Hydrogen adsorption and desorption on the Pt and Pd subnano clusters — a review

In this review, we present our recent first principles studies on the sequential H₂ dissociative chemisorption and H desorption on the Pt _n and Pd _n clusters (n=2–9, 13). Upon full saturation by H atoms, the calculated H2 dissociative chemisorption energy and H desorption energy on Pt₁₃ and Pd₁₃ clusters are similar to the corresponding values on smaller close-packed clusters. Indeed, the catalytic performances of these subnano clusters do not vary significantly with the particle sizes or shapes. Instead, they are dependent on the surface metal atoms which can be accessed by H atoms. In addition to the coverage dependency of the H₂ dissociative chemisorption and H sequential desorption energies, the phase transition of both Pt₁₃ and Pd₁₃ from the icosahedral to fcc-like structures at certain H coverage was also investigated.      

Spatiotemporal self-organization in the oscillatory HCOOH oxidation on a Pt ribbon electrode – Theory and experiments

Since the current density near the edges of ribbon and disk electrodes is enhanced, the resulting stationary and non-stationary double layer potential is generally inhomogeneous in all electrochemical reactions. We investigate the impact of this edge effect induced spatial inhomogeneity on the pattern formation of the oscillatory formic acid oxidation on thin Pt ribbon electrodes. In order to be able to theoretically describe the spatiotemporal behavior of the double layer potential distribution, we derive and discuss the properties of the electrochemical ribbon coupling function for various distances of the reference electrode. The resulting reaction–migration equation is analyzed in connection with a chemical model accounting for the specific reaction mechanism of the formic acid oxidation. The interaction of structural inhomogeneity, chemically induced temporal instability and nonlocal spatial coupling due to ion migration gives rise to novel types of spatiotemporal behavior. The results compare favorably with experiments conducted so far, which are presented as well and can be explained within the framework of reaction–migration equations.     

Ethylene and acetylene adsorption on a Pt(111) face: Comparative Δφ and coverage measurements

The saturation coverages of ethylene and acetylene on a Pt(111) face have been compared both at 120 and 300 K, on the basis of TDS and AES experiments. The corresponding Δφ changes have also been recorded allowing the calculation of the average dipole moments per adspecies. The results, as discussed in related work, are consistent with the temperature induced changes in nature and structure of the surface complexes.     

Arsenic pentafluoride surface adsorption studies on Kagome-phosphorene – a DFT outlook

Arsenic pentafluoride (AsF₅) is a highly toxic gas molecule that finds its application in the manufacturing of electro-conductive polymers. Besides, exposure to AsF₅ molecule may invite several health issues, for instance, central-nervous-system disorders. Thus, the detection of AsF₅ gas is a significant and important concern for public health. For the very first time, we built a novel Kagome phosphorene nanosheet (Kagome-PNS) to study the adsorption behavior of AsF₅ molecule on the Kagome-PNS surface using density-functional theory method. The Kagome-PNS owns semiconductor property with an energy gap value of 1.22 eV. Initially, the geometrical stability of Kagome-PNS was verified with the negative value of cohesive formation energy. The transport properties of Kagome-PNS have also been carried out using current-voltage characteristics. Moreover, AsF₅ gas molecules are physisorbed on Kagome-PNS, the adsorption energy of the preferential complex structures is found to be −0.099 to −0.377 eV. An innovative finding of the present study acclaims that Kagome-PNS can be proficiently used as a chemical sensor to detect AsF₅ gas molecules.     

The influence of the composition of eight-atom Pt–Ir clusters on the magnetic properties

The energetic stability, electronic structure and magnetic properties of Pt_8–nIr_n clusters have been investigated by employing the spin-polarised generalised gradient approximation. The cubic structure is expected to be the effective building block in Ir-rich clusters after optimisation extensively. The average binding energy of all the clusters presents the linear increment trend with iridium atoms, due to the stronger interaction between Ir atoms than Pt atoms. Bader charge analysis shows how tiny charge transfers from iridium to platinum. The atomic moments of Ir are larger than that of Pt, and the Ir-rich clusters show greater moments than the Pt-rich cluster, with the exception of Ir₈ and Ir₇Pt. A unique magnetic property is found in the Pt₄Ir₄ cluster, where two Pt atoms show antiferromagnetic alignment and the other atoms are found to be aligned ferromagnetically.     

