ar adatoms on crystal surfaces, the model is proved to be much more accurate than the Arrhenius law and the transition state theory. Applying this model, the theoretical predictions agree well with the experimental values in the presented paper about the self-diffusion of Pt （Cu） adatoms on the surfaces.

Transport properties of zigzag graphene nanoribbons adsorbed with single iron atom

We have performed density-functional calculations of the transport properties of the zigzag graphene nanoribbon （ZGNR） adsorbed with a single iron atom. Two adsorption configurations are considered, i.e., iron adsorbed on the edge and on the interior of the nanoribbon. The results show that the transport features of the two configurations are similar. However, the transport properties are modified due to the scattering effects induced by coupling of the ZGNR band states to the localized 3d-orbital state of the iron atom. More importantly, one can find that several dips appear in the transmission curve, which is closely related to the above mentioned coupling. We expect that our results will have potential applications in graphene-based spintronic devices,

Influence of Pb adatom on adsorption of oxygen molecules on Pb(111) surface:a first-principles study

Using first-principles calculations, we systematically study the influence of Pb adatom on the adsorption and the dissociation of oxygen molecules on Pb（111） surface, to explore the effect of a point defect on the oxidation of the Pb（111） surface. We find that when an oxygen molecule is adsorbed near an adatom on the Pb surface, the molecule will be dissociated without any obvious barriers, and the dissociated 0 atoms bond with both the adatom and the surface Pb atoms. The adsorption energy in this situation is much larger than that on a clean Pb surface. Besides, for an adsorbed oxygen molecule on a clean Pb surface, a diffusing Pb adatom can also change its adsorption state and enlarge the adsorption energy for O, but it does not make the oxygen molecule dissociated. And in this situation, there is a molecule-like PbO2 cluster formed on the Pb surface.

Growth and characterization of straight InAs/GaAs nanowire heterostructures on Si substrate

Vertical InAs/GaAs nanowire （NW） heterostructures with a straight InAs segment have been successfully fabricated on Si （111） substrate by using AlGaAs/GaAs buffer layers coupled with a composition grading InGaAs segment. Both the GaAs and InAs segments are not limited by the misfit strain induced critical diameter. The low growth rate of InAs NWs is attributed to the AlGaAs/GaAs buffer layers which dramatically decrease the adatom diffusion contribution to the InAs NW growth. The crystal structure of InAs NW can be tuned from zincblende to wurtzite by controlling its diameter as well as the length of GaAs NWs. This work helps to open up a road for the integration of high-quality III-V NW heterostructures with Si.

Density behaviors of Ge nanodots self-assembled by ion beam sputtering deposition

Self-assembled Ge nanodots with areal number density up to 2.33× 1010 cm-2 and aspect ratio larger than 0.12 are prepared by ion beam sputtering deposition. The dot density, a function of deposition rate and Ge coverage, is observed to be limited mainly by the transformation from two-dimensional precursors to three-dimensional islands, and to be associated with the adatom behaviors of attachment and detachment from the islands. An unusual increasing temperature dependence of nanodot density is also revealed when a high ion energy is employed in sputtering deposition, and is shown to be related to the breaking down of the superstrained wetting layer. This result is attributed to the interaction between energetic atoms and the growth surface, which mediates the island nucleation.

Topological Transition in Monolayer Blue Phosphorene with Transition-Metal Adatom under Strain

We carried out first-principles calculations to investigate the electronic properties of the monolayer blue phosphorene(BlueP)decorated by the group-IVB transition-metal adatoms(Cr,Mo and W),and found that the Cr-decorated BlueP is a magnetic half metal,while the Mo-and W-decorated BlueP are semiconductors with band gaps smaller than 0.2 eV.Compressive biaxial strains make the band gaps close and reopen,and band inversions occur during this process,which induces topological transitions in the Mo-decorated BlueP(with strain of-5.75%)and W-decorated BlueP(with strain of-4.25%)from normal insulators to topological insulators(TIs).The TI gap is 94 meV for the Mo-decorated BlueP and218 me V for the W-decorated BlueP.Such large TI gaps demonstrate the possibility to engineer topological phases in the monolayer BlueP with transition-metal adatoms at high temperature.

