Equivalent Monolayers Research Articles

Combined Experimental and Periodic DFT Study of the Size Dependence of Adsorption Properties of Oxide‐Supported Metal Nanoclusters: A Case of NO on Ni/Al2O3

ABSTRACTIt is demonstrated by means of ultra high vacuum (UHV) surface‐sensitive techniques and periodic density functional theory (DFT) calculations that the electronic and NO− adsorption properties of nanosized Ni clusters deposited onto the α‐Al2O3 (0001) surface significantly depend upon the size of the cluster. The properties of the Ni cluster of the size of 2 nm and lower are predominantly determined by the formation of the Ni/Al2O3 interface bond notably polarized towards the oxide. As a result, the metal cluster acquires a net positive charge manifested by the bond strengthening of adsorbed NO compared to the bulk Ni substrate. With the increasing size of the cluster, the Ni/Al2O3 interfacial bond depolarizes due to the growing of lateral Ni–Ni interaction. With a mean coverage of Ni on the alumina surface exceeding 0.25 equivalent monolayers, their properties in terms of adsorption behavior of NO resemble those that are characteristic for the bulk Ni substrate. Such a size dependence offers an opportunity to tune the properties of metal clusters and the metal/oxide system as a whole, for example, to achieve the required electronic and adsorption‐reaction properties.

In situ Low-Energy Electron Microscopy of Chemical Waves on a Composite V-oxide/Rh(110) Surface.

Chemical wave patterns and V-oxide redistribution in catalytic methanol oxidation on a VOx/Rh(110) surface have been investigated in the 10-4 mbar range with low-energy electron microscopy (LEEM) and micro spot low-energy electron diffraction (micro-LEED) as in situ methods. V coverages of θV=0.2 and 0.4 MLE (monolayer equivalents) were studied. Pulses display a c(2×2) pattern in the reduced part and (1×2) and c(2×8) structures in the oxidized part of the surface. At θV=0.4 MLE (1×2)/(1×4) patterns with streaks along the [001]-direction at the 1/8 positions are present on the oxidized part of the surface. This phase can be assigned to V-oxide. On a tentative basis, an excitation mechanism for pulses is presented, Annealing the surface to 990 K under reaction conditions results in a macroscopic hole pattern in which holes of low VOx coverage are surrounded by a V-oxide layer. Chemical waves propagate inside the holes as well as on the VOx covered parts of the surface. The results demonstrate for the first time that also in supported oxidic overlayers selforganization processes can take place leading to chemical waves and a large scale redistribution of the oxide.

How far the chemistry of self-assembled monolayers on gold surfaces affects their work function?

Self-assembled monolayers composed of various long-chain aliphatic molecules and different tail functional groups have been synthesized on the Au(111) surface and characterized by Kelvin probe force microscopy and ultraviolet photoelectron spectroscopy. Carboxy, amino, thio and methyl terminal groups have been considered in the design of self-assembled monolayers with different aliphatic chain lengths (from C6 to C16). Work function measurements by Kelvin probe force microscopy have been carried out under a controlled and room atmosphere. Remarkably, a reduction of the relative humidity from 40% to 3% has induced a work function shift of up to 0.3 eV. As expected, the changes of the chain length of the aliphatic moiety and of the tail group have a significant impact on the tuning of the measured work function (3.90 eV for dodecanethiol versus 4.57 eV for mercaptohexadecylamine). Surprisingly, the change of the net dipole moment of the tail group (sign and amplitude) does not dominate the work function variations. In contrast, the change of the chain length and the possibility of the tail group to form a complex hydrogen bond network between molecules lead to significant modulations of the work function. In order to interpret these original findings, density functional theory models of equivalent self-assembled monolayers adsorbed on the Au(111) surface have been developed at an unprecedented level of description with large supercells including simultaneously 27 co-adsorbed molecules and weak van der Waals interactions between them. Such large systems have allowed the theoretical modeling of complex hydrogen bond networks between molecules when possible (carboxy tail group). The comparison between computed and measured work functions shows a striking agreement, thus allowing the disentanglement of the previously mentioned competing effects. This consistency between experiment and theory will help in designing the electronic properties of self-assembled monolayers in the context of molecular electronics and organic transistors.

