Size-dependent bond dissociation enthalpies in single-walled carbon nanotubes

We report the bond dissociation enthalpy (BDE) and the local electronic properties of Single-Walled Carbon Nanotubes (SWCNT) using density functional theory. Our analysis shows that there is a strong size-dependence of the BDE of these SWCNTs, which is inversely proportional to the radius-squared (1/r2) and the length (1/l) of SWCNT. We derive quantitative relationships from which the BDE can be calculated as a function of size and radius of the SWCNT. We find that the BDE of SWCNT outside the size-dependent region is about 480 kJ mol−1, which can be used for thermochemical calculations

A DFT and KMC based study on the mechanism of the water gas shift reaction on the Pd(100) surface

We present a combined density functional theory (DFT) and Kinetic Monte Carlo (KMC) study of the water gas shift (WGS) reaction on the Pd(100) surface. We propose a mechanism comprising both the redox and the associative pathways for the WGS within a single framework, which consists of seven core elementary steps, which in turn involve splitting of a water molecule followed by the production of an H-atom and an OH-species on the Pd(100) surface. In the following steps, these intermediates then recombine with each other and with CO leading to the evolution of CO2, and H2. Seven other elementary steps, involving the diffusion and adsorption of the surface intermediate species are also considered for a complete description of the mechanism. The geometrical and electronic properties of each of the reactants, products, and the transition states of the core elementary steps are presented. We also discuss the analysis of Bader charges and spin densities for the reactants, transition states and the products of these elementary steps. Our study indicates that the WGS reaction progresses simultaneously via the direct oxidation and the carboxyl paths on the Pd(100) surface

Spin-Valley Kondo Effect in Multi-electron Silicon Quantum Dots

We study the spin-valley Kondo effect of a silicon quantum dot occupied by $\mathcal{N}$ electrons, with $\mathcal{N}$ up to four. We show that the Kondo resonance appears in the $\mathcal{N}=1,2,3$ Coulomb blockade regimes, but not in the $\mathcal{N}=4$ one, in contrast to the spin-1/2 Kondo effect, which only occurs at $\mathcal{N}=$ odd. Assuming large orbital level spacings, the energy states of the dot can be simply characterized by fourfold spin-valley degrees of freedom. The density of states (DOS) is obtained as a function of temperature and applied magnetic field using a finite-U equation-of-motion approach. The structure in the DOS can be detected in transport experiments. The Kondo resonance is split by the Zeeman splitting and valley splitting for double- and triple-electron Si dots, in a similar fashion to single-electron ones. The peak structure and splitting patterns are much richer for the spin-valley Kondo effect than for the pure spin Kondo effect.Comment: 8 pages, 4 figures, in PRB format. This paper is a sequel to the paper published in Phys. Rev. B 75, 195345 (2007

A computational investigation of the adsorption of small copper clusters on the CeO_{2}(110) surface

We report a detailed density functional theory (DFT) study of the geometrical and electronic properties, and the growth mechanism of a Cu_{n} (n = 1–4) cluster on a stoichiometric, and especially on a defective CeO_{2} (110) surface with one surface oxygen vacancy, without using pre-assumed gas-phase Cun cluster shapes. This gives new and valuable theoretical insight into experimental work regarding debatable active sites of promising CuO_{x}/Ceo_{2} - nanorod catalysts in many reactions. We demonstrate that CeO_{2}(110) is highly reducible upon Cun adsorption, with electron transfer from Cu_{n} clusters, and that a Cu_{n} cluster grows along the long bridge sites until Cu_{3}, so that each Cu atom can interact strongly with surface oxygen ions at these sites, forming stable structures on both stoichiometric and defective CeO_{2}(110) surface. Cu–Cu interactions are, however, limited, since Cu atoms are distant from each other, inhibiting the formation of Cu–Cu bonds. This monolayer then begins to grow into a bilayer as seen in the Cu_{3} to Cu_{4} transition, with long-bridge site Cu as anchoring sites. Our calculations on Cu_{4} adsorption reveal a Cu bilayer rich in Cu^{+} species at the Cu–O interface

Surface-Oxygen Induced Electrochemical Self-Assembly of Mesoporous Conducting Polymers for Electrocatalysis

