Mo Surface Research Articles

Engaging the Concepts of Bimetallicity and Mechanical Strain for N2 Activation: A Computational Exploration.

N2 activation is a vital step in the process toward NH3 production. NH3 synthesis has been considered a crucial process for the production of value-added chemicals and/or hydrogen carriers over recent years. In this work, density functional theory (ab initio) calculations are implemented for a thorough screening of bimetallic alloy surfaces using Fe, Ru, and Mo as the matrix (host) metals and Ag, Au, Co, Cu, Fe, Mo, Ni, Pd, Pt, Rh, and Rh as heterometals toward exploring the N2 catalytic activation (electronic and chemical characteristics); the monometallic surfaces are used for critical comparison in terms of their N2 activation behavior. In particular, adsorption geometries/energetics, density of states (DOS), and charge transfer are discussed. From the N2 activation on the surfaces, we could precisely capture the transition state of the N2 dissociation reaction/step. The effect of the metal alloying (geometrical and electronic factors) as well as the effect of applied mechanical strain, as a tuning factor of alloying, are both studied and thoroughly discussed. DOS studies revealed that the d-band center moved toward the negative direction for all late-TM-based alloys, thereby allowing the nitrogen molecule to adsorb weakly as compared to the early-TM surface alloys. In terms of the mechanical strain, for most of the alloy surfaces studied, apart from the Mo/Fe(110) one, the N2 binding energy varies as a linear function of the applied strain. The mechanical effect trend is in agreement with the charge transfer descending order followed: Fe/Mo(110) > Rh/Mo(110) > Au/Mo(110) > Pt/Mo(110) > Ni/Mo(110) > Ru/Mo(110) > Cu/Mo(110) > Ag/Mo(110) > Pd/Mo(110) > Au/Mo(110), pointing out that Fe-functionalized Mo(110) surface presents the highest charge transfer of -2.14 |e| to the N2 molecule. This study aspires to provide navigation criteria through the abundant design criteria of N2 activation catalysts.

A new attempt to further reduce the work function of the cesiated surface: The strongest electronegative element fluorine co-adsorption with cesium on Mo (001) surface

The efficiency of hydrogen negative ion production in negative ion sources depends on the work function of the molybdenum surface. Deposition of cesium (Cs) atoms on the Mo surface reduces the work function from over 4.0 eV to about 1.50–1.80 eV. However, the Fermi level remains below the affinity level (−0.75 eV) of hydrogen negative ions. To explore further reduction methods, the work function of Cs co-adsorbed with fluorine on the Mo (001) surface was studied using DFT calculations. The results show that at 4/16 θ Cs coverage, adding fluorine can reduce the work function, achieving the lowest value of 1.40 eV at 8/16 θ F coverage. Analysis reveals a significant vacuum-inward dipole moment with fluorine-Cs co-adsorption, favorably reducing the work function. However, fluorine’s strong electronegativity also creates a surface-directed dipole moment, increasing the work function. Introducing fluorine is beneficial only at 4/16 θ Cs coverage, indicating that precise control of Cs coverage is necessary to achieve lower work functions.

Releasing Au Electrons to Mo Site for Weakened Mo─H Bond of Mo2C MXene Cocatalyst Toward Improved Photocatalytic H2 Production.

Mo2C MXene (Mo2CTx) is one of the most promising noble-metal-free cocatalysts for photocatalytic H2 production because of its excellent electron transport capacity and abundant Mo sites. However, Mo2CTx typically exhibits a strong Mo─Hads bond, resulting in that the produced H2 difficultly desorbs from the Mo surface for the limited activity. To effectively weaken the Mo─Hads bond, in this paper, a regulation strategy of electron donor Au releasing electrons to the d-orbitals of Mo sites in Mo2CTx is proposed. Herein, the Mo2CTx-Au/CdS photocatalysts are prepared through a two-step process, including the initial loading of Au nanoparticles on the Mo2CTx surface and the subsequent in situ growth of CdS onto the Mo2CTx-Au surface. Photocatalytic measurements indicate that the maximal H2-production rate of Mo2CTx-Au/CdS reaches up to 2799.44µmol g-1h-1, which is 30.99 and 3.60 times higher than that of CdS and Mo2CTx/CdS, respectively. Experimental and theoretical data corroborate that metallic Au can transfer free electrons to Mo2CTx to generate electron-enriched Moδ- sites, thus causing the increased antibonding-orbital occupancy state and the weakened Mo─Hads bond for the boosted H2-production efficiency. This research provides a promising approach for designing Mo2CTx-based cocatalysts by regulating the antibonding-orbital occupancy of Mo sites for improved photocatalytic performance.

