Systemic thrombolysis with intravenous tissue plasminogen activator (tPA) remains the only proven treatment that is effective in improving the clinical outcome of patients with acute ischemic stroke. However, thrombolytic therapy has some major limitations such as hemorrhage, neurotoxicity, and the short time window for the treatment. In this study, we designed iron oxide (Fe3O4) nanorods loaded with 6% tPA, which could be released within ~30 min. The Fe3O4 nanorods could be targeted to blood clots under magnetic guidance. In addition, the release of tPA could be significantly increased using an external rotating magnetic field, which subsequently resulted in a great improvement in the thrombolytic efficiency. Systematic and quantitative studies revealed the fundamental physical processes involved in the enhanced thrombolysis, while the in vitro thrombolysis assay showed that the proposed strategy could improve thrombolysis and recanalization rates and reduce the risk of tPA-mediated hemorrhage in vivo. Such a strategy will be very useful for the treatment of ischemic stroke and other deadly thrombotic diseases such as myocardial infarction and pulmonary embolism in clinical settings.
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.
A facile strategy was designed for the fabrication of Fe3O4-nanoparticle-decorated TiO2 nanofiber hierarchical heterostructures (FTHs) by combining the versatility of the electrospinning technique and the hydrothermal growth method. The hierarchical architecture of Fe3O4 nanoparticles decorated on TiO2 nanofibers enables the successful integration of the binary composite into batteries to address structural stability and low capacity. In the resulting unique architecture of FTHs, the 1D heterostructures relieve the strain caused by severe volume changes of Fe3O4 during numerous charge-discharge cycles, and thus suppress the degradation of the electrode material. As a result, FTHs show excellent performance including higher reversible capacity, excellent cycle life, and good rate performance over a wide temperature range owing to the synergistic effect of the binary composition of TiO2 and Fe3O4 and the unique features of the hierarchical nanofibers.
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.
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.
Yolk/shell nanoparticles (NPs), which integrate functional cores (likes Fe3O4) and an inert SiO2 shell, are very important for applications in fields such as biomedicine and catalysis. An acidic medium is an excellent etchant to achieve hollow SiO2 but harmful to most functional cores. Reported here is a method for preparing sub-100 nm yolk/shell Fe3O4@SiO2 NPs by a mild acidic etching strategy. Our results demonstrate that establishment of a dissolution–diffusion equilibrium of silica is essential for achieving yolk/shell Fe3O4@SiO2 NPs. A uniform increase in the silica compactness from the inside to the outside and an appropriate pH value of the etchant are the main factors controlling the thickness and cavity of the SiO2 shell. Under our “standard etching code”, the acid-sensitive Fe3O4 core can be perfectly preserved and the SiO2 shell can be selectively etched away. The mechanism of regulation of SiO2 etching and acidic etching was investigated.
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.
We report the preparation of nanocomposites of reduced graphene oxide with embedded Fe3O4/Fe nanorings (FeNR@rGO) by chemical hydrothermal growth. We illustrate the use of these nanocomposites as novel electromagnetic wave absorbing materials. The electromagnetic wave absorption properties of the nanocomposites with different compositions were investigated. The preparation procedure and nanocomposite composition were optimized to achieve the best electromagnetic wave absorption properties. Nanocomposites with a GO:α-Fe2O3 mass ratio of 1:1 prepared by annealing in H2/Ar for 3 h exhibited the best properties. This nanocomposite sample (thickness = 4.0 mm) showed a minimum reflectivity of–23.09 dB at 9.16 GHz. The band range was 7.4–11.3 GHz when the reflectivity was less than–10 dB and the spectrum width was up to 3.9 GHz. These figures of merit are typically of the same order of magnitude when compared to the values shown by traditional ferric oxide materials. However, FeNR@rGO can be readily applied as a microwave absorbing material because the production method we propose is highly compatible with mass production standards.
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 developed a strategy based on coordination polymer to synthesize singleatom site Fe/N and S-codoped hierarchical porous carbon (Fe1/N,S-PC). The as-obtained Fe1/N,S-PC exhibited superior oxygen reduction reaction (ORR) performance with a half-wave potential (E1/2, 0.904 V vs. RHE) that was better than that of commercial Pt/C (E1/2, 0.86 V vs. RHE), single-atom site Fe/N-doped hierarchical porous carbon (Fe1/N-PC) without S-doped (E1/2, 0.85 V vs. RHE), and many other nonprecious metal catalysts in alkaline medium. Moreover, the Fe1/N,S-PC revealed high methanol tolerance and firm stability. The excellent electrocatalytic activity of Fe1/N,S-PC is attributed to the synergistic effects from the atomically dispersed porphyrin-like Fe-N4 active sites, the heteroatom codoping (N and S), and the hierarchical porous structure in the carbon materials. The calculation based on density functional theory further indicates that the catalytic performance of Fe1/N,S-PC is better than that of Fe1/N-PC owing to the sulfur doping that yielded different rate-determining steps.
