Enhanced Thermoelectric Performance in Black Phosphorene via Tunable Interlayer Twist.

Twist-angle two-dimensional (2D) systems are attractive in their exotic and tunable properties by the formation of the moiré superlattices, allowing easy access to manipulating intrinsic electrical and thermal properties. Here, the angle-dependent thermoelectric properties of twisted bilayer black phosphorene (tbBP) by first-principles calculations are reported. The simulations show that significantly enhanced Seebeck coefficient and power factor can be achieved in p-type tbBP due to merging of the multi-valley electronic states and flat moiré bands. Moreover, the twisted layers bring in a strong anharmonic phonon scattering and thus very low lattice thermal conductivity of 4.51 W m-1  K-1 at 300 K. Consequently, a maximal ZT value can be achieved in p-type 10.11° tbBP along the armchair direction up to 0.57 and 1.06 at 300 and 500 K, respectively. The room-temperature ZT value along the zigzag direction is also significantly increased by almost 40 times compared to pristine BP when the twist angle is close to 70.68°. This work demonstrates a platform to manipulate thermoelectric performance in 2D materials by creating moiré patterns, leading tbBP as a promising eco-friendly candidate for thermoelectric applications.

Liquid-exfoliation of S-doped black phosphorus nanosheets for enhanced oxygen evolution catalysis.

Black phosphorus (BP) has recently drawn great attention in the field of electrocatalysis due to its distinct electrocatalytic activity for the oxygen evolution reaction (OER). However, the slow OER kinetics and the poor environmental stability of BP seriously limits its overall OER performance and prevents its electrocatalysis application. Here, sulfur (S)-doped BP nanosheets, which are prepared using high-pressure synthesis followed by liquid exfoliation, have been demonstrated to have much better OER electrocatalytic activity and environmental stability compared to their undoped counterparts. The S-doped BP nanosheets display a Tafel slope of 75 mV dec-1, which is a favorable value refered to the kinetics of OER in electrochemical tests. Notably, there is no degradation of S-doped BP nanosheets after six days exposure to ambient, indicating an excellent environmental stability of the S-doped BP. The density functional theory calculations show that the OER activity of BP originate from its crystal defects and heteroatom S doping can effectively enhance its OER activity and stability. These results highlight the doping effect on electrocatalytic activities and stability of BP and provide a simple and effective method to design highly efficient OER catalysts based on the modification of BP.

Enhanced stability of black phosphorus field-effect transistors with SiO2 passivation.

Few-layer black phosphorus (BP) has attracted much attention due to its high mobility and suitable band gap for potential applic5ations in optoelectronics and flexible devices. However, its instability under ambient conditions limits its practical applications. Our investigations indicate that by passivation of the mechanically exfoliated BP flakes with a SiO2 layer, the fabricated BP field-effect transistors (FETs) exhibit greatly enhanced environmental stability. Compared to the unpassivated BP devices, which show a fast drop of on/off current ratio by a factor of 10 after one week of ambient exposure, the SiO2-passivated BP devices display a high retained on/off current ratio of over 600 after one week of exposure, just a little lower than the initial value of 810. Our investigations provide an effective route to passivate the few-layer BPs for enhancement of their environmental stability.

Three-dimensional sp(2)-hybridized carbons consisting of orthogonal nanoribbons of graphene and net C.

We identify two sp(2) hybridized network models of carbon, namely GT-8 and CT-12, based on first-principles calculation results. Parallel nanoribbon rows of graphene and net C are found to be interlinked with orthogonal nanoribbons to construct GT-8 and CT-12, and their series of isomorphic analogs (named GTs and CTs) are assembled with the widening of the nanoribbon components. GTs and CTs are dynamically and mechanically stable and energetically more favorable than many previous sp(2) carbons, including K4, C20, and H6 carbon. They are two-dimensional conductors with insulating properties along the z-axis. Remarkably, GTs are superconductive with increased superconducting transition temperatures, Tc, as the nanoribbons widen. The Tcs of GT-8 and GT-16 are 5.2 and 14.0 K respectively, which are higher than that of boron-doped diamond under the same value of Coulomb pseudopotential µ*. They possess higher bulk moduli than graphite and behave as excellent ductile materials. The Young's modulus of GT-8 along the z-axis is comparable with that of graphene and it significantly increases as the nanoribbons widen.

