All-inorganic cesium lead halide perovskite quantum dots (QDs) have been a promising candidate for optoelectronic devices in recent years, such as light-emitting diodes, photodetectors and solar cells, owing to their superb optoelectronic properties. Still, the stability issue of nanocrystals is a bottleneck for their practical application. Herein, we report a facile method for the synthesis of a series of phosphine ligand modified CsPbBr3 QDs with high PL intensity. By introducing organic phosphine ligands, the tolerance of CsPbBr3 QDs to ethanol, water and UV light was dramatically improved. Moreover, the phosphine ligand modified QD films deposited on the glass subtracts exhibit superior PL intensity and optical stability to those of pristine QD based films.
The rapid development of solar cells based on lead halide perovskites (LHPs) has prompted very active research activities in other closely-related fields. Colloidal nanostructures of such materials display superior optoelectronic properties. Especially, one-dimensional (1D) LHPs nanowires show anisotropic optical properties when they are highly oriented. However, the ionic nature makes them very sensitive to external environment, limiting their large scale practical applications. Here, we introduce an amphiphilic block copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-P4VP), to chemically modify the surface of colloidal CsPbBr3 nanowires. The resulting core-shell nanowires show enhanced photoluminescent emission and good colloidal stability against water. Taking advantage of the stability enhancement, we further applied a modified Langmuir-Blodgett technique to assemble monolayers of highly aligned nanowires, and studied their anisotropic optical properties.
Living electronics that converges the unique functioning modality of biological and electrical circuits has the potential to transform both fundamental biophysical/biochemical inquiries and translational biomedical/engineering applications. This article will review recent progress in overcoming the intrinsic physiochemical and signaling mismatches at biological/electronic interfaces, with specific focus on strategic approaches in forging the functional synergy through: (1) biohybrid electronics, where genetically encoded bio-machineries are hybridized with electronic transducers to facilitate the translation/interpretation of biologically derived signals; and (2) biosynthetic electronics, where biogenic electron pathways are designed and programmed to bridge the gap between internal biological and external electrical circuits. These efforts are reconstructing the way that artificial electronics communicate with living systems, and opening up new possibilities for many cross-disciplinary applications in biosynthesis, sensing, energy transduction, and hybrid information processing.
We describe a route to the preparation of (metal yolk)/(porous ceria shell) nanostructures through the heterogeneous growth of ceria on porous metal nanoparticles followed by the calcination-induced shrinkage of the nanoparticles. The approach allows for the control of the ceria shell thickness, the metal yolk composition and size, which is difficult to realize through common templating approaches. The yolk/shell nanostructures with monometallic Pt and bimetallic PtAg yolks featuring plasmon-induced broadband light absorption in the visible region are rationally designed and constructed. The superior photocatalytic activities of the obtained nanostructures are demonstrated by the selective oxidation of benzyl alcohol under visible light. The excellent activities are ascribed to the synergistic effects of the metal yolk and the ceria shell on the light absorption, electron-hole separation and efficient mass transfer. Our synthesis of the (metal yolk)/(porous ceria shell) nanostructures points out a way to the creation of sophisticated heteronanostructures for high-performance photocatalysis.
Anisotropic two-dimensional (2D) materials exhibit lattice-orientation dependent optical and electrical properties. Carriers doping of such materials has been used to modulate their energy band structures for opto-electronic applications. Herein, we show that by stacking monolayer rhenium disulfide (ReS2) on a flat gold film, the electrons doping in ReS2 can affect the in-plane anisotropic Raman enhancement of molecules adsorbed on ReS2. The change of enhancement factor and the degree of anisotropy in enhancement with layer number are sensitively dependent on the doping level of ReS2 by gold, which is further confirmed by Kelvin probe force microscopy (KPFM) measurements. These findings could open an avenue for probing anisotropic electronic interactions between molecules and 2D materials with low symmetry using Raman enhancement effect.
Oligo(p-phenyleneethynylene)s (OPEs) end-capped with (alkynyl)bis(diphosphine)ruthenium and thiol/thiolate groups stabilize ca. 2 nm diameter gold nanoparticles (AuNPs). The morphology, elemental composition and stability of the resultant organometallic OPE/AuNP hybrid materials have been defined using a combination of molecular- and nano-material chacterization techniques. The hybrids display long-term stability in solution (more than a month), good solubility in organic solvents, reversible ruthenium-centered oxidation, and transparency beyond 800 nm, and possess very strong nonlinear absorption activity at the first biological window, and unprecedented two-photon absorption activity in the second biological window (σ2 up to 38,000 GM at 1,050 nm).
A diverse range of remarkable boron nitride (BN) nanostructures subsuming nano-horns, nano-rods, nano-platelets, and clusters of hollow nanospheres (nano-onions, arguably of greatest applied and fundamental interest) have been produced exclusively from crystalline BN precursor powder via lamp ablation. The procedure is safe, devoid of toxic reagents, simple, rapid and scalable—generating some genres of nanoparticles that had previously proved elusive. Product structure and composition were unambiguously assessed by high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy.
