Dissociation Of Hydrogen Molecules Research Articles

Effective Screening of Metal Dopants for In2O3 Catalyst to Tune Catalytic Performance of CO2 Hydrogenation to Formic Acid

The metal doping is an effective strategy to adjust catalytic performance for indium oxide catalyst in CO2 hydrogenation. In current work, a series dopant, Co, Fe, Ni, Pd, Pt, Rh and Ru, are selected and examined in CO2 hydrogenation to formic acid by DFT based microkinetic simulation. It is found that substitutional doping is local effect which mainly promotes the reactivity of adjacent oxygen atoms. The calculations of both CO2 adsorption and hydrogen molecule dissociation certify the positive effects induced by doping, and the adsorption energy of CO2 has a linear relation with the transferred charges for all investigated catalysts which helps to explain the C‐O bond activation mechanism. Two pathways, Formate and Carboxyl, are investigated under same footing. It is noted that doping significantly reduces the hydrogenation barriers on two pathways compared with undoped surfaces. Moreover, the calculated TOF of formic acid formation is greatly increased on doped surfaces and Pt, Pd, Ru are identified as the most active dopants. In the end, it is concluded that reaction obeys Carboxyl mechanism and a valid descriptor of trans‐HCOOH* and H* formation energy is proposed for the screening of effective dopants.

Research on the modification of magnesium hydride by two-dimensional layered Mo2Ti2C3 MXene

One of the most important technologies for the sustainable development of energy in the future is solid-state hydrogen storage. This study employed etching methods to fabricate two-dimensional layered catalyst Mo2Ti2C3 MXene, which was compared with unetched MAX phases Mo2Ti2AlC3 and Ti3C2, as well as Mo2C. Through mechanical ball milling, these materials were mixed with MgH2 to prepare composite materials, including MgH2 + Ti2C3, MgH2 + Mo2C, MgH2 + Mo2Ti2AlC3, and MgH2 + Mo2Ti2C3. According to the study, Mo2Ti2C3 demonstrates the synergistic catalytic actions of Ti and Mo in contrast to Ti2C3 and Mo2C. The composite material MgH2 + Mo2Ti2C3 lowers the initial dehydrogenation temperature of MgH2 to 180 °C, which is 165 °C lower than pure MgH2. After 30 min at 250 °C, the dehydrogenation amount is approximately 5.85 wt%. Hydrogen absorption begins at 40 °C and reaches approximately 5.75 wt% at 150 °C. Additionally, it maintains a reversible hydrogen storage capacity of up to 96 % even after 20th cycles at 300 °C. This is because Mo2Ti2C3 has one less layer of Al than Mo2Ti2AlC3, which results in a wider interlayer spacing, more active sites for MgH2, and facilitates hydrogen molecule dissociation and recombination.

Significant Promotional Effect of Nb Doping in Bifunctional Pd/WOx Nanocatalysts on One‐Step Benzene Hydroalkylation

AbstractThe development of high‐efficiency heterogeneous bifunctional metal‐acid catalysts with an appropriate metal‐acid balance for the production of cyclohexylbenzene (CHB) via the one‐step tandem benzene hydroalkylation still faces a dilemma because of the difficulty in inhibiting the over hydrogenation of benzene substrate and cyclohexene intermediate and controlling target product selectivity. In this study, Nb‐doped WOx supported Pd nanocatalysts were developed. It has been shown that doping Nb into WOx supports altered surface properties and microstructures of catalysts, resulting in the generation of more surface acidic sites and defective W−Ov−Nb structures (Ov: oxygen vacancies). As‐constructed Pd‐based nanocatalyst with only 0.1 wt % Pd loading and a Nb/(Nb+W) molar ratio of 0.25 exhibited superior catalytic benzene hydroalkylation performance to undoped supported Pd catalyst, with a much higher yield of CHB (35.6 %) at 220 °C. It was authenticated that highly dispersed Pd sites facilitated the dissociation of hydrogen molecules, defective W−Ov−Nb structures were conductive to the surface transfer of active hydrogen species, a large number of acidic sites favored benzene/cyclohexene intermediate adsorption, and abundant Brønsted acidic sites promoted the alkylation between cyclohexene intermediate formed and benzene. Accordingly, excellent cooperative catalysis between Pd sites, acidic sites, and oxygen vacancies contributed to improved catalytic performance of Nb‐doped WOx supported Pd catalysts in benzene hydroalkylation. This research presents an alternative for the creation of low‐cost practical bifunctional metal‐acid catalysts for highly efficient benzene hydroalkylation.