A metallic superhard boron carbide: first-principles calculations.

A monoclinic BC3 phase (denoted M-BC3) has been predicted using first principles calculations. The M-BC3 structure is formed by alternately stacking sequences of metallic BC-layers and insulating C atom layers, thus, the structure exhibits two-dimensional conductivity. Its stability has been confirmed by our calculations of the total energy, elastic constants, and phonon frequencies. The pressure of phase transition from graphite-like BC3 to M-BC3 is calculated to be 9.3 GPa, and the theoretical Vickers hardness of M-BC3 is 43.8 GPa, this value indicates that the compound is a potentially superhard material. By comparing Raman spectral calculations of M-BC3 and previously proposed structures with the experimental data, we speculate that the experimentally synthesized BC3 crystal may simultaneously contain M-BC3 and Pmma-b phases.

Utilization of cross-linked chitosan/bentonite composite in the removal of methyl orange from aqueous solution.

A kind of biocomposite was prepared by the intercalation of chitosan in bentonite and the cross-linking reaction of chitosan with glutaraldehyde, which was referred to as cross-linked chitosan/bentonite (CCS/BT) composite. Adsorptive removal of methyl orange (MO) from aqueous solutions was investigated by batch method. The adsorption of MO onto CCS/BT composite was affected by the ratio of chitosan to BT and contact time. pH value had only a minor impact on MO adsorption in a wide pH range. Adsorption kinetics was mainly controlled by the pseudo-second-order kinetic model. The adsorption of MO onto CCS/BT composite followed the Langmuir isotherm model, and the maximum adsorption capacity of CCS/BT composite calculated by the Langmuir model was 224.8 mg/g. Experimental results indicated that this adsorbent had a potential for the removal of MO from aqueous solutions.

Adsorption of fluoride from aqueous solution by enhanced chitosan/bentonite composite.

In this work, enhanced chitosan/bentonite composite was prepared by treating chitosan/bentonite composite with concentrated hydrochloric acid (HCl). The adsorption of fluoride ions from aqueous solution onto the enhanced chitosan/bentonite composite was investigated. Adsorption studies were performed in a batch system, and the effects of various parameters, such as the pH value of the solution, adsorbent dosage and initial fluoride concentration, were evaluated. The optimum operating conditions for fluoride removal by the enhanced chitosan/bentonite composite were pH = 7 or so, and adsorbent dosage =1.2 g. Increasing initial fluoride concentration reduced the adsorption of fluoride onto the enhanced chitosan/bentonite composite. Furthermore, the presence of other co-anions weakened the adsorption of fluoride onto this adsorbent. The equilibrium adsorption isotherms were well described by both the Freundlich and Langmuir models. The maximum monolayer adsorption capacity was 2.95 mg/g at 293 K.

Observation of non-superconducting phase changes in nitrogen doped lutetium hydrides.

The recent report of near-ambient superconductivity and associated color changes in pressurized nitrogen doped lutetium hydride has triggered worldwide interest and raised major questions about the nature and underlying physics of these latest claims. Here we report synthesis and characterization of high-purity nitrogen doped lutetium hydride LuH2±xNy. We find that pressure conditions have notable effects on Lu-N and Lu-NH chemical bonding and the color changes likely stem from pressure-induced electron redistribution of nitrogen/vacancies and interaction with the LuH2 framework. No superconducting transition is found in all the phases at temperatures 1.8-300 K and pressures 0-38 GPa. Instead, we identify a notable temperature-induced resistance anomaly of electronic origin in LuH2±xNy, which is most pronounced in the pink phase and may have been erroneously interpreted as a sign of superconducting transition. This work establishes key benchmarks for nitrogen doped lutetium hydrides, allowing an in-depth understanding of its novel pressure-induced phase changes.

