CO oxidation on Pd(100) and Pd(111): A comparative study of reaction pathways and reactivity at low and medium coverages

We have performed density functional theory calculations with the generalized gradient approximation to investigate CO oxidation on a close-packed transition metal surface, Pd(lll), and a more open surface, Pd(100), aiming to shed light on surface structure effects on reaction pathways and reactivity, an important issue in catalysis. Reaction pathways on both surfaces at two different coverages have been studied. It is found that the reaction pathways on both surfaces possess crucial common features despite the fact that they have different surface symmetries. Having determined reaction barriers in these systems, we find that the reaction on Pd(lll) is strongly coverage dependent. Surface coverages, however, have little effect on the reaction on Pd(100). Calculations also reveal that the low coverage reactions are structure sensitive while the medium coverage reactions are not. Detailed discussions on these results are given.

Absolute photoionization cross sections for Xe4+, Xe5+, and Xe6+ near 13.5 nm: Experiment and theory

Absolute photoionization cross-section measurements for a mixture of ground and metastable states of Xe4+, Xe5+, and Xe6+ are reported in the photon energy range of 4d -> nf transitions, which occur within or adjacent to the 13.5 nm window for extreme ultraviolet lithography light source development. The reported values allow the quantification of opacity effects in xenon plasmas due to these 4d -> nf autoionizing states. The oscillator strengths for the 4d -> 4f and 4d -> 5f transitions in Xeq+ (q=1-6) ions are calculated using nonrelativistic Hartree-Fock and random phase approximations. These are compared with published experimental values for Xe+ to Xe3+ and with the values obtained from the present experimental cross-section measurements for Xe4+ to Xe6+. The calculations assisted in the determination of the metastable content in the ion beams for Xe5+ and Xe6+. The experiments were performed by merging a synchrotron photon beam generated by an undulator beamline of the Advanced Light Source with an ion beam produced by an electron cyclotron resonance ion source.

Theory of the Kinetics of Chemical Potentials in Heterogeneous Catalysis

Simple and powerful: The reaction kinetics at surfaces of heterogeneous catalysts is reformulated in terms of the involved chemical potentials. Based on this formulism, an approach of searching for good catalysts is proposed without recourse to extensive calculations of reaction barriers and detailed kinetic analyses. (see picture; R=reactant, I=surface intermediate, P=product, and =standard chemical potential).

Enhancement Factor for Gas Absorption in a Finite Liquid Layer. Part 1: Instantaneous Reaction in a Liquid in Plug Flow

An approximate analysis of gas absorption with instantaneous reaction in a liquid layer of finite thickness in plug flow is presented. An approximate solution to the enhancement factor for the case of unequal diffusivities between the dissolved gas and the liquid reactant has been derived and validated by numerical simulation. Depending on the diffusivity ratio of the liquid reactant to the dissolved gas (?), the enhancement factor tends to be either lower or higher than the prediction of the classical enhancement factor equation based on the penetration theory (Ei,pen) at Fourier numbers typically larger than 0.1. An empirical correlation valid for all Fourier numbers is proposed to allow a quick estimation of the enhancement factor, which describes the prediction of the approximate solution and the simulation data with a relative error below 5?% under the investigated conditions (? = 0.34, Ei,pen = 21000).

Density Functional Theory Study on the Cleavage Mechanism of the Carbonyl Bond in Amides on Flat and Stepped Ru Surfaces: Hydrogen-Induced or Direct C-O Bond Breaking?

We have performed density functional theory (DFT) calculations to investigate the reaction mechanism of the cleavage of the carbonyl bond in amides on both flat and stepped Ru surfaces. The simplest amide molecule, N,N-dimethylacetamide (DMA), was used as the exemplar model molecule. Through the calculations, the most stable transition states (TSs) in all the pathways on both flat and stepped Ru surfaces are identified. Comparing the energy profiles of different reaction pathways, we find that a direct cleavage mechanism is always energetically favored as compared with an alternative hydrogen-induced mechanism on either the flat or stepped Ru surface. It is easier for the dissociation process to occur on the stepped surface than on the flat surface. However, as compared with the terrace, the superiority of step sites boosting the C-O bond dissociation is not as evident as that on CO dissociation.

Cognitive biases and addiction: an evolution in theory and method

An evolution in theoretical models and methodological paradigms for investigating cognitive biases in the addictions is discussed. Anomalies in traditional cognitive perspectives, and problems with the self-report methods which underpin them, are highlighted. An emergent body of cognitive research, contextualized within the principles and paradigms of cognitive neuropsychology rather than social learning theory, is presented which, it is argued, addresses these anomalies and problems. Evidence is presented that biases in the processing of addiction-related stimuli, and in the network of propositions which motivate addictive behaviours, occur at automatic, implicit and pre-conscious levels of awareness. It is suggested that methods which assess such implicit cognitive biases (e.g. Stroop, memory, priming and reaction-time paradigms) yield findings which have better predictive utility for ongoing behaviour than those biases determined by self-report methods of introspection. The potential utility of these findings for understanding "loss of control" phenomena, and the desynchrony between reported beliefs and intentions and ongoing addictive behaviours, is discussed. Applications to the practice of cognitive therapy are considered.