The Correlation of Strain and Catalytic Activity of Au, Pt, and Pd on Graphene

The catalytic activity of transition metals is highly influenced by the shape of their d-bands. This can be influenced by adjacent materials through two mechanisms: the strain effect, where the degree of orbital overlap affects their electronic structure; and the ligand effect, where the orbital overlap of two different atoms convolves their electronic structures, altering the energy distribution of their bands and transferring charge between them. Benefits derived from manipulating these effects are usually obtained through alloying or the use of core-shell structures, but a support substrate will produce these as well, although they are more difficult to attribute to a substrate as these effects only have an effective range of a few atoms. In a previous study looking at a few monolayer equivalents of Pt on graphene, it was observed that the two effects dominated at different amounts of deposition, with detrimental ligand effects dominating at less than three monolayer equivalents of deposition while beneficial strain effects dominated at higher deposition amounts. Normally, these effects are inseparable, but these effects could be decoupled due to the way that Pt bonds with graphene allowing it to alleviate strain at low dimensions. This seeks to expand on that study by characterizing the interactions between Au and Pd in addition to Pt by depositing up to five monolayer equivalents of each metal and observing how the structure and catalytic activity of each change with the increasing self-influence of each metal.The average atomic strain in Au and Pt were measured using extended X-ray absorption fine structure analysis, while the atomic structure of Pd was observed through scanning transmission electron microscopy. It was found that Pt and Au both show a compressive strain while graphene imposes a tensile strain on Pd, but this strain gradually lessened with deposition amount for Au while it remained relatively constant for Pt and Pd. This demonstrated that the catalysts were highly influenced by their strain as their catalytic activity showed similar trends, with the Pt and Pd catalysts being relatively invariant in catalytic activity over the deposition range observed while the Au samples showed a gradual decline in activity with deposition amount. In comparison to reference samples, all three catalysts are improved by their interactions with graphene, which is supported by computational analysis, but the nature of its influence is different on each.

Variation in zinc phthalocyanine molecular orientation on SrTiO3(100) surface

The molecular orientation of zinc phthalocyanine (ZnPc) thin films grown on SrTiO3(100) substrate was studied using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The results revealed that the molecular orientation changed with the deposition of ZnPc. At the deposition of 0.4 monolayer equivalent (MLE), the π* resonance at grazing incidence was more prominent than that at normal incidence, indicating a lying configuration. By comparing the experimental results with theoretical calculations, the molecular orientation angle for the ZnPc ultrathin film was estimated to be 30°. During the deposition upto 4.3 MLE, the orientation angle increased with increasing ZnPc molecular density in the layer and reached 61°, which is close to that of the α-crystalline films. The dependence of the molecular orientation on the deposition amount indicates that the molecular orientation in the ZnPc ultrathin films is governed by the ZnPc molecular density on the SrTiO3(100) substrate surface.