The development of high-efficiency peroxidase mimetics is highly desirable in view of high cost and low stability of natural enzymes. From the perspective of mimicking active site microenvironment at low cost, we herein report a novel histidine-functionalized graphene quantum dot (His-GQD)/hemin complex, which exhibits the highest catalytic rate for the peroxidase-based chromogenic reaction among the hemin-containing mimetics reported so far. Also, our peroxidase mimetic shows excellent tolerance to strongly acidic conditions and can function in a wide temperature range. Lineweaver-Burk plots and comprehensive electron paramagnetic resonance analysis reveal a ping-pong type catalytic mechanism for this mimetic. In addition, His-GQD/hemin demonstrates high efficiency and accuracy in detecting H2O2 and blood glucose. Our work provides an effective design of artificial enzymes for practical applications.
Realizing the reduction of N2 to NH3 at low temperature and pressure is always the unremitting pursuit of scientists and then electrochemical nitrogen reduction reaction offers an intriguing alternative. Here, we develop a feasible way, gamma irradiation, for constructing defective structure on the surface of WO3 nanosheets, which is clearly observed at the atomic scale by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The abundant oxygen vacancies ensure WO3 nanosheets with a Faradaic efficiency of 23% at −0.3 V vs. RHE. Moreover, we start from the regulation of the surface state to suppress proton availability towards hydrogen evolution reaction (HER) on the active site and thus boost the selectivity of nitrogen reduction.
Neutral water splitting is attractive for its use of non-corrosive and environmentally friendly electrolytes. However, catalyst development for hydrogen and oxygen evolution remains a challenge under neutral conditions. Here we report a simple electrodeposition and reductive annealing procedure to produce a highly active Ni-Co-Cr metal/metal oxide heterostructured catalyst directly on Ni foam. The resulting electrocatalyst for hydrogen evolution reaction (HER) requires only 198 mV of overpotential to reach 100 mA/cm2 in 1 M potassium phosphate (pH = 7.4) and can operate for at least two days without significant performance decay. Scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) imaging reveals a Ni-Co alloy core decorated with blended oxides layers of NiO, CoO and Cr2O3. The metal/metal oxide interfaces are suggested to be responsible for the high HER activity.
After nanocrystals synthesis, the purification process with anti-solvents is an essential step to get clean nanocrystals, which could get rid of the by-products of the synthesis. It is generally recognized that this process could bring a positive effect for the afterward optoelectronic applications. Unfortunately, we found that the optical properties and photostability of perovskite CsPbBr3 nanocrystals were unavoidably deteriorated after they were washed with anti-solvents, and this deterioration is strongly related to the decreasing of surface ligands density. Therefore, in this paper, we tried to purposely not wash the CsPbBr3 nanocrystals solution after adding didodecyl dimethylammonium bromide (DDAB), and found the existing of DDAB in solution could result in a dramatically enhanced photostability. Inspired by these results, we proposed a new strategy to stabilize perovskite nanocrystals from the view of packaging process: adding protective ligands into the perovskite nanocrystals resin directly, then encapsulating them on blue light-emitting diodes (LED) chips. Surprisingly, stable LED devices (20 mA, 2.7V) were achieved by this way, which can keep 80% of the initial photoluminescence (PL) intensity for more than 50 h, while the devices with CsPbBr3 nanocrystals without adding protective ligands into resin dropped to 50% of their initial PL intensity within 6 h. This approach offers a new thought to stabilize perovskite nanocrystals as down-conversion phosphor in quantum dots liquid crystal display.
Two-dimensional nanosheet membranes with responsive nanochannels are appealing for controlled mass transfer/separation, but limited by everchanging thicknesses arising from unstable interfaces. Herein, an interfacially stable, thermo-responsive nanosheet membrane is assembled from twin-chain stabilized metal-organic framework (MOF) nanosheets, which function via two cyclic amide-bearing polymers, thermo-responsive poly(N-vinyl caprolactam) (PVCL) for adjusting channel size, and non-responsive polyvinylpyrrolidone for supporting constant interlayer distance. Owing to the microporosity of MOF nanosheets and controllable interface wettability, the hybrid membrane demonstrates both superior separation performance and stable thermo-responsiveness. Scattering and correlation spectroscopic analyses further corroborate the respective roles of the two polymers and reveal the microenvironment changes of nanochannels are motivated by the dehydration of PVCL chains.
