The fabrication of heterostructures of two-dimensional semiconductors with specific bandgaps is an important approach to realizing the full potential of these materials in electronic and optoelectronic devices. Several groups have recently reported the direct growth of lateral and vertical heterostructures based on monolayers of typical semiconducting transition metal dichalcogenides (TMDCs) such as WSe2, MoSe2, WS2, and MoS2. Here, we demonstrate the single-step direct growth of lateral and vertical heterostructures based on bandgap-tunable Mo1-xWxS2 alloy monolayers by the sulfurization of patterned thin films of WO3 and MoO3. These patterned films are capable of generating a wide variety of concentration gradients by the diffusion of transition metals during the crystal growth phase. Under high temperatures, this leads to the formation of monolayer crystals of Mo1-xWxS2 alloys with various compositions and bandgaps, depending on the positions of the crystals on the substrates. Heterostructures of these alloys are obtained through stepwise changes in the ratio of W/Mo within a single domain during low-temperature growth. The stabilization of the monolayer Mo1-xWxS2 alloys, which often degrade even under gentle conditions, was accomplished by coating the alloys with other monolayers. The present findings demonstrate an efficient means of both studying and optimizing the optical and electrical properties of TMDC-based heterostructures to allow use of the materials in future device applications.
Sodium-ion batteries (SIBs) have been increasingly attracting attention as a sustainable alternative to lithium-ion batteries for scalable energy storage. The key to advanced SIBs relies heavily upon the development of reliable anodes. In this respect, Bi2S3 has been extensively investigated because of its high capacity, tailorable morphology, and low cost. However, the common practices of incorporating carbon species to enhance the electrical conductivity and accommodate the volume change of Bi2S3 anodes so as to boost their durability for Na storage have met with limited success. Herein, we report a simple method to realize the encapsulation of Bi2S3 nanorods within three-dimensional, nitrogen-doped graphene (3DNG) frameworks, targeting flexible and active composite anodes for SIBs. The Bi2S3/3DNG composites displayed outstanding Na storage behavior with a high reversible capacity (649 mAh·g–1 at 62.5 mA·g–1) and favorable durability (307 and 200 mAh·g–1 after 100 cycles at 125 and 312.5 mA·g–1, respectively). In-depth characterization by in situ X-ray diffraction revealed that the intriguing Na storage process of Bi2S3 was based upon a reversible reaction. Furthermore, a full, flexible SIB cell with Na0.4MnO2 cathode and as-prepared composite anode was successfully assembled, and holds a great promise for next-generation, wearable energy storage applications.
Although In2O3 nanofibers (NFs) are well-known candidates as active materials for next-generation, low-cost electronics, these NF based devices still suffer from high leakage current, insufficient on–off current ratios (Ion/Ioff), and large, negative threshold voltages (VTH), leading to poor device performance, parasitic energy consumption, and rather complicated circuit design. Here, instead of the conventional surface modification of In2O3 NFs, we present a one-step electrospinning process (i.e., without hot-press) to obtain controllable Mg-doped In2O3 NF networks to achieve high-performance enhancement-mode thin-film transistors (TFTs). By simply adjusting the Mg doping concentration, the device performance can be manipulated precisely. For the optimal doping concentration of 2 mol%, the devices exhibit a small VTH (3.2 V), high saturation current (1.1 × 10–4 A), large on/off current ratio (>108), and respectable peak carrier mobility (2.04 cm2/(V·s)), corresponding to one of the best device performances among all 1D metal-oxide NFs based devices reported so far. When high-κ HfOx thin films are employed as the gate dielectric, their electron mobility and VTH can be further improved to 5.30 cm2/(V·s) and 0.9 V, respectively, which demonstrates the promising prospect of these Mg-doped In2O3 NF networks for highperformance, large-scale, and low-power electronics.