Synergistic catalytic effect of LPSO structure and nano (Ni-TiO2)@C on hydrogen storage properties of Mg-Ni-Y alloy

Fine multiphase structure and LPSO structure are formed in the hydrogen storage alloy Mg88.7Ni6.3Y5 by microalloying with small amounts of Ni and Y elements. The catalyst (Ni-TiO2)@C is torn as a carbon layer encapsulating on the surface of the alloy particles by ball milling to form Mg88.7Ni6.3Y5+1 wt.% (Ni-TiO2)@C hydrogen storage composites. The Ni and TiO2 in the catalyst accelerate the dissociation of hydrogen molecules. The carbon carrier prevents the agglomeration of nanocatalysts Ni and TiO2. The alloy exhibited exceptional hydrogen ab/desorption kinetics. It can reach 80% hydrogen absorption saturation content within 1 min. The initial hydrogen desorption temperature has been reduced to 200 °C, and the dehydrogenation content is 4.26 wt.% at 250 °C. The adsorption energies of hydrogen atoms at different sites are calculated by Density Functional Theory (DFT). Synergistic catalytic effects were observed in LPSO and (Ni-TiO2)@C.

Adsorption and dissociation of hydrogen molecules over S-vacancies in a Nb-doped MoS2 monolayer

Motivated by the recent interest in the hydrogen energy, we have carried out a complete study of the catalytic activity of a defective molybdenum disulfide monolayer (MoS2) by means of density functional theory (DFT) calculations. The MoS2 monolayer is characterized by a nonreactive basal plane. In principle, its catalytic activity is concentrated at the edges, but an alternative way to increase such activity is obtained by creating active sites where the molecules can dissociate. These defects can be easily produced experimentally by different techniques. In our study, we have performed an atomic, energetic and electronic analysis of a hydrogen molecule adsorbed on a MoS2 monolayer. In a first step, we have found that the H2 molecule remains physisorbed over both doped-free and Nb-doped MoS2 monolayers, showing that the Nb atom does not increase the poor reactivity of the clean MoS2 layer. Interestingly, our energetic results suggest that the vacancies will prefer to be formed close to the Nb atoms in the doped monolayer, but the small energy difference would allow the formation in non-doped like sites. Theoretically, we found out the conditions for the molecular dissociation on a S vacancy. In both cases, with and without Nb, the molecule should rotate from the original perpendicular position to an almost parallel orientation jumping an energetic barrier. After that, the atoms are separated binding to the Mo atoms around the missing S atom. Our ab initio molecular dynamics simulations show that for low pressure conditions (using one single molecule in the system) the H2 prefers to desorb from the vacancy, while for larger pressures (when additional H2 molecules are added to the system) the molecule is finally dissociated on the vacancy. Our long simulations confirm the great stability of the structure with the two H atoms binding to the Mo atoms close to the vacancy. Finally, the inclusion of a third (or a fourth) H atom in the vacancy leads to the formation and desorption of a H2 molecule, leaving one (or two) atoms in the vacancy.

