Colloidal nanoparticles with anisotropic architectures have attracted a variety of interest and attention due to different physical and chemical properties compared with the isotropic counterparts, making them promising candidates in many fundamental studies and practical applications. Particularly, carbon and silica-based anisotropic nanoparticles can be one stand out by combing both intrinsic merits of carbons and silica, such as structural stability, biocompatibility, large surface area, and ease of functionalization with the anisotropic structural complexity. In this review, we aim to provide an updated summary of the research related to the anisotropic carbon and silica-based nanostructures, covering both their synthesis and applications.
Two-dimensional (2D) nanomaterials have attracted a great deal of attention since the discovery of graphene in 2004, due to their intriguing physicochemical properties and wide-ranging applications in catalysis, energy-related devices, electronics and optoelectronics. To maximize the potential of 2D nanomaterials for their technological applications, controlled assembly of 2D nanobulding blocks into integrated systems is critically needed. This mini review summarizes the reported strategies of 2D materials-based assembly into integrated functional nanostructures, from in-situ assembly method to post-synthesis assembly. The applications of 2D assembled integrated structures are also covered, especially in the areas of energy, electronics and sensing, and we conclude with discussion on the remaining challenges and potential directions in this emerging field.
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.
DNA-based nanofabrication of inorganic nanostructures has potential application in electronics, catalysis, and plasmonics. Previous DNA metallization has generated conductive DNA-assembled nanostructures; however, the use of semiconductors and the development of well-connected nanoscale metal—semiconductor junctions on DNA nanostructures are still at an early stage. Herein, we report the first fabrication of multiple electrically connected metal—semiconductor junctions on individual DNA origami by location-specific binding of gold and tellurium nanorods. Nanorod attachment to DNA origami was via DNA hybridization for Au and by electrostatic interaction for Te. Electroless gold plating was used to create nanoscale metal—semiconductor interfaces by filling the gaps between Au and Te nanorods. Two-point electrical characterization indicated that the Au—Te—Au junctions were electrically connected, with current—voltage properties consistent with a Schottky junction. DNA-based nanofabrication of metal—semiconductor junctions opens up potential opportunities in nanoelectronics, demonstrating the power of this bottom-up approach.
Utilizing vacuum-tuned-atmosphere induced dip coating method, we achieve the cross-dimensional macroscopic diverse self-assemblies by using one building block with one chemical functionality. Coordinated modulating the vacuum degree, colloid concentration and evaporation atmosphere, Au@Ag core/shell NCs can controllably assemble into diverse multi-dimensional superstructures. Under 0.08 MPa, we obtained the two-dimensional (2D) stepped superstructures with continuously tunable step width. In addition, we generated a series of tailorable nanoscale-roughened 2D Au@Ag NCs superstructures at 0.04 MPa, which exhibited the label-free ultrasensitive SERS detection for the different mutants of IAPP8-37 proteins. Under 0.01 MPa, we obtained the cross-dimensional tailorable Au@Ag NCs assemblies from random to macroscale 2D and three-dimensional (3D) densest superstructures by adjusting the capping ligand-environmental molecule interactions. This is a flexible method to generate as-prepared Au@Ag core/shell NCs into well-defined macroscopic diverse superstructures and to promote the exploitation into biological applications.
Graphene-h-BN hybrid nanostructures are grown in one step on the Pt(111) surface by ultra-high vacuum chemical vapor deposition using a single precursor, the dimethylamino borane complex. By varying the deposition conditions, different nanostructures ranging from a fully continuous hybrid monolayer to well-separated Janus nanodots can be obtained. The growth starts with heterogeneous nucleation on morphological defects such as Pt step edges and proceeds by the addition of small clusters formed by the decomposition of the dimethylamino borane complex. Scanning tunneling microscopy measurements indicate that a sharp zigzag in-plane boundary is formed when graphene grows aligned with the Pt substrate and consequently with the h-BN layer as well. When graphene is rotated by 30°, the graphene armchair edges are seamlessly connected to h-BN zigzag edges. This is confirmed by a thorough density functional theory (DFT) study. Angle resolved photoemission spectroscopy (ARPES) data suggests that both h-BN and graphene present the typical electronic structure of self-standing non-interacting materials.
