Application of GaS nanotubes as efficient catalysts in photocatalytic hydrolysis: a first principles study.

Photocatalytic hydrogen production is a promising and sustainable technology that converts solar energy into hydrogen energy with the assistance of semiconductor photocatalysts. Herein, we investigated the geometric structure and electronic and photocatalytic properties of single-walled GaS nanotubes under the framework of density functional theory with HSE06 as an exchange-correlation function. This paper presents the first study on the geometric structure, electron, and photocatalytic properties of single-walled GaS nanotubes. The results show that the strain energy and formation energy of GaS nanotubes decrease, while the structure is more stable, with increasing radius. Our study shows that after rolling from the slab, the nanotubes undergo a transition from an indirect band gap to a direct band gap and have appropriate band gaps for absorbing visible light. Moreover, it is speculated that the large disparity between the effective mass of electrons and holes can reduce charge carrier recombination. Among them, the nanotube with a diameter larger than (35, 0) showed promising band edge positions for photocatalytic hydrolysis redox potential with pH values between 0 and 7. Based on these properties, we believe that GaS nanotubes will be promising in photocatalytic hydrolysis.

Structural and electronic properties of double-walled G-C3N4 nanotubes: a density functional theory study.

In the present work, we investigated the geometric, electronic, and photocatalytic properties of g-C3N4single-walled nanotube (SWCNNTs) and g-C3N4double-walled nanotubes (DWCNNTs). The negative strain energy indicates that the SWCNNTs have a stable structure, while the most stable combination in the DWCNNT is (6, 0)@(12, 0). The energy band gaps of (n, 0) SWCNNTs increase while that of (n,n) SWCNNTs decrease as the diameter increase. Moreover, the calculated nanotubes have the ability of photocatalytic water splitting, and the valance band maximum of nanotubes are much lower than that of the monolayer, indicating that the nanotubes have better oxidation capacity than the monolayer. On the other hand, our calculations show that DWCNNTs have type II band alignment with a band gap width significantly smaller than that of SWCNNTs. Interestingly, DWCNNT exhibited a smaller effective mass of electrons than SWCNNTs, which is beneficial to electron migration. Therefore, the construction of nanotube is an effective way to improve the photocatalytic performance of g-C3N4monolayer materials.

Janus Ga2SSe nanotubes as efficient photocatalyst for overall water splitting.

Using sunlight to decompose water into hydrogen and oxygen is one of the most important ways to solve the current global environmental issues and energy problems. In this paper, we use density functional theory to predict the photocatalytic performance of Janus Ga2SSe nanotubes (JGSSe NTs) for the first time. The result shows that the small formation energy and strain energy ensure the stability of the nanotubes. Compared with monolayers, the visible light absorption range of JGSSe NTs is wider, and the large radius (>26.60 A) nanotubes all meet the hydrolysis potential. Surprisingly, the hole mobility of JGSSe NT was estimated to be as high as 2.89 × 104cm2V-1S-1. In conclusion, JGSSe nanotubes are expected to be an excellent photocatalyst due to their low electron-hole recombination rate, high hole mobility, solar absorption in the visible light range, and good oxidation capacity. In addition, the nanotube band gap can be effectively regulated by applying strain. It is hoped that our research will provide meaningful progress in the development of novel and efficient photocatalysts. We hope that our research will provide a possible way to develop novel and efficient photocatalysts.

New Opportunity for in Situ Exsolution of Metallic Nanoparticles on Perovskite Parent.

One of the main challenges for advanced metallic nanoparticles (NPs) supported functional perovskite catalysts is the simultaneous achievement of a high population of NPs with uniform distribution as well as long-lasting high performance. These are also the essential requirements for optimal electrode catalysts used in solid oxide fuel cells and electrolysis cells (SOFCs and SOECs). Herein, we report a facile operando manufacture way that the crystal reconstruction of double perovskite under reducing atmosphere can spontaneously lead to the formation of ordered layered oxygen deficiency and yield segregation of massively and finely dispersed NPs. The real-time observation of this emergent process was performed via an environmental transmission electron microscope. Density functional theory calculations prove that the crystal reconstruction induces the loss of coordinated oxygen surrounding B-site cations, serving as the driving force for steering fast NP growth. The prepared material shows promising capability as an active and stable electrode for SOFCs in various fuels and SOECs for CO2 reduction. The conception exemplified here could conceivably be extended to fabricate a series of supported NPs perovskite catalysts with diverse functionalities.

Tuning photocatalytic performance of the near-infrared-driven photocatalyst Cu2(OH)PO4 based on effective mass and dipole moment.

