Bi<Subscript>2</Subscript>S<Subscript>3</Subscript> nanostructures: A new photocatalyst

Uniform colloidal Bi₂S₃ nanodots and nanorods with different sizes have been prepared in a controllable manner via a hot injection method. X-ray diffraction (XRD) results show that the resulting nanocrystals have an orthorhombic structure. Both the diameter and length of the nanorods increase with increasing concentration of the precursors. All of the prepared Bi₂S₃ nanostructures show high efficiency in the photodegradation of rhodamine B, especially in the case of small sized nanodots—which is possibly due to their high surface area. The dynamics of the photocatalysis is also discussed.      

Surface active sites on Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanobelt and nanocube model catalysts for CO oxidation

CO oxidation has been performed on Co₃O₄ nanobelts and nanocubes as model catalysts. The Co₃O₄ nanobelts which have a predominance of exposed {011} planes are more active than Co₃O₄ nanocubes with exposed {001} planes. Temperature programmed reduction of CO shows that Co₃O₄ nanobelts have stronger reducing properties than Co₃O₄ nanocubes. The essence of shape and crystal plane effect is revealed by the fact that turnover frequency of Co³⁺ sites of {011} planes on Co₃O₄ nanobelts is far higher than that of {001} planes on Co₃O₄ nanocubes.      

Synthesis,characterization, theoretical investigation,and properties of monoclinic-phase InWO<Subscript>4</Subscript> hollow nanospheres

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 ų, 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 ⁴G_11/2 (384 nm), ²H_9/2 (411 nm), and ⁴F_7/2 (487 nm) levels to the ground state (⁴I_15/2) 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.

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Controllable synthesis of elongated hexagonal bipyramid shaped La(OH)<Subscript>3</Subscript> nanorods and the distribution of electric property by off-axis electron holography

Rare earth oxides/hydroxides are important emerging materials owing to their unique properties. Shape-controlled synthesis of elongated hexagonal bipyramid shaped La(OH)₃ nanorods with different aspect ratios and trigram-shaped LaCO₃OH nanosheets was systematically carried out by controlling the reaction conditions. Hydrazine and polyvinylpyrrolidone (PVP) surfactants used in synthesis are assumed to play a key “dual-template” role in determining the aspect ratio and shape of the resulting nanostructures. Elongated hexagonal bipyramid shaped La(OH)₃ nanorods were found to grow along the preferred orientation [0001]. Six equivalent crystallographic facets, \((20\bar 20)\), \((02\bar 20)\), \((2\bar 200)\), \((0\bar 220)\), \((\bar 2200)\), and \((\bar 2020)\) lattice planes, were found to be exposed on the side surfaces on each nanorod as confirmed by combined transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and selected area electron diffraction (SAED) analyses. A double-polarization phenomenon was found to occur at the nanorod surfaces by employing off-axis electron holography, implying that the material could be used as an effective dielectric microwave absorber. La(OH)₃ nanorods with larger aspect ratios exhibit better absorption properties with respect to the maximum reflection loss and effective absorbing bandwidth. Thus, a novel method towards the reasonable design of bipyramid shaped La(OH)₃ nanorods exhibiting tunable microwave absorption properties is proposed based on our synthesis strategy.

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Monodisperse upconversion NaYF4 nanocrystals: Syntheses and bioapplications

A facile strategy using cheap and readily available precursors has been successfully developed for the synthesis of rare-earth doped hexagonal phase NaYF₄ nanocrystals with uniform shape and small particle size as well as strong photoluminescence. Due to their optical properties and good biocompatibility, these multicolor nanocrystals were successfully used as a bio-tag for cancer cell imaging. This novel synthetic method should also be capable of extension to the synthesis of other fluoride nanocrystals such as YF₃ and LaF₃.      