Preparation and characterization of CTAB-HACC bentonite and its ability to adsorb phenol from aqueous solution.

A novel type of adsorbent was prepared by modifying bentonite with N-2-hydroxypropyl trimethyl ammonium chloride chitosan (HACC) with cetyl trimethylammonium bromide (CTAB). The adsorbent was named CTAB-HACC bentonite. Its characteristics were investigated using thermogravimetric, Fourier-transform infrared spectroscopy (FTIR) and X-ray diffraction. The adsorption of phenol onto CTAB-HACC bentonite was evaluated by changing various parameters, such as contact time, adsorbent dosage, initial pH of the solution, and temperature. The maximum adsorption was observed at pH 12. Adsorption of phenol on CTAB-HACC bentonite favored at lower temperature and established the equilibrium in 30 min. The adsorption efficiency reached 82.1%, and the adsorption capacity was 7.12 mg/g from the phenol solution with a concentration of 500 mg/L at pH 12.0 and 20 degrees C.

Superior Conversion Efficiency Achieved in GeP3/h-BN Heterostructures as Novel Flexible and Ultralight Thermoelectrics.

GeP3 materials are attracting broad research interest due to their typical puckered layer structure, high carrier mobility, and chemical stability. This peculiarity expedites the independent control of anisotropic electrical and thermal conductance, which is thus expected to possess great thermoelectric potential. Nevertheless, the metal characteristics of GeP3 in the bulk and thick films are adverse to real application because of the low Seebeck coefficient. Thus, it is highly desirable to explore effective solutions to broaden the band gap and also maintain its excellent electrical conductance. Herein, we designed the interlaced GeP3/hexagonal boron nitride (h-BN) bulk heterostructure using various component thicknesses. By using ab initio calculations based on the Boltzmann transport theory, we found that capping h-BN layer can obviously increase the band gap of the GeP3 layer by 0.24 eV, and more interestingly, the anisotropic electronic structure in the GeP3/h-BN heterostructure was accordingly modulated toward a favorable direction for high thermoelectricity. An ultrahigh ZT value of around 5 was predicted at 300 K in p-type GeP3/h-BN, attributed to the adjusted multivalley band structure. Overall, our work provided an effective route to design novel high-performance thermoelectrics through the appropriate construction of heterostructures.

Crystalline Structures and Energetic Properties of Lithium Pentazolate under Ambient Conditions.

Recently, it has been reported that high-pressure synthesized lithium pentazolates could be quenched down to ambient conditions. However, the crystalline structures of LiN5 under ambient conditions are still ambiguous. In this work, the structures of LiN5 compound were directly explored at atmospheric pressure by using a new constrain structure search method. By using this method, three new allotropes were confirmed, and they show lower energy than the previous reported LiN5 phases. Both their thermodynamic and dynamic stability were confirmed through formation enthalpies, phonon spectrum, and ab initio molecular dynamics simulations under ambient conditions. Moreover, these three allotropes show similar formation enthalpies and properties, which suggests that it is hard to obtain a single LiN5 phase, which is well consistent with the experimental phenomenon. Furthermore, because of their low formation energy, all of them possess low energy density when they directly decompose to Li3N and nitrogen (0.52 kJ/g). Instead, the decomposed energy could be further improved to 3.78 kJ/g when they decompose under an oxygen-rich environment.

Stabilization of the High-Energy-Density CuN5 Salts under Ambient Conditions by a Ligand Effect.

A series of excellent works have demonstrated that high-nitrogen-content metal pentazolate (cyclo-N5 -) compounds could be stabilized by high pressure. However, under ambient conditions, low stability precludes their synthesis and application in the field of high-energy-density material. In this work, by using a constrained structure search method, we predicted two new structures as P212121-CuN5 and P21/c-CuN5 containing cyclo-N5 - with strong N-N and Cu-N bonds. In both structures, cyclo-N5 - form four coordination with the Cu+ ligand, which increases the structural stability by lowering the disturbance to the aromaticity of cyclo-N5 -. The calculated results show that the P212121-CuN5 and P21/c-CuN5 structures exhibit high dynamic and thermal stability up to 400 K, indicating that they can be stabilized under ambient conditions. The decomposing energy of P212121-CuN5 and P21/c-CuN5 can reach up to 2.40 and 2.42 kJ/g, respectively. Strikingly, the detonation velocity and the pressure of P212121-CuN5 is predicted to be up to 10.42 km/s and 617.46 kbar, respectively, indicating that they are promising high-energy candidates in the field of explosive combustion.

