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.
Nanocomposites combining magnetic and plasmonic components have received widespread attention in recent years due to their potential applications in biomedical research. Herein, we describe a facile method for growing small iron oxide nanoparticles on various plasmonic core materials with different shapes and surfaces by utilizing a polypyrrole interlayer. By focusing on Au nanorod@polypyrrole@iron oxide (Au NR@PPy@FexO) nanocomposites, we show that these systems exhibit a low r2/r1 ratio of 4.8, making them efficient T1 positive contrast-enhancing agents for magnetic resonance imaging (MRI). Moreover, we show that the nanocomposites are excellent photothermal agents in the second near infrared region, with high photothermal conversion efficiency, reaching up to 46%. In addition, the Au NR@PPy@FexO nanocomposites show very low cytotoxicity. In summary, the present results highlight the great potential of the synthetic method and the nanocomposites developed in this study for T1 MRI and/or infrared thermal imaging-guided photothermal cancer therapeutic applications.
Although nanotechnology has led to important advances in in vitro diagnostics, the development of nanosensors for in vivo detection remains very challenging. Here, we demonstrated the proof-of-principle of in vivo detection of nucleic acid targets using a promising type of surface-enhanced Raman scattering (SERS) nanosensor implanted in the skin of a large animal model (pig). The in vivo nanosensor used in this study involves the “inverse molecular sentinel” detection scheme using plasmonics-active nanostars, which have tunable absorption bands in the near infrared region of the “tissue optical window”, rendering them efficient as an optical sensing platform for in vivo optical detection. Ex vivo measurements were also performed using human skin grafts to demonstrate the detection of SERS nanosensors through tissue. In this study, a new core–shell nanorattle probe with Raman reporters trapped between the core and shell was utilized as an internal standard system for self-calibration. These results illustrate the usefulness and translational potential of the SERS nanosensor for in vivo biosensing.
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.
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 in situ physicochemical analysis of nanostructured functional materials is crucial for advances in their design and production. X-ray coherent diffraction imaging (CDI) methods have recently demonstrated impressive potential for characterizing such materials with a high spatial resolution and elemental sensitivity; however, moving from the current ex situ static regime to the in situ dynamic one remains a challenge. By combining soft X-ray ptychography and single-shot keyhole CDI, we performed the first in situ spatiotemporal study on an electrodeposition process in a sealed wet environment, employed for the fabrication of oxygen-reduction catalysts, which are key components for alkaline fuel cells and metal-air batteries. The results provide the first experimental demonstration of theoretically predicted Turing–Hopf electrochemical pattern formation resulting from morphochemical coupling, adding a new dimension for the in-depth in situ characterization of electrodeposition processes in space and time.
Controllable pyrolysis of metal?organic frameworks (MOFs) in confined spaces is a promising strategy for the design and development of advanced functional materials. In this study, Co-Co3O4@carbon composites were synthesized via pyrolysis of a Co-MOFs@glucose polymer (Co-MOFs@GP) followed by partial oxidation of Co nanoparticles (NPs). The pyrolysis of Co-MOFs@GP generated a core–shell structure composed of carbon shells and Co NPs. The controlled partial oxidation of Co NPs formed Co-Co3O4 heterojunctions confined in carbon shells. Compared with Co-MOFs@GP and Co@carbon-n (Co@C-n), Co-Co3O4@carbon-n (Co-Co3O4@C-n) exhibited higher catalytic activity during NaBH4 hydrolysis. Co-Co3O4@C-II provided a maximum specific H2 generation rate of 5,360 mL·min?1·gCo?1 at room temperature due to synergistic interactions between Co and Co3O4 NPs. The Co NPs also endowed Co-Co3O4@C-n with the ferromagnetism needed to complete the magnetic momentum transfer process. This assembly-pyrolysis-oxidation strategy may be an efficient method of preparing novel nanocomposites.
We have demonstrated the improved performance of oxygen evolution reactions (OER) using Au/nickel phosphide (Ni12P5) core/shell nanoparticles (NPs) under basic conditions. NPs with a Ni12P5 shell and a Au core, both of which have well-defined crystal structures, have been prepared using solution-based synthetic routes. Compared with pure Ni12P5 NPs and Au-Ni12P5 oligomer-like NPs, the core/shell crystalline structure with Au shows an improved OER activity. It affords a current density of 10 mA/cm2 at a small overpotential of 0.34 V, in 1 M KOH aqueous solution at room temperature. This enhanced OER activity may relate to the strong structural and effective electronic coupling between the single-crystal core and the shell.
