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Engineering of solid electrolytes of Li-ion batteries is carried out for achieving high levels of ionic conductivity and preserving low levels of electrical conductivity.

Developing highly active catalysts for hydrogen evolution reaction based on earth-abundant materials is challenging. Nitrogen doping has recently been reported to improve catalytic properties by modifying the electrochemical properties of titanium carbide MXene. However, systematic doping engineering, such as optimization of doping concentration, doping site, and thermodynamic phase stabilization have not been systematically controlled, which retards the reliable production of high-activity MXene catalysts. In this study, the optimum doping concentration of nitrogen and doping process conditions on O-functionalized Ti2C MXene for hydrogen evolution reaction were investigated using density functional theory with thermodynamics. To confirm the optimum nitrogen concentration, the catalytic properties are examined considering the Gibbs free energy of hydrogen adsorption and conductivity for 2.2-11.0 at % nitrogen concentration. It was confirmed that 8.8 at % nitrogen-doped Ti2CO2 had optimum catalytic properties under standard conditions. Moreover, when the doping concentration was higher, the decrease in the adsorption energies of hydrogen and the transition in the energy dispersion of the conduction band led to deterioration of the catalytic properties. Through theoretical results, the feasible process conditions for optimum nitrogen concentration while maintaining the structure of MXene are presented using a thermodynamics model taking into account chemical reactions with various nitrogen sources. This study provides further understanding of the nitrogen-doping mechanism of Ti2CO2 for hydrogen evolution reactions.

Borosulfates are classified as silicate analogue materials. The number of crystallographically characterized compounds is still limited, whereas the structural diversity is already impressive. The anionic substructures of borosulfates exhibit vertex-connected (BO4 )- and (SO4 )-tetrahedra, whereas bridging between two (SO4 )- or even between two (BO4 )-tetrahedra is scarce. The herein presented compound Sr[B3 O(SO4 )4 (SO4 H)] is the first borosulfate with a triple-vertex linkage of three (BO4 ) tetrahedra via one common oxygen atom. DFT calculations complement the experimental studies. Bader charges (calculated for all atoms) as well as charge-density calculations give hint to the electron distribution within the anionic substructure and density-of-states calculations support the interpretation of the bonding situation.

In this study, vertically aligned p–n junction TiO2 nanotubes can be formed by anodization of the Ti substrate following the addition of a high electric field in a Pd precursor-containing electrolyte. The bottom region of the TiO2 nanotubes with a high concentration of Pd because of the high electric field which was induced to be p-type. In contrast, the region with a low Pd concentration (top of the TiO2 nanotubes) was determined to be n-type, similar to the pristine TiO2. The concentration profile of the dopant in TiO2 nanotubes was investigated via TOF-SIMS and XPS. Defect formation energies in TiO2 nanotubes were estimated using density-functional theory calculation to understand the p–n junction formation. The p–n junction TiO2 nanotubes showed a high photocatalytic hydrogen production rate of 25.2 μL cm−2 h−1 under solar light irradiation as a result of the enhancement of visible light photoactivity.

The development of efficient, low-cost, and stable bifunctional catalysts is necessary for renewable energy storage and conversion, but it remains a challenge. Herein, we first report a novel strat...

Brookite, the least studied crystalline phase of TiO2, recently has been found to have excellent photocatalytic activities, comparable to that of anatase TiO2. However, its activity is highly depen...

Here we report the miscibility gap of CuSb1-xBixS2 (CABS), a promising photo energy conversion material for band gap engineered solar cells, and evaluate its applicability via a combination of theoretical predictions and experimental verifications. Our ab initio calculations and thermodynamic modeling revealed that the CABS random alloy system has optimal band gap values in the range of 1.1–1.5 eV when synthesized at room temperature. The CABS system, synthesized by mechanochemical methods, exhibited optical band gap values in very good agreement with theoretical predictions, as well as lowered kinetic energy barriers for enhanced nucleation.