Nucleation and Growth of Copper on Cobalt in Advanced Interconnect Metallization

Copper was implemented as a conductor for advanced back-end-of-line (BEOL) interconnects based on its low electrical resistivity and improved electromigration life relative to the aluminum baseline.1, 2 Over the past two decades, the smallest dimension of Cu interconnects has decreased from about 300 to the range of 10-20 nanometers.3 Until recently, damascene Cu electroplating on PVD Cu seed has been optimized to provide void-free Cu metallization using a process relying on inorganic and organic additives toenable bottom-up growth from the base of vias and trenches.1,2,4 With ever-decreasing feature size, the conventional damascene process is becoming increasingly limited by the inability to deposit a sufficiently continuous Cu seed on a barrier/Co liner stack without resulting in pinch-off of the PVD seed.In this talk we will report on the development of direct Cu plating on Co using a range of deposition processes to illustrate the challenges and possible direction for improvement of the nucleation and subsequent growth of Cu on the Co seed. One challenge is to create a Cu layer without significantly etching the Co in the plating bath. This can be achieved by reducing the electrode potential difference between Cu electrodeposition and Co corrosion using proper additives in the plating bath to increase suppression (Figure 1). Such a large overpotential translates into improved nucleation density, which effectively inhibits the complete dissolution of the ultrathin Co layers. This effect is also illustrated by measuring the galvanic displacement reaction between Cu ions and Co at open circuit potential (OCP). Figure 2 reveals quick deposition of a monolayer equivalent of Cu followed by a slight increase in Cu thickness over time.A second challenge involves generation of dense nucleation which results in a smooth initially plated Cu film. The number of protrusions is reduced noticeably when a potential-controlled entry is replaced by leaving the electrode at OCP for a short time before any current is applied (Figures 3a and 3b). A short OCP time allows Co oxides to first dissolve, thereby making more surface sites available for nucleation. The smoothness can be further enhanced by increasing the acidity of the bath (Figure 3c). Higher acid could have modulated the reactivities of additive(s) to promote lateral growth. Improved nucleation can also be attained through substrate engineering. This is shown in Figure 4(a-c), where the morphology/continuity of the electroless film exhibits a strong dependency on Co thickness. Furthermore, agglomeration caused by diffusion of Cu across the substrate during deposition can have a large effect on the final film morphology. This can be seen in figure 4 (d-f), in which differences in deposition morphology across a range of conditions are captured in a simple lateral diffusion simulation.We will discuss the mechanisms leading to these effects and their impact on the design of systems to produce improved film morphology.References(1) P.C. Andricacos, C. Uzoh, J. O. Dukovic, J. Horkans, H. Deligianni, IBM J. Res. Develop. 42, 567 (1998)(2) J. Reid, Jpn. J. Appl. Phys. 40, 2650 (2001)(3) I. Ciofi, P. J. Roussel, R. Baert, A. Contino, A. Gupta, K. Croes, C. J. Wilson, D. Mocuta, Z. Tokei, IEEE Trans. Electron. Devices, 66, 2339 (2019).(4) T.P. Moffat, D. Wheeler, S. K. Kim, D. Josell, J. Electrochem. Soc. 153, C127, (2006) Figure 1

Mg‐Facilitated Growth of Cubic Boron Nitride by Ion Beam‐Assisted Molecular Beam Epitaxy

Trace amounts of Mg deposited on a diamond (100) substrate surface facilitate the growth of cubic boron nitride (c‐BN) by ion beam‐assisted molecular beam epitaxy. Fourier transform infrared spectroscopy indicates that films grown with Mg are cubic, while those without Mg are either hexagonal BN or lacking measurable cubic or hexagonal signatures. Initiating the growth with 0.005 monolayer equivalent of Mg is sufficient to yield epitaxial films with >99% c‐BN. Reflection high energy electron diffraction, electron energy loss spectroscopy, and X‐Ray photoelectron spectroscopy indicate the surface of the film to be sp2‐bonded BN, consistent with the results of other groups. High‐resolution scanning transmission electron microscopy reveals c‐BN with a high density of stacking faults and twinning. A model is proposed by which Mg locally diminishes the energy barrier to dissociation of the as‐deposited sp2‐bonded BN, facilitating the nucleation of c‐BN.