Porous polymers have immense potential in catalysis, energy conversion and storage, separation sciences and life sciences due to their high surface area and high diffusion flux. Developing porous polymers with micro and mesoscale porosity with long-range order is challenging and involves multistep templated approaches. Here we demonstrate a simple surface-oxygen induced electropolymerization route to directly obtain self-assembled porous polymers of polyparaphenylene (PPP) and PPP based copolymers in ionic liquids. By combining experimental and theoretical studies, we show that surface oxygen on Cu changes the orientation and assembly of benzene which then results in a change in electropolymerization mechanism leading to a self-assembled porous structure with porosity between 2 and 5 μm. Furthermore, with controlled experimental parameters, bicontinuous conducting polymers with porosity of >10 μm are obtained. The porous conducting polymers show absorption of light in the visible range which was also used as an efficient electrode for investigation of the photoelectrochemical oxygen evolution reaction.We acknowledge the use of Athena at HPC Midlands+ in this research, which was funded by the EPSRC (grant EP/P020232/1) via the EPSRC RAP call of spring 2018 and 2019. Supercomputer Wales is also thanked for the computing time. In this work ARCHER - the UK National Supercomputing Service (https://www.archer.ac.uk) was also used via the membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202)

Carbidisation of Pd nanoparticles by ethene decomposition, with methane production

In the presence of oxygenated organic molecules pure Pd, which is widely used in chemicals processing and the pharmaceutical industry, tends to defunctionalise and dehydrogenate such molecules to H2, CO and surface/bulk carbon, in the form of a palladium carbide. We have investigated the formation of this carbide by ethene adsorption using a variety of techniques, including pulsed flow reaction measurements, XAS and DFT calculations of the lattice expansion during carbidisation. These experiments show that two main reactions take place above 500K, that is, both total dehydrogenation, but also disproportionation to methane and the carbide, after which the activity of the Pd is completely lost. We estimate the value of x in PdCx to be 0.28 (±0.03), and show by computer modelling that this fits the lattice expansion observed by XAFS, and that there is charge transfer to C from Pd of around 0.2-0.4 e

The adsorption of Cu on the CeO2(110) surface

We report a detailed density functional theory (DFT) study in conjunction with extended X-ray absorption fine structure (EXAFS) experiments on the geometrical and local electronic properties of Cu adatoms and Cu(II) ions in presence of water molecules and of CuO nanoclusters on the CeO2(110) surface. Our study of (CuO)n(=1,2&4) clusters on CeO2(110) shows that based on the Cu–O environment, the geometrical properties of these clusters may vary and their presence may lead to relatively high localization of charge on the exposed surfaces. We find that in the presence of an optimum concentration of water molecules, Cu has a square pyramidal geometry, which agrees well with our experimental findings; we also find that Cu(II) facilitates water adsorption on the CeO2(110) surface. We further show that a critical concentration of water molecules is required for the hydrolysis of water on Cu(OH)2/CeO2(110) and on pristine CeO2(110) surfaces

Selectivity of the Lindlar catalyst in alkyne semi-hydrogenation: a direct liquid-phase adsorption study

We study the alkyne semi-hydrogenation selectivity over Pd and Lindlar catalyst with liquid phase adsorption. The results indicate that there are strongly-adsorbing alkyne and alkene sites; alkenes react non-selectively over the alkene adsorption sites. DFT studies indicate that the non-selective sites are low-coordination Pd atoms in the nanoparticles

A DFT and KMC Based Study on the Mechanism of Water Gas Shift Reaction on Pd(100) Surface

We present a combined density functional theory (DFT) and Kinetic Monte Carlo (KMC) study of the water gas shift (WGS) reaction on the Pd(100) surface. We propose a mechanism comprising both the redox and the associative pathways for the WGS within a single framework, which consists of seven core elementary steps, which in turn involve splitting of a water molecule followed by the production of an Hatom and an OH-species on the Pd(100) surface. In the following steps, these intermediates then recombine with each other and with CO leading to the evolution of CO2, and H2. Seven other elementary steps, involving the diffusion and adsorption of the surface intermediate species are also considered for a complete description of the mechanism. The geometrical and electronic properties of each of the reactants, products, and the transition states of the core elementary steps are presented. We also discuss the analysis of Bader charges and spin densities for the reactants, transition states and the products of these elementary steps. Our study indicates that the WGS reaction progresses simultaneously via the direct oxidation and the carboxyl paths on the Pd(100) surface