Bi layers on the Mo(112) surface: A DFT study

Relativistic DFT calculations performed for Bi layers adsorbed on the Mo(112) surface have shown that Bi atoms tend to occupy adsorption sites in furrows and, at a half-monolayer coverage, form a rectangular p(2 × 1) structure. For a complete Bi monolayer, the most preferred structure is the centered c(2 × 1) structure, with one half of Bi adatoms in on-row sites. No Bi-induced surface states have been indicated along Γ – X, corresponding to the direction along furrows, which can explain only minor changes in the band structure and density of states in vicinity of EF with increasing Bi coverage. On the contrary, changes in the band structure along Γ – Y turn out to be very significant. Specifically, the SOC-splitting band, associated with surface states generated by the Bi adlayer, moves upward and twice crosses EF thus becoming a valence band. This feature may be important in the search for new layered structures for nano and spin-electronics.

A novel Se-diffused selenization strategy to suppress bulk and interfacial defects in Sb2Se3 thin film solar cell

In recent years, vacuum-based deposition of antimony selenide (Sb2Se3) thin films has garnered significant attention owing to its easy and impurity-free fabrication, along with exceptional power conversion efficiency (PCE). However, the necessary post-selenization process comes with a shortcoming of instigating buried Sb2Se3/molybdenum (Mo) back-contact interface defects. This study introduces a novel Se-diffusion post-selenization technique to precisely regulate the selenium reaction atmosphere, preventing void formation on the Sb2Se3 thin film surface and maintaining film quality for enhanced device efficiency. An optimized selenization condition with a precise Se precursor film thickness led to obtaining highly crystalline, preferentially (hk1) oriented, and large-grained Sb2Se3 films. Furthermore, a meticulous Se diffusion in Sb2Se3 film reduced the inevitable MoSe2 layer thickness at the Mo surface, thereby enhancing the quality of the back contact interface. The Sb2Se3 solar cell that was selenized to optimal level showed significant enhancements, raising the fill factor from 40.06 % to 45.12 % and improving the device efficiency from 2.89 % to 3.57 %. Our newly developed selenization strategy establishes a successful approach to regulate the Sb2Se3 film quality by addressing a crucial challenge in improving the efficiency of antimony chalcogenide solar cells.

Bacterial adhesion and corrosion behavior of different pure metals induced by sulfate reducing bacteria

The corrosion behaviors of four pure metals (Fe, Ni, Mo and Cr) in the presence of sulfate reducing bacteria (SRB) were investigated in enriched artificial seawater (EASW) after 14-day incubation. Metal Fe and metal Ni experienced weight losses of 1.96 mg cm−2 and 1.26 mg cm−2, respectively. In contrast, metal Mo and metal Cr exhibited minimal weight losses, with values of only 0.05 mg cm−2 and 0.03 mg cm−2, respectively. In comparison to Mo (2.2 × 106 cells cm−2) or Cr (1.4 × 106 cells cm−2) surface, the sessile cell counts on Fe (4.0 × 107 cells cm−2) or Ni (3.1 × 107 cells cm−2) surface was higher.