In-plane symmetry is an important contributor to the physical properties of two-dimensional layered materials, as well as atomically thin heterojunctions. Here, we demonstrate anisotropic/isotropic van der Waals (vdW) heterostructures of ReS2 and MoS2 monolayers, where interlayer coupling interactions and charge separation were observed by in situ Raman-photoluminescence spectroscopy, electrical, and photoelectrical measurements. We believe that these results could be helpful for understanding the fundamental physics of atomically thin vdW heterostructures and creating novel electronic and optoelectronic devices.
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.
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.
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.
By combining ab initio calculations and experiments, we demonstrate how the band gap of the transition metal trichalcogenide TiS3 can be modified by inducing tensile or compressive strain. In addition, using our calculations, we predicted that the material would exhibit a transition from a direct to an indirect band gap upon application of a compressive strain in the direction of easy electrical transport. The ability to control the band gap and its nature could have a significant impact on the use of TiS3 for optical applications. We go on to verify our prediction via optical absorption experiments that demonstrate a band gap increase of up to 9% (from 0.99 to 1.08 eV) upon application of tensile stress along the easy transport direction.
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.
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.
Regulating the selectivity of CO2 photoreduction is particularly challenging. Herein, we propose ideal models of atomic layers with/without element doping to investigate the effect of doping engineering to tune the selectivity of CO2 photoreduction. Prototypical ZnCo2O4 atomic layers with/without Ni-doping were first synthesized. Density functional theory calculations reveal that introducing Ni atoms creates several new energy levels and increases the density-of-states at the conduction band minimum. Synchrotron radiation photoemission spectroscopy demonstrates that the band structures are suitable for CO2 photoreduction, while the surface photovoltage spectra demonstrate that Ni doping increases the carrier separation efficiency. In situ diffuse reflectance Fourier transform infrared spectra disclose that the CO2·? radical is the main intermediate, while temperature-programed desorption curves reveal that the ZnCo2O4 atomic layers with/without Ni doping favor the respective CO and CH4 desorption. The Ni-doped ZnCo2O4 atomic layers exhibit a 3.5-time higher CO selectivity than the ZnCo2O4 atomic layers. This work establishes a clear correlation between elemental doping and selectivity regulation for CO2 photoreduction, opening new possibilities for tailoring solar-driven photocatalytic behaviors.
The rational design of earth-abundant catalysts with excellent water splitting activities is important to obtain clean fuels for sustainable energy devices. In this study, mixed transition metal oxide nanoparticles encapsulated in nitrogendoped carbon (denoted as AB2O4@NC) were developed using a one-pot protocol, wherein a metal–organic complex was adopted as the precursor. As a proof of concept, MnCo2O4@NC was used as an electrocatalyst for water oxidation, and demonstrated an outstanding electrocatalytic activity with low overpotential to achieve a current density of 10 mA·cm?1 (η10 = 287 mV), small Tafel slope (55 mV·dec?1), and high stability (96% retention after 20 h). The excellent electrochemical performance benefited from the synergistic effects of the MnCo2O4 nanoparticles and nitrogen-doped carbon, as well as the assembled mesoporous nanowire structure. Finally, a highly stable all-solid-state supercapacitor based on MnCo2O4@NC was demonstrated (1.5% decay after 10,000 cycles).
Iron oxides have attracted considerable interest as abundant materials for high-capacity Li-ion battery anodes. However, their fast capacity fading owing to poorly controlled reversibility of the conversion reactions greatly hinders their application. Here, a sandwich-structured nanocomposite of N-doped graphene and nearly monodisperse Fe3O4 nanoparticles were developed as high-performance Li-ion battery anode. N-doped graphene serves as a conducting framework for the self-assembled structure and controls Fe3O4 nucleation through the interaction of N dopants, surfactant molecules, and iron precursors. Fe3O4 nanoparticles were well dispersed with a uniform diameter of ~15 nm. The unique sandwich structure enables good electron conductivity and Li-ion accessibility and accommodates a large volume change. Hence, it delivers good cycling reversibility and rate performance with a capacity of ~1,227 mA·h·g–1 and 96.8% capacity retention over 1,000 cycles at a current density of 3 A·g–1. Our work provides an ideal structure design for conversion anodes or other electrode materials requiring a large volume change.