A facile “ship-in-a-bottle” approach to construct nanorattles based on upconverting lanthanide-doped fluorides

Rattle structure is a topic of great interest in design and application of nanomaterials due to the unique core@void@shell architecture and the integration of functions. Herein, we developed a novel “ship-in-a-bottle” method to fabricate upconverting (UC) luminescent nanorattles by incorporating lanthanide-doped fluorides into hollow mesoporous silica. The size of nanorattles and the filling amount of fluorides can be well controlled. In addition, the modification of silica shell (with phenylene and amine groups) and the variation of efficient UC fluorides (NaYF₄:Yb,Er, NaLuF₄:Yb,Er, NaGdF₄:Yb,Er and LiYF₄:Yb,Er) were readily achieved. The resulting nanorattles exhibited a high capacity and pH-dependent release of the anti-cancer drug doxorubicin (DOX). Furthermore, we employed these nanorattles in proof-of-concept UC-monitoring drug release by utilizing the energy transfer process from UC fluorides to DOX, thus revealing the great potential of the nanorattles as efficient cancer theranostic agent.

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Photocatalytic hydrogenation of nitroarenes using Cu<Subscript>1.94</Subscript>S-Zn<Subscript>0.23</Subscript>Cd<Subscript>0.77</Subscript>S heteronanorods

Catalytic hydrogenation is an important process in the chemical industry. Traditional catalysts require the effective cleavage of hydrogen molecules on the metal-catalyst surface, which is difficult to achieve with non-noble metal catalysts. In this work, we report a new hydrogenation method based on water/proton reduction, which is completely different from the catalytic cleavage of hydrogen molecules. Active hydrogen species and photo-generated electrons can be directly applied to the hydrogenation process with Cu_1.94S-Zn_0.23Cd_0.77S semiconductor heterojunction nanorods. Nitrobenzene, with a variety of substituent groups, can be efficiently reduced to the corresponding aniline without the addition of hydrogen gas. This is a novel and direct pathway for hydrogenation using non-noble metal catalysts.

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Hierarchical CoNiSe<Subscript>2</Subscript> nano-architecture as a high-performance electrocatalyst for water splitting

Hierarchical nano-architectures comprised of ultrathin ternary selenide (CoNiSe₂) nanorods were directly grown on nickel foam (NF). The integrated CoNiSe₂/NF functions as a robust electrocatalyst with an extremely high activity and stability for emerging renewable energy technologies, and electrochemical oxygen and hydrogen evolution reactions (OER and HER, respectively). The overpotentials required to deliver a current density of 100 mA·cm^?2 are as low as 307 and 170 mV for the OER and HER, respectively; therefore, the obtained CoNiSe₂ is among the most promising earth-abundant catalysts for water splitting. Furthermore, our synthetic sample validates a two-electrode electrolyzer for reducing the cell voltage in the full water splitting reaction to 1.591 V to achieve a current density of 10 mA·cm^?2, which offers a novel, inexpensive, integrated selenide/NF electrode for electrocatalytic applications.

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Shape control of CoO and LiCoO<Subscript>2</Subscript> nanocrystals

Shape control of nanocrystals has become a significant subject in materials science. In this work, we describe a convenient way to achieve morphology-controllable synthesis of CoO nanocrystals including octahedrons and spheres as well as LiCoO₂ polyhedrons and spheres. In particular, we explain the formation of CoO octahedrons exposing only high-energy (111) facets using theoretical calculations; these should also be a useful tool for directing future face-controlled preparation of other nanocrystals. More importantly, the as-obtained LiCoO₂ nanocrystals showed different electrochemical performance depending on their morphology, indicating that Li-insertion/deintercalation dynamics might be crystal face-sensitive.      

Shape-controlled synthesis of Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocrystals and their catalysis of the degradation of methylene blue

Various sizes and shapes of Mn₃O₄ nanocrystals have been prepared in a one-pot synthesis in extremely dilute solution by soft template self-assembly. To better control size and shape, the effects of varying the growth time, reaction temperature, surfactant, and manganese source were examined. The average size of octahedral Mn₃O₄ crystallites was found to be related to the reaction time, while higher reaction temperature (150 °C) and the use of a cetyltrimethylammonium bromide/poly(vinylpyrrolidone) (CTAB/PVP) mixture allowed construction of a better-defined octahedral morphologies. When PVP or poly(ethylene oxide)-poly(propylene oxide) (P123) was used as template, large-scale agglomeration resulting in loss of the octahedral morphology occurred and crystallites with a quasi-spherical shape were obtained. The nano-octahedral crystallites were shown to be an efficient catalyst for the oxidation of methylene blue.      