The development of high-resolution nanosized photoacoustic contrast agents is an exciting yet challenging technological advance. Herein, antibody (breast cancer-associated antigen 1 (Brcaa1) monoclonal antibody)- and peptide (RGD)-functionalized gold nanoprisms (AuNprs) were used as a combinatorial methodology for in situ photoacoustic imaging, angiography, and localized hyperthermia using orthotopic and subcutaneous murine gastric carcinoma models. RGD-conjugated PEGylated AuNprs are available for tumor angiography, and Brcaa1 monoclonal antibody-conjugated PEGylated AuNprs are used for targeting and for in situ imaging of gastric carcinoma in orthotopic tumor models. In situ photoacoustic imaging allowed for anatomical and functional imaging at the tumor site. In vivo tumor angiography imaging showed enhancement of the photoacoustic signal in a time-dependent manner. Furthermore, photoacoustic imaging demonstrated that tumor vessels were clearly damaged after localized hyperthermia. This is the first proof-of-concept using two AuNprs probes as highly sensitive contrasts and therapeutic agents for in situ tumor detection and inhibition. These smart antibody/peptide AuNprs can be used as an efficient nanotheranostic platform for in vivo tumor detection with high sensitivity, as well as for tumor targeting therapy, which, with a single-dose injection, results in tumor size reduction and increases mice survival after localized hyperthermia treatment.
The acid-catalyzed ring-opening reaction of styrene oxide was used as a probe reaction for evaluating the acidic properties of carboxylated carbocatalysts. Significant discrepancies in the initial reaction rates were normalized using the total number of carboxyl groups, and demonstrated that the average catalytic activities of the carboxyl moieties on the carbocatalysts differed. Comparisons between the apparent activation energy Ea and the pre-exponential factor A, derived from Arrhenius analysis, demonstrated that A varied more significantly, and therefore had a more significant effect on the reaction rates than Ea. The variation in the calculated pKa values of the carboxyl groups was attributed to the electronic effects of the nitro groups. This hypothesis was supported by the temperature programmed desorption profiles of nitrogen monoxide ions.
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.
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.
To promote commercialization of perovskite solar cells (PSCs), low-temperature processed electron transport layer (ETL) with high carrier mobility still needs to be further developed. Here, we reported two-dimensional (2D) tin disulfide (SnS2) nanosheets as ETL in PSCs for the first time. The morphologies of the 2D SnS2 material can be easy controlled by the in situ synthesized method on the conductive fluorine-doped tin oxide (FTO) substrate. We achieved a champion power conversion efficiency (PCE) of 13.63%, with the short-circuit current density (JSC) of 23.70 mA/cm2, open-circuit voltage (VOC) of 0.95 V, and fill factor (FF) of 0.61. The high JSC of PSCs results from effective electron collection of the 2D SnS2 nanosheets from perovskite layer and fast electron transport to the FTO. The low VOC and FF are the results of the lower conduction band of 2D SnS2 (4.23 eV) than that of TiO2 (4.0 eV). These results demonstrate that 2D material is a promising candidate for ETL in PSCs.
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.
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.
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.
C dots (CDs) have shown great potential in bioimaging and phototherapy. However, it is challenging to manipulate their fluorescent properties and therapeutic efficacy to satisfy the requirements for clinic applications. In this study, we prepared S, Se-codoped CDs via a hydrothermal method and demonstrated that the doping resulted in excitation wavelength-independent near-infrared (NIR) emissions of the CDs, with peaks at 731 and 820 nm. Significantly, the CDs exhibited a photothermal conversion efficiency of ~58.2%, which is the highest reported value for C nanostructures and is comparable to that of Au nanostructures. Moreover, the CDs had a large two-photon absorption cross section (~30,045 GM), which allowed NIR emissions and the photothermal conversion of the CDs through the two-photon excitation (TPE) mechanism. In vitro and in vivo tests suggested that CDs can function as new multifunctional phototheranostic agents for the TPE fluorescence imaging and photothermal therapy of cancer cells.
Graphene oxide/gold nanorod (GO/GNR) nanohybrids were synthesized with a GO- and gold-seed-mediated in situ growth method at room temperature by mixing polystyrene sulfonate (PSS) functionalized GO, secondary growth solution, and gold seeds. Compared with ex situ preparation methods of GO/GNRs or graphene (G)/GNRs, the in situ synthesis of GO/GNRs addressed the issue of the aggregation of the GNRs before their attachment onto the GO. The method is straightforward and environment-friendly. The GO/GNRs showed a remarkable photothermal effect in vitro. The temperature of the GO/GNR nanohybrids increased from 25 to 49.9 °C at a concentration of 50 μg/mL after irradiation with an 808-nm laser (0.4 W/cm2) for 6 min. Additionally, the GO/GNRs exhibited good optical and morphological stability and photothermal properties after six cycles of laser irradiation. Upon injection of the GO/GNRs into xenograft tumors, excellent computed tomography (CT) imaging properties and photothermal effect were obtained. The preclinical CT agent iohexol was combined with the GO/GNRs and further enhanced CT imaging. Therefore, the GO/GNR nanohybrids have great potential for precise CT-image-guided tumor photothermal treatment.
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.