Development of Nb-based alloy membranes with improved resistance to corrosion by H2S

At present, the interest in non-Pd hydrogen permeation membranes mainly focuses on group 5 B metals (Nb, V, Ta) and their alloys. To solve the problem of easy oxidation and weak dissociation of hydrogen molecules, a "Pd catalytic layer" needs to be deposited on the membrane surface. Due to its limited stability towards sulfur, issues of irreversible poisoning by sulfur compounds must be addressed. To this end, Pd-, Pd65Ag35-, Pd90Cu10-, Pd80Au20-, and Pd55Ag35Au10-coated Nb30Hf35Co35 membranes were firstly synthesised by magnetron sputtering, and their hydrogen permeation behaviour in pure H2 and/or in different H2/H2S mixtures for up to 1000 ppm at 673 K were evaluated. At these conditions, the permeabilities of the Pd-coated membranes decrease rapidly with increasing the H2S concentration and cannot recover after removal of H2S from the feed mixtures. In comparison, the Pd–Ag-containing membrane greatly increases the pure H2 permeability, whereas the membrane doped with Au can effectively improve the response to H2S. Specifically, the Pd65Ag35-coated membrane shows the highest pure H2 permeability, but it loses maximum permeability value on exposure to H2/H2S feed mixtures. In contrast, Pd80Au20-containing membranes exhibit good tolerance of H2S poisoning and displayed a high fractional recovery (∼83%) of initial H2 permeability. The degradation of permeability for Pd- or Pd65Ag35-coated membranes after the H2S exposure can be ascribed to the deterioration of the structure caused by the possible formation of bulk Pd4S, which has been corroborated with EDS analysis, XRD, and XPS after testing. Finally, to improve both permeability and chemical tolerance, a Pd55Ag35Au10-coated membrane was successfully fabricated, and it possesses excellent comprehensive performance with respect to the permeability and H2S response. At 120 ppm H2S in the feed, the H2 flux equals ca. 43% of its original value at 673 K and can be stable for at least 166 h. Bulk sulfides did not form on the membrane surface after the testing. This paper not only developed a new type of group 5 B alloy membrane with improved resistance to corrosion by H2S, but also further confirmed the feasibility of improving H2S corrosion resistance by adjusting the catalytic layer type or composition of the outermost coating.

The Adsorption Behavior of Hydrogen on the PuO2(111) Surface: A DFT+U Study

Based on density functional theory, a first-principles study of the adsorption behavior of hydrogen atoms on the PuO2(111) surface is carried out in this work. Models for three different surface morphologies of PuO2(111) are established. It is found that the surface with the outermost oxygen atom (sub outer Pu atom) morphology has the best stability. Based on this model, the adsorption energy, bader charge, and electronic density of the states of a hydrogen atom at different adsorption sites are calculated. Finally, we analyzed the process of hydrogen dissociation into hydrogen atoms on the surface using the cNEB method. The results indicate that the top position of the outermost oxygen atom and the bridge position of the second outermost plutonium atom are relatively stable adsorption configurations, where hydrogen atoms lose electrons and release heat, forming O-H bonds with oxygen atoms. The density of states of O-p orbital electrons will undergo significant changes, reflecting the hybridization of O-p and H-s orbital electrons, forming a stable bonding effect. The dissociation of hydrogen molecules into two hydrogen atoms adsorbed on the top of oxygen atoms requires crossing an energy barrier of 1.06 eV. The decrease in total energy indicates that hydrogen tends to exist on the PuO2(111) surface in a hydrogen atom state. The research results lay the foundation for theoretically exploring the hydrogenation corrosion mechanism of the PuO2(111) surface, providing theoretical support for exploring the corrosion aging of plutonium oxide, predicting the material properties of plutonium oxide under extreme and special environments.

Strong-field effects in the photo-induced dissociation of the hydrogen molecule on a silver nanoshell.