Electrochemical water splitting (EWS) is a highly clean and efficient method for high-purity hydrogen production. Unfortunately, EWS suffers from the sluggish and complex oxygen evolution reaction (OER) kinetics at anode. At present, the efficient, stable, and low-cost non-precious metal based OER electrocatalyst is still a great and long-term challenge for the future industrial application of EWS technology. Herein, we develop a simple and fast approach for gram-scale synthesis of flower-like cobalt-based layered double hydroxides nanosheet aggregates by ultrasonic synthesis, which show outstanding electrocatalytic performance for the oxygen evolution reaction in alkaline media, such as preeminent stability, small overpotential of 300 mV at 10 mA·cm−2 and small Tafel slope of 110 mV·dec−1.
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.
Benzaldehyde byproduct is an imperative intermediate in the production of fine chemicals and additives. Tuning selectivity to benzaldehyde is therefore critical in alcohol oxidation reactions at the industrial level. Herein, we report a simple but innovative method for the synthesis of palladium hydride and nickel palladium hydride nanodendrites with controllable morphology, high stability, and excellent catalytic activity. The synthesized dendrites can maintain the palladium hydride phase even after their use in the chosen catalytic reaction. Remarkably, the high surface area morphology and unique interaction between nickel-rich surface and palladium hydride (β-phase) of these nanodendrites are translated in an enhanced catalytic activity for benzyl alcohol oxidation reaction. Our Ni/PdH0.43 nanodendrites demonstrated a high selectivity towards benzaldehyde of about 92.0% with a conversion rate of 95.4%, showing higher catalytic selectivity than their PdH0.43 counterparts and commercial Pd/C. The present study opens the door for further exploration of metal/metal-hydride nanostructures as next-generation catalytic materials.
The capping agents for liquid metal (LM) nanodroplets in aqueous solutions are restricted to thiol-containing and positively-charged molecules or macromolecules. However, both thiolate-metal complex and electrostatic interaction are liable to detachment upon strong mechanical forces such as sonication, leading to limited stability and applications. To address this, we utilized ultrasmall water soluble melanin nanoparticles (MNPs) as the capping agent, which exhibited strong metal binding capability with the oxide layer of gallium based LMs and resulted in enhanced stability. Interestingly, shape-controlled synthesis of LM nanodroplets can be achieved by the incorporation of MNPs. Various EGaIn nanostructures including nanorice, nanosphere and nanorod were obtained by simply tuning the feed ratio, sonication time, and suspension temperature. Among these shapes, EGaIn nanorice has the best photothermal conversion efficiency, which could be leveraged for photothermal therapy.
Single-atom catalysts (SACs) have recently attracted broad attention in the catalysis field due to their maximized atom efficiency and unique catalytic properties. An atomic-level understanding of the interaction between the metal atoms and support is vital for developing stable and high-performance SACs. In this work, Pt1 single atoms with loadings up to 4 wt.% were fabricated on ceria nanorods using the atomic layer deposition technique. To understand the Pt–O–Ce bond interfacial interactions, the stability of Pt1 single atoms in the hydrogen reducing environment was extensively investigated by using in situ diffuse reflectance infrared Fourier transform spectroscopy CO chemisorption measurements. It was found that ceria defect sites, metal loadings and high-temperature calcination are effective ways to tune the stability of Pt1 single atoms in the hydrogen environment. X-ray photoemission spectroscopy further showed that Pt1 single atoms on ceria are dominantly at a +2 valence state at the defect and step edge sites, while those on terrace sites are at a +4 state. The above tailored stability and electronic properties of Pt1 single atoms are found to be strongly correlated with the catalytic activity in the dry and water-mediated CO oxidation reactions.
DNA is a self-assembled, double stranded natural molecule that can chelate and align nickel ions between its base pairs. The fabrication of a DNA-guided nickel ion chain (Ni-DNA) device was successful, as indicated by the conducting currents exhibiting a Ni ion redox reaction-driven negative differential resistance effect, a property unique to mem-elements (1). The redox state of nickel ions in the Ni-DNA device is programmable by applying an external bias with different polarities and writing times (2). The multiple states of Ni-DNA-based memristive and memcapacitive systems were characterized (3). As such, the development of Ni-DNA nanowire device-based circuits in the near future is proposed.