Shape-controlled synthesis of octahedral α-NaYF4 and its rare earth doped submicrometer particles in acetic acid

Submicrometer sized pure cubic phase, Eu³⁺ doped, and Yb³⁺/Er³⁺ co-doped α-NaYF₄ particles with octahedral morphology have been prepared in acetic acid. The acetate anion plays a critical role in the formation of such symmetric octahedral structures through its selective adsorption on the (111) faces of the products. The size of the as-prepared octahedra can be tuned by varying the amount of sodium acetate added to the acetic acid. A possible formation mechanism for these octahedra has been proposed. The doped α-NaYF₄ octahedral submicrometer particles show down-conversion and up-conversion photoluminescence typical of these materials. This article is published with open access at Springerlink.com     

Active-layer evolution and efficiency improvement of (CH<Subscript>3</Subscript>NH<Subscript>3</Subscript><Subscript>3</Subscript>Bi<Subscript>2</Subscript>I<Subscript>9</Subscript>-based solar cell on TiO<Subscript>2</Subscript>-deposited ITO substrate

We systematically investigated the development of film morphology and crystallinity of methyl-ammonium bismuth (III) iodide (MA₃Bi₂I₉) through onestep spin-coating on TiO₂-deposited indium tin oxide (ITO)/glass. The precursor solution concentration and substrate structure have been demonstrated to be critically important in the active-layer evolution of the MA₃Bi₂I₉-based solar cell. This work successfully improved the cell efficiency to 0.42% (average: 0.38%) with the mesoscopic architecture of ITO/compact-TiO₂/mesoscopic-TiO₂ (meso-TiO₂)/MA₃Bi₂I₉/2,2′,7,7′-tetrakis(N,N-di-4-methoxyphenylamino)-9,9′spiro-bifluorene (spiro-MeOTAD)/MoO₃/Ag under a precursor concentration of 0.45 M, which provided the probability of further improving the efficiency of the Bi³⁺-based lead-free organic–inorganic hybrid solar cells.

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Hierarchical porous onion-shaped LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> as ultrahigh-rate cathode material for lithium ion batteries

Spinel LiMn₂O₄ is a widely utilized cathode material for Li-ion batteries. However, its applications are limited by its poor energy density and power density. Herein, a novel hierarchical porous onion-like LiMn₂O₄(LMO) was prepared to shorten the Li⁺ diffusion pathway with the presence of uniform pores and nanosized primary particles. The growth mechanism of the porous onion-like LiMn₂O₄ was analyzed to control the morphology and the crystal structure so that it forms a polyhedral crystal structure with reduced Mn dissolution. In addition, graphene was added to the cathode (LiMn₂O₄/graphene) to enhance the electronic conductivity. The synthesized LiMn₂O₄/graphene exhibited an ultrahigh-rate performance of 110.4 mAh·g^–1 at 50 C and an outstanding energy density at a high power density, maintaining 379.4 Wh·kg^–1 at 25,293 W·kg^–1. Besides, it shows durable stability, with only 0.02% decrease in the capacity per cycle at 10 C. Furthermore, the (LiMn₂O₄/graphene)/graphite full-cell exhibited a high discharge capacity. This work provides a promising method for the preparation of outstanding, integrated cathodes for potential applications in lithium ion batteries.