Recently, Cu2(OH)PO4 was found as the first photocatalyst active in the near-infrared(NIR) region of the solar spectrum (Angew. Chem., Int. Ed., 2013, 52, 4810; Chem. Eng. News, 2013, 91, 36), motivating us to explore systemically its photocatalytic mechanism under near-infrared light and how to improve and tune its photocatalytic performance. Herein, electronic structures, and effective masses of electron and hole at energy band edges are theoretically investigated by employing spin-polarized density functional theory calculations. The calculated energy band structure supports the absorption spectra of Cu2(OH)PO4 in the NIR region corresponding to the electron excitation from the valence band to the unoccupied bands in the gap. Our charge density analysis indicates that the O atoms in the hydroxyl serves as the effective bridge for the favoring separation of the photogenerated electron-hole pairs. Furthermore, the effective masses of electron and hole analysis demonstrate that the separation and transfer of photogenerated carriers along the [011] direction may be more effective than other possible directions. A qualitative comparison of carrier transfer ability along all the directions in the specific planes is displayed by the three-dimensional band structure. Interestingly, the calculated net dipole moment for the two basic units of Cu2(OH)PO4, octahedron and trigonal bipyramid, indicate that the macroscopic dipole moment for Cu2(OH)PO4 is zero, however, the distorted octahedron unit has a net dipole moment, which enables us to tune the macroscopic dipole moment by doping. The present work provides theoretical insight leading to a better understanding of the photocatalytic performance of Cu2(OH)PO4 and it may be beneficial to prepare more efficient Cu2(OH)PO4 for NIR light photocatalysis, which will also be helpful to design and prepare novel photocatalysts.

Synergistic modification of electronic and photocatalytic properties of TiO2 nanotubes by implantation of Au and N atoms.

The structural and electronic properties of N-doped, Au-adsorbed, and Au/N co-implanted TiO2 nanotubes (NTs) were investigated by performing first-principle density functional theory (DFT) calculations. For all the possible implanted configurations, the radius and bond length do not change significantly relative to the clean NTs. Our results indicate that the introduction of N into NTs is in favor of implantation of Au, and Au pre-adsorption on the NTs can also enhance the N concentration in NTs. The synergistic stability can be mainly attributed to charge transfer between Au and N atoms. In co-implanted configurations, the empty N 2p states in the band gap are occupied by one electron; denoted by Au 5s states. Thus, the associated electron transition among the valence band, the conduction band and the gap states results in redshift of the light absorption. In addition, the disappearance of N 2p empty states can effectively decrease the photogenerated carrier combination. Therefore, the Au/N implanted NTs should be regarded as a promising photocatalytic material under the visible light region.

Strain-engineered modulation on the electronic properties of phosphorous-doped ZnO.

The modulation of strain on the electronic properties of ZnO:P is investigated by density functional theory calculations. The variation of formation energy (E(f)) and band structure with strains ranging from -0.1 to 0.1 are considered. Although both the conduction band minimum (CBM) and the valence band maximum of ZnO are antibonding states, the CBM is more sensitive to strain, reducing the band gap with an increase in strain. P-substituted O (PO) defects show poor p-type conductivity due to a smaller E(f) and lower lying acceptor levels as a consequence of lattice expansion. The E(f) of P-substituted Zn (PZn) defects decreases under tension, owing to the release of strong repulsive stress induced by excess electrons from PZn. The donor energy band of PZn broadens under tensile strain, which benefits n-type conductivity. For Zn vacancies (VZn) and PZn-2VZn complexes, the distances between the O atoms around VZn are so large that repulsive and attractive interactions become weak, which results in an easy release of the strain. We herein present for the first time that the E(f) values of VZn and PZn-2VZn complexes decrease under both tension and compression, or in the high-pressure rock-salt phase. Under a strain of 0.1 the PZn-2VZn complex shows the smallest E(f). Under -0.07 strain the wurtzite/rock-salt phase transition occurs and the direct band gap becomes an indirect one. The variation of band structures in the rock-salt phase is similar to that in the wurtzite phase. Consequently, the p-type conductivity of ZnO:P can be improved with an increase in solubility of PZn-2VZn or VZn defects.

Insights into the adsorption and energy transfer of Ag clusters on the AgCl(100) surface.