Plasmonic catalysis is a rapidly growing field of research, both from experimental and computational perspectives. Experimental observations demonstrate an enhanced dissociation rate for molecules in the presence of plasmonic nanoparticles under low-intensity visible light. The hot-carrier transfer from the nanoparticle to the molecule is often claimed as the mechanism for dissociation. However, the charge transfer time scale is on the order of a few femtoseconds and cannot be resolved experimentally. In this situation, ab initio non-adiabatic calculations can provide a solution. Such simulations, however, have their own limitations related to the computational cost. To accelerate plasmonic catalysis simulations, many researchers resort to applying high-intensity external fields to nanoparticle-molecule systems. Here, we show why such an approach can be problematic and emphasize the importance of considering strong-field effects when interpreting the results of time-dependent density functional theory simulations of plasmonic catalysis. By studying the hydrogen molecule dissociation on the surface of a silver nanoshell and analyzing the electron transfer at different field frequencies and high intensities, we demonstrate that the molecule dissociates due to multiphoton absorption and subsequent ionization.

Enhanced room-temperature hydrogen storage by CuNi nanoparticles decorated in metal-organic framework UiO-66(Zr)

This study demonstrates the significant effect of incorporating inexpensive transition metal nanoparticles into metal-organic frameworks (MOFs) to improve their room-temperature hydrogen storage properties. Low-cost nanoparticles (Cu, Ni, and CuNi) were incorporated into UiO-66(Zr) via the double-solvent approach (DSA) plus chemical reduction processes. All composites exhibited higher hydrogen storage capacity compared to pure UiO-66 at both room temperature and 60 bar. Notably, the hydrogen spillover efficiency of CuNi nanoparticles loaded in UiO-66 was comparable to that of MOF adsorbents embedded with noble metals such as Pd and Pt. The hydrogen storage capacity of CuNi@UiO-66 was significantly increased from 0.20 wt% to 0.74 wt%. DFT calculations showed that the CuNi alloys facilitated the adsorption and dissociation of hydrogen molecules in comparison to the single metal nanoparticles, thus favoring the hydrogen spillover effect and improving the hydrogen storage performance. This work demonstrates the potential of designing MOF loaded with inexpensive metal nanoparticles for optimized room-temperature hydrogen storage.

3-D Nanostructure Palladium Synthesis By Electrochemical Deposition for Hydrogen Sensor with Switching Resistance Characteristic in Normal Temperature and Pressure

In the hydrogen industry, it is crucial to detect hydrogen leaks and monitor its concentration due to its highly explosive, flammable, and diffusive properties in the concentration range of 4%-75%. Until now, hydrogen sensors have been focused on oxide materials at high temperature and pressure conditions such as semiconductor and steel processes. However, in the future of the hydrogen industry, it is important to sense hydrogen at normal temperature and pressure (NTP). To develop hydrogen sensors with fast response time and high sensitivity specifically designed for NTP conditions, various material properties and structural aspects such as film, nanostructure, and multilayer are being experimentally explored.Metal resistance hydrogen sensors utilize changes in resistance due to hydrogen adsorption and absorption. Compared to other sensors such as catalytic and thermal conductivity sensors, metal resistance hydrogen sensors have advantages such as excellent sensitivity, response time, and selectivity. Palladium metal exhibits superior characteristics with regard to hydrogen compared to other metals, due to its low activation energy for hydrogen molecule dissociation reaction and high reactivity in absorbing hydrogen at NTP.[1] Also, palladium with 3-D nanostructures exhibits a switching resistance characteristic, where the resistance initially decreases rapidly and then increases because of hydrogen and palladium reaction.[2] This depends on the hydrogen concentration and exposure time, which is due to a phenomenon where the combined effects of characteristics such as hydrogen interstitial, phase transition, and volume expansion lead to different responses of hydrogen and palladium.In this study, we focused on the resistance switching characteristic of palladium, specifically its response to changes in hydrogen concentration and exposure time. We used this characteristic to experiment with both the material and structural properties of palladium nanostructures. We varied impurities and additives in the palladium electrodeposition solution to control the material properties, and varied parameters such as concentration, pH, and voltage using electrochemical methods for structural properties. Structural and material properties were analyzed using Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), and X-ray Photoelectron Spectroscopy (XPS). Sensing characteristics were then analyzed using a hand-made sensor platform with a Source Meter.[Reference][1] Dekura, S., Kobayashi, H., Kusada, K., & Kitagawa, H. (2019). Hydrogen in Palladium and Storage Properties of Related Nanomaterials: Size, Shape, Alloying, and Metal‐Organic Framework Coating Effects. ChemPhysChem, 20(10), 1158-1176.[2] Cho, S. Y., Ahn, H., Park, K., Choi, J., Kang, H., & Jung, H. T. (2018). Ultrasmall grained Pd nanopattern H2 sensor. ACS sensors, 3(9), 1876-1883.