To overcome the reliability issue of phase-change memory, the development of stable phase-change materials is extremely important. In this study, we analyze 13 dopants for Ge2Sb2Te5 (GST) based on two criteria: i) the change in thermal stability by doping and ii) a lattice distortion. After doping the elements, 11 elements showed a negative doping formation energy compared with pure GST. The angular distortion of the Zn dopant is the largest. The hole carrier decreases, and the electrical resistance increases through Zn-doping in GST. The increased resistance of the material can lead to low power consumption with a high energy effectiveness.

Recent advancements in MoS2 nanofilms have aided in the development for important water-related environmental applications. However, a MoS2 nanofilm-coated sensor has yet to have been applied for heavy metal detection in water-related environmental samples. In this study, a novel vertically aligned two-dimensional (2D) MoS2 (edge exposed) nanofilm was applied for in situ lead ion (Pb2+) detection. The developed sensor showed an excellent linear relationship toward Pb2+ between 0 and 20 ppb at -0.45 V vs Ag/AgCl using square wave anodic stripping voltammetry (SWASV) with the improved limit of detection (LOD) of 0.3 ppb in a tap water environment. The vertically aligned 2D MoS2 sensor exhibited improved detection sensitivity (2.8 folds greater than a previous metallic [Bi] composite electrode) with lower relative standard deviation for repetitive measurements (n = 11), indicating enhanced reproducibility for Pb2+ detection. The vertically aligned 2D MoS2 layers exhibited 2.6 times higher sensitivity than horizontally aligned 2D MoS2 (basal plane exposed). Density functional theory calculations demonstrated that adsorption energy of Pb on the MoS2 side edge was much higher (4.11 eV) than those on the basal plane (0.36 and 0.07 eV). In addition, the band gap center of vertical MoS2 was found to be higher than the Pb2+ → Pb reduction potential level and capable of reducing Pb2+. Overall, the newly developed vertically aligned 2D MoS2 sensor showed excellent performance for detecting Pb2+ in a real drinking water environment with good reliability.

In order to be able to control the phase transition of engineered phase-change materials, the specific understanding of phase transition processes is essential. To understand the effect of dopant o...

Methods for oxygen vacancy engineering usually require high-temperature heating processes, which are substantially time-consuming. Laser irradiation techniques are a viable alternative to conventional methods, as they enable room-temperature tuning of material functionality using a simple, swift, and inexpensive process. In this report, the effects of pulsed laser irradiation on the formation of oxygen vacancies and its positive relationship with the sensing performance of SnO2 have been investigated. Based on density functional theory calculations, we suggest that the formation of laser-induced bridging oxygen defects and the resulting excess electrons on the SnO2 surface change the surface orbital structures of the Sn atoms in a manner favorable for NO2 adsorption, thus playing a key role in improving its sensing performance.

It has recently been demonstrated that the OER activity of transition metal sulfides (TMSs) could be enhanced by the introduction of a thin amorphous layer on a pristine surface. We report here a novel strategy to enhance the OER by developing cobalt nickel sulfide (CoxNi1−xS2, CNS) with a high density of crystalline and amorphous phase boundaries. Electrochemical activation (ECA) can partially amorphize hollow CNS nanoparticles derived from surface-selective sulfidation. The ECA-treated CNS (ECA-CNS) electrocatalyst, which is comprised of CNS nanodots separated by thin amorphous layers, shows high densities of crystalline and amorphous phase boundaries. This catalyst shows superior OER catalytic performance with a current density of 10 mA cm−2 at a small overpotential of 290 mV, a low Tafel slope of 46 mV dec−1, a high mass activity of 217 A g−1, a high turnover frequency of 0.21 s−1 at an overpotential of 340 mV, and excellent stability in alkaline media.

The development of cost-effective and high-performance electrocatalysts for water oxidation has attracted intense research interest. It was reported recently that the interface between the amorphous and crystalline phases plays a significant role in the electrocatalytic activity of transition metal compounds. It was reckoned therefore that an increase in the density of the crystalline–amorphous phase boundary would enhance the electrochemical water oxidation on the catalyst. In this work we develop a new and facile strategy for inducing high density crystalline–amorphous phase boundaries via selective fluorination surface doping. This resulted in excellent characteristics of the engineered material for electrochemical water splitting. An initial computational simulation is carried out to design the crystalline–amorphous phase boundary material and an experimental verification follows for demonstration and optimization of the impact of surface doping. We conclude that the engineering of the interface using this facile and cost-effective strategy maximizes the crystalline and amorphous phases of metal–metalloids, which can be used to fabricate low-cost and efficient electrocatalysts for water oxidation.