It is fundamental to uncover the real adsorption properties of Ag clusters on an AgCl surface and the energy transfer mechanisms at the interface to understand the highly active photocatalytic performance and the stability of the plasmonic photocatalyst Ag@AgCl. Based on density functional theory calculations we provide valuable insights into the binding nature of Ag clusters on AgCl surface, where the binding between Ag atoms in the cluster and on the surface plays a decisive role in determining the most stable adsorption configurations. Our results demonstrate that there is energy transfer from the plasmonic metals to substrate. The hot holes excited by the decay of surface plasmon resonance on the metals can diffuse into the Cl ions in the outermost two layers of the surface producing highly oxidative Cl atoms. The dipole-dipole interaction between the plasmonic metal clusters and substrate Cl ions can also generate electron-hole pairs in the surface layers. It is deduced that the positively charged nature of adsorbed clusters acting as electron trapping centers and reduction sites plays a crucial role in keeping the stability of the Ag@AgCl system during the photocatalytic process. Finally, the validity of the cluster adsorption model for energy transfer is verified with respect to the nucleation and aggregation process of Ag atoms on the AgCl surface and a detailed description of the formation and evolution of Ag nanoparticles on an AgCl surface is provided. The present study may be helpful for understanding and designing this novel plasmonic photocatalyst and can be useful for investigating other relevant photocatalysts as well.

Hydrodynamically-driven distribution and remobilization of heavy metals in surface sediments around the coastal area of Shandong Peninsula, China.

Heavy metals (HMs) are considered a major pollutant of the surface sediments of the continental shelf. However, there remains little in-depth research on their fate in the ocean, and particularly on their abundance in sediments and the water column and the underlying drivers. This study examined the concentrations of HMs (Cu, Zn, Cr, Pb, Cd, and As) in surface sediments and suspended particulate matter (SPM) around the coastal area of Shandong Peninsula, China. The division of the sedimentary environment and influencing factors were also analyzed using multivariate statistical analysis Fuzzy c-means (FCM) cluster and Non-Linear Mapping (NLM). The study attempted to understand the distribution and remobilization of HMs in the shallow marginal sea using multi-disciplinary approaches, including satellite remote sensing and numerical simulation. The results showed higher HMs in the surface sediments in Weihai Bay (Zone I) than in the junction of the Chengshantou Cap (Zone III) and north of Wei Bay (Zone II). In addition, the results suggested that Cu, Zn, Cr and Pb originated from natural weathering, with their spatial distributions in the three zones highly regulated by sediment grain size, total nitrogen (TN), and total carbon (TC). In contrast, Cd and As originated from anthropogenic contamination (e.g., industrial discharges and aquaculture) in Zone I. HMs (except As) were influenced by terrigenous total organic carbon (TOC) in Zone III. The results of this study suggest that the difference in sediment re-suspension intensity has an important influence on the distribution of HM concentrations in the north Yellow Sea. This study can act as a reference for understanding the fates and source-sink processes of HMs in offshore sediments. The coupling behaviors and microscopic suspension properties of HMs in surface sediments and SPM require further investigation.

Structural, electronic, and magnetic properties of Fe3C2 cluster.

On the basis of density-functional theory and all-electron numerical basis set, 20 stable isomers of Fe(3)C(2) cluster are found through optimization calculations and frequency analysis from 108 initial structures. A nonplanar C(s) structure with nonet spin multiplicity and 482.978 kcal/mol of binding energy is found as the candidate of global minimum geometry of Fe(3)C(2) cluster. The binding energies, the energy gaps between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, and the magnetic moments of all the isomers are reported. The relationship between the molecular properties and geometrical structures is also investigated.

Realization of tunable Dirac cone and insulating bulk states in topological insulators (Bi(1-x)Sb(x))(2)Te(3).

The bulk-insulating topological insulators with tunable surface states are necessary for applications in spintronics and quantum computation. Here we present theoretical evidence for modulating the topological surface states and achieving the insulating bulk states in solid-solution (Bi(1-x)Sb(x))(2)Te(3). Our results reveal that the band inversion occurs in (Bi(1-x)Sb(x))(2)Te(3), indicating the non-triviality across the entire composition range, and the Dirac point moves upwards till it lies within the bulk energy gap accompanying the increase of Sb concentration x. In addition, with increasing x, the formation of prominent native defects becomes much more difficult, resulting in the truly insulating bulk. The solid-solution system is a promising way of tuning the properties of topological insulators and designing novel topologically insulating devices.

Evidence of the existence of magnetism in pristine VX2 monolayers (X = S, Se) and their strain-induced tunable magnetic properties.

First-principles calculations are performed to study the electronic and magnetic properties of VX(2) monolayers (X = S, Se). Our results unveil that VX(2) monolayers exhibit exciting ferromagnetic behavior, offering evidence of the existence of magnetic behavior in pristine 2D monolayers. Furthermore, interestingly, both the magnetic moments and strength of magnetic coupling increase rapidly with increasing isotropic strain from -5% to 5% for VX(2) monolayers. It is proposed that the strain-dependent magnetic moment is related to the strong ionic-covalent bonds, while both the ferromagnetism and the variation in strength of magnetic coupling with strain arise from the combined effects of both through-bond and through-space interactions. These findings suggest a new route to facilitate the design of nanoelectronic devices for complementing graphene.