Regulating interface interaction in alumina/graphene composites with nano alumina coating transition layers.

The structure and properties of graphene/alumina composites are affected by the interface interaction. To demonstrate the influence of interface interaction on the structure of composite materials, a composite without graphene/matrix alumina interface was designed and prepared. We introduced a nano transition layer into the composite by pre-fabricating nano alumina coating on the surface of graphene, thus regulating the influence of interface interaction on the structure of the composite. According to the analysis of laser micro Raman spectroscopy, the structure of graphene was not seriously damaged during the modification process, and graphene was subjected to tensile or compressive stress along the 2D plane. The fracture behavior of the modified graphene/alumina composites is similar to that of pure alumina, but significantly different from that of pure graphene/alumina composites. The elastic modulus and hardness of composite material G/A/A are higher, while its microstructure has better density and uniformity. In situ HRSEM observation showed that there was a transition layer of alumina in the modified graphene/alumina composite. The transition layer blocks or buffers the interfacial stress interaction, therefore, the composite material exhibits a fracture behavior similar to that of pure alumina at this time. This work demonstrates that interface interactions have a significant impact on the structure and fracture behavior of graphene/alumina composites.

Enhanced Electron-Hole Separation in Phosphorus-Coordinated Co Atom on g-C3N4 toward Photocatalytic Overall Water Splitting.

Revealing the decoration mode of g-C3N4 and understanding the physical mechanism of overall water splitting is important for the further improvement of the photocatalytic activity of g-C3N4-based materials. With core level shift and molecular dynamics simulations based on first-principles calculations, Co1(PHx)3 anchored on the triazine of g-C3N4 is determined as a stable single-atom catalyst with high efficiency for photocatalytic overall water splitting. The separated spin-polarized charge density distribution of valence-band maximum and conduction-band minimum states is beneficial for the long lifetime of photoexcited electrons and holes. An anchored Co single atom site is the active site for oxygen evolution reaction, and nitrogen atoms act as active sites for hydrogen evolution reaction. This new decoration mode of g-C3N4 opens a possible way to functionalize g-C3N4 on both triazine and void sites to realize the separation of OER and hydrogenation reaction by water splitting.

Effect of Copper Doping on Electronic Structure and Optical Absorption of Cd33Se33 Quantum Dots.

The photophysical properties of Cu-doped CdSe quantum dots (QDs) can be affected by the oxidation state of Cu impurity, but disagreement still exists on the Cu oxidation state (+1 or +2) in these QDs, which is debated and poorly understood for many years. In this work, by using density functional theory (DFT)-based calculations with the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid functional, we clearly demonstrate that the incorporation of Cu dopants into the surface of the magic sized Cd33Se33 QD leads to non-magnetic Cu 3d orbitals distribution and Cu+1 oxidation state, while doping Cu atoms in the core region of QDs can lead to both Cu+1 and Cu+2 oxidation states, depending on the local environment of Cu atoms in the QDs. In addition, it is found that the optical absorption of the Cu-doped Cd33Se33 QD in the visible region is mainly affected by Cu concentration, while the absorption in the infrared regime is closely related to the oxidation state of Cu. The present results enable us to use the doping of Cu impurity in CdSe QDs to achieve special photophysical properties for their applications in high-efficiency photovoltaic devices. The methods used here to resolve the electronic and optical properties of Cu-doped CdSe QDs can be extended to other II-VI semiconductor QDs incorporating transition-metal ions with variable valence.

The thermodynamic stability and mechanical properties of TiCxN1-x(0⩽x⩽ 1) compounds by cluster expansion method and first-principles calculations.

The thermodynamic stability and mechanical properties of titanium carbonitrides TiCxN1-x(0 ⩽x⩽ 1) are investigated by a combination of the universal cluster expansion method and the first-principles calculations. By considering the ordering of the N/C distributions on the anion sublattice sites of TiCxN1-x, a binary diagram of the heat of formation is constructed, and seven kinds of ground-state structures are predicted in the whole range of 0 ⩽x⩽ 1. These predicted ground-state TiCxN1-xstructures are further proved to be dynamically and mechanically stable by examining their phonon dispersion spectra and elastic constants. Further studies indicate that the mechanical and thermodynamic properties of the ternary TiCxN1-xstructures are generally better than those of the binary TiC or TiN, while the differences within the ternary systems are insignificant. The possible origin of the enhancement of the mechanical and thermodynamic properties of the predicted ground-state TiCxN1-xare discussed together with the electronic structures.