Enhanced strength of nano-polycrystalline diamond by introducing boron carbide interlayers at the grain boundaries.

Polycrystalline diamond with high mechanical properties and excellent thermal stability plays an important role in industry and materials science. However, the increased inherent brittle strength with the increase of hardness has severely limited its further widespread application. In this work, we produced well-sintered nano-polycrystalline (np) diamond by directly sintering fine diamond powders with the boron carbide (B4C) additive at high pressure and high temperatures. The highest hardness value of up to ∼90 GPa was observed in the np-diamond (consisting of fine grains with a size of 16 nm) by adding 5 wt% B4C at 18 GPa and 2237 K. Moreover, our results reveal that the produced samples have shown noticeably enhanced strength and toughness (18.37 MPa m0.5) with the assistance of the soft phase at the grain boundaries, higher than that of the hardest known nano-twined diamond by ∼24% and a little greater than that of the toughest CVD diamond (18 MPa m0.5). This study offers a novel functional approach in improving and controlling the hardness and stiffness of polycrystalline diamond.

Heat treatment to improve the wear resistance of PTFE/PMMA composites.

Polytetrafluoroethylene/poly(methyl methacrylate) (PTFE/PMMA) composites were prepared by a self-curing method. The influence of heat treatment processes on the friction and wear behaviors of PTFE/PMMA composites against bearing steel balls were studied by a ball-on-disk tribometer. The thermal performance of PTFE/PMMA composites with heat treatment was analyzed by Thermogravimetric Analysis (TGA). The surface morphologies and element distribution of PTFE/PMMA composites in a PMMA matrix were detected by Field Emission Scanning Electron Microscopy (FE-SEM) and Energy Dispersive Spectroscopy (EDS). The results indicated that the wear rates of PTFE/PMMA composites with different heat treatments significantly declined compared with the unheated treatment composite. The wear rate of the PTFE/PMMA composite decreased firstly and then increased with molding temperature and time increasing, and reduced with the molding pressure increasing. The main wear mechanisms of PTFE/PMMA composites with different heat treatments were fatigue wear and abrasive wear.

Sulfur-Doped Black Phosphorus Field-Effect Transistors with Enhanced Stability.

Black phosphorus (BP) has drawn great attention owing to its tunable band gap depending on thickness, high mobility, and large Ion/ Ioff ratio, which makes BP attractive for using in future two-dimensional electronic and optoelectronic devices. However, its instability under ambient conditions poses challenge to the research and limits its practical applications. In this work, we present a feasible approach to suppress the degradation of BP by sulfur (S) doping. The fabricated S-doped BP few-layer field-effect transistors (FETs) show more stable transistor performance under ambient conditions. After exposing to air for 21 days, the charge-carrier mobility of a representative S-doped BP FETs device decreases from 607 to 470 cm2 V-1 s-1 (remained as high as 77.4%) under ambient conditions and a large Ion/ Ioff ratio of ∼103 is still retained. The atomic force microscopy analysis, including surface morphology, thickness, and roughness, also indicates the lower degradation rate of S-doped BP compared to BP. First-principles calculations show that the dopant S atom energetically prefers to chemisorb on the BP surface in a dangling form and the enhanced stability of S-doped BP can be ascribed to the downshift of the conduction band minimum of BP below the redox potential of O2/O2-. Our work suggests that S doping is an effective way to enhance the stability of black phosphorus.

Weak antilocalization effect in exfoliated black phosphorus revealed by temperature- and angle-dependent magnetoconductivity.

