To develop highly efficient electrochemical catalysts for N2 fixation is important to sustainable ambient NH3 production through the N2 reduction reaction (NRR). Herein, we demonstrate the development of vanadium phosphide nanoparticle on V foil as a high-efficiency and stable catalyst for ambient NH3 production with excellent selectivity. The high Faradaic efficiency of 22% with a large NH3 yield of 8.35 × 10−11 mol·s−1·cm−2 was obtained at 0 V vs. the reversible hydrogen electrode in acid solution, superior to all previously studied V-based NRR catalysts. Density functional theory calculations are also utilized to have an insight into the catalytic mechanism.
The electrochemical nitrogen reduction reaction (NRR) as an energy-efficient approach for ammonia synthesis is hampered by the low ammonia yield and ambiguous reaction mechanism. Herein, phosphorus-doped carbon nanotube (P-CNTs) is developed as an efficient metal-free electrocatalyst for NRR with a remarkable NH3 yield of 24.4 μg·h−1·mg−1cat. and partial current density of 0.61 mA·cm−2. Such superior activity is found to be from P doping and highly conjugated CNTs substrate. Experimental and theoretical investigations discover that the electron-deficient phosphorus sites with Lewis acidity should be genuine active sites and NRR on P-CNTs follows the distal pathway. These findings provide insightful understanding on NRR processes on P-CNTs, opening up opportunities for the rational design of highly-active cost-effective metal-free catalysts for electrochemical ammonia synthesis.
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.
Industrial production of NH3 from N2 and H2 significantly relies on Haber–Bosch process, which suffers from high energy consume and CO2 emission. As a sustainable and environmentally-benign alternative process, electrochemical artificial N2 fixation at ambient conditions, however, is highly required efficient electrocatalysts. In this study, we demonstrate that hexagonal boron nitride nanosheet (h-BNNS) is able to electrochemically catalyze N2 to NH3. In acidic solution, h-BNNS catalyst attains a high NH3 formation rate of 22.4 μg·h–1·mg–1cat. and a high Faradic efficiency of 4.7% at–0.75 V vs. reversible hydrogen electrode, with excellent stability and durability. Density functional theory calculations reveal that unsaturated boron at the edge site can activate inert N2 molecule and significantly reduce the energy barrier for NH3 formation.
The ammonia synthesis from nitrogen and water under ambient conditions is one of the most inviting but challenging reaction routes. Although nitrogen is abundant in the atmosphere and the ammonia synthesis reaction is exothermic on the thermodynamics, the conversion of N2 to ammonia is actually hard to proceed owing to the chemical inertness and stability of N2 molecules. In industry, ammonia synthesis is carried out by the Haber-Bosch process under harsh conditions (300–500 °C, 20–30 MPa) associated with the requirement of substantial energy input and the enormous emission of greenhouse gases (e.g., CO2). Recently, a growing number of studies on photo(electro)catalytic and electrocatalytic nitrogen reduction reaction (NRR) in aqueous solution have attracted extensive attention, which holds great promise for nitrogen fixation under room temperature and atmospheric pressure. However, the very low efficiency and ambiguous mechanism still remain as the major hurdles for the development of photochemical and electrochemical NRR systems. Here we provide an overview of the latest progresses, remaining challenges and future prospects in photocatalytic and electrocatalytic nitrogen fixation. Moreover, this review offers a helpful guidance for the reasonable design of photocatalysts and electrocatalysts towards NRR by combining theory predictions and experiment results. We hope this review can stimulate more research interests in the relatively understudied but highly promising research field of NRR.
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.
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.
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.
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.
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.
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.
Atomically thin transition metal dichalcogenides (TMDs) have distinct opto-electronic properties including enhanced luminescence and high on-off current ratios, which can be further modulated by making more complex TMD heterostructures. However, resolution limits of conventional optical methods do not allow for direct nanoscale optical-structural correlation measurements in these materials, particularly of buried interfaces in TMD heterostructures. Here we use, for the first time, electron beam induced cathodoluminescence in a scanning transmission electron microscope (CL-STEM) to measure optical properties of monolayer TMDs (WS2, MoS2 and WSSe alloy) encapsulated between layers of hBN. We observe dark areas resulting from localized (~ 100 nm) imperfect interfaces and monolayer folding, which shows that the intimate contact between layers in this application-relevant heterostructure is required for proper inter layer coupling. We also realize a suitable imaging method that minimizes electron-beam induced changes and provides measurement of intrinsic properties. To overcome the limitation of small electron interaction volume in TMD monolayer (and hence low photon yield), we find that encapsulation of TMD monolayers with hBN and subsequent annealing is important. CL-STEM offers to be a powerful method to directly measure structure-optical correspondence in lateral or vertical heterostructures and alloys.
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.
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.
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.
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.
In this work, homogeneous Ni0.33Co0.67Se hollow nanoprisms were synthesized successfully in virtue of Kirkendall effect. It is the first time for bimetallic Ni-Co compounds Ni0.33Co0.67Se to be used in lithium-ion batteries (LIBs). Impressively, the Ni0.33Co0.67Se hollow nanoprisms show superior specific capacity (1,575 mAh/g at the current density of 100 mA/g) and outstanding rate performance (850 mAh/g at 2,000 mA/g) as anode material for LIBs. This work proves the potential of bimetallic chalcogenide compounds as high performance anode materials for LIBs.