Influence of surface structures, subsurface carbon and hydrogen, and surface alloying on the activity and selectivity of acetylene hydrogenation on Pd surfaces: A density functional theory study

The selective hydrogenation of acetylene to ethylene on several Pd surfaces (Pd(111), Pd(100), Pd(211), and Pd(211)-defect) and Pd surfaces with subsurface species (carbon and hydrogen) as well as a number of Pd-based alloys (Pd-M/Pd(111) and Pd-M/Pd(211) (M = Cu, Ag and Au)) are investigated using density functional theory calculations to understand both the acetylene hydrogenation activity and the selectivity of ethylene formation. All the hydrogenation barriers are calculated, and the reaction rates on these surfaces are obtained using a two-step model. Pd(211) is found to have the highest activity for acetylene hydrogenation while Pd(100) gives rise to the lowest activity. In addition, more open surfaces result in over-hydrogenation to form ethane, while the close-packed surface (Pd(111)) is the most selective. However, we also find that the presence of subsurface carbon and hydrogen significantly changes the reactivity and selectivity of acetylene toward hydrogenation on Pd surfaces. On forming surface alloys of Pd with Cu, Ag and Au, the selectivity for ethylene is also found to be changed. A new energy decomposition method is used to quantitatively analyze the factors in determining the changes in selectivity. These surface modifiers are found to block low coordination unselective sites, leading to a decreased ethane production. (C) 2013 The Authors. Published by Elsevier Inc. All rights reserved.

The reaction path of CO and Fe2O3 in a chemical-looping combustion system

The reaction mechanism of CO and Fe₂O₃ in a chemical-looping combustion (CLC) was studied based on density functional theory (DFT) at B3LYP level in this paper. The structures of all reactants, intermediate, transition structures and products of this reaction had been optimized and characterized. The reaction path was validated by means of the intrinsic reaction coordinate (IRC) approach. The result showed that the reaction was divided into two steps, the adsorbed CO molecule on Fe ₂O₃ surface formed a medium state with one broken Fe-O bond in step1, and in step2, O atom broken here oxidized a subsequent CO molecule in the fuel reactor. Thus, Fe₂O₃ molecule transport O from air to oxide CO continually in the CLC process. The activation energy and rate coefficients of the two steps were also obtained.

Density Functional Study on Reaction Activity of Steam Decomposition Products Adsorbed on Carbonaceous Surface

A systematic theoretical study on the adsorption of steam and its thermal decomposition products on carbon both zigzag and armchair surface was performed to provide molecular-level understanding of the reaction activity of all these reactants in biomass steam gasification process. All the calculations were carried out using density functional theory (DFT) at the B3LYP/6-31+g(d,p) level. The structures of carbonaceous surfaces, all reactants and surface complexes were optimized and characterized. Based on the value of adsorption heat been obtained from the calculation, the activity of all reactants can be ordered as: O > O2 >H2 >H >OH >H2O for both zigzag and armchair surface, and the adsorption style is physisorption to water molecule and chemisorption to the other dissociated components.

Application of Asymmetric Marcus-Hush Theory to Voltammetry in Room-Temperature Ionic Liquids

Asymmetric MarcusHush (AMH) theory is applied for the first time in ionic solvents to model the voltammetric reduction of oxygen in 1-butyl-1-methylpyrrolidinium bis-(trifluoromethylsulfonyl)-imide and of 2-nitrotoluene (2-NT), nitrocyclopentane (NCP), and 1-nitro-butane (BuN) in trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate on a gold microdisc electrode. An asymmetry parameter, gamma, was estimated for all systems as -0.4 for the reduction of oxygen and -0.05, 0.25, and 0 +/- 0.05 for the reductions of 2-NT, NCP, and BuN, respectively, which suggests equal force constants of reactants and products in the case of 2-NT and BuN and unequal force constants for oxygen and NCP where the force constants of the oxidized species are greater than the reduced species in the case of oxygen and less than the reduced species in the case of NCP. Previously measured values for a, the Butler-Volmer transfer coefficient, reflect this in each case. Where appreciable asymmetry occurs, AMH theory was seen to parametrize the experimental data better than either Butler-Volmer or symmetric Marcus-Hush theory, allowing additionally the extraction of reorganization energy. This is the first study to provide key physical insights into electrochemical systems in room-temperature ionic liquids using AMH theory, allowing elucidation of the reorganization energies and the relative force constants of the reactants and products in each reaction.