Effect of 300 and 500 MPa pressure treatments on starch–water adsorption/desorption isotherms and hysteresis

Pressure treatments of 300 and 500?MPa during 15?min were found to change starch–water sorption (adsorption and desorption) isotherms and the hysteresis effect, particularly the 500?MPa. This last treatment shifted the adsorption/desorption isotherms downward, compared with non-treated starch and starch treated at 300?MPa. The observed hysteresis effect decreased with the increase in pressure level in the whole a_w range, indicating that adsorption and desorption isotherms became closer. Guggenheim–Anderson–De Boer and Brunauer–Emmett–Teller model parameters Cb, Cg, K and Mm also showed changes caused by pressure, the latter being lower in the pressure-processed samples, thus indicating possible changes on microbial and (bio)chemical stabilities of pressure-processed food products containing starch.     

States and homomorphisms on the Pták sum

Summing of a Boolean algebra and a quantum logic has been defined by P. Pták and studied by, e.g., V. Jani, Z. Rieanová, O. Nánásiová, and C. A. Drossos. It was shown that there is a special case when this structure is a direct product. Drossos has studied the connection between this structure and a Boolean power. In this paper we investigate the conditions when the Pták sum is a free product and when the connection is between the center ofL and the structure of states onBL.     

The effect of sulfur on co adsorption/desorption on Pt(S)-[9(111) × (100)]

CO adsorption/desorption on clean and sulfur covered Pt(S)-[9(111) × (100)] surfaces was studied using AES, TPD, and modulated beam experiments. CO desorption occurred from two states on the clean surface — a low temperature state associated with the (111) terraces and a high temperature state associated with the steps/defects. Thermal desorption results indicated that above small CO coverages conversion from the low temperature state into the high temperature state was activated and that back conversion was slow. Sulfur preferentially adsorbed at step/defect sites and decreased the population of the high temperature desorption state. Modulated beam experiments were performed in order to determine CO adsorption/desorption parameters as a function of sulfur coverage on the Pt crystal. The sticking coefficient and binding energy of CO decreased as the sulfur concentration increased. Sulfur adsorption at step/defect sites decreased the CO sticking coefficient only slightly but increased the effective rate constant for CO desorption significantly. Sulfur adsorption on the terraces affected CO adosrption more than sulfur at step sites. On the clean surface the effective rate constant for CO desorption was

$\text{1 × 10}{}^{15}\text{s}{}^{\mathrm{?1}}\text{exp (}\text{?36.2 kcal/mole}\text{RT}\text{)}$

Desorption occurred from both terrace and step/defect sites, but the kinetics were characteristic of the step/defect sites. For the surface on which step/defect sites were blocked by sulfur the effective desorption rate constant was

$\text{k}{}_{\mathrm{eff}}\text{= 1 × 10}{}^{13}\text{s}{}^{\mathrm{?1}}\text{exp (?}\text{27.5 kcal/mole}\text{RT}\text{)}$

indicating an appreciable decrease in CO binding on the terraces, though sulfur-CO repulsive interactions had probably made k_eff larger than the true rate constant for desorption from clean (111) planes. The results showed clearly a compensation effect in activation energy and preexponential factor.     

Surface adsorption studies of benzyl bromide and bromobenzyl cyanide vapours on black phosphorene nanosheets – a first-principles perception

In this research, two-dimensional material, black-phosphorene nanosheets (Black-PNS) have been deployed as a sensing substrate for detecting two tear gas molecules, namely, benzyl bromide and bromobenzyl cyanide. The stability of black phosphorene sheet structure can be ensured by observing its formation energy, which is found to have ?3.895?eV/atom. Besides, the semiconducting nature of Black-PNS reinforces that it can be a potential base material to get deployed as a chemical sensor. The deviations in the density of states are noticed upon adsorption of benzyl bromide and bromobenzyl cyanide molecules on black phosphorene nanosheets. The energy of adsorption, energy gap variation and Bader charge transfer analysis are intended to investigate the assimilation properties of benzyl bromide and bromobenzyl cyanide on Black-PNS. The final results exhibit the possibility of using Black-PNS as a nanosensor substrate for lachrymator agents such as benzyl bromide and bromobenzyl cyanide.     