Metallofullerenes as Robust Single-Atom Catalysts for Adsorption and Dissociation of Hydrogen Molecules: A Density Functional Study.

Hydrogen is currently considered as the best alternative for traditional fuels due to its sustainable and ecofriendly nature. Additionally, hydrogen dissociation is a critical step in almost all hydrogenation reactions, which is crucial in industrial chemical production. A cost-effective and efficient catalyst with favorable activity for this step is highly desirable. Herein, transition-metal-doped fullerene (TM@C60) complexes are designed and investigated as single-atom catalysts for the hydrogen splitting process. Interaction energy analysis (Eint) is also carried out to demonstrate the stability of designed TM@C60 metallofullerenes, which reveals that all the designed complexes have higher thermodynamic stability. Furthermore, among all the studied metallofullerenes, the best catalytic efficiency for hydrogen dissociation is seen for the Sc@C60 catalyst Ea = 0.13 eV followed by the V@C60 catalyst Ea = 0.19 eV. The hydrogen activation and dissociation processes over TM@C60 metallofullerenes is further elaborated by analyzing charge transfer via the natural bond orbital and electron density difference analyses. Additionally, quantum theory of atoms in molecule analysis is carried out to investigate the nature of interatomic interactions between hydrogen molecules and TMs@C60 metallofullerenes. Overall, results of the current study declare that the Sc@C60 catalyst can act as a low cost, highly efficient, and noble metal-free single-atom catalyst to efficiently catalyze hydrogen dissociation reaction.

Envisioning the hydrogen dissociation in Σ5 (100) grain boundary in diamond

Diamonds hold the potential to revolutionize the development of devices by introducing unique properties into next-generation technologies. However, hydrogen is a prevalent impurity in synthetic diamonds and significantly impacts their mechanical properties. In the present investigation, we proposed to comprehend the effect of hydrogen on the stability of the Σ5 (100) grain boundary in diamond at its electronic level. The results show that the hydrogen concentration significantly affects the grain boundary deformation. By applying the nudged elastic band and periodic energy decomposition analysis, we have uncovered the fundamental principle behind the structural changes during hydrogen molecule dissociation within the grain boundaries, as well as the interactions and bonds that influence the overall properties of the system. Results indicate that the dissociation of hydrogen molecules is achieved without any activation energy. The covalent bond is further explained by attractive orbital interactions of hydrogen atom and dangling bonds present within the void of Σ5 (100) grain boundary in diamond. Examination of the mechanical properties of the grain boundaries revealed that a change in the elasticity of the grain boundaries as the concentration of hydrogen increases. The grain boundary energy calculations indicate that the studied Σ5 (100) grain boundary is stable.

First-principle calculation of hydrogen adsorption on the surface of Ni3Al (110)

Nickel-based superalloy has good mechanical properties and corrosion resistance, and is widely used in the oil and natural gas industry. However, hydrogen brittle is a serious problem that the application of nickel-based superalloy must face. In this study, the first principle calculation method based on density functional theory was used to calculate the adsorption energy of the molecules of hydrogen and hydrogen atoms on the Ni3Al (110) surface. The calculated results show that the adsorption of hydrogen molecules on the surface of Ni3Al (110) is physical adsorption. The preferential adsorption site of hydrogen molecules is at the top site of Ni atoms, and Ni can promote the dissociation of hydrogen molecules. Hydrogen atoms tend to adsorb in the bridge, and the Ni-Ni bridge site is the preferential adsorption site.