Effects of Alloying Element on Hydrogen Adsorption and Diffusion on α-Fe(110) Surfaces: First Principles Study

Based on first principles density functional theory (DFT) methods, this study employed the Cambridge Serial Total Energy Package (CASTEP) module within Materials Studio (MS) software under the generalized gradient approximation to investigate the adsorption, diffusion behavior, and electronic properties of hydrogen atoms on α-Fe(110) and α-Fe(110)-Me (Mn, Cr, Ni, Mo) surfaces, including calculations of their adsorption energies and density of states (DOS). The results demonstrated that doping with alloy atoms Me increased the physical adsorption energy of H2 molecules on the surface. Specifically, Mo doping elevated the adsorption energy from −1.00825 eV to −0.70226 eV, with the largest relative change being 30.35%. After doping with Me, the chemical adsorption energy of two hydrogen atoms does not change significantly, among which doping with Cr results in a decrease in the chemical adsorption energy. Building on this, further analysis of the chemical adsorption of single atoms on the surface was conducted. By comparing the adsorption energy and the bond length between a hydrogen atom and iron/dopant metal atom, it was found that Mo doping has the greatest impact, increasing the bond length by 58.58%. Analysis of the DOS functions under different doping conditions validated the interaction between different alloy elements and H atoms. Simultaneously, simulations were carried out on the energy barrier crossed by H atoms diffusing into the metal interior. The results indicate that Ni doping facilitates the diffusion of H atoms, while Cr, Mn, and Mo hinder their diffusion, with Mo having the most significant effect, where its barrier is 21.88 times that of the undoped surface. This conclusion offers deep insights into the impact of different doping elements on hydrogen adsorption and diffusion, aiding in the design of materials resistant to hydrogen embrittlement.

AgO and PdO monolayers on the Mo(112) surface: A DFT study

With performed DFT calculations it is shown that AgO as well as PdO monolayer is bound to the Mo(112) surface with Ag or Pd atoms lying in surface furrows and O atoms situated in sites on Mo surface rows. The intrinsic corrugation of the surface facilitates the placement of oxide monolayers on the surface by effectively compensating for the difference in the sizes of O and Ag or Pd atoms, resulting in the adsorbed AgO and PdO layers becoming almost flat, which is typical of free monolayers. The surface states associated with the oxide layers on Mo(112) are either significantly above or below the EF, which does not lead to any noticeable changes in the band structures and densities of states in the vicinity of the EF of these layered systems. Nevertheless, it can be expected that adsorbed oxide monolayers can exhibit useful catalytic properties due to the adsorption-modified structure of the layers.

Tuning Mo cations dissolution and surface reconstruction of CoMoO4 for efficient oxygen evolution reaction

Structural distortion enables modulating surface reconstruction of transition metal oxides by manipulating cation dissolution for oxygen evolution reaction (OER), while revealing reconstruction mechanism is stuck by the demand to precisely regulate exact sites of these structural distortions and further make a robust correlation between surface reconstruction and OER performance. In this work, controllable Mo dissolution in CoMoO4 is adjusted by the structural distortion level of MoO4 tetrahedrons with different annealing temperatures. The structural distortion level of MoO4 tetrahedrons is positively correlated with annealing temperatures and spontaneous Mo cations dissolution in alkaline solution. The moderate amount of spontaneous Mo cations dissolution, in accompany with maximum dissolution amount of Mo cations derived from potential, could expose more Co sites to reconstruct into active species CoOOH at a lower potential, resulting in more catalytically active sites whose overpotential at 100 mA cm−2 with 346 mV and Tafel slope of 92.22 mV dec−1. This work indicates the importance of controlled cation dissolution in modulating the kinetics of surface reconstruction and OER performance of electrocatalysts.

Effect of metal impurities on the adsorption energy of cesium and work function of the cesiated Mo (0 0 1) surface

Based on the DFT method, the effects of copper and tungsten impurities present in the negative ion source of neutral beams on the cesiated surface were studied, including their effects on the adsorption energy of cesium on the surface and the surface work function. The results indicate that copper impurities significantly increase the average adsorption energy of cesium, whereas tungsten has limited enhancement on the average adsorption energy of cesium and may even reduce it. The work function calculations show that, at cesium coverages below 4/16 θ, copper impurities cause a significant increase in the work function. However, at cesium coverages above 6/16 θ, high-coverage copper impurities lead to a further decrease in the work function, causing the cesium coverage corresponding to the lowest work function to shift towards higher cesium coverage. Under any tungsten impurity and cesium coverage, tungsten impurities can significantly increase the surface work function, with the maximum increase reaching 0.50 eV. The dipole moment density analysis shows that in most cases, impurities significantly reduce the dipole moment density of the cesiated surface, except when the coverage of cesium and copper impurities is above 6/16 θ. The charge transfer results show that the copper impurity layer has more positive charge compared to the tungsten impurity layer, which significantly affects the dipole moment density of the surface system. In addition, adsorbed atoms cause electrons in the molybdenum atomic layer to migrate to the surface, resulting in the molybdenum substrate having a pronounced negative dipole moment.