Effect of phosphorus and copper additions on the structure of Pt and Pt–Cu nanoparticles in a radiation-induced reduction method

A facile chemical process has been developed for the preparation of magnetic FeCo nanoparticles. The FeCo nanoparticles were mono-dispersed, obtained by the safe and ecofriendly method, possessed saturation magnetization up to 187 emu/g, and demonstrated excellent chemical stability. In this work, we have studied how to control Fe/Co ratio by variation of precursor ratio, and how to vary particle size from 9.3 to 12.3 nm by surfactant amount used. The cytotoxicity of as-synthesized nanoparticles was investigated after coating with the poly(methyl methacrylate-co-butyl acrylate) by the emulsion process and the results demonstrated high biocompatibility. Similarly, the same synthesis method was used with the single precursor FeO(OH) or Co₃O₄. The results showed that this method can also fabricate 10 nm mono-dispersed spherical Fe₃O₄ particles and self-assembly Co nanoneedles.     

Surface corrugation effects on the adsorption dynamics of xenon on Pt(110)−(1 × 2)

The adsorption probability of xenon on Pt(110)(1 × 2) shows a strong dependence on both the polar (θ_i) and aximuthal angles of incidence. For atoms incident along the (11̄0) direction the adsorption probability increases slowly with increasing angle of incidence, scaling as E_i, cos^0.5θ, whereas along the (100) azimuth it decreases with increasing angle of incidence, exhibiting “negative” energy scaling. The hard cube washboard model does not account quantitatively for these differences with a single consistent set of parameters.     

Electroweak phase transition and some related phenomena – a brief review

Pramana - In this review we have outlined a very brief history of the Higgs boson search and the development of the strategies for searching for the Higgs boson in its diphoton decay channel. We...     

Expedition on surface adsorption of N-nitrosodiethylamine from rubber fumes on blue phosphorene sheets – a first-principles insight

In recent days, humans are easily exposed to many work-related health issues. N-nitrosodiethylamine (NDE), which is considered to be a harmful carcinogenic agent released from rubber-based industries imparts a long-lasting effect on human health and immunity system. The current research investigates the ability of the two-dimensional nanomaterial, blue phosphorene nanosheet (BPNS) to detect the presence of NDE in the environment. Besides, the electronic and structural characteristics of BPNS are initially explored and NDE target vapour is permitted to interact with the chief component, BPNS. We have also designed blue phosphorene device to study the adsorption properties of NDE vapours based on current–voltage characteristics. The adsorption attributes are accounted for the target vapour adsorbed chief component, the results suggest that BPNS can be employed in detecting NDE vapours.     

MoEDAL – a new light on the high-energy frontier

In 2010, the MoEDAL (MOnopole and Exotics Detector at the LHC) experiment at the Large Hadron Collider (LHC) was unanimously approved by European Centre for Nuclear Research’s Research Board to start data taking in 2015. MoEDAL is a pioneering experiment designed to search for highly ionising manifestations of new physics such as magnetic monopoles or massive (pseudo-)stable charged particles. Its groundbreaking physics programme defines a number of scenarios that yield potentially revolutionary insights into such foundational questions as: are there extra dimensions or new symmetries; does magnetic charge exist; what is the nature of dark matter; and, how did the Big Bang develop. MoEDAL’s purpose is to meet such far-reaching challenges at the frontier of the field. The innovative MoEDAL detector employs unconventional methodologies tuned to the prospect of discovery physics. The largely passive MoEDAL detector, deployed at Point 8 on the LHC ring, has a dual nature. First, it acts like a giant camera, comprised of nuclear track detectors – analysed offline by ultra fast scanning microscopes – sensitive only to new physics. Second, it is uniquely able to trap the particle messengers of physics beyond the Standard Model for further study. MoEDAL’s radiation environment is monitored by a state-of-the-art real-time TimePix pixel detector array. A new MoEDAL sub-detector designed to extend MoEDAL reach to mini-charged, minimally ionising particles is under study.     