We report the synthesis and electrochemical sodium storage of cobalt disulfide (CoS2) with various micro/nano-structures. CoS2 with microscale sizes are either assembled by nanoparticles (P-CoS2) via a facile solvothermal route or nanooctahedrons constructed solid (O-CoS2) and hollow microstructures (H-CoS2) fabricated by hydrothermal methods. Among three morphologies, H-CoS2 exhibits the largest discharge capacities and best rate performance as anode of sodium-ion batteries (SIBs). Furthermore, H-CoS2 delivers a capacity of 690 mA·h·g?1 at 1 A·g?1 after 100 cycles in a potential range of 0.1–3.0 V, and ～240 mA·h·g?1 over 800 cycles in the potential window of 1.0–3.0 V. This cycling difference mainly lies in the two discharge plateaus observed in 0.1–3.0 V and one discharge plateau in 1.0–3.0 V. To interpret the reactions, X-ray diffraction (XRD) and transmission electron microscopy (TEM) are applied. The results show that at the first plateau around 1.4 V, the insertion reaction (CoS2 + xNa+ + xe? → NaxCoS2) occurs; while at the second plateau around 0.6 V, the conversion reaction (NaxCoS2 + (4 ? x) Na+ + (4 ? x)e? → Co + 2Na2S) takes place. This provides insights for electrochemical sodium storage of CoS2 as the anode of SIBs.
The development of new non-precious metal catalysts and understanding the origin of their activity for the hydrogen evolution reaction (HER) are essential for rationally designing highly active low-cost catalysts as alternatives to state-of-the-art precious metal catalysts. Herein, manganese oxide/hydroxide was demonstrated as a highly active electrocatalysts for the HER by fabricating MnO2 nanosheets coated with Cu2O nanowire arrays (Cu2O@MnO2 NW@NS) on Cu foam followed by an in situ chronopotentiometry (CP) treatment. It was discovered that the in situ transformation of Cu2O@MnO2 into Cu@Mn(OH)2 NW@NS by the CP treatment drastically boosted the catalytic activity for the HER due to an enhancement of its intrinsic activity. Together with the benefits from such three-dimensional (3D) core–shell arrays for exposing more accessible active sites and efficient mass and electron transfers, the resulting Cu@Mn(OH)2 NW@NS exhibited excellent HER activity and outstanding durability in terms of a low overpotential of 132 mV vs. RHE at 10 mA/cm2. Overall, we expect these findings to generate new opportunities for the exploration of other Mn-based nanomaterials as efficient electrocatalysts and enable further understanding of their catalytic processes.
One-dimensional hollow nanostructures have potential applications in many fields and can be fabricated using various methods. Herein, a selective-oxidation route for the synthesis of unique TexSey nanotubes (STNTs) with a controlled morphology using TexSey@Se core–shell nanowires (TSSNWs) as a template is reported. Because of the lower redox potential of TeO2/Te compared to that of H2SeO3/Se, the Te in TSSNWs can be preferentially oxidized by an appropriate oxidant of HNO2 to form STNTs. The inner diameters and wall thicknesses of the STNTs can be tuned by modulating the core diameters and shell thicknesses of the TSSNWs, respectively. The STNTs can be assembled into a monolayer composed of well-arranged nanotubes using the Langmuir–Blodgett technique. A device based on films stacked with 10 STNT monolayers was fabricated to investigate the photocoductivity of the STNTs. The STNTs exhibited a good photoresponse over the whole ultraviolet–visible spectrum, revealing their potential for application in optoelectronic devices.