From high temperature phase formation to transition metal substitution in the Fe/Al9Co2(001) system

We report the formation of several complex intermetallics as surface alloys upon the adsorption of Fe on Al9Co2(001) for different dosing conditions. Up to 4 monolayers equivalent (MLE) of Fe deposited on the substrate held at 593 K, the low energy electron diffraction pattern consists of a (2×2)R45° phase with two additional domain types rotated by ±8∘ from it. The scanning tunneling microscopy (STM) measurements show that these three types of domains have the same crystallographic structure. The lattice parameters and structural motifs point towards the formation of the high-temperature Al8Fe5 phase (γ-brass of Zn8Cu5-type structure). For Fe deposition between 593 K and 873 K, we have identified the formation of two phases, tentatively assigned to a ternary disordered Al9(Co,Fe)2 overlayer and to the monoclinic Al13Fe4(100). The stoichiometric evolution of the grown structures have been characterized by angle-resolved x-ray photoelectron spectroscopy measurements. Density functional theory based calculations have been performed to model the Al8Fe5(100)/Al9Co2(001) interface, its structural stability and to simulate the corresponding STM images.

Numerical study for energy performance optimization of hollow concrete blocks for roofing in a hot climate of Morocco

• A numerical approach is performed for calculating the thermal inertia parameters. • The traditional roofs had the most significant total thermal load over 24-hours. • Integrate passive techniques into hollow blocks enhances their energy performance. • The inside heat transfer coefficient strongly impacts the roof's thermal inertia. • The outside heat transfer coefficient has no effect on the roof's thermal inertia. The roof is the component of the envelope more subjected to climatic excitations, and it contributes to a significant part of the total building's cooling load in hot climates. Therefore, the thermal optimization of hollow concrete blocks for roofing can considerably reduce the enormous energy consumption used for cooling buildings. For this purpose, the thermal inertia of different configurations of roofs built with traditional concrete blocks used in Morocco with three and six cavities was studied numerically. First, a two-dimensional coupled heat transfer by conduction, convection, and radiation was investigated in the steady-state using the Galerkin finite element method to generate an equivalent homogeneous monolayer block with similar thermal behaviour to the original hollow-block roof. After that, the transient heat conduction equation under real thermal solicitations is solved using a numerical inversion of the Laplace domain solution by utilizing the De Hoog algorithm to evaluate the dynamic thermal characteristics of the roofs. The results report that the emissivity and inside combined convection and radiation heat transfer coefficients significantly impact the roof's thermal inertia. In addition, it is shown that the configuration based on using a low emissivity coating and inserting an insulating material between the outer surface of the block and the slab could reduce the total thermal load over 24-hours by about 93.1% compared to the traditional configuration, which is beneficial to minimize the energy consumption used for cooling buildings.

Study of Ruthenium Contamination Effect on Oxygen Reduction Activity of Platinum-Based PEMFC and DMFC Cathode Catalyst

Proton exchange membrane fuel cells (PEMFC) and PEM-based direct methanol fuel cells (DMFC) are promising energy sources for vehicular, stationary and portable applications. While PEMFC-based power systems have already reached a limited commercialization level, durability remains to be one of the main obstacles on the path towards their broad commercialization. One of the degradation mechanisms reducing durability of reformate-based PEMFC and DMFC is ruthenium contamination of the cathode catalyst [i] following ruthenium dissolution from the anode PtRu catalyst and its cross-over to the cathode [ii].The aim of our research is to quantitatively measure the effect of ruthenium contamination on the oxygen reduction reaction (ORR) activity of a typical cathode catalyst. For this purpose, various and precisely known amounts of ruthenium (equivalent to 0.15-4 ruthenium monolayers) were deposited on a commercial 50%Pt/C catalyst (Johnson Matthey HiSPEC8000) using electroless reduction method. The obtained Ru-contaminated Pt/C catalysts were examined using TGA, SEM-EDS, XPS, HR-TEM and STEM-EDS to determine their composition, particles size distribution and structure. Cyclic-voltammetry with rotating–disk–electrode was used to quantitatively determine the effect of ruthenium contamination on the ORR specific activity.It was found that ORR activity exhibits a pseudo-exponential decay with increased ruthenium coverage. At a contamination level of 0.15 equivalent ruthenium monolayer (EDS %at Ru3Pt97, XPS %at Ru7Pt93) a massive, ~45%, decrease in ORR specific activity was measured. At a contamination level of 1 equivalent ruthenium monolayer (EDS %at Ru27Pt73, XPS %at Pt50Ru50) almost a complete inhibition of ORR activity was observed. Ruthenium deposition on platinum in the form of bi-layer islands and 3d-clusters and deactivation of platinum atoms surrounding ruthenium deposition sites were proposed as a possible explanation for the pseudo-exponential decay of the ORR activity. The obtained results allowed us to estimate the decrease in power density of reformate-based PEMFC and DMFC due to ruthenium contamination by 0.15 equivalent monolayer at roughly 10%.Assuming that the decrease in ORR activity is originating from the strong O and OH binding to ruthenium, DFT-calculated O and OH binding energies to ruthenium and platinum were used to estimate ORR activity on model Run/Pt(111) surfaces that represent Ru-contaminated Pt/C catalyst. The estimated ORR activities have shown a dependence on ruthenium contamination that was qualitatively similar to experimental results, indicating that the strong O and OH binding to ruthenium have indeed a negative effect on the ORR activity.[i] L. Gancs, B. N. Hult, N. Hakim, S. Mukerjee, Electrochem. Solid-State Lett., 2007, 10, 9, B150[ii] P. Piela, C. Eickes, E. Brosha, F. Garzon, P. Zelenay, Journal of The Electrochemical Society, 2004, 151 (12), A2053–A2059