First-Principles Study of 3d Transition-Metal-Atom Adsorption onto Graphene Embedded with the Extended Line Defect.

A type of line defect (LD) composed of alternate squares and octagons (4-8) as the basic unit is currently an experimentally available topological defect in the graphene lattice, which brings some interesting modifications to the magnetic and electronic properties of graphene. The transitional-metal (TM) atoms adsorb on graphene with a line defect (4-8), and they show interesting and attractive structural, magnetic, and electronic properties. For different TMs such as Fe, Co, Mn, Ni, and V, the complex systems show different magnetic and electronic properties. The TM atoms can spontaneously adsorb at quadrangular sites, forming a metallic atomic chain along LD on graphene. The most stable configuration is the hollow site of a regular tangle. The TMs (TM = Co, Fe, Mn, Ni, V) tend to form extended metal lines, showing a ferromagnetic (FM) ground state. For the Co, Fe, and V atoms, the system is half-metal. The spin-α electron is insulating, while the spin-ß electron is conductive. For the Mn and Ni atoms, Mn-LD and Ni-LD present a spin-polarized metal; for the Fe atom, Fe-LD shows a semimetal with Dirac cones. For Fe and V atoms, both Fe-LD and V-LD show spin-polarized half-metallic properties. And its spin-α electron is conducting, while the spin-ß electron is insulating. Different TMs adsorbing on a graphene nanoribbon forming the same stable configurations of metal lines show different electronic properties. The adsorption of TMs induces magnetism and spin polarization. These metal lines have potential applications in spintronic devices and work as a quasi-one-dimensional metallic wire, which may form building blocks for atomic-scale electrons with well-controlled contacts at the atomic level.

Effect of Electrolyte on the Proton Transport through Graphane in the Electrochemical Cell: A First-Principles Study.

The proton transport behaviors through graphane in the electrochemical environment are not only determined by the film but also correlated with the properties of the electrolytes. Here, the effect of electrolytes is studied for this transport process. The step of proton transfer from electrolyte to graphane is the rate-determining step of the whole transport process in most of the studied cases and is indeed influenced much by the electrolytes, while the following steps are affected little. Its energy barrier increases significantly with the number of water molecules but only fluctuates with the number of mimicked Nafion molecules until the bulk case. This barrier could be further affected by the hydration number of Nafion and be reduced by increasing local proton concentrations. The dynamical effect of the environment and the nuclear quantum effect are found to further reduce the energy barrier of the transport process but by a relatively small amount.

Prediction of the Au4S crystal via a superatom network model: from clusters to solids.

Owing to their unique properties, thiolate-protected gold clusters (denoted as Aun(SR)m) have attracted intense research interest both experimentally and theoretically. The superatom complex (SAC) and superatom network (SAN) models are significantly well-known concepts to explain the electronic stability of Aun(SR)m. Based on the structural characters of Aun(SR)m, the tetrahedral Au4 unit was found to be an elementary building block and used to design a series of tetrahedron-network clusters. In this work, we first build a Au22(µ4-S)(SH)12 cluster consisting of a network of four non-conjugated tetrahedral Au4 units and confirm that it is a local minimum on the potential energy surface by density functional theory calculations. Chemical bonding analysis by the AdNDP method reveals that the electronic structure of Au22(µ4-S)(SH)12 follows the SAN (4 × 2e) model. Based on the structural character of the Au22(µ4-S)(SH)12 cluster, we utilize the diamond lattice as a template to construct a stable Au4S crystal in which each S atom binds to four Au4 superatoms. The computational results demonstrate that the structure has rather good dynamic and thermal stabilities, and it is an indirect semiconductor with a band gap of 2.68 eV at the HSE06 level. Chemical bonding analysis performed by the SSAdNDP method reveals that the Au4S can be seen as a SAN crystal. These bonding patterns and properties of the solid provide references for further investigation of cluster-assembled materials.

Tuning the Electronic and Magnetic Properties of Graphene Flake Embedded in Boron Nitride Nanoribbons with Transverse Electric Fields: First-Principles Calculations.