A seed-like structured Mo@ZrS2 catalyst on graphene nanosheets for boosting the performance of rechargeable Zn-air batteries.

Novel composite materials are being studied by researchers for energy storage and renewable energy applications. Here, a seed-like Mo-doped ZrS2 catalyst was developed on a reduced graphene oxide (rGO) surface by an annealing and hydrothermal method. Using photoelectron spectroscopy, scanning microscopy, and X-ray diffraction analyses, the structure of Mo@ZrS2/rGO and the impact of heteroatoms are demonstrated, providing insight into the catalyst. Furthermore, it is demonstrated that Mo@ZrS2/rGO has been utilized as an efficient energy storage electrocatalyst by offering a very low half-wave potential of 0.80 V for the oxygen reduction reaction in an alkaline solution. Furthermore, Zn-air batteries with a high-power density of 128.6 mW cm-2 and exceptional cycling stability are demonstrated by the developed array electrocatalyst. Ultimately, the research findings suggest novel perspectives on the structure of ZrS2 nanoseeds created by Mo surface doping, promote the usage of Zn-air batteries in practical scenarios, and offer a fascinating idea for creating a redox electrocatalyst.

Morphology, phase composition, surface roughness evolution and growth mechanism of hot-dip aluminum coating on Mo substrate

The Al-rich hot-dip aluminum composite coatings were synthesized on Mo surface by hot-dip aluminizing under different deposition processes. The aluminide coatings present a very smooth dense coating structure with a lower surface roughness and fine grain size, the average surface roughness (RSa) values are only 0.118–0.869 μm, and the corresponding surface area growth rate (Sdr) values are 3.85–80.19 %. Increasing the deposition temperature is beneficial for the transition of low melting point compounds of the coating surface to high melting point compounds, and extending the hot dip time is profit for the diffusion and enrichment of Al atoms on the coating surface. Besides, increasing the deposition temperature or time can also promote the growth of Al4Mo grains, thereby significantly increasing the coating thickness. When the deposition temperature is 750 °C, the thicknesses of Al4Mo and Al8Mo3 layers increases in a parabolic law with deposition time, and the Kp values both of them are 3.46 × 10−13 m2/s and 1.47 × 10−15 m2/s, respectively. The growth of the coating depends on the continuous diffusion of Al atoms towards the substrate direction, and the difference in chemical potential between Al atoms in each phase is the main driving force for coating growth.

Morphology, Composition, and Electronic Structure of the Surface of Thin CdS Films Grown on a Mo(III) Surface

Morphology, Composition, and Electronic Structure of the Surface of Thin CdS Films Grown on a Mo(III) Surface

Effect of H atoms and O impurities on the adsorption stability and work function of the cesiated Mo(0 0 1) surface: A study about negative hydrogen ion sources for neutral beam injection systems

The impact of H atoms and O impurities on the adsorption stability and work function of cesiated Mo (001) surface are investigated in this paper through DFT calculations. The 53 surface structures with different surface coverages are constructed in this work. Two types of co-deposition structures are considered: Cs-O (or Cs-H) bonds (1) leaning towards and (2) perpendicular to the surface. Our results demonstrate that the minimum work function corresponds to a 0.5 ML coverage of Cs for any surface coverage of H (or O) when the bonds are tilted. Compared to pure Cs deposition, the work function of Cs and H (or O) co-deposition surface increases at low or saturated Cs coverage, while decreases at 0.5 ML. Analysis of the surface dipole moment revealed that the work function changed inversely with the surface dipole moment density. Comparing charge transfer and polarization, it is evident that charge polarization has a significant impact on dipole moment changes. The presence of O impurities significantly enhances the adsorption stability of Cs, with higher coverage of O impurities leading to greater adsorption stability. The average adsorption energy of Cs atoms increases by ∼0.36 eV when co-deposits with O (0.5 θ). The effect of the H atoms on the adsorption stability of Cs atoms is limited. We also find that the vertical co-deposition case did not offer an advantage in terms of adsorption stability and low work function.