Activated dissociation of H2 on the Cu(001) surface: The role of quantum tunneling

The activation and dissociation of hydrogen molecules (H2) on the Cu(001) surface are studied theoretically. Using first-principles calculations, the activation barrier for the dissociation of H2 on Cu(001) is determined to be ∼ 0.59 eV in height. It is found that the electron transfer from the copper substrate to H2 plays a key role in the activation and breaking of the H–H bond, and the formation of the Cu–H bonds. Two stationary states are identified at around the critical height of bond breaking, corresponding to the molecular and the dissociative states, respectively. Using the transfer matrix method, we also investigate the role of quantum tunneling in the dissociation process along the minimum energy pathway (MEP), which is found to be significant at or below room temperature. At a given temperature, the tunneling contributions due to the translational and the vibrational motions of H2 are quantified for the dissociation process. Within a wide range of temperature, the effects of quantum tunneling on the effective barriers of dissociation and the rate constants are observed. The deduced energetic parameters associated with the thermal equilibrium and non-equilibrium (molecular beam) conditions are comparable to experimental data. In the low-temperature region, the crossover from classical to quantum regime is identified.

On the Catalytic Mechanism of 3d and 4d Transition-Metal-Based Materials on the Hydrogen Sorption Properties of Mg/MgH2

The slow hydrogenation/dehydrogenation kinetics and high thermodynamic stability of the Mg–H bond are the two major limitations for the large-scale utilization of MgH2. In this review, we introduce the catalytic mechanism of 3d and 4d transition metal (TM) on the hydrogen sorption properties of Mg/MgH2. The relative contribution of interatomic interactions to the thermodynamic stability of the TM-substituted MgH2 system is discussed. A synergy effect between the electronegativity and the radius of the TM element is proposed to explain the charge transfer process between TM and H in the TM-substituted MgH2 system. The catalytic mechanism of TM nearby the surface of Mg is more complicated than that in the volume of Mg, as the surface-doped TM can experience more options for doping sites, leading to the hindrance effect and causing various contributions of the d band center to the dissociation of hydrogen molecules and the diffusion of hydrogen atoms nearby the surface of Mg. In terms of the catalytic mechanism of TM for hydrogen sorption kinetics of Mg/MgH2, we particularly focused on the “hydrogen pump” effect existing in the Mg–TM–H system. Other mechanisms, such as a possible catalytic mechanism of TM for the hydrogen sorption properties of nano-sized freestanding Mg/MgH2, were also presented.

Theoretical study of hydrogen adsorption kinetics: Mg17Al12 vs pure Mg

The adsorption and dissociation of hydrogen molecules on Mg17Al12(100), Mg17Al12(110), Mg17Al12(111) and Mg(0001) surfaces are investigated by the first-principles calculations. We find that the H adsorption on Mg17Al12 systems are all stronger than that of Mg(0001). Among them, the lowest adsorption energies of H atoms are obtained in the Mg17Al12(110) system, which is −0.278 and −0.247 eV/H when the H coverage is 1/11 and 2/11 ML, respectively. Furthermore, the Mg17Al12(110) surface presents an energy path of hydrogen dissociation with a minimum barrier of 0.59 eV, which is smaller than that of Mg(0001) surface (0.84 eV). The electronic structure analysis illustrates that the bonding between H atoms and Mg17Al12(110) surface is enhanced, although H atoms obtain similar charges on the Mg17Al12(110) and Mg(0001) surfaces. Moreover, the lowered dissociation barrier on the three studied Mg17Al12 surfaces, are likely ascribed to the stronger hybridization of H 1s and Al 3s orbitals, leading to the accelerated hydrogen adsorption kinetics on Mg17Al12 surface with respect to the pure Mg surface.