Natural radioactivity in groundwater – a review

The issue of natural radioactivity in groundwater is reviewed, with emphasis on those radioisotopes which contribute in a significant way to the overall effective dose received by members of the public due to the intake of drinking water originating from groundwater systems. The term ‘natural radioactivity’ is used in this context to cover all radioactivity present in the environment, including man-made (anthropogenic) radioactivity. Comprehensive discussion of radiological aspects of the presence of natural radionuclides in groundwater, including an overview of current regulations dealing with radioactivity in drinking water, is provided. The presented data indicate that thorough assessments of the committed doses resulting from the presence of natural radioactivity in groundwater are needed, particularly when such water is envisaged for regular intake by infants. They should be based on a precise determination of radioactivity concentration levels of the whole suite of radionuclides, including characterisation of their temporal variability. Equally important is a realistic assessment of water intake values for specific age groups. Only such an evaluation may provide the basis for possible remedial actions.     

Hydrogen permeability of thin condensed Pd–Cu foil: Dependence on temperature and phase composition

The hydrogen permeability of thin (about 4 μm thick) magnetron-sputtered Pd–Cu foil and structural transformations during temperature cycling (heating–cooling process) are studied. It is found that the hydrogen permeability is maximal when the content of the β-phase is 100%. Upon annealing of Pd–Cu alloy in hydrogen, the temperature range where a regular structure exists expands.     

First-principles study of Ar adsorptions on the （111） surfaces of Pd, Pt, Cu, and Rh

In the present paper we give a detailed report on the results of our first-principles investigations of Ar adsorptions at the four high symmetry sites on M （111） （M =Pd, Pt, Cu, and Rh） surfaces. Our studies indicate that the most stable adsorption sites of Ar on Pd （111） and Pt （111） surfaces are found to be the fcc-hollow sites. However, for Ar adsorptions on Cu （111） and Rh （111） surfaces, the most favorable site is the on-top site. The density of states （DOS） is analyzed for Ar adsorption on M （111） surfaces, and it is concluded that the adsorption behavior is dominated by the interaction between 3s, 3p orbits of Ar atoms and the d orbit of the base metal atoms.     

The Influence of a Crystallographically Atypical Pentagonal Nanostructured Coating on the Limiting Stage of Low-Temperature Hydrogen Transport through Pd–Cu Membranes

Doklady Physics - A new approach to the acceleration of the surface processes of hydrogen transport through Pd–40%Cu membranes by depositing a developed catalytic coating consisting of...     

Application of a parallel genetic algorithm to the global optimization of medium-sized Au–Pd sub-nanometre clusters

To contribute to the discussion of the high activity and reactivity of Au–Pd system, we have adopted the BPGA-DFT approach to study the structural and energetic properties of medium-sized Au–Pd sub-nanometre clusters with 11–18 atoms. We have examined the structural behaviour and stability as a function of cluster size and composition. The study suggests 2D–3D crossover points for pure Au clusters at 14 and 16 atoms, whereas pure Pd clusters are all found to be 3D. For Au–Pd nanoalloys, the role of cluster size and the influence of doping were found to be extensive and non-monotonic in altering cluster structures. Various stability criteria (e.g. binding energies, second differences in energy, and mixing energies) are used to evaluate the energetics, structures, and tendency of segregation in sub-nanometre Au–Pd clusters. HOMO–LUMO gaps were calculated to give additional information on cluster stability and a systematic homotop search was used to evaluate the energies of the generated global minima of mono-substituted clusters and the preferred doping sites, as well as confirming the validity of the BPGA-DFT approach.     

Morphology and structural stability of Pt–Pd bimetallic nanoparticles

The morphologies and structures of Pt–Pd bimetallic nanoparticles determine their chemical and physical properties.Therefore, a fundamental understanding of their morphologies and structural stabilities is of crucial importance to their applications. In this article, we have performed Monte Carlo simulations to systematically explore the structural stability and structural features of Pt–Pd alloy nanoparticles. Different Pt/Pd ratios, and particle sizes and shapes were considered.The simulated results reveal that the truncated octahedron, which has the remarkably lowest energy among all the considered shapes, exhibits the best structural stability while the tetrahedron has the worst invariably. Furthermore, all the structures of Pt–Pd alloy nanoparticles present Pd-rich in the outmost layer but Pt-rich in the sub-outmost layer. Especially, atomic distribution and chemical short-range order parameter were applied to further characterize the structural features of Pt–Pd alloy nanoparticles. This study provides a significant insight not only into the structural stability of Pt–Pd alloy nanoparticles with different compositions, and particle sizes and shapes but also to the design of bimetallic nanoparticles.