Bi2–хLaхFe4O9 and Bi2Fe4–2xTixCoxO9 ferrites have been prepared by solid-state reactions at a temperature of 1073 K. X-ray diffraction data indicate that, in the Bi2–хLaхFe4O9 system, the limiting degree of La3+ substitution for Bi3+ ions in Bi2Fe4O9 does not exceed 0.05 and that the limiting degree of substitution in the Bi2Fe4–2xTixCoxO9 system lies in the range 0.05 < x < 0.1. The specific magnetization and specific magnetic susceptibility of the samples have been measured at temperatures from 5 to 300 K in a magnetic field of 0.86 T. The field dependences of magnetization obtained for the Bi2–хLaхFe4O9 and Bi2Fe4–2xTixCoxO9 ferrites at temperatures of 300 and 5 K demonstrate that partial isovalent substitution of La3+ for Bi3+ ions in Bi2Fe4O9 and heterovalent substitution of Ti4+ and Co2+ ions for two Fe3+ ions leads to partial breakdown of the antiferromagnetic state and nucleation of a ferromagnetic state. 相似文献
A highly active and stable oxygen evolution reaction (OER) electrocatalyst is critical for hydrogen production from water splitting. Herein, three-dimensional Ni3S2@graphene@Co92S8 (Ni3S2@G@Co9S8), a sandwich-structured OER electrocatalyst, was grown in situ on nickel foam; it afforded an enhanced catalytic performance when highly conductive graphene is introduced as an intermediary for enhancing the electron transfer rate and stability. Serving as a free-standing electrocatalytic electrode, Ni3S2@G@Co9S8 presents excellent electrocatalytic activities for OER: A low onset overpotential (2 mA·cm?2 at 174 mV), large anode current density (10 mA·cm?2 at an overpotential of 210 mV), low Tafel slope (66 mV·dec?1), and predominant durability of over 96 h (releasing a current density of ～14 mA·cm?2 with a low and constant overpotential of 215 mV) in a 1 M KOH solution. This work provides a promising, cost-efficient electrocatalyst and sheds new light on improving the electrochemical performance of composites through enhancing the electron transfer rate and stability by introducing graphene as an intermediary.
Edge structures are highly relevant to the electronic, magnetic, and catalytic properties of two-dimensional (2D) transition metal dichalcogenides (TMDs) and their one-dimensional (1D) counterparts, i.e., nanoribbons, and should be precisely tailored for the desired application. In this work, we report the formation of novel Mo6S6 nanowire (NW)-terminated edges in monolayer molybdenum disulfide (MoS2) via an e–beam irradiation process combined with high temperature heating. The atomic structures of the NW-terminated edges and the dynamic formation process were observed experimentally using scanning transmission electron microscopy. Further analysis showed that the NW-terminated edge could be formed on both the Mo-zigzag (ZZ) edge and S-ZZ edge and could exhibit a stability superior to that of the pristine ZZ and armchair (AC) edges. In addition, analogous edge structures could also be formed in MoS2 nanoribbons and other TMD materials such as MoxW1?xSe2. We believe that these novel edge structures may impart novel properties to the 2D and 1D TMD materials and provide new opportunities for their applications in catalytic, spintronic, and electronic devices.
The oxygen reduction reaction (ORR) is essential in research pertaining to life science and energy. In applications, platinum-based catalysts give ideal reactivity, but, in practice, are often subject to high costs and poor stability. Some cost-efficient transition metal oxides have exhibited excellent ORR reactivity, but the stability and durability of such alternative catalyst materials pose serious challenges. Here, we present a facile method to fabricate uniform CoxOy nanoparticles and embed them into N-doped carbon, which results in a composite of extraordinary stability and durability, while maintaining its high reactivity. The half-wave potential shows a negative shift of only 21 mV after 10,000 cycles, only one third of that observed for Pt/C (63 mV). Furthermore, after 100,000 s testing at a constant potential, the current decreases by only 17%, significantly less than for Pt/C (35%). The exceptional stability and durability results from the system architecture, which comprises a thin carbon shell that prevents agglomeration of the CoxOy nanoparticles and their detaching from the substrate.
As a newly discovered member of the tungstate family, InWO4 hollow nanospheres with a monoclinic wolframite structure were synthesized successfully. The crystal phase of InWO4 was investigated via a combination of CASTEP geometric optimization and experimental simulation. InWO4 has a space group of P2/c with two InWO4 formula units per unit cell. The optimized cell dimensions are a = 5.16 Å, b = 5.97 Å, and c = 5.23 Å, with α = 90°, β = 92.11°, γ = 90°, giving a unit cell volume of 161.10 Å3, which is consistent with the experimental measurements. More importantly, InWO4 was a promising host material for different Ln3+ (Ln = Eu and Yb/Er) ions. For InWO4:Yb3+/Er3+ excited at 980 nm, transitions from the 4G11/2 (384 nm), 2H9/2 (411 nm), and 4F7/2 (487 nm) levels to the ground state (4I15/2) of Er3+ were observed. In addition to the aforementioned properties, the InWO4 hollow nanospheres can be used to improve the performance of dye-sensitized solar cells, which is chiefly attributed to theirlight scattering.