The electronic and magnetic properties of h-BN nanoribbions embedded with graphene nanoflakes (CBNNRs) are systematically studied by ab initio calculations. The CBNNRs with zigzag or armchair edges are all bipolar magnetic semiconductors (BMSs). The band gaps of zigzag CBNNRs (zCBNNRs) change linearly with the transverse electric field (E-field) for the first-order Stark effect, whereas for the armchair CBNNRs (aCBNNRs), the band gaps vary quadratically with the E-field for the second-order Stark effect. For zCBNNRs and aCBNNRs, they could transform from BMS to spin gapless semiconductor (SGS), metal, and half-metal (HM) under different transverse E-fields. The CBNNRs may transform into a semiconductor or HM, under the same E-fields, depending on the position of graphene flakes. The CBNNRs introduce local magnetic moment at carbon atoms, and the magnetic moment is determined by the size of the graphene flakes. These observations open the door to applications of CBNNRs in spintronic devices.

Carbon storage potential and seasonal dynamics of phytolith from different vegetation types in a subtropical region, China.

Terrestrial biogeochemical silicon (Si) and carbon (C) cycles couple through various processes, such as silicate weathering and the dynamics resulting from different phytolith assemblages. For example, small amounts of organic C (typically ranging from 0.2 to 5.8%) can be occluded during phytolith formation. Phytoliths play an important role in coupled Si and C cycles. In this study, we analyzed variations in C sequestration and the seasonal dynamics of phytoliths formed in different vegetation types in order to clarify the processes and characteristics of phytolith-occluded-carbon (PhytOC) cycles. Firstly, we measured the variation range of phytolith content in the litter and soil of different vegetation types at 11.87-151.90 and 1.81-14.72 g kg-1, respectively, while we measured the corresponding variation range of PhytOC content at 3.58-24.13 and 0.04-0.65 g kg-1, respectively. We also found that seasonal changes in phytolith and PhytOC content were significant (P < 0.01), both exhibiting a significant decreasing trend from litter to soil and from the surface soil to 0-60 cm of soil layers. Secondly, we measured the variation range of PhytOC storage in the litter and soil (0-60 cm) of different vegetation types at 1.26-6.89 and 28.24-75.2 t, respectively. Finally, our study determined the contribution of PhytOC storage in soil (0.42%) compared with conventionally recognized soil C sequestration storage (0.64%). The phytolith C pool is an important component of the forest ecosystem C pool, which plays a critical role in mitigating global warming.

Hydrogen Isotope Separation via Ion Penetration through Group-IV Monolayer Materials in Electrochemical Environment.

Based on density functional theory calculations, the chemical penetration behaviors and separation properties of hydrogen isotope ions through pristine and fully hydrogenated group-IV monolayer materials are investigated. Both the penetration energy profiles and kinetic isotope effects are studied to evaluate the performance of four group-IV (C, Si, Ge, and Sn) monolayer materials for hydrogen isotope separation. To examine the thermodynamically stable morphologies of these monolayer materials in electrochemical aqueous environment, the Pourbaix diagrams varying with pH and external bias are constructed. The fully hydrogenated monolayer materials are found to be thermodynamically favorable in some conditions, and the proton penetration and hydrogen isotope separation behaviors are different from their pristine counterparts. The silicene is found to be a suitable candidate material for hydrogen isotope separation in an electrochemical environment.

A uranium capture strategy based on self-assembly in a hydroxyl-functionalized ionic liquid extraction system.

A novel and efficient uranium capture strategy based on self-assembly is developed in an ionic liquid extraction system, by which the one-step separation and solidification of uranium are realized. This not only provides a promising method for separating metal ions but also promotes the development of a supramolecular assembly both in mechanism and application.

Ultrastrong Translucent Glass Ceramic with Nanocrystalline, Biomimetic Structure.

