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1.
The development of efficient electrocatalysts with low cost and earth abundance for overall water splitting is very important in energy conversion. Although many electrocatalysts based on transition metal dichalcogenides have been developed, rational design and controllable synthesis of fine nanostructures with subtle morphologies and sequential chemical compositions related to these materials remains a challenge. This study reports a series of peapod‐like composites with component‐controllable Co(Sx Se1–x )2 nanoparticles encapsulated in carbon fibers, which are obtained by using Co(CO3)0.5(OH)·0.11H2O nanowires as a precursor followed by coating carbon fiber and an adjustable sulfuration/selenylation process. Due to its increased exposure of active sites and improved charge and mass transport capability derived from the unique structure and morphology, the Co(Sx Se1–x )2 samples display favorable catalytic activities. It is found that Co(S0.71Se0.29)2 exhibits the best hydrogen evolution reaction (HER) performance and Co(S0.22Se0.78)2 shows the highest activity for the oxygen evolution reaction (OER). When using Co(S0.71Se0.29)2 as a cathode and Co(S0.22Se0.78)2 as an anode, it demonstrates a durable activity for overall water splitting to deliver 10 mA cm?2 at a cell voltage of 1.63 V, thus offering an attractive cost‐effective earth abundant material system toward water splitting.  相似文献   

2.
High‐quality single‐crystalline ternary (Sb1‐xBix)2Se3 nanowires (NWs) (x = 0–0.88) are synthesized by chemical vapor deposition. Nanowires with x from 0 to 0.75 are indexed as an orthorhombic structure. With increasing Bi incorporation ratio, (Sb1‐xBix)2Se3 NWs exhibit remarkable photoresponsivities, which originate from growing surface Se vacancies and augmented oxygen chemisorptions. Notably, spectra responsivity and external quantum efficiency of an (Sb0.44Bi0.56)2Se3 NW photodetector reach as high as ≈8261.4 A/W and ≈1.6 × 106 %, respectively. Those excellent performances unambiguously demonstrate that Sb–Bi–Se NWs are promising for the utilizations of high‐sensitivity and high‐speed photodetectors and photoelectronic switches.  相似文献   

3.
Edges of 2D transition metal dichalcogenides (TMDs) are well known as highly reactive sites, thus researchers have attempted to maximize the edge site density of 2D TMDs. In this work, metal‐organic framework (MOF) templates are introduced to synthesize few‐layered WS2 nanoplates (a lateral dimension of ≈10 nm) confined in Co, N‐doped hollow carbon nanocages (WS2_Co‐N‐HCNCs), for highly sensitive NO2 gas sensors. WS2 precursors are assembled in the surface cavity of Co‐based zeolite imidazole framework (ZIF‐67) and subsequent pyrolysis produced WS2_Co‐N‐HCNCs. During the pyrolysis, the carbonized ZIF‐67 are doped by Co and N elements, and the growth of WS2 is effectively suppressed, creating few‐layered WS2 nanoplates functionalized Co‐N‐HCNCs. The WS2_Co‐N‐HCNCs exhibit outstanding NO2 sensing characteristics at room temperature, in terms of response (48.2% to 5 ppm), selectivity, response and recovery speed, and detection limit (100 ppb). These results are attributed to the enhanced adsorption and desorption kinetics of NO2 on abundant WS2 edges, confined in the gas permeable HCNCs. This work opens up an efficient way for the facile synthesis of edge abundant few‐layered TMDs combined with porous carbon matrix via MOF templating route, for applications relying on highly active sites.  相似文献   

4.
The synergistic effects derived from optimizing the chemical and structural features of electrocatalysts permit them to attain remarkable activity and stability. Herein, 1D/2D cobalt‐based nanohybrid (CoNH) electrodes are developed; the structural design consists of Co3O4 electrospun nanoribbons (NRs) deposited onto a carbon fiber paper substrate where Co3O4 nanosheets are subsequently grown via an electrodeposition step and UV/ozone treatment. The content of noncovalently functionalized carbon nanotubes within the Co3O4 NRs is first tuned to enhance their charge transfer properties and mechanical stability. The electrocatalytic activity of the electrodes is further improved by a phosphorus modification of the 1D NRs, resulting in the formation of NaCoPO4. The optimized 1D/2D CoNH electrode, i.e., ED‐0.09 wt% fCNTs/P‐CoNHs, displays a similar performance to that of platinum in 0.25 m Na2S/0.35 m Na2SO3 (Tafel slope ≈102 mV dec?1 for the former and ≈96 mV dec?1 for the latter) and outstanding stability for up to 48 h. The versatility and high activity of this electrode is also demonstrated according to tests in a conventional water splitting system (cell voltage 1.55V, to produce 10 mA cm?2) and a solar‐driven electrolyzer (1 m KOH).  相似文献   