Exploring the growth and oxidation of 2D-TaS2 on Cu(111)

In this work, the growth and stability towards O2 exposure of two dimensional (2D) TaS2 on a Cu(111) substrate is investigated. Large area (∼1 cm2) crystalline 2D-TaS2 films with a metallic character are prepared on a single crystal Cu(111) substrate via a multistep approach based on physical vapor deposition. Analytical techniques such as Auger electron spectroscopy, low energy electron diffraction, and photoemission spectroscopy are used to characterize the composition, crystallinity, and electronic structure of the surface. At coverages below one monolayer equivalent (ML), misoriented TaS2 domains are formed, which are rotated up to relative to the Cu(111) crystallographic directions. The TaS2 domains misorientation decreases as the film thickness approaches 1 ML, at which the crystallographic directions of TaS2 and Cu(111) are aligned. The TaS2 film is found to grow epitaxially on Cu(111). As revealed by low energy electron diffraction in conjunction with an atomic model simulation, the (3 × 3) unit cells of TaS2 match the (4 × 4) supercell of Cu(111). Furthermore, the exposure of TaS2 to O2, does not lead to the formation of a robust tantalum oxide film, only minor amounts of stable oxides being detected on the surface. Instead, the exposure of TaS2 films to O2 leads predominantly to a reduction of the film thickness, evidenced by a decrease in the content of both Ta and S atoms of the film. This is attributed to the formation of oxide species that are unstable and mainly desorb from the surface below room temperature. Temperature programmed desorption spectroscopy confirms the formation of SO2, which desorbs from the surface between 100 and 500 K. These results provide new insights into the oxidative degradation of 2D-TaS2 on Cu(111).

Bioengineered model of the human motor unit with physiologically functional neuromuscular junctions