Poor optical absorbance and charge recombination are the major drawbacks of polymeric graphitic carbon nitride (g-C3N4)-based photocatalysts. In this paper, we show for the first time a single-step in situ technique to control the porosity of two-dimensional g-C3N4 sheets and exfoliate them by introducing ascorbic acid (AA) molecules. The AA simultaneously acts as the carbon (C) source and deposits amorphous C onto g-C3N4 sheets. Nanosized pores are also introduced into the g-C3N4 sheets, leading to a large number of active sites. The as-prepared C-doped porous g-C3N4 nanosheets demonstrate a high visible light-photocatalytic H2 production activity of 793 μmol g−1 with the optimum structure, which is almost 25 times higher than the value obtained with bulk g-C3N4 (31 μmol g−1). This exceptional photocatalytic performance arises from the C-doped conjugated system and porous nanosheets. The enhanced photocatalytic H2 evolution was attributed to the effective separation and transport of charge carriers by the deposition of C onto the nanosheets and an increased number of active sites resulting from the nanopores created inside the g-C3N4 sheets. Moreover, molecular dynamics (MD) simulations confirm that the interaction between AA and melamine molecules at elevated temperatures results in the formation of C-doped porous and exfoliated g-C3N4 structures. Therefore, the present approach is very promising for application to the design of new and efficient photocatalysts for photocatalytic H2 evolution under visible irradiation.

Carbon-based materials are considered to be promising cadidates for energy storage systems because of their superior conductivity, low price, and high specific surface area. Moreover, heteroatom-doped graphene or graphitic carbons are prepared by various methods for modulating their physicochemical properties, improving their wettabililty, and achieving favorable pseudocapacity for use in electrochemical supercapacitors. Here we report a simple solvent-free scale-up technique to synthesis fluorine-doped graphene oxide (FGO) by direct plasma treatment of graphene oxide (GO) powder at ambient pressure. The FGO enabled fast electrochemical charge transfer and provided a large number of active sites for redox reactions during supercapacitor operation, and the mechanisms were thoroughly studied by various electrochemical analyses. As a result, fabricated symmetric supercapacitor using FGO electrodes exhibited a maximum power density (~3200 W/kg) and energy density (~25.87 Wh/kg) with superior cycle stability (20000 cycles) without capacitance loss. Furthermore, the computational calculation results clarified the roles of semi-ionic C–F bonding of FGO: huge charge accumulation on the electrodes and superior electrical conductivity. Thus, our study demonstrates a facile strategy to develop promising functionalized materials, which can enhance the viability of supercapacitor for the next generation of energy storage systems.

Highlights Single-atom M-N4/N-doped carbons (M = Fe, Co) prepared as OER/ORR catalysts.Ultrasonication-assisted plasma engineering used for catalyst synthesis.Co-N4/NC outperformed benchmark commercial catalysts in practical Zn–air battery test.DFT calculations provided insights into the origin of superior ORR/OER performance. Supplementary Information The online version contains supplementary material available at 10.1007/s40820-020-00581-4, As bifunctional oxygen evolution/reduction electrocatalysts, transition-metal-based single-atom-doped nitrogen–carbon (NC) matrices are promising successors of the corresponding noble-metal-based catalysts, offering the advantages of ultrahigh atom utilization efficiency and surface active energy. However, the fabrication of such matrices (e.g., well-dispersed single-atom-doped M-N4/NCs) often requires numerous steps and tedious processes. Herein, ultrasonic plasma engineering allows direct carbonization in a precursor solution containing metal phthalocyanine and aniline. When combining with the dispersion effect of ultrasonic waves, we successfully fabricated uniform single-atom M-N4 (M = Fe, Co) carbon catalysts with a production rate as high as 10 mg min−1. The Co-N4/NC presented a bifunctional potential drop of ΔE = 0.79 V, outperforming the benchmark Pt/C-Ru/C catalyst (ΔE = 0.88 V) at the same catalyst loading. Theoretical calculations revealed that Co-N4 was the major active site with superior O2 adsorption–desorption mechanisms. In a practical Zn–air battery test, the air electrode coated with Co-N4/NC exhibited a specific capacity (762.8 mAh g−1) and power density (101.62 mW cm−2), exceeding those of Pt/C-Ru/C (700.8 mAh g−1 and 89.16 mW cm−2, respectively) at the same catalyst loading. Moreover, for Co-N4/NC, the potential difference increased from 1.16 to 1.47 V after 100 charge–discharge cycles. The proposed innovative and scalable strategy was concluded to be well suited for the fabrication of single-atom-doped carbons as promising bifunctional oxygen evolution/reduction electrocatalysts for metal–air batteries. Supplementary Information The online version contains supplementary material available at 10.1007/s40820-020-00581-4