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One-pot synthesis and strong near-infrared upconversion luminescence of poly(acrylic acid)-functionalized YF<Subscript>3</Subscript>:Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript> nanocrystals

This paper describes the synthesis of new upconverting luminescent nanoparticles that consist of YF₃:Yb³⁺/Er³⁺ functionalized with poly(acrylic acid) (PAA). Unlike the upconverting nanocrystals previously reported in the literature that emit visible (blue-green-red) upconversion fluorescence, these as-prepared nanoparticles emit strong near-infrared (NIR, 831 nm) upconversion luminescence under 980 nm excitation. Scanning electron microscopy, transmission electron microscopy, and powder X-ray diffraction were used to characterize the size and composition of the luminescent nanocrystals. Their average diameter was about 50 nm. The presence of the PAA coating was confirmed by infrared spectroscopy. The particles are highly dispersible in aqueous solution due to the presence of carboxylate groups in the PAA coating. By carrying out the synthesis in the absence of PAA, YF₃:Yb³⁺/Er³⁺ nanorice materials were obtained. These nanorice particles are larger (∼700 nm in length) than the PAA-functionalized nanoparticles and show strong typical visible red (668 nm), rather than NIR (831 nm), upconversion fluorescence. The new PAA-coated luminescent nanoparticles have the pottential be used in a variety of bioanalytical and medical assays involving luminescence detection and fluorescence imaging, especially in vivo fluorescence imaging, due to the deep penetration of NIR radiation.      

One-dimension carbon self-doping g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> nanotubes: Synthesis and application in dye-sensitized solar cells

One-dimension carbon self-doping g-C₃N₄ nanotubes (CNT) with abundant communicating pores were synthesized via thermal polymerization of saturated or supersaturated urea inside the framework of a melamine sponge for the first time. A ～16% improvement in photoelectric conversion efficiency (η) is observed for the devices fabricated with a binary hybrid composite of the obtained CNT and TiO₂ compared to pure TiO₂ device. The result of EIS analysis reveals that the interfacial resistance of the TiO₂-dye|I₃^?/I^? electrolyte interface of TiO₂-CNT composite cell is much lower than that of pure TiO₂ cell. In addition, the TiO₂-CNT composite cell exhibits longer electron recombination time, shorter electron transport time, and higher charge collection efficiency than those of pure TiO₂ cell. Systematic investigations reveal that the CNT boosts the light harvesting ability of the photovoltaic devices by enhancing not only the visible light absorption but also the charge separation and transfer.

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Sandwich-structured nanocomposites of N-doped graphene and nearly monodisperse Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles as high-performance Li-ion battery anodes

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.

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Ni-doped ZnCo<Subscript>2</Subscript>O<Subscript>4</Subscript> atomic layers to boost the selectivity in solar-driven reduction of CO<Subscript>2</Subscript>

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.

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Enhanced electrical and optical properties of single-layered MoS<Subscript>2</Subscript> by incorporation of aluminum

Electrical and optical enhancements of single-layer semiconducting materials such as transition metal dichalcogenides have recently been studied to achieve sensitive properties via external treatments, such as the formation of organic/inorganic protecting layers on field-effect transistors (FETs), thermal annealing, and nano-dot doping of sensors and detectors. Here, we propose a new analytical approach to electrical and optical enhancement through a passivation process using atomic layer deposition (ALD), and demonstrate a synthesized MoS₂ monolayer incorporated with Al atoms in an Al₂O₃ passivation layer. The incorporated Al atoms in the MoS₂ monolayer are clearly observed by spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM) and TEM-energy-dispersive X-ray spectroscopy results. We demonstrate that the chemically incorporated FETs exhibit highly enhanced mobilities of approximately 3.7 cm²·V^?1·s^?1, forty times greater than that of as-synthesized MoS₂, with a three-fold improvement in the photoluminescence properties.

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Polyol synthesis and chemical conversion of Cu<Subscript>2</Subscript>O nanospheres

Polyol synthesis route, which is a popular and effective way of synthesizing noble metal nanocrystals, has been employed for the fabrication of Cu₂O nanospheres. With this method, the particle size of the product can be readily tailored by tuning the concentration of Cu(NO₃)₂ and/or poly(vinyl pyrrolidone). It has been demonstrated that the main driving force of this reaction is the difference in redox potentials between ethylene glycol (EG) and NO₃⁻, and not that between those of EG and Cu²⁺. The resulting Cu₂O nanospheres were used as a solid precursor for generating hollow nanospheres of copper sulfide with different sulfiