Time-Dependent Density Functional Theory Calculations of N- and S-Doped TiO2 Nanotube for Water-Splitting Applications.

On the basis of time-dependent density functional theory (TD-DFT) we performed first-principle calculations to predict optical properties and transition states of pristine, N- and S-doped, and N+S-codoped anatase TiO2 nanotubes of 1 nm-diameter. The host O atoms of the pristine TiO2 nanotube were substituted by N and S atoms to evaluate the influence of dopants on the photocatalytic properties of hollow titania nanostructures. The charge transition mechanism promoted by dopants positioned in the nanotube wall clearly demonstrates the constructive and destructive contributions to photoabsorption by means of calculated transition contribution maps. Based on the results of our calculations, we predict an increased visible-light-driven photoresponse in N- and S-doped and the N+S-codoped TiO2 nanotubes, enhancing the efficiency of hydrogen production in water-splitting applications.

Modeling of Nanoscale Electromagnets Based on Gold Finite Nanosolenoids.

Magnetic fields generated by the nanosolenoids based on the (5, 3) and (10,7) gold nanotubes (AuNTs) 12-600 Å long with numbers of Au atoms 20-2000 are calculated. The electron energy levels of the finite length tubules were determined using the linearized augmented cylindrical waves method with Born-von Karman cyclic boundary conditions and on account of a helical symmetry of the AuNTs. Using these data, the numbers of conducting channels N F and the low-temperature ballistic electron currents in the finite AuNTs are determined, and finally, the magnetic fields B of the gold nanosolenoids are obtained. Due to the increase in the number of conduction channels with the increase in the length of the tubes, the internal magnetic field gradually increases from 1.6 T/V in a tubule with L = 12 Å up to 12 T/V in a tube with L = 600 Å, slowly approaching the magnetic field of 14 T/V of the infinite (5, 3) AuNT. At a distance of 5 Å from the ends of the tubes (near z = L/2 - 5 Å), this field decreases rapidly, halving at z = L/2 and almost zeroing near z = L/2 + 5 Å. The field from the outside of the tubes is weak but not zero as in the infinite tubule. It is minimal at z = 0 and reaches a maximum at the edge of the AuNTs, where it is about 3-4 times less than the internal field. These results pave the way for a more realistic design of the nanosolenoids.

First-Principles Evaluation of the Morphology of WS2 Nanotubes for Application as Visible-Light-Driven Water-Splitting Photocatalysts.

One-dimensional tungsten disulfide (WS2) single-walled nanotubes (NTs) with either achiral, i.e., armchair (n, n) and zigzag-type (n, 0), or chiral (2n, n) configuration with diameters d NT > 1.9 nm have been found to be suitable for photocatalytic applications, since their band gaps correspond to the frequency range of visible light between red and violet (1.5 eV < Δεgap < 2.6 eV). We have simulated the electronic structure of nanotubes with diameters up to 12.0 nm. The calculated top of the valence band and the bottom of the conduction band (εVB and εCB, respectively) have been properly aligned relatively to the oxidation (εO2/H2O) and reduction (εH2/H2O) potentials of water. Very narrow nanotubes (0.5 < d NT < 1.9 nm) are unsuitable for water splitting because the condition εVB < εO2/H2O < εH2/H2O < εCB does not hold. For nanotubes with d NT > 1.9 nm, the condition εVB < εO2/H2O < εH2/H2O < εCB is fulfilled. The values of εVB and εCB have been found to depend only on the diameter and not on the chirality index of the nanotube. The reported structural and electronic properties have been obtained from either hybrid density functional theory and Hartree-Fock linear combination of atomic orbitals calculations (using the HSE06 functional) or the linear augmented cylindrical waves density functional theory method. In addition to single-walled NTs, we have investigated a number of achiral double-walled (m, m)@(n, n) and (m, 0)@(n, 0) as well as triple-walled (l, l)@(m, m)@(n, n) and (l, 0)@(m, 0)@(n, 0) nanotubes. All multiwalled nanotubes show a common dependence of their band gap on the diameter of the inner nanotube, independent of chirality index and number of walls. This behavior of WS2 NTs allows the exploitation of the entire range of the visible spectrum by suitably tuning the band gap.