The size and density of Ag nanoparticles on n-layer MoS2 exhibit thicknessdependent behavior. The size and density of these particles increased and decreased, respectively, with increasing layer number (n) of n-layer MoS2. Furthermore, the surface-enhanced Raman scattering (SERS) of Ag on this substrate was observed. The enhancement factor of this scattering varied with the thickness of MoS2. The mechanisms governing the aforementioned thickness dependences are proposed and discussed.
Two-dimensional ZrS2 materials have potential for applications in nanoelectronics because of their theoretically predicted high mobility and sheet current density. Herein, we report the thickness and temperature dependent transport properties of ZrS2 multilayers that were directly deposited on hexagonal boron nitride (h-BN) by chemical vapor deposition. Hysteresis-free gate sweeping, metalinsulator transition, and T–γ (γ ~ 0.82–1.26) temperature dependent mobility were observed in the ZrS2 films.
Photocatalytic CO2 reduction on metal-oxide-based catalysts is promising for solving the energy and environmental crises faced by mankind. The oxygen vacancy (Vo) on metal oxides is expected to be a key factor affecting the efficiency of photocatalytic CO2 reduction on metal-oxide-based catalysts. Yet, to date, the question of how an Vo influences photocatalytic CO2 reduction is still unanswered. Herein, we report that, on Vo-rich gallium oxide coated with Pt nanoparticles (Vo-rich Pt/Ga2O3), CO2 is photocatalytically reduced to CO, with a highly enhanced CO evolution rate (21.0 μmol·h?1) compared to those on Vo-poor Pt/Ga2O3 (3.9 μmol·h?1) and Pt/TiO2(P25) (6.7 μmol·h?1). We demonstrate that the Vo leads to improved CO2 adsorption and separation of the photoinduced charges on Pt/Ga2O3, thus enhancing the photocatalytic activity of Pt/Ga2O3. Rational fabrication of an Vo is thereby an attractive strategy for developing efficient catalysts for photocatalytic CO2 reduction.
An inverted planar heterojunction perovskite solar cell (PSC) is one of the most competitive photovoltaic devices exhibiting a high power conversion efficiency (PCE) and nearly free hysteresis in the voltage–current output. However, the band alignment between the transport materials and the perovskite absorber has not been optimized, resulting in a lower open-circuit voltage (Voc) than that of regular PSCs. To address this issue, we tune the band alignment in perovskite photovoltaic architecture by introducing bilayer structured transport materials, e.g., the hole transport material poly(ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/V2O5. In this study, solution processed inorganic V2Ox interlayer is incorporated into PEDOT:PSS for achieving improved film surface properties as well as optical and electrical properties. For example, the work function (WF) was changed from 5.1 to 5.4 eV. A remarkably high PCE of 17.5% with nearly free hysteresis and a stabilized efficiency of 17.1% have been achieved. Electronic impedance spectra (EIS) demonstrate a significant increase in the recombination resistance after introducing the interlayer, associated with the high Voc output value of 1.05 V. Transient photocurrent and photovoltage measurements indicate that a comparable charge transport process and an inhibited recombination process occur in the PSC with the introduction of the V2Ox interlayer.
We systematically investigated the development of film morphology and crystallinity of methyl-ammonium bismuth (III) iodide (MA3Bi2I9) through onestep spin-coating on TiO2-deposited indium tin oxide (ITO)/glass. The precursor solution concentration and substrate structure have been demonstrated to be critically important in the active-layer evolution of the MA3Bi2I9-based solar cell. This work successfully improved the cell efficiency to 0.42% (average: 0.38%) with the mesoscopic architecture of ITO/compact-TiO2/mesoscopic-TiO2 (meso-TiO2)/MA3Bi2I9/2,2′,7,7′-tetrakis(N,N-di-4-methoxyphenylamino)-9,9′spiro-bifluorene (spiro-MeOTAD)/MoO3/Ag under a precursor concentration of 0.45 M, which provided the probability of further improving the efficiency of the Bi3+-based lead-free organic–inorganic hybrid solar cells.