Transparent/translucent glass ceramics (GCs) have broad applications in biomedicine, armor, energy, and constructions. However, GCs with improved optical properties typically suffer from impaired mechanical properties, compared to traditional sintered full-ceramics. We present a method of obtaining high-strength, translucent GCs by preparing ZrO2-SiO2 nanocrystalline glass ceramics (NCGCs) with a microstructure of monocrystalline ZrO2 nanoparticles (NPs), embedded in an amorphous SiO2 matrix. The ZrO2-SiO2 NCGC with a composition of 65%ZrO/35%SiO2 (molar ratio, 65Zr) achieved an average flexural strength of 1 GPa. This is one of the highest flexural strength values ever reported for GCs. ZrO2 NPs bond strongly with SiO2 matrix due to the formation of a thin (2-3 nm) amorphous Zr/Si interfacial layer between the ZrO2 NPs and SiO2 matrix. The diffusion of Si atoms into the ZrO2 NPs forms a Zr-O-Si superlattice. Electron tomography results show that some of the ZrO2 NPs are connected in one direction, forming in situ ZrO2 nanofibers (with length of ∼500 nm), and that the ZrO2 nanofibers are stacked in an ordered way in all three dimensions. The nanoarchitecture of the ZrO2 nanofibers mimics the architecture of mineralized collagen fibril in cortical bone. Strong interface bonding enables efficient load transfer from the SiO2 matrix to the 3D nanoarchitecture built by ZrO2 nanofibers and NPs, and the 3D nanoarchitecture carries the majority of the external load. These two factors synergistically contribute to the high strength of the 65Zr NCGC. This study deepens our fundamental understanding of the microstructure-mechanical strength relationship, which could guide the design and manufacture of other high-strength, translucent GCs.

Asymmetric interaction of point defects and heterophase interfaces in ZrN/TaN multilayered nanofilms.

Materials with a high density of heterophase interfaces, which are capable of absorbing and annihilating radiation-induced point defects, can exhibit a superior radiation tolerance. In this paper, we investigated the interaction behaviors of point defects and heterophase interfaces by implanting helium atoms into the ZrN/TaN multilayered nanofilms. It was found that the point defect-interface interaction on the two sides of the ZrN/TaN interface was asymmetric, likely due to the difference in the vacancy formation energies of ZrN and TaN. The helium bubbles could migrate from the ZrN layers into the TaN layers through the heterophase interfaces, resulting in a better crystallinity of the ZrN layers and a complete amorphization of the TaN layers. The findings provided some clues to the fundamental behaviors of point defects near the heterophase interfaces, which make us re-examine the design rules of advanced radiation-tolerant materials.

First-principles study of line-defect-embedded zigzag graphene nanoribbons: electronic and magnetic properties.

Based on first-principles calculations, we present the electronic and magnetic properties of a class of line defect-embedded zigzag graphene nanoribbons, with one edge saturated by two hydrogen atoms per carbon atom and the other edge terminated by only one hydrogen atom. Such edge-modified nanoribbons without line defects are found to be typical bipolar magnetic semiconductors (BMS). In contrast, when the line defect is introduced into the ribbons, the ground state is ferromagnetic, and the resulting nanoribbons can be tuned to spin-polarized metal, metal with Dirac point, or half-metal by varying the position of the line defect, owing to the defect-induced self-doping of the BMS. Specifically, when the line defect is far away from the edges of the ribbon, the system shows half-metallicity. We further confirm the structural and magnetic stability at room temperature by first-principles molecular dynamics simulations. Our findings reveal the possibility of building metal-free electronic/spintronic devices with magnetic/half-metallic graphene nanoribbons.

Adsorption of formic acid on rutile TiO2 (110) revisited: an infrared reflection-absorption spectroscopy and density functional theory study.

Formic acid (HCOOH) adsorption on rutile TiO2 (110) has been studied by s- and p-polarized infrared reflection-absorption spectroscopy (IRRAS) and spin-polarized density functional theory together with Hubbard U contributions (DFT+U) calculations. To compare with IRRAS spectra, the results from the DFT+U calculations were used to simulate IR spectra by employing a three-layer model, where the adsorbate layer was modelled using Lorentz oscillators with calculated dielectric constants. To account for the experimental observations, four possible formate adsorption geometries were calculated, describing both the perfect (110) surface, and surfaces with defects; either O vacancies or hydroxyls. The majority species seen in IRRAS was confirmed to be the bridging bidentate formate species with associated symmetric and asymmetric frequencies of the ν(OCO) modes measured to be at 1359 cm(-1) and 1534 cm(-1), respectively. The in-plane δ(C-H) wagging mode of this species couples to both the tangential and the normal component of the incident p-polarized light, which results in absorption and emission bands at 1374 cm(-1) and 1388 cm(-1). IRRAS spectra measured on surfaces prepared to be either reduced, stoichiometric, or to contain surplus O adatoms, were found to be very similar. By comparisons with computed spectra, it is proposed that in our experiments, formate binds as a minority species to an in-plane Ti5c atom and a hydroxyl, rather than to O vacancy sites, the latter to a large extent being healed even at our UHV conditions. Excellent agreement between calculated and experimental IRRAS spectra is obtained. The results emphasize the importance of protonation and reactive surface hydroxyls - even under UHV conditions - as reactive sites in e.g., catalytic applications.