On-demand hydrogen generation is desired for fuel cells, energy storage, and clean energy applications. Silicon nanowires (SiNWs) and nanoparticles (SiNPs) have been reported to generate hydrogen by reacting with water, but these processes usually require external assistance, such as light, electricity or catalysts. Herein, we demonstrate that a porous SiNWs array, which is fabricated via the metal-assisted anodic etching (MAAE) method, reacts with water under ambient and dark conditions without any energy inputs. The reaction between the SiNWs and water generates hydrogen at a rate that is about ten times faster than the reported rates of other Si nanostructures. Two possible sources of enhancement are discussed: SiNWs maintain their high specific surface area as they don’t agglomerate, and the intrinsic strain of the nanowires promotes the reactivity. Moreover, the porous SiNWs array is portable, reusable, and environmentally friendly, yielding a promising route to produce hydrogen in a distributed manner.
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.
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.
Anisotropy and inhomogeneity are ubiquitous in spark plasma sintered thermoelectric devices. However, the origin of inhomogeneity in thermoelectric nanocomposites has rarely been investigated so far. Herein, we systematically study the impact of inhomogeneity in spark plasma sintered bismuth antimony telluride (BiSbTe) thermoelectric nanocomposites fabricated from solution-synthesized nanoplates. The figure of merit can reach 1.18, which, however, can be overestimated to 1.88 without considering the inhomogeneity. Our study reveals that the inhomogeneity in thermoelectric properties is attributed to the non-uniformity of porosity, textures and elemental distribution from electron backscatter diffraction and energy-dispersive spectroscopy characterizations. This finding suggests that the optimization of bulk material homogeneity should also be actively pursued in any future thermoelectric material research.
The application of nanoparticles as selective drug delivery platforms arises as one the most promising therapeutic strategies in the biomedical field. Such systems can encapsulate drugs, prevent its premature degradation, transport and promote the drugs specific delivery to the target site. Among the different nanostructures, gold-core mesoporous silica shell (AuMSS) nanorods have been one of the most explored due to their unique physical and chemical properties. The mesoporous silica biocompatibility, high surface area that can be easily functionalized, tubular pores that can store the drugs, conjugated with the intrinsic capacity of gold nanorod to absorb near-infrared radiation, allows the combination of hyperthermia (i.e., photothermal effect) with drug delivery, making them a nanoplatforms with a huge potential for cancer therapy. Nevertheless, the successful application of AuMSS nanoparticles as an effective cancer nanomedicine is hindered by the uncontrolled release of the therapeutic payloads, limited blood circulation time and unfavorable pharmacokinetics.
In this review, an overview of the modifications performed to improve the AuMSS nanorods application in nanomedicine is provided, highlighting the practical approaches that enhanced the AuMSS nanorods targeting, responsiveness to different stimuli, and blood circulation time. Further, the basics of AuMSS nanorods synthesis procedures, general properties, and its application in cancer therapy are also described.
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.
Elliptical metallic nanohole arrays possess much higher transmission and enhanced sensitivity compared with circular nanohole arrays. However, fabricating elliptical metallic nanohole arrays in large area with highly tunable aspect ratio remains a challenge. Herein, a brand-new method combining stretchable imprinting with colloidal lithography is figured out to fabricate deep-elliptical-silver-nanowell arrays (d-EAgNWAs). In this method, large area highly ordered silicon nanopillar arrays fabricated by colloidal lithography were taken as a master to transfer large area polydimethylsiloxane (PDMS) nanohole arrays. Benefit from the high elasticity of PDMS mold, the aspect ratio of d-EAgNWAs achieved can be facilely regulated from 1.7 to 5.0. Through optimization of polarization direction and the structural parameters including nanowell depth, aspect ratio, and hole size, the sensing performance of d-EAgNWAs was finally improved up to 1,414.1 nm/RIU. The best sensing behaved d-EAgNWAs were employed as an immunoassay platform finally to prove their great potential in label-free biosensing.
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.