Investigations of the human neuromuscular junction (NMJ) have predominately utilised experimental animals, model organisms, or monolayer cell cultures that fail to represent the physiological complexity of the synapse. Consequently, there remains a paucity of data regarding the development of the human NMJ and a lack of systems that enable investigation of the motor unit. This work addresses this need, providing the methodologies to bioengineer 3D models of the human motor unit. Spheroid culture of iPSC derived motor neuron progenitors augmented the transcription of OLIG2, ISLET1 and SMI32 motor neuron mRNAs ~ 400, ~ 150 and ~ 200-fold respectively compared to monolayer equivalents. Axon projections of adhered spheroids exceeded 1000 μm in monolayer, with transcription of SMI32 and VACHT mRNAs further enhanced by addition to 3D extracellular matrices in a type I collagen concentration dependent manner. Bioengineered skeletal muscles produced functional tetanic and twitch profiles, demonstrated increased acetylcholine receptor (AChR) clustering and transcription of MUSK and LRP4 mRNAs, indicating enhanced organisation of the post-synaptic membrane. The number of motor neuron spheroids, or motor pool, required to functionally innervate 3D muscle tissues was then determined, generating functional human NMJs that evidence pre- and post-synaptic membrane and motor nerve axon co-localisation. Spontaneous firing was significantly elevated in 3D motor units, confirmed to be driven by the motor nerve via antagonistic inhibition of the AChR. Functional analysis outlined decreased time to peak twitch and half relaxation times, indicating enhanced physiology of excitation contraction coupling in innervated motor units. Our findings provide the methods to maximise the maturity of both iPSC motor neurons and primary human skeletal muscle, utilising cell type specific extracellular matrices and developmental timelines to bioengineer the human motor unit for the study of neuromuscular junction physiology.

In-plane modal studies of arbitrary laminated triangular plates with elastic boundary constraints by the Chebyshev-Ritz approach

Firstly, the Chebyshev-Ritz method is applied to the free in-plane vibration of arbitrary shaped laminated triangular plates with elastic boundary conditions. In order to facilitate the calculation of energy, the arbitrary shaped triangular laminated plate is mapped into a square plate by the coordinate transformation. The constitutive equation of laminated materials is constructed by the equivalent monolayer theory. The displacement functions of the square plate after transformation are generally expressed as two-dimensional Chebyshev polynomials multiplied by coefficients. By means of artificial virtual spring technology, the arbitrary elastic boundary conditions of the plate can be obtained by changing the stiffness values of each spring. The in-plane free vibration characteristics of the triangular laminated plate under different boundary conditions are calculated and the accuracy of this method is verified by comparing with finite element results and experimental results. In this paper, modal experiments of three different triangular plates with free boundary and cantilever support boundary are carried out. The comparison results show that the present method has good convergence, high efficiency and satisfactory actuarial accuracy. Finally, novelty numerical analysis is carried out, the influence of geometrical properties, material parameters and boundary conditions on in-plane modal characteristics of laminated triangular plates are studied in detail.

Simulated Raman spectra of bulk and low-dimensional phosphorus allotropes.

We present a comprehensive theoretical and experimental Raman spectroscopic comparative study of bulk Phosphorus allotropes (white, black, Hittorf's, fibrous) and their monolayer equivalents, demonstrating that the application of the Placzek approximation to density functional theory calculated frequencies allows reliable and accurate reproduction of the bulk spectra at a relatively low computational cost. As well as accurate frequencies, peak intensities are also reproduced with reasonable accuracy. Having established the viability of the method we apply it to other less well characterised phosphorus forms such as isolated P4 cages and the planar blue-phosphorus phase. There are several speculative structural models in the literature for amorphous red phosphorus, and we predict Raman spectra for several of these. Via comparison with experiment this allows us to eliminate many of them such as the P2P2-zigzag chain and connected P4 models. The combination of Density functional theory (DFT) modelling, Placzek approximation for intensities with experimental Raman spectroscopy is demonstrated as a powerful combination for accurate characterisation of phosphorus species.

Adsorption of nitrogen heterocyclic compounds (NHC) on soil minerals: Quinoline as an example