On the missing single collision peak in low energy heavy ion scattering

We present experimental and simulation data on the oblique angle scattering of heavy Sn ions at 14keV energy from a Mo surface. The simulations are performed with the binary collision approximation codes TRIM, TRIDYN, TRI3DYN, SDTrimSP, and IMSIL. Additional simulations were performed in the molecular dynamics framework with LAMMPS. Our key finding is the absence of an expected peak in the experimental energy spectrum of backscattered Sn ions associated with the pure single collision regime. In sharp contrast to this, however, all simulation codes we applied do show a prominent single collision signature both in the energy spectrum and in the angular scatter pattern. We discuss the possible origin of this important discrepancy and show in the process, that widely used binary collision approximation codes may contain hidden parameters important to know and to understand.

Surfaces with Lowered Electron Work Function: Problems of Their Creation and Theoretical Description. A Review

Experimental studies devoted to the creation of the modern photocathodes or efficient field emission cathodes with lowered work function or low/negative electron affinity are reviewed. We present theoretical models, where the electron affinity lowering is associated with the influence of electrically charged layers at the semiconductor/insulator interface. Modern experimental techniques of measuring the work function or the electron affinity and technologies aimed at fabricating the surfaces with low work function/electron affinity are described. In the framework of a simple theoretical model developed by the authors, it has been demonstrated that the presence of a dipole layer (e.g., composed of negatively charged oxygen ions and positively charged rare earth ions) at the semiconductor surface can lower the electron affinity by up to 3 eV provided equal concentrations of oppositely charged adsorbate ions. It is also shown that if the surface concentration of negatively charged oxygen ions is higher than the surface concentration of positively charged metal ions, the lowering of the electron affinity becomes smaller due to the upward band bending in the space charge region in the semiconductor; otherwise, the lowering of the electron affinity becomes larger due to the downward band bending. This effect allows technological proposals to be formulated for obtaining surfaces with minimum work function values in modern field-emission-based electronic devices. In the framework of the proposed model, the work function was evaluated for the OH-functionalized MXene. The corresponding value for the unfunctionalized MXene equals about 4.5 eV, being practically independent of the number of Ti and C layers (from 1 to 9 layers). The OH-functionalization lowers it down to about 1.6 eV, and this value is also practically independent of the number of atomic layers in MXene. Experimental approaches to obtain cathodes with low work function/low electron affinity are described. They are aimed at creating a spatial separation of electric charges in the near-surface cathode region perpendicularly to the surface plane. The corresponding spatial distributions of positive and negative charges are characterized by their localization either in two different atomic planes or in one plane and an extended space region (the latter variant is typical of semiconductor substrates). The technologies for producing such surfaces are based on various methods of adsorbate deposition onto the metal or semiconductor substrate: physical vapor deposition, chemical vapor deposition, liquid phase deposition, diffusion from the substrate bulk, and so forth. Particular attention is paid to the experimental works dealing with the adsorbtion of rare earth metals (Ce, Gd, Eu) and the coadsorbtion of oxygen onto the Si, Ge, and Mo surfaces (in a nano-structured state as well), which results in the dipole layer formation and the work function reduction.