Room-temperature large magnetic-dielectric coupling in new phase anatase VTiO(4).

The synthetic new-phase VTiO4, as a new solid solution structure of anatase type, brings a large magnetodielectric ratio (Δε/ε0) of 7.2% at 300 K, representing a new simple-oxide structural catalogue exhibiting a room-temperature large magnetic-dielectric effect.

Hydrogen-incorporated TiS2 ultrathin nanosheets with ultrahigh conductivity for stamp-transferrable electrodes.

As a conceptually new class of two-dimensional (2D) materials, the ultrathin nanosheets as inorganic graphene analogues (IGAs) play an increasingly vital role in the new-generation electronics. However, the relatively low electrical conductivity of inorganic ultrathin nanosheets in current stage significantly hampered their conducting electrode applications in constructing nanodevices. We developed the unprecedentedly high electrical conductivity in inorganic ultrathin nanosheets. The hydric titanium disulfide (HTS) ultrathin nanosheets, as a new IGAs, exhibit the exclusively high electrical conductivity of 6.76 × 10(4) S/m at room temperature, which is superior to indium tin oxide (1.9 × 10(4) S/m), recording the best value in the solution assembled 2D thin films of both graphene (5.5 × 10(4) S/m) and inorganic graphene analogues (5.0 × 10(2) S/m). The modified hydrogen on S-Ti-S layers contributes additional electrons to the TiS2 layered frameworks, rendering the controllable electrical conductivity as well as the electron concentrations. Together with synergic advantages of the excellent mechanical flexibility, high stability, and stamp-transferrable properties, the HTS thin films show promising capability for being the next generation conducting electrode material in the nanodevice fields.

Two-Dimensional Hexagonal Transition-Metal Oxide for Spintronics.

Two-dimensional materials have been the hot subject of studies due to their great potential in applications. However, their applications in spintronics have been blocked by the difficulty in producing ordered spin structures in 2D structures. Here we demonstrated that the ultrathin films of recently experimentally realized wurtzite MnO can automatically transform into a stable graphitic structure with ordered spin arrangement via density functional calculation, and the stability of graphitic structure can be enhanced by external strain. Moreover, the antiferromagnetic ordering of graphitic MnO single layer can be switched into half-metallic ferromagnetism by small hole-doping, and the estimated Curie temperature is higher than 300 K. Thus, our results highlight a promising way toward 2D magnetic materials.

Fabrication of flexible and freestanding zinc chalcogenide single layers.

Inorganic graphene analogues (IGAs) are a conceptually new class of materials with attractive applications in next-generation flexible and transparent nanodevices. However, their species are only limited to layered compounds, and the difficulty in extension to non-layered compounds hampers their widespread applicability. Here we report the fabrication of large-area freestanding single layers of non-layered ZnSe with four-atomic thickness, using a strategy involving a lamellar hybrid intermediate. Their surface distortion, revealed by means of synchrotron radiation X-ray absorption fine structure spectroscopy, is shown to give rise to a unique electronic structure and an excellent structural stability, thus determining an enhanced solar water splitting efficiency and photostability. The ZnSe single layers exhibit a photocurrent density of 2.14 mA cm(-2) at 0.72 V versus Ag/AgCl under 300 W Xe lamp irradiation, 195 times higher than that of bulk counterpart. This work opens the door for extending atomically thick IGAs to non-layered compounds and holds promise for a wealth of innovative applications.

Giant moisture responsiveness of VS2 ultrathin nanosheets for novel touchless positioning interface.

Utilizing a thin film of VS(2) ultrathin nanosheets with giant and fast moisture responsiveness, a brand-new model of moisture-based positioning interface is put forward here, by which not only the 2D position information of finger tips can be acquired, but also the relative height can be detected as the third dimensionality, representing a promising platform for advanced man-machine interactive systems.