Identifying the distinct features of geometric structures for hole trapping to generate radicals on rutile TiO2(110) in photooxidation using density functional theory calculations with hybrid functional

Using density functional theory calculations with HSE 06 functional, we obtained the structures of spin-polarized radicals on rutile TiO2(110), which is crucial to understand the photooxidation at the atomic level, and further calculate the thermodynamic stabilities of these radicals. By analyzing the results, we identify the structural features for hole trapping in the system, and reveal the mutual effects among the geometric structures, the energy levels of trapped hole states and their hole trapping capacities. Furthermore, the results from HSE 06 functional are compared to those from DFT + U and the stability trend of radicals against the number of slabs is tested. The effect of trapped holes on two important steps of the oxygen evolution reaction, i.e. water dissociation and the oxygen removal, is investigated and discussed.

Activity and coke formation of nickel and nickel carbide in dry reforming: A deactivation scheme from density functional theory

Dry reforming is a promising reaction to utilise the greenhouse gases CO2 and CH4. Nickel-based catalysts are the most popular catalysts for the reaction, and the coke formation on the catalysts is the main obstacle to the commercialisation of dry reforming. In this study, the whole reaction network of dry reformation on both flat and stepped nickel catalysts (Ni(111) and Ni(211)) as well as nickel carbide (flat: Ni3C(001); stepped: Ni3C(111)) is investigated using density functional theory calculations. The overall reaction energy profiles in the free energy landscape are obtained, and kinetic analyses are utilised to evaluate the activity of the four surfaces. By careful examination of our results, we find the following regarding the activity: (i) flat surfaces are more active than stepped surfaces for the dry reforming and (ii) metallic nickel catalysts are more active than those of nickel carbide, and therefore, the phase transformation from nickel to nickel carbide will reduce the activity. With respect to the coke formation, the following is found: (i) the coke formation probability can be measured by the rate ratio of CH oxidation pathway to C oxidation pathway (r(CH)/r(C)) and the barrier of CO dissociation, (ii) on Ni(111), the coke is unlikely to form, and (iii) the coke formations on the stepped surfaces of both nickel and nickel carbide can readily occur. A deactivation scheme, using which experimental results can be rationalised, is proposed. 

Density functional theory study on the activation of molecular oxygen on a stepped gold surface in an aqueous environment: a new approach for simulating reactions in solution

The activation of oxygen molecules is an important issue in the gold-catalyzed partial oxidation of alcohols in aqueous solution. The complexity of the solution arising from a large number of solvent molecules makes it difficult to study the reaction in the system. In this work, O-2 activation on an Au catalyst is investigated using an effective approach to estimate the reaction barriers in the presence of solvent. Our calculations show that O-2 can be activated, undergoing OOH* in the presence of water molecules. The OOH* can readily be formed on Au(211) via four possible pathways with almost equivalent free energy barriers at the aqueous-solid interface: the direct or indirect activation of O-2 by surface hydrogen or the hydrolysis of O-2 following a Langmuir-Hinshelwood mechanism or an Eley-Rideal mechanism. Among them, the Eley-Rideal mechanism may be slightly more favorable due to the restriction of the low coverage of surface H on Au(211) in the other mechanisms. The results shed light on the importance of water molecules on the activation of oxygen in gold-catalyzed systems. Solvent is found to facilitate the oxygen activation process mainly by offering extra electrons and stabilizing the transition states. A correlation between the energy barrier and the negative charge of the reaction center is found. The activation barrier is substantially reduced by the aqueous environment, in which the first solvation shell plays the most important role in the barrier reduction. Our approach may be useful for estimating the reaction barriers in aqueous systems.

Mn ion dissolution from MnS:a density functional theory study

The dissolution of MnS inclusions could induce pitting corrosion in stainless steels, but its dissolution mechanism is poorly understood at the atomic scale. With the help of ab initio molecular dynamics calculations, one inevitable step in the dissolution of MnS is studied by simulating the process of one Mn ion leaving the surface. The reaction mechanism is determined to contain three steps with two large barriers and a small one, leading to two slow steps in the Mn ion dissolution. Comparing to the Na ion dissolution from NaCl, the barriers of the Mn ion dissolution are much larger, which is a reflection of their different electronic structures.

A density functional theory study of hydrogen dissociation and diffusion at the perimeter sites of Au/TiO2

Reactivity of supported gold catalysts is a hot topic in catalysis for many years. This communication reports an investigation on the dissociation of molecular hydrogen at the perimeter sites of Au/TiO2 and the spillover of hydrogen atoms from the gold to the support using density functional theory calculations. It is found that the heterolytic dissociation is favoured in comparison with homolytic dissociation of molecular hydrogen at the perimeter sites. However, the surface oxygen of the rutile TiO2(110) surface at these sites can be readily passivated by the formed OH, suggesting that further dissociation of molecular hydrogen may occur at pure gold sites.