Design of sensitive materials for nitrogen oxides detection

Although the d-band center theory can well describe the interaction between gas molecules and transition metal surfaces, the detailed reaction process and specific adsorption conditions are unclear. Hence, in this work, we systematically studied the adsorption mechanism, adsorption conditions, and recovery time of NO and NO2 molecules on different transition metals (Cu, Ag, Au, Ni, Pd, Pt, Rh, Ru, Tc, Mo, Nb, and Zr) surfaces by first-principles. The results indicated that the charge transfers from the dz2, dxz, and dyz orbitals of substrate atoms to the HOMOs/LUMOs of NO and NO2. Moreover, we demonstrate that the interaction orbitals between the NO/NO2 and the metal atoms excellently correspond with the match of energy level and parity, and the maximum overlap of the orbital wave function. Interestingly, the excellent linear scaling between charge transfer and the d-band center, work function, and matrix element (V2ad) of metals has been confirmed. Specifically, the different recovery times of these systems at different temperatures were explored. Our results can provide a feasible way for exploring gas-sensitive materials in the experiments.

Controlled and Uniform Wet Etching of Molybdenum Nanowires

We achieved the controlled recess of molybdenum (Mo), which is alternative interconnect material for copper (Cu), by wet chemical etching. This wet etching process includes two main steps which are chemical oxidation of Mo and its subsequent dissolution, respectively. Firstly, Mo nanowires (NWs) are uniformly oxidized with potassium permanganate (KMnO4) solution in acetone. Secondly, the Mo oxide is dissolved using an aqueous solution of HCl. Mo NWs are characterized through transmission electron microscopy (TEM) imaging after each of the above steps. Cyclic etching experiments including oxidation and dissolution of Mo showed that Mo recess is linear and can be controlled for each cycle, where the etching produced the smooth Mo surface. This controlled Mo recess is crucial for the fabrication of next-generation metal interconnects.

Interfacial insight of core@double‐shell Mo@MoO3@PS/PVDF composites towards prominently meliorative dielectric performances

AbstractPolymer dielectrics with synergistically large dielectric permittivity (ε') and breakdown strength (Eb) but prohibited loss is of crucial applications in the electronic devices and power equipment. In this study, we aim to elevate the integrated dielectric performances of molybdenum (Mo)/polyvinylidene fluoride (PVDF) by constructing a semiconducting molybdenum oxide (MoO3) shell and insulating polystyrene (PS) shell on the Mo surface through high‐temperature oxidation followed by suspension polymerization. The resulting core@double‐shell Mo@MoO3@PS particles were compounded with PVDF to achieve high ε' and Eb while minimizing the loss. The results reveal that the Mo@MoO3@PS/PVDF composites indicate simultaneously ameliorative ε' and Eb along with restrained loss owing to the existence of the MoO3@PS double‐shell, which not only prominently enhances the interfacial compatibility and interactions between fillers and PVDF, but significantly inhibits the conductivity and loss through impeding the long‐distance motion of carrier charges. The dielectric capabilities could be improved by adjusting the thickness of the PS interlayer. The Havriliak‐Negami equation was used to fit the experimental results, which showed the impact of the PS shell on the polarization mechanism and how it inhibits carrier migration. The Mo@MoO3@PS/PVDF with high ε' and Eb yet exceptionally low loss exhibit potential applications in microelectronics and electrical industries.

A molybdenum nanostructured-film target for tunable x-ray sources: surface-structure controllable preparing and radiation intensity selecting

Tunable x-ray sources have attracted interest due to providing selective focal spots and radiation intensities for different specific uses. Surface-structure of the anode target has a non-negligible impact on the radiation intensity of x-ray sources. The metal molybdenum (Mo) Lα characteristic x-ray exhibits great potential in solving key scientific problems of material analysis. However, there is still a lack of research on how to flexibly use Mo structure targets to meet the application requirements of different x-ray radiation devices. The reliable preparation of Mo targets with suitable surface-structure is also a significant challenge, particularly for those nanostructured-film targets that cannot be machined. In this study, we successfully prepared a series of self-assembled Mo nanostructured-films with controllable surface structures as a class of reflection-type x-ray sources’ anode target. The structure-activity relationship between the Mo surface nanostructures and the radiating Lα x-ray performance at different anode target angles was studied in a reflecting device layout. Mo nanostructures with smoother surface typically show better radiation performance at small inclination angles (0° to 30°), while the Mo films with a large number of nanoparticles and rough surface exhibit advantages at large inclination angles (60° to 80°). The results provide a feasible scheme for the future application of multi-functional tunable x-ray sources.