5.
Solution‐processed, low cost thin films of layered semiconductors such as transition metal dichalcogenides (TMDs) are potential candidates for future printed electronics. Here, n‐type electrolyte‐gated transistors (EGTs) based on porous WS2 nanosheet networks as the semiconductor are demonstrated. The WS2 nanosheets are liquid phase exfoliated to form aqueous/surfactant stabilized inks, and deposited at low temperatures (T < 120 °C) in ambient atmosphere by airbrushing. No solvent exchange, further additives, or complicated processing steps are required. While the EGTs are primarily n‐type (electron accumulation), some hole transport is also observable. The EGTs show current modulations > 104 with low hysteresis, channel width‐normalized on‐conductances of up to 0.27 µS µm?1 and estimated electron mobilities around 0.01 cm2 V?1 s?1. In addition, the WS2 nanosheet networks exhibit relatively high volumetric capacitance values of 30 F cm?3. Charge transport within the network depends significantly on the applied lateral electric field and is thermally activated, which supports the notion that hopping between nanosheets is a major limiting factor for these networks and their future application.  相似文献   

6.
Bundles of homogeneously alloyed Cu2?x(SySe1?y) nanowires with various compositions (0 ≤ y ≤ 1) are controllably prepared via a simple water‐evaporation method under mild conditions. It is found that the nanowire bundles have similar copper contents (0.37 ≤ x ≤ 0.44) and morphologies, and the same face centered cubic (fcc) crystal structure and growth orientation of [110] over the entire composition range of y. To the best of the authors' knowledge, this is the first report on cubic phased ternary Cu2?x(SySe1?y) compounds. It is found that lattice parameter of the Cu2?x(SySe1?y) compound changes linearly with the S content. It is also shown that the direct and the indirect bandgaps of the nanowires vary quadratically with the S content and have bowing parameters of 0.20 and 0.21 eV respectively. Energy‐gap‐tuning via compositional change is achieved for both the direct (1.48?1.87 eV) and the indirect (0.50?0.90 eV) bandgaps. The trends of lattice parameter and bandgap variations are consistent with those described by Végard's Law.  相似文献   

7.
Vertical and in‐plane heterostructures based on van der Waals (vdW) crystals have drawn rapidly increasing attention owning to the extraordinary properties and significant application potential. However, current heterostructures are mainly limited to vdW crystals with a symmetrical hexagonal lattice, and the heterostructures made by asymmetric vdW crystals are rarely investigated at the moment. In this contribution, it is reported for the first time the synthesis of layered orthorhombic SnS–SnSxSe(1?x) core–shell heterostructures with well‐defined geometry via a two‐step thermal evaporation method. Structural characterization reveals that the heterostructures of SnS–SnSxSe(1?x) are in‐plane interconnected and vertically stacked, constructed by SnSxSe(1?x) shell heteroepitaxially growing on/around the pre‐synthesized SnS flake with an epitaxial relationship of (303)SnS//(033)SnSxSe(1?x), [010]SnS//[100]SnSxSe(1?x). On the basis of detailed morphology, structure and composition characterizations, a growth mechanism involving heteroepitaxial growth, atomic diffusion, as well as thermal thinning is proposed to illustrate the formation process of the heterostructures. In addition, a strong polarization‐dependent photoresponse is found on the device fabricated using the as‐prepared SnS?SnSxSe(1?x) core–shell heterostructure, enabling the potential use of the heterostructures as functional components for optoelectronic devices featured with anisotropy.  相似文献   

8.
The Bi2Te3?xSex family has constituted n‐type state‐of‐the‐art thermoelectric materials near room temperature (RT) for more than half a century, which dominates the active cooling and novel heat harvesting application near RT. However, the drawbacks of a brittle nature and Te‐content restricts the possibility for exploring potential applications. Here, it is shown that the Mg3+δSbxBi2?x family ((ZT)avg = 1.05) could be a promising substitute for the Bi2Te3?xSex family ((ZT)avg = 0.9–1.0) in the temperature range of 50–250 °C based on the comparable thermoelectric performance through a synergistic effect from the tunable bandgap using the alloy effect and the suppressible Mg‐vacancy formation using an interstitial Mn dopant. The former is to shift the optimal thermoelectric performance to near RT, and the latter is helpful to partially decouple the electrical transport and thermal transport in order to get an optimal RT power factor. The positive temperature dependence of the bandgap suggests this family is also a superior medium‐temperature thermoelectric material for the significantly suppressed bipolar effect. Furthermore, a two times higher mechanical toughness, compared with the Bi2Te3?xSex family, allows for a promising substitute for state‐of‐the‐art n‐type thermoelectric materials near RT.  相似文献   