α-SiAlON ceramics have been in use as engineering ceramics in the most arduous industrial environments such as molten metal handling, cutting tools, gas turbine engines, extrusion molds, thermocouple sheaths, protective cover for high-temperature sensors, etc., owing to their outstanding mechanical, thermal and chemical stability. Taking advantage of the intrinsic properties of α-SiAlONs, we investigate, in this paper, the possibility of using the Er-doped α-SiAlON (Er-α-SiAlON) ceramic as a high-temperature sensing material via its unique near-infrared to visible upconversion property. We first use neutron diffraction and density functional theory calculations to study the electronic structure and thermodynamic stability of Er-α-SiAlON. It is found that the interstitial doping of Er stabilizes the α-SiAlON structure via chemical bonds with O-atoms with N:O ratio of 5:2 in the seven-fold coordination sites of the Er3+ ion. Temperature-dependent upconversion emissions are then studied under 980 and 793 nm excitations over a temperature range of 298–1373 K and the fluorescence intensity ratio (FIR) technique has been employed to investigate the temperature sensing behavior. Temperature-dependent Raman behavior is also investigated. We demonstrate that using Er-α-SiAlON as a sensing material, the limit of temperature measurement via the FIR technique can be pushed well beyond 1200 K.

Low-crystalline TiNb2O7 shows a high practical capacity of ∼280 mAh g−1 by size and morphology controls, composites, doping foreign atoms. However, the defect chemistry of TiNb2O7 has rarely been investigated. We report an effect of point/line defects on a crystal structure and lithium storage properties of TiNb2O7−x engineered by different calcination temperatures and vacuum conditions. X-ray diffraction studies reveal an evolution of oxygen vacancies aligned to ( h ¯ 0 l ) and (0k0) planes can cause an increase in lattice constants and a cell volume expansion to ∼3%. Transmission electron microscopy observation shows calcination at 800℃ in vacuum results in not only a size reduction of particles but also a development of edge/screw dislocations generated on ( 3 ¯ 03 ) plane as a slip system, which can drive microstrain correlated to the lattice parameter change. TiNb2O7−x shows remarkable lithium storage properties including charge (lithiation)/discharge (delithiation) capacities of 324/284 mAh g− 1 and capacity retentions of 100% at a 2C rate over 500 cycles and at a 5C rate over 1500 cycles, respectively. The achievement is attributed to a synergetic effect of short Li+ ion path by a size reduction and reduce Li+ ion migration by an expansion of the lattice constants and the cell volume.

Charge storage in supercapacitors is strongly related to the bond characteristics and electronic structure of electrode materials. Graphene-based materials are widely used in a supercapacitor due to the easily tunable properties and high surface/volume ratios. However, we claim that the typical covalent bond characteristics of 2D carbon materials originating from this 2pπ orbital is not very suitable to the application in supercapacitor. Here, we suggest an efficient way to improve the supercapacitor performance by tuning the covalency of bonding between the graphene-based electrode and potassium ion. We, for the first time, also introduce a simple solvent-free scale-up doping technique to prepare fluorine-doped graphene oxide (FGO) by direct plasma treatment on graphene oxide (GO) powder at ambient pressure. The FGO enabled fast electrochemical charge transfer and provided a large number of active sites for redox reactions during supercapacitor operation, and those mechanisms were thoroughly studied by various electrochemical analyses. As a result, the fabricated symmetric supercapacitor using FGO electrodes exhibited a maximum power density (~3200 W/kg) and energy density (~25.87 Wh/kg) with superior cycle stability (20000 cycles) without capacitance loss. Furthermore, the computational calculation results clarified the roles of semi-ionic C–F bonding of FGO: huge charge accumulation on the electrodes and superior electrical conductivity. Thus, our study demonstrates a facile strategy to develop promising functionalized materials, which can enhance the viability of supercapacitor for the next generation of energy storage systems.