Understanding the adsorption behavior of nitrogen heterocyclic compounds (NHCs) on soil minerals underlies more effective design of wastewater treatment and soil/groundwater remediation. We investigated adsorption of quinoline, a representative NHC, on quartz sand (using Berea sandstone as a model), at 3 < pH < 9, in low (0.05 M) and high (0.7 M) ionic strength solutions where NaCl was the background electrolyte. Minor clay (kaolinite) in the sandstone contributed significantly to quinoline uptake. Adsorption peaked at pH∼6. It decreased from 2 equivalent monolayers at low ionic strength to a monolayer at NaCl activity approaching that of seawater. A triple layer surface complexation model fits the data well, where quartz and kaolinite contributed sites for three types of quinoline (Q) complexes: 1) innersphere ≡SiOHQ; 2) outersphere ≡SiO-QH+ and 3) innersphere ≡AlOHQ2. Aluminol kaolinite sites promote multilayer quinoline adsorption, whereas only monolayers form on silanol sites. Site density calculations and molecular dynamics (MD) confirmed that quinoline adsorbs upright, on edge, and multilayer adsorption follows formation of the initial monolayer. Our results confirm the effectiveness of sand(stones) and clays for removing NHCs from waste and groundwaters.

Metastable Al-Fe intermetallic stabilised by epitaxial relationship

We report the adsorption of Fe for several dosing conditions on Al(1 0 0) surface held at different temperatures. For 2 monolayer equivalent of Fe deposited on the substrate held at 593 K, we observe two rotational domains of a (5×5)R26.6° structure by low energy electron diffraction and scanning tunneling microscopy. We identify this structure as the formation of the metastable Al9Fe2 intermetallic phase. The segregation energy and the structural stability of this intermetallic has been analysed using density functional theory based calculations. We propose that the formation of the Al9Fe2(0 0 1) metastable phase at the expense of other thermodynamically stable Al-Fe compounds, relies on a specific structural similarity between pure Al (0 0 1) planes of the intermetallic and Al(1 0 0) layers. These ‘common’ planes lead to the epitaxial relationship (1 0 0)Al [0 0 1]Al∥(001)Al9Fe2[13¯0]Al9Fe2. The Al9Fe2-Al matrix interface is sharp as revealed by transmission electron microscopy measurements.

Moiré Structure of the 2-Mercaptobenzothiazole Corrosion Inhibitor Adsorbed on a (111)-Oriented Copper Surface.

The adsorption of 2-mercaptobenzothiazole (2-MBT) vapor on a Cu(111) surface under ultra-low pressure was investigated. For an exposure of 45 L at 150 °C, a Moiré pattern was observed as a result of the superposition of an underlying R30° structure and an outer layer compressed by 18% and rotated by 1.2°. The Moiré pattern was rich in S bonded to Cu as a result of molecular decomposition and partial desorption and was transformed to a R19.1° structure when the sample temperature was increased above 250 °C during deposition. This pre-adsorbed Moiré structure led to the sharp decrease of the oxidation kinetics, which better protects copper against corrosion than the non-ordered 2-MBT monolayer formed at room temperature. Upon further exposure to 2-MBT at room temperature, an equivalent monolayer of the molecule was adsorbed on the Moiré structure at saturation whereas a multilayer was formed for the direct deposition on Cu(111) at room temperature.

MoO3/Al2O3 catalysts for chemical-looping oxidative dehydrogenation of ethane.

MoO3/γ-Al2O3 catalysts containing 0.3-3 monolayer (ML) equivalents of MoO3 were prepared, characterized, and tested for ethane oxidative dehydrogenation (ODH) in cyclic redox and co-feed modes. Submonolayer catalysts contain highly dispersed (2D) polymolybdate structures; a complete monolayer and bulk Al2(MoO4)3 are present at >1ML loadings. High ethylene selectivity (>90%) in chemical looping (CL) ODH correlates with Mo+VI to Mo+V reduction; COx selectivity is <10% under these conditions. Mo+V and Mo+IV species trigger CH4 production resulting in much higher conversion albeit with <20% selectivity. In CL-ODH, submonolayer catalysts exhibit ethylene selectivities that decrease linearly from 96% at near-zero conversion to 70% at 45% conversion. >1ML catalysts provide higher conversions albeit with 10%-18% lower selectivity and greater selectivity loss with increasing conversion. In co-feed mode, ethylene selectivity drops to <50% at 46% conversion for a 0.6ML catalyst, but selectivity is virtually unaltered for a 3ML catalyst. We infer that at <1ML loadings, small domain size and strong Mo-O-Al bonds decrease 2D polymolybdate reducibility and enhance ethylene selectivity in CL-ODH.