9.
The design of advanced functional materials with customized properties often requires the use of an alloy. This approach has been used for decades, but only recently to create van der Waals (vdW) alloys for applications in electronics, optoelectronics, and thermoelectrics. A route to engineering their physical properties is by mixing isoelectronic elements, as done for the SnSe2(1?x)S2x alloy. Here, by experiment and first‐principles modeling, it is shown that the value of x can be adjusted over a wide range, indicating good miscibility of the SnS2 and SnSe2 compounds. The x‐dependence of the indirect bandgap energy from Eind = 1.20 eV for SnSe2 to Eind = 2.14 eV for SnS2, corresponds to a large bowing coefficient b ≈ 1 eV, arising from volume deformation and charge exchange effects due to the different sizes and orbital energies of the S‐ and Se‐atoms. This also causes composition‐dependent phonon energy modes, electron–phonon interaction, and temperature dependence of Eind. The alloys are exfoliable into thin layers with properties that depend on the composition, but only weakly on the layer thickness. This work shows that the electronic and vibrational properties of the SnSe2(1?x)S2x alloy and its thin layers provide a versatile platform for development and exploitation.  相似文献   

10.
Near IR properties of the mixed TlInS2xSe2(1?x) have been studied previously by the present authors. In this work the temperature and frequency dependence's of the conductivity and the current-voltage characteristics (in relatively weak electric field), have been investigated for monoclinic TlInS2xSe2(1?x) crystals, which are perspective materials for IR applications. From the temperature dependence's of conductivity in the direction perpendicular to c- axis the band gap Eg = 2.22 eV was determined for β--TlInS2 crystals. The impurity centres were determined located at 0.43, 0.73 eV and 0.35, 0.48, 1.12 eV for the direction of current i//c and i ⊥ c, respectively. The concentration of the centres located at 0.48 and 1.12 eV were calculated to be NA ? ND = 4.8 · 109 cm?3 and 1.9 · 1011 cm?3, respectively. It was found that in the solid solutions TlInS2xSe2(1?x) for 0.3 ≤ x ≤ 1, the conductivity follows the dependence σ (v) = σ0·υs in the temperature range between 100 to 600 K. In the temperature range of 80-400 K charge bounce plays an important role in the conductivity mechanism. Occurrence of the deep and low-levels impurity centres and a “tail” of the density of energy states in TlInS2xSe2(1?x) crystals make them perspective for practical applications: switching and memory effects, N-type current-voltage characteristics, induced conductivity etc.  相似文献   

11.
2D ternary semiconductor single crystals, an emerging class of new materials, have attracted significant interest recently owing to their great potential for academic interest and practical application. In addition to other types of metal dichalcogenides, 2D tin dichalcogenides are also important layered compounds with similar capabilities. Yet, multi‐elemental single crystals enable to assist multiple degrees of freedom for dominant physical properties via ratio alteration. This study reports the growth of single crystals Se‐doped SnS2 or SnSSe alloys, and demonstrates their capability for the fabrication of phototransistors with high performance. Based on exfoliation from bulk high quality single crystals, this study establishes the characteristics of few‐layered SnSSe in structural, optical, and electrical properties. Moreover, few‐layered SnSSe phototransistors are fabricated on both rigid (SiO2/Si) and versatile polyethylene terephthalate substrates and their optoelectronic properties are examined. SnSSe as a phototransistor is demonstrated to exhibit a high photoresponsivity of about 6000 A W?1 with ultra‐high photogain ≈8.8 × 105, fast response time ≈9 ms, and specific detectivity (D*) ≈8.2 × 1012 J. These unique features are much higher than those of recently published phototransistors configured with other few‐layered 2D single crystals, making ultrathin SnSSe a highly qualified candidate for next‐generation optoelectronic applications.  相似文献   

12.
The reflection spectra in the infrared range and the optical Raman spectra are investigated in single crystals of the ternary compounds CuInS2 and CuInSe2 and in CuInS2x Se2(1−x) solid solutions, all grown by the method of chemical transport reactions. The frequencies of the optical modes in the given materials are determined, and the type of behavior of these modes in the solid solutions are established. Fiz. Tekh. Poluprovodn. 31, 49–52 (January 1997)  相似文献   