The electrocatalytic performance of transition metal sulfide (TMS)–graphene composites has been simply regarded as the results of high conductivity and the large surface/volume ratio. However, unavoidable factors such as degree of oxidation of TMSs have been hardly considered for the origin of this catalytic activity of TMS–graphene composites. To accomplish the reliable application of TMS-based electrocatalytic materials, a clear understanding of the thermodynamic stability of TMS and effects of oxidation on catalytic activity is necessary. In addition, the mechanism of charge transfer at the TMS–graphene interface must be studied in depth to properly design composite materials. Herein, we report a comprehensive study of the physical chemistry at the junction of a Co1–xNixS2–graphene composite, which is a prototype designed to unravel the mechanisms of charge transfer between TMS and graphene. Specifically, the thermodynamic stability and the effects of oxidation of TMSs during the oxygen evolution react...

A key issue with Na-ion batteries is the development of active materials with stable electrochemical reversibility through the understanding of their sodium storage mechanisms. We report a sodium storage mechanism and properties of a new anode material, digenite Cu1.8S, based on its crystallographic study. It is revealed that copper sulfides (CuxS) can have metal-rich formulas (x ≥ 1.6), due to the unique oxidation state of +1 found in group 11 elements. These phases enable the unit cell to consist of all strong Cu–S bonds and no direct S–S bonds, which are vulnerable to external stress/strain that could result in bond cleavage as well as decomposition. Because of its structural rigidness, the Cu1.8S shows an intercalation/deintercalation reaction mechanism even in a low potential window of 0.1–2.2 V versus Na/Na+ without irreversible phase transformation, which most of the metal sulfides experience through a conversion reaction mechanism. It uptakes, on average, 1.4 Na+ ions per unit cell (∼250 mAh g–1) and exhibits ∼100% retention over 1000 cycles at 2C in a tuned voltage range of 0.5–2.2 V through an overall solid solution reaction with negligible phase separation.

Black anatase TiO2 has surprisingly enhanced solar energy harvesting efficiency and electrical conductivity, which makes it a promising material in a wide range of energy and environmental applications. Several experimental and theoretical studies have successfully revealed the mechanisms of band gap reduction by surface hydrogenation of anatase TiO2. However, recent experimental evidence suggests the existence of bulk point defects that yield infrared (∼1.0 eV) photoabsorption and high conductivity of black anatase TiO2. In the current study, using a combination of ab initio molecular dynamics simulations and electronic structure calculations, we successfully explain the physical properties, metallicity, and infrared/microwave absorption (i.e., black color) of highly reduced anatase TiO2 crystal in a hydrogenated state with a newly found pair defect (Tii-VO)4+. Hydrogen atoms in the bulk are unnecessary to understand the observed properties.

A combined solvothermal method and post-annealing to synthesize highly active ZnS-ZnO nanosheets is presented. ZnO was produced on ZnS nanosheets by thermal annealing ZnS/ethylenediamine in air. From combined studies of experimental and computational works, we revealed that during annealing, carbon (C) element was a major dopant from the decomposition of ethylenediamine, which was unintentionally doped into the ZnS-ZnO, and gave major impacts on enhanced visible-light photocatalysis. Rhodium (Rh) was deposited by in situ photoreduction to form a ZnS-ZnO/Rh catalyst composite. This multijunctioned photocatalyst was outstanding for H2 generation from pure water under solar simulating light due to effective charge separation by Z-scheme heterojunction of ZnS and ZnO and Schottky junction of Rh-cocatalysts/semiconductors. This facile method realizes multijunctioned ZnS-ZnO/Rh photocatalysts with substantial defects that are very promising for solar-energy harvesting applications.