In-situ study of the carbon gasification reaction of highly oriented pyrolytic graphite promoted by cobalt oxides and the novel nanostructures appeared after reaction

Cobalt interaction and its effects on carbon-based systems at the nanoscale have recently attracted much attention in different fields, such as catalysis of carbon nanotubes or graphene and graphite nano-patterning taking advantage of its ferromagnetic behavior. Experiments performed in our laboratories show how the re-oxidation process of two equivalent monolayers of CoO deposited on highly oriented pyrolytic graphite at 400 °C leads to the formation of nanochannels at lower temperature than using other methods. Here we present the in-situ characterization of the carbon gasification reaction that drives this process by means of near ambient pressure X-ray photoelectron spectroscopy performed at the ALBA synchrotron facility. The reason why this reaction takes place at such low temperature compared to other methods is due to the weakening of the carbon σ bonds by the initial CoO wetting layer formed at the early stages of growth on the graphite surface. Besides nanochannels, ex-situ atomic force microscopy measurements also show the appearance of two more kinds of nanostructures: nano-strips and nano-rings. The appearance of these nanostructures reveals the impressive modification of the surface after the re-oxidation process mediated by the cobalt oxide.

Quantifying the Effect of Ruthenium Contamination on the ORR Activity of DMFC Cathode Catalyst

Direct methanol fuel cell (DMFC) technology is a promising energy source for portable, stationary and light transportation applications in the range of several watts and up to a few kW. Currently, one of the main drawbacks preventing widespread commercialization of DMFCs is their relatively short lifetime, up to a few thousands of hours at best. Usually a DMFC lifetime is not defined by a complete failure of the cell but by a slow and continuous degradation of the performance, up to the point when the delivered power is too low for the intended application. Several different degradation mechanisms contribute to this degradation [i], one of them is ruthenium contamination of the cathode catalyst [ii] following ruthenium dissolution from the anode PtRu catalyst and its cross-over to the cathode [iii]. The aim of our research is to quantitatively measure the effect of ruthenium contamination on the ORR performance of the cathode catalyst. For this purpose, different amounts of ruthenium (equivalent of 0.15-3 monolayers) were deposited on commercial Pt/C nanopowder to simulate ruthenium deposition on the cathode during a DMFC operation. The ruthenium-contaminated Pt/C powders were prepared using electroless polyol reduction method with methanol as the reducing agent. Johnson Matthey HiSPEC 8000 50%Pt/C was chosen to simulate a DMFC cathode catalyst. The composition, particles size and structure of these RuPt/C powders were verified by TGA, SEM-EDS, XPS, HR-TEM and STEM-EDS. Electrochemical characterization was performed with the use of cyclic-voltammetry and rotating–disk–electrode (RDE) techniques and compared to that of HiSPEC 8000. It was found that already at 0.25 equivalent monolayer of ruthenium (EDS %At Pt92Ru8, XPS %At Pt90Ru10) there is a massive, more that 25%, decrease in ORR specific activity of the commercial Pt/C catalyst. This decrease grows rapidly up to a complete inhibition of ORR at approximately 1 equivalent monolayer of ruthenium (EDS %At Pt64Ru36, XPS %At Pt50Ru50). The obtained results quantitatively show that ruthenium contamination indeed has a major role in the performance degradation of DMFCs. [i] A. Mehmood, M. A. Scibioh, J. Prabhuram, M. G. An, H.Y. Ha, Journal of Power Sources, 2015, 297,224–241 [ii] L. Gancs, B. N. Hult, N. Hakim, S. Mukerjee, Electrochem. Solid-State Lett., 2007, 10, 9, B150 [iii] P. Piela, C. Eickes, E. Brosha, F. Garzon, P. Zelenay, Journal of The Electrochemical Society, 2004, 151 (12), A2053–A2059