13.
The construction of a novel 3D self‐supported integrated NixCo2?xP@NC (0 < x < 2) nanowall array (NA) on Ni foam (NF) electrode constituting highly dispersed NixCo2?xP nanoparticles, nanorods, nanocapsules, and nanodendrites embedded in N‐doped carbon (NC) NA grown on NF is reported. Benefiting from the collective effects of special morphological and structural design and electronic structure engineering, the NixCo2?xP@NC NA/NF electrodes exhibit superior electrocatalytic performance for water splitting with an excellent stability in a wide pH range. The optimal NiCoP@NC NA/NF electrode exhibits the best hydrogen evolution reaction (HER) activity in acidic solution so far, attaining a current density of 10 mA cm?2 at an overpotential of 34 mV. Moreover, the electrode manifests remarkable performances toward both HER and oxygen evolution reaction in alkaline medium with only small overpotentials of 37 mV at 10 mA cm?2 and 305 mV at 50 mA cm?2, respectively. Most importantly, when coupling with the NiCoP@NC NA/NF electrode for overall water splitting, an alkali electrolyzer delivers a current density of 20 mA cm?2 at a very low cell voltage of ≈1.56 V. In addition, the NiCoP@NC NA/NF electrode has outstanding long‐term durability at j = 10 mA cm?2 with a negligible degradation in current density over 22 h in both acidic and alkaline media.  相似文献   

14.
Argyrodites with a general chemical formula of A8BC6 are known for complex phase transitions, ultralow lattice thermal conductivity, and mixed electronic and ionic conduction. The coexistence of ionic conduction and promising thermoelectric performance have recently been reported in selenide and telluride argyrodites, but scarcely in sulfide argyrodites. Here, the thermoelectric properties of Ag8Sn(S1?xSex)6 are reported. Specifically, Ag8SnS6 exhibits intrinsically ultralow lattice thermal conductivities of 0.61–0.31 W m?1 K?1 over the whole temperature range from 32 to 773 K due to distorted local crystal structure, relatively weak chemical bonding, rattler‐like Ag atoms, low‐lying optical modes, and dynamic disorder of Ag ions at high temperatures. Se doping shifts the orthorhombic–cubic phase transition from 457 K at x = 0 to 430 K at x = 0.10, thereby expanding the temperature range of the thermoelectrically favored cubic phase. A figure of merit zT value ≈ 0.80 is achieved at 773 K in Ag8Sn(S1?xSex)6 (x = 0.03), the highest zT value reported in sulfide argyrodites. These results fill a knowledge gap of the thermoelectric study of argyrodites and contribute to a comprehensive understanding of the chemical bonding, lattice dynamics, and thermal transport of argyrodites.  相似文献   

15.
In this work, uniform molybdenum disulfide (MoS2)/tungsten disulfide (WS2) quantum dots are synthesized by the combination of sonication and solvothermal treatment of bulk MoS2/WS2 at a mild temperature. The resulting products possess monolayer thickness with an average size about 3 nm. The highly exfoliated and defect‐rich structure renders these quantum dots plentiful active sites for the catalysis of hydrogen evolution reaction (HER). The MoS2 quantum dots exhibit a small HER overpotential of ≈120 mV and long‐term durability. Moreover, the strong fluorescence, good cell permeability, and low cytotoxicity make them promising and biocompatible probes for in vitro imaging. In addition, this work may provide an alternative facile approach to synthesize the quantum dots of transition metal dichalcogenides or other layered materials on a large scale.  相似文献   

16.
The very recently rediscovered group‐10 transition metal dichalcogenides (TMDs) such as PtS2 and PtSe2, have joined the 2D material family as potentially promising candidates for electronic and optoeletronic applications due to their theoretically high carrier mobility, widely tunable bandgap, and ultrastability. Here, the first exploration of optoelectronic application based on few‐layered PtS2 using h‐BN as substrate is presented. The phototransistor exhibits high responsivity up to 1.56 × 103 A W?1 and detectivity of 2.9 × 1011 Jones. Additionally, an ultrahigh photogain ≈2 × 106 is obtained at a gate voltage V g = 30 V, one of the highest gain among 2D photodetectors, which is attributed to the existence of trap states. More interestingly, the few‐layered PtS2 phototransistor shows a back gate modulated photocurrent generation mechanism, that is, from the photoconductive effect dominant to photogating effect dominant via tuning the gate voltage from the OFF state to the ON state. Such good properties combined with gate‐controlled photoresponse of PtS2 make it a competitive candidate for future 2D optoelectronic applications.  相似文献   