Porous graphitic carbon nanorings (PGCNs) are proposed by smart catalytic graphitization of nano-sized graphene quantum dots (GQDs). The as-prepared PGCNs show unique ring-like morphology with diameter around 10 nm, and demonstrate extraordinary mesoporous structure, controllable graphitization degree and highly defective nature. The mechanism from GQDs to PGCNs is proven to be a dissolution-precipitation process, undergoing the procedure of amorphous carbon, intermediate phase, graphitic carbon nanorings and graphitic carbon nanosheets. Further, the relationship between particles size of GQDs precursor and graphitization degree of PGCNs products is revealed. The unique microstructure implies PGCNs a broad prospect for energy storage application. When applied as negative electrode materials in dual-carbon lithium-ion capacitors, high energy density (77.6 Wh·kg−1) and super long lifespan (89.5% retention after 40,000 cycles at 5.0 A·g−1) are obtained. The energy density still maintains at 24.5 Wh·kg−1 even at the power density of 14.1 kW·kg−1, demonstrating excellent rate capability. The distinct microstructure of PGCNs together with the strategy for catalytic conversion from nanocarbon precursors to carbon nanorings opens a new window for carbon materials in electrochemical energy storage.
Electrochemical N2 reduction offers a promising alternative to the Haber-Bosch process for sustainable NH3 synthesis at ambient conditions, but it needs efficient catalysts for the N2 reduction reaction (NRR). Here, we report that FeOOH quantum dots decorated graphene sheet acts as a superior catalyst toward enhanced electrocatalytic N2 reduction to NH3 under ambient conditions. In 0.1 M LiClO4, this hybrid attains a large NH3 yield rate and a high Faradaic efficiency of 27.3 µg·h−1·mg−1cat. and 14.6% at −0.4 V vs. reversible hydrogen electrode, respectively, rivalling the current efficiency of all Fe-based NRR electrocatalysts in aqueous media. It also shows strong durability during the electrolytic process.
Sub-stoichiometric MoO3−x nanostructures with plasmonic absorption via creating oxygen vacancies have attracted extensive attentions for many intriguing applications. However, the synthesis of one-dimensional (1D) plasmonic MoO3−x nanostructures with widely tunable plasmonic absorption has remained a significant challenge because of their serious morphological destruction and phase change with increasing the concentration of oxygen vacancies. Here we demonstrate a surface-ligand protected reduction strategy for the synthesis of 1D MoO3−x nanobelts with tunable plasmonic absorption in a wide wavelength range from 200 to 2,500 nm. Polyethylene glycol (PEG-400) is used as both the reductant to produce oxygen vacancies and the surface protected ligands to maintain 1D morphology during the formation process of MoO3−x nanobelts, enabling the widely tunable plasmonic absorption. Owing to their broad plasmonic absorption and unique 1D nanostructure, we further demonstrate the application of 1D MoO3−x nanobelts as photothermal film for interfacial solar evaporator. The surface-ligand protected reduction strategy provides a new avenue for the developing plasmonic semiconductor oxides with maintained particle morphology and thus enriching their wide applications.
Nanoparticles (NPs) which are innovation and research focus in drug delivery systems, still have some disadvantages limiting its application in clinical use, such as short circulation time, recognition and clearance by reticuloendothelial system (RES) and passive targeting in certain organs. However, the recent combination of natural components and nanotechnology has offered new solutions to address these problems. A novel biomimetic platform consisting of nanoparticle core and membrane shell, such as cell membrane, exosome or vesicle vastly improves properties of nanoparticles. These coated nanoparticles can replicate the unique functions of the membrane, such as prolonged blood circulation, active targeting capability and enhanced internalization. In this review, we focus on the newest development of biological-camouflaged nanoparticles and mainly introduce its application related to cancer therapy and toll-like receptor.
We propose a process of quantum-confined ion superfluid (QISF), which is enthalpy-driven confined ordered fluid, to explain the transmission of nerve signals. The ultrafast Na+ and K+ ions transportation through all sodium-potassium pump nanochannels simultaneously in the membrane is without energy loss, and leads to QISF wave along the neuronal axon, which acts as an information medium in the ultrafast nerve signal transmission. The QISF process will not only provide a new view point for a reasonable explanation of ultrafast signal transmission in the nerves and brain, but also challenge the theory of matter wave for ions, molecules and particles.
Laser-activated perfluorocarbon nanodroplets are an emerging class of phase-change, dual-contrast agents that can be utilized in ultrasound and photoacoustic imaging. Through the ability to differentiate subpopulations of nanodroplets via laser activation at different wavelengths of near-infrared light, optically-triggered color-coded perfluorocarbon nanodroplets present themselves as an attractive tool for multiplexed ultrasound and photoacoustic imaging. In particular, laser-activated droplets can be used to provide quantitative spatiotemporal information regarding distinct biological targets, allowing for their potential use in a wide range of diagnostic and therapeutic applications. In the work presented, laser-activated color-coded perfluorocarbon nanodroplets are synthesized to selectively respond to laser irradiation at corresponding wavelengths. The dynamic ultrasound and photoacoustic signals produced by laser-activated perfluorocarbon nanodroplets are evaluated in situ prior to implementation in a murine model. In vivo, these particles are used to distinguish unique particle trafficking mechanisms and are shown to provide ultrasound and photoacoustic contrast for up to 72 hours within lymphatics. Overall, the conducted studies show that laser-activated color-coded perfluorocarbon nanodroplets are a promising agent for multiplexed ultrasound and photoacoustic imaging.