In situ observation of an atomically modified glassy carbon surface: From synthesis of an Fe-N-C catalyst to intrinsic combined reactions of hydrogen dissociation and the oxygen reduction reaction

We carried out an in situ ambient-pressure X-ray photoemission spectroscopy (AP-XPS) study on the catalytically active surface of glassy carbon subjected to nitrogen-ion implantation and subsequent iron deposition. We also used argon ions to intentionally induce carbon defects on the glassy carbon to compare the effects of substrate defects. Notably, water was produced spontaneously on the modified glassy carbon surface. We compared and clarified the surface structures of the samples in situ by AP-XPS and observed some differences among the pristine glassy carbon (PGC), Fe and N co-doped PGC, Ar-sputtered glassy carbon (AGC), and Fe and N co-doped AGC samples. These differences reveal the potential active site of oxygen reduction reaction and the inherent source for spontaneous dissociation of hydrogen molecules on the atomically modified surface of glassy carbon. The analysis illuminates the new property of glassy carbon itself and offer new direction of Fe-N-C catalyst preparation. • Spontaneous dissociative behavior of hydrogen molecules is possible on Ar sputtered glassy carbon. • Glassy carbon with N 2 sputtering and Fe thermal evaporation have catalytic ability for oxygen reduction. • Using AP-XPS, glassy carbon with treatments is observed in situ.

A density functional theory study of adsorption and dissociation of H2 molecule on small PdnAgm (n + m ≤ 4) metal clusters

The adsorption and dissociation of hydrogen molecule on small PdnAgm (n + m ≤ 4) clusters is studied employing density functional theory (DFT) calculations. The lowest energy structures of the PdnAgm clusters are initially presented. Based on the obtained structures, various geometries of H2 adsorption and dissociation with these clusters are examined. The cluster size and composition of the PdnAgm clusters are found to control the nature of the adsorption process. The results suggest that molecular adsorption is more favorable on the Pd atom and mixed clusters, while hydrogen dissociation is more favorable on the Pdn (n = 2–4) clusters. The Pd dimer and trimer are found to be the most reactive clusters for hydrogen adsorption, while single Ag atom is the least reactive one. The natural bond orbital (NBO) population analysis indicates that hydrogen atoms tend to draw electrons from the metal clusters in the dissociative form and donate electrons to the metal clusters in the molecular adsorption form. The density of states (DOS) of the PdnAgm trimers are also presented and discussed. The interaction and stabilities of cluster on the graphene support has also been performed.

Ionicity and hydrogen affinity of water layers on metals.

The ability of metal surfaces to dissociate hydrogen molecules is key to many ways that metals react to their environment. Often, the barrier to dissociation is linked to the formation of surface hydrogen adatoms. Here, we show that hydrogen can be more strongly bound to water-covered surfaces in the form of hydronium ions than as adatoms. Density functional theory reveals that the hydronium binding is proportional to the surface electronic work function. For the case of Pt(111), a particularly high work function surface, the proton affinity of adsorbed water films can be 0.4eV larger than that of the bare metal surface. This binding is large enough to make the water films susceptible to the formation of hydroxyl and hydronium ion pairs. We present evidence from scanning tunneling microscopy for the existence of hydronium ions in water films on Pt(111). This new insight into the stability of hydronium-containing water layers provides a basis for more realistic models of the chemical reactivity of water films on metals.

Confinement-Induced Catalytic Dissociation of Hydrogen Molecules in a Scanning Tunneling Microscope.

The catalytic scission of single chemical bonds has been induced by the nanoscale confinement in a scanning tunneling microscope (STM) junction. Individual hydrogen molecules sandwiched between the STM tip and a copper substrate can be dissociated solely by the reciprocating movement of the tip. The reaction rate depends sensitively on the local molecular environment, as exemplified by the effects of a nearby carbon monoxide molecule or a gold adatom. Detailed mechanisms and the nature of the transition states are revealed by density functional theory (DFT) calculations. This work provides insights into chemical reactions at the atomic scale induced by localized confinement applied by the STM tip. Furthermore, a single diatomic molecule can act as a molecular catalyst to enhance the reaction rate on a surface.