17.
Direct observation of the growth dynamics of 2D transition metal dichalcogenides (TMDs) is of key importance for understanding and controlling the growth modes and for tailoring these intriguing materials to desired orientations and layer thicknesses. Here, various stages and multiple growth modes in the formation of WS2 layers on different substrates through thermolysis of a single solid-state (NH4)2WS4 precursor are revealed using in situ transmission electron microscopy. Control over vertical and horizontal growth is achieved by varying the thickness of the drop-casted precursor from which WS2 is grown during heating. First depositing platinum (Pt) and gold (Au) on the heating chips much enhance the growth process of WS2 resulting in an increased length of vertical layers and in a self-limited thickness of horizontal layers. Interference patterns are formed by the mutual rotation of two WS2 layers by various angles on metal deposited heating chips. This shows detailed insights into the growth dynamics of 2D WS2 as a function of temperature, thereby establishing control over orientation and size. These findings also unveil the important role of metal substrates in the evolution of WS2 structures, offering general and effective pathways for nano-engineering of 2D TMDs for a variety of applications.  相似文献   

18.
Planar 2D materials are possibly the ideal channel candidates for future field effect transistors (FETs), due to their unique electronic properties. However, the performance of FETs based on 2D materials is yet to exceed those of conventional silicon based devices. Here, a 2D channel thin film made from liquid phase exfoliated molybdenum oxide nanoflake inks with highly controllable substoichiometric levels is presented. The ability to induce oxygen vacancies by solar light irradiation in an aqueous environment allows the tuning of electronic properties in 2D substoichiometric molybdenum oxides (MoO3?x). The highest mobility is found to be ≈600 cm2 V?1 s?1 with an estimated free electron concentration of ≈1.6 × 1021 cm?3 and an optimal IOn/IOff ratio of >105 for the FETs made of 2D flakes irradiated for 30 min (x = 0.042). These values are significant and represent a real opportunity to realize the next generation of tunable electronic devices using electronic inks.  相似文献   

19.
Room‐temperature Na‐ion batteries (NIBs) have recently attracted attention as potential alternatives to current Li‐ion batteries (LIBs). The natural abundance of sodium and the similarity between the electrochemical properties of NIBs and LIBs make NIBs well suited for applications requiring low cost and long‐term reliability. Here, the first successful synthesis of a series of Na3(VO1?x PO4)2F1+2x (0 ≤ x ≤ 1) compounds as a new family of high‐performance cathode materials for NIBs is reported. The Na3(VO1?x PO4)2F1+2x series can function as high‐performance cathodes for NIBs with high energy density and good cycle life, although the redox mechanism varies depending on the composition. The combined first‐principles calculations and experimental analysis reveal the detailed structural and electrochemical mechanisms of the various compositions in solid solutions of Na3(VOPO4)2F and Na3V2(PO4)2F3. The comparative data for the Na y (VO1?x PO4)2F1+2x electrodes show a clear relationship among V3+/V4+/V5+ redox reactions, Na+?Na+ interactions, and Na+ intercalation mechanisms in NIBs. The new family of high‐energy cathode materials reported here is expected to spur the development of low‐cost, high‐performance NIBs.  相似文献   

20.
Since transition metal dichalcogenide (TMD) semiconductors are found as 2D van der Waals materials with a discrete energy bandgap, many 2D‐like thin field effect transistors (FETs) and PN diodes are reported as prototype electrical and optoelectronic devices. As a potential application of display electronics, transparent 2D FET devices are also reported recently. Such transparent 2D FETs are very few in report, yet no p‐type channel 2D‐like FETs are seen. Here, 2D‐like thin transparent p‐channel MoTe2 FETs with oxygen (O2) plasma‐induced MoOx/Pt/indium‐tin‐oxide (ITO) contact are reported for the first time. For source/drain contact, 60 s short O2 plasma and ultrathin Pt‐deposition processes on MoTe2 surface are sequentially introduced before ITO thin film deposition and patterning. As a result, almost transparent 2D FETs are obtained with a decent mobility of ≈5 cm2 V?1 s?1, a high ON/OFF current ratio of ≈105, and 70% transmittance. In particular, for normal MoTe2 FETs without ITO, O2 plasma process greatly improves the hole injection efficiency and device mobility (≈60 cm2 V?1 s?1), introducing ultrathin MoOx between Pt source/drain and MoTe2. As a final device application, a photovoltaic current modulator, where the transparent FET stably operates as gated by photovoltaic effects, is integrated.  相似文献   

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