Recently, there have increasingly been debates on whether there exists a surface resonance state (SRS) in black phosphorus (BP), as suggested by recent angle-resolved photoemission spectroscopy results. To resolve this issue, we have performed temperature- and angle-dependent magnetoconductivity measurements on exfoliated, high-quality BP single crystals. A pronounced weak-antilocalization (WAL) effect was observed within a narrow temperature range of 8-16 K, with the electrical current flowing parallel to the cleaved ac-plane (along the a- or c-axis) and the magnetic field along the b-axis. The angle-dependent magnetoconductivity and the Hikami-Larkin-Nagaoka model-fitted results have revealed that the observed WAL effect shows surface-bulk coherent features, which supports the existence of SRS in BP.

Flexible Black-Phosphorus Nanoflake/Carbon Nanotube Composite Paper for High-Performance All-Solid-State Supercapacitors.

We proposed a simple route for fabrication of the flexible BP nanoflake/carbon nanotube (CNT) composite paper as flexible electrodes in all-solid-state supercapacitors. The highly conductive CNTs not only play a role as active materials but also increase conductivity of the hybrid electrode, enhance electrolyte shuttling and prevent the restacking between BP nanoflakes. The fabricated flexible all-solid-state supercapacitor (ASSP) device at the mass proportion of BP/CNTs 1:4 was found to deliver the highest volumetric capacitance of up to 41.1 F/cm3 at 0.005 V/s, superior to the ASSP based on the bare graphene or BP. The BP/CNTs (1:4) device delivers a rapid charging/discharging up to 500 V/s, which exhibits the characteristic of a high power density of 821.62 W/cm3, while having outstanding mechanical flexibility and high cycling stability over 10 000 cycles (91.5% capacitance retained). Moreover the BP/CNTs (1:4) ASSP device still retains large volumetric capacitance (35.7 F/cm3 at the scan rate of 0.005 V/s) even after 11 months. In addition, the ASSP of BP/CNTs (1:4) exhibits high energy density of 5.71 mWh/cm3 and high power density of 821.62 W/cm3. As indicated in our work, the strategy of assembling stacked-layer composites films will open up novel possibility for realizing BP and CNTs in new-concept thin-film energy storage devices.

Large and Anisotropic Linear Magnetoresistance in Single Crystals of Black Phosphorus Arising From Mobility Fluctuations.

Black Phosphorus (BP) is presently attracting immense research interest on the global level due to its high mobility and suitable band gap for potential application in optoelectronics and flexible devices. It was theoretically predicted that BP has a large direction-dependent electrical and magnetotransport anisotropy. Investigations on magnetotransport of BP may therefore provide a new platform for studying the nature of electron transport in layered materials. However, to the best of our knowledge, magnetotransport studies, especially the anisotropic magnetoresistance (MR) effect in layered BP, are rarely reported. Here, we report a large linear MR up to 510% at a magnetic field of 7 Tesla in single crystals of BP. Analysis of the temperature and angle dependence of MR revealed that the large linear MR in our sample originates from mobility fluctuations. Furthermore, we reveal that the large linear MR of layered BP in fact follows a three-dimensional behavior rather than a two-dimensional one. Our results have implications to both the fundamental understanding and magnetoresistive device applications of BP.

Flexible All-Solid-State Supercapacitors based on Liquid-Exfoliated Black-Phosphorus Nanoflakes.

Flexible all-solid-state supercapacitors are fabricated with liquid-exfoliated black-phosphorus (BP) nanoflakes as an electrode material. These devices deliver high specific volumetric capacitance, power density, and energy density, up to 13.75 F cm(-3) , 8.83 W cm(-3) , and 2.47 mW h cm(-3) , respectively, and an outstanding long life span of over 30 000 cycles, demonstrating the excellent performance of the BP nanoflakes as a flexible electrode material in electrochemical energy-storage devices.

Te-Doped Black Phosphorus Field-Effect Transistors.

Element doping allows manipulation of the electronic properties of 2D materials. Enhanced transport performances and ambient stability of black-phosphorus devices by Te doping are presented. This provides a facile route for achieving airstable black-phosphorus devices.