How interfacial electron-donating defects influence the structure and charge of gold nanoparticles on TiO_(2)support

The reduction degree of TiO_(2)support is critical to the performances of metal catalysts.In many previous theoretical calculations,only the bridge oxygen vacancy(Ov)was considered as the electron-donating defect on reduced rutile TiO_(2)(r-TiO_(2−x))supports.However,titanium adatoms(Tiad.),oxidized titanium islands(Tiad.On),and acid hydroxyls(ObrH)also exist at the metal/support interface.By conducting density functional theory(DFT)calculations and ab initio molecular dynamics(AIMD)simulations,we compared r-TiO_(2−x)surfaces with Ov,Tiad.,Tiad.On,and ObrH sites loaded with Au nanoparticles(NPs).The results showed the Au NPs were oxygen-phobic but titanium-philic,resulting in wetting of Ov and Tiad.but short contact with Tiad.On and ObrH.The Bader charges of Au NPs(QM)showed a good linear relationship with the ideal number of donating electrons(Ne)from the defective sites(QM=−KeNe+QM,S),demonstrating the intrinsic electron allocation at the interface.The Ov,Tiad.,and Tiad.On exhibited similar slopes(Ke),relatively steeper than that of ObrH.That means in the scope of Au NP charge state,the Tiad.and Tiad.On have a close electron-donating ability with Ov,but the ObrH donates relatively fewer electrons.This linear relationship can be extended approximately to other metals.The higher the metal work function,the steeper the Ke for easier electron donation from defective sites.The stronger the metal oxygen affinity,the more positive the intercept(QM,S).That explains the easy generation of metallic or negative Pt and Au NPs on r-TiO_(2−x),but hard for Cu and Zn in experiment.That provides theoretical guidance for regulating the charge of metal NPs over TiO_(2−x)supports.

Stacking-faults-free zinc blende GaAs/AlGaAs axial heterostructure nanowires during vapor-liquid-solid growth

Pure zinc blende structure GaAs/AlGaAs axial heterostructure nanowires （NWs） are grown by metal organic chemical vapor deposition on GaAs（111） B substrates using Au-catalyzed vapor-liquid-solid mechanism. Al adatom enhances the influence of diameters on NWs growth rate. NWs are grown mainly through the contributions from the direct impingement of the precursors onto the alloy droplets and not so much from adatom diffusion. The results indicate that the droplet acts as a catalyst rather than an adatom collector.

Self-formation of hexagonal nanotemplates for growth of pyramidal quantum dots by metalorganic vapor phase epitaxy on patterned substrates

We demonstrate the self-formation of hexagonal nanotemplates on GaAs （111）B substrates patterned with arrays of inverted tetrahedral pyramids during metal-organic vapor phase epitaxy and its role in producing high-symmetry, site-controlled quantum dots （QDs）. By combining atomic force microscopy measurements on progressively thicker GaAs epitaxial layers with kinetic Monte Carlo growth simulations, we demonstrate self-maintained symmetry elevation of the QD formation sites from three-fold to six-fold symmetry. This symmetry elevation stems from adatom fluxes directed towards the high-curvature sites of the template, resulting in the formation of a fully three-dimensional hexagonal template after the deposition of relatively thin GaAs layers. We identified the growth conditions for consistently achieving a hexagonal pyramid bottom, which are useful for producing high-symmetry QDs for efficient generation of entangled photons.

Anomalously enhanced thermal stability of phosphorene via metal adatom doping: An experimental and first-principles study

Atomically thin black phosphorus, also known as phosphorene, is an emerging two-dimensional (2D) material, which has attracted increasing attention due to its unique electronic and optoelectronic properties. However, the reduced thermal stability of phosphorene limits its suitability for high-temperature fabrication processes, which could be detrimental for the performance of phosphorenebased devices. Here, we investigate the impact of doping by Al and Hf transition metal adatoms on the thermal stability of phosphorene. The formation of Al–P covalent bonds was found to significantly improve the thermal coefficients of the Ag1, B2g, and Ag2phonon modes to 0.00044, 0.00081, and 0.00012 cm–1·°C–1, respectively, which are two orders of magnitude lower than those observed for pristine P–P bonds (~0.01 cm–1·°C–1). First-principles calculations within the density functional theory framework reveal that the observed thermal stability enhancement in the Al-doped material reflects a significantly higher Al binding energy, due to the stronger Al–P bonds compared to the weak van der Waals interactions between adjacent P atoms in the undoped material. The present work thus paves the way towards phosphorene materials with improved structural stability, which could be promising candidates for potential nanoelectronic and optoelectronic applications. [Figure not available: see fulltext.] © 2016, Tsinghua University Press and Springer-Verlag Berlin Heidelberg.