TiS2 Monolayer as an Emerging Ultrathin Bifunctional Catalyst: Influence of Defects and Functionalization.

We have envisaged the hydrogen evolution and oxygen evolution reactions (HER and OER) on a two-dimensional (2D) noble-metal-free titanium disulfide (TiS2 ) monolayer, which belongs to the exciting family of transition metal dichalcogenides (TMDCs). Our theoretical investigation to probe the HER and OER on both the H and T phases of 2D TiS2 is based on electronic-structure calculations witihin the framework of density functional theory (DFT). Since TiS2 is the lightest compound among the group-IV TMDCs, it is worth exploring the catalytic activity of a TiS2 monolayer through the functionalization at the anion (S) site, substituting with P, N, and C dopants as well as by incorporating single sulfur vacancy defects. We have investigated the effect of functionalization and vacancy defects on the structural, electronic, and optical response of a TiS2 monolayer by determining the density of states, work-function, and optical absorption spectra. We have determined the HER and OER activities for the functionalized and defective TiS2 monolayers based on the reaction coordinate, which can be constructed from the adsorption free energies of the intermediates (H*, O*, OH* and OOH*, where * denotes the adosrbed state) in the HER and OER mechanisms. Finally, we have shown that TiS2 monolayers are emerging as a promising material for the HER and OER mechanisms under the influence of functionalization and defects.

Investigation of ORR Performances on Graphene/Phthalocyanine Nanocomposite in Neutral Medium.

The drive to replace scarce and expensive Pt-based electrocatalysts for oxygen reduction reaction (ORR) has led to the development of a group of electrocatalysts composed of transition-metal ion centers coordinated with four nitrogen groups (M-N4). Among these, metal phthalocyanines (MPcs), due to low cost of preparation, highly conjugated structure as well as high thermal and chemical stability, have received a great interest. The catalytic activity of MPcs can be improved by employing conducting supports. Here, in this report, we have solvothermally synthesized graphene-supported zinc phthalocyanine nanostructures, and their ORR kinetics and mechanism have been investigated in neutral solution (pH = 7) by using the rotating disk electrode technique. The as-synthesized nanocomposite followed a 4e- reduction pathway. The onset potential (-0.04 V versus Ag/AgCl) found in this work can be comparable with other state-of-the-art material, demonstrating good performance in neutral solution. The fascinating performance leads the nanocomposite material toward future energy applications.

Chemical Bonding in Large Systems Using Projected Population Analysis from Real-Space Density Functional Theory Calculations.

We present an efficient and scalable computational approach for conducting projected population analysis from real-space finite-element (FE)-based Kohn-Sham density functional theory calculations (DFT-FE). This work provides an important direction toward extracting chemical bonding information from large-scale DFT calculations on materials systems involving thousands of atoms while accommodating periodic, semiperiodic, or fully nonperiodic boundary conditions. Toward this, we derive the relevant mathematical expressions and develop efficient numerical implementation procedures that are scalable on multinode CPU architectures to compute the projected overlap and Hamilton populations. The population analysis is accomplished by projecting either the self-consistently converged FE discretized Kohn-Sham orbitals or the FE discretized Hamiltonian onto a subspace spanned by a localized atom-centered basis set. The proposed methods are implemented in a unified framework within the DFT-FE code where the ground-state DFT calculations and the population analysis are performed on the same FE grid. We further benchmark the accuracy and performance of this approach on representative material systems involving periodic and nonperiodic DFT calculations with LOBSTER, a widely used projected population analysis code. Finally, we discuss a case study demonstrating the advantages of our scalable approach to extract the quantitative chemical bonding information of hydrogen chemisorbed in large silicon nanoparticles alloyed with carbon, a candidate material for hydrogen storage.

The origin of diverse lattice dynamics in the graphene family.

We employ first principles based density functional theory calculations to explore the lattice dynamics of members of the graphene family. We explore the changes observed in the lattice thermal conductivity via adopting physical models for estimating phonon lifetimes. This allows us to establish a connection between the parameters such as group velocity, Grüneisen parameter, and Debye temperature of the acoustic phonon modes and the lattice thermal conductivity. Our calculations show that the presence of buckling reduces the group velocity and the Debye temperature of the sheets down the group, and hence, reduces their lattice thermal conductivity. However, there is no linear dependence between the buckling height and the observed lowering. An increase in buckling height in sheets with different geometries of the same atomic species, beyond a certain limit, does not lead to change in the group velocity and the Debye temperature of the sheets.

Heteroepitaxial Junction in Au-ZnSe Nanostructure: Experiment versus First-Principle Simulation.

Composing together the experimental as well as the simulated results, we demonstrate here the atomic placements and the electronic structure at the epitaxial junction of a solution-processed heteronanostructure Au-ZnSe. Despite the large lattice mismatch (∼32%) between fcc Au and zinc-blende structured ZnSe, the heterostructures are formed via coincidence site epitaxy, which appears periodically because of the arrangements of their proper unit cell placements at the junction. This reduces the interface energy and drives the formation of such heteronanostructures. Details of the physical processes involved in the formation of these nanostructures have been discussed in this letter, and epitaxy at the heterojunction is strongly supported by HRTEM measurement and DFT calculation. This material has the possibility of plasmon-exciton coupling and therefore might be a futuristic material for utilizations in catalysis, nanoelectronics, and other related applications.