Superexchange effects play an important role in the determination of crystal structures; however, there has been much less reported on how they determine the stability of clusters. Using evolutionary search strategies and DFT+U (density functional theory with the Hubbard U correction) calculations, we investigate the global minimum-energy structures of Fe12On clusters. Among predicted Fe12On clusters, a cage-shaped Fe12O12 cluster with unexpected stability was observed. In addition, the bare Fe12O12 cluster is shown to possess an extremely large energy gap (2.00 eV), which is greater than that of C60, Au20 and Al13?clusters. Using a Heisenberg model, we traced the origin of the unexpected stability of the bare Fe12O12 cluster to magnetic competition between the nearest-neighbor exchange constant J1 and the next-nearest neighbor exchange constant J2 that was induced by the superexchange interactions. The bare Fe12O12 cluster is thus a unique molecule that is stable and chemically inert.
Hollow nanostructures have attracted considerable attention owing to their large surface area, tunable cavity, and low density. In this study, a unique flower-like C@SnOX@C hollow nanostructure (denoted as C@SnOX@C-1) was synthesized through a novel one-pot approach. The C@SnOX@C-1 had a hollow carbon core and interlaced petals on the shell. Each petal was a SnO2 nanosheet coated with an ultrathin carbon layer ~2 nm thick. The generation of the hollow carbon core, the growth of the SnO2 nanosheets, and the coating of the carbon layers were simultaneously completed via a hydrothermal process using resorcinol-formaldehyde resin-coated SiO2 nanospheres, tin chloride, urea, and glucose as precursors. The resultant architecture with a large surface area exhibited excellent lithium-storage performance, delivering a high reversible capacity of 756.9 mA·h·g–1 at a current density of 100 mA·g–1 after 100 cycles.
The development of an electrocatalyst based on abundant elements for the oxygen evolution reaction (OER) is important for water splitting associated with renewable energy sources. In this study, we develop an interconnected Ni(Fe)OxHy nanosheet array on a stainless steel mesh (SSNNi) as an integrated OER electrode, without using any polymer binder. Benefiting from the well-defined three-dimensional (3D) architecture with highly exposed surface area, intimate contact between the active species and conductive substrate improved electron and mass transport capacity, facilitated electrolyte penetration, and improved mechanical stability. The SSNNi electrode also has excellent OER performance, including low overpotential, a small Tafel slope, and long-term durability in the alkaline electrolyte, making it one of the most promising OER electrodes developed.
T-Nb2O5/reduced graphene oxide nanohybrids were fabricated via the hydrothermal attachment of Nb2O5 nanowires to dispersed graphene oxide nanosheets followed by a high-temperature phase transformation. Electrochemical measurements showed that the nanohybrid anodes possessed enhanced reversible capacity and superior cycling stability compared to those of a pristine T-Nb2O5 nanowire electrode. Owing to the strong bonds between graphene nanosheets and T-Nb2O5 nanowires, the nanohybrids achieved an initial capacity of 227 mAh·g?1. Additionally, non-aqueous asymmetric supercapacitors (ASCs) were fabricated with the synthesized nanohybrids as the anode and activated carbon as the cathode. The 3 V Li-ion ASC with a LiPF6-based organic electrolyte achieved an energy density of 45.1 Wh·kg?1 at 715.2 W·kg?1. The working potential could be further enhanced to 4 V when a polymer ionogel separator (PVDF-HFP/LiTFSI/EMIMBF4) and formulated ionic liquid electrolyte were employed. Such a quasi-solid state ASC could operate at 60 °C and delivered a maximum energy density of 70 Wh·kg?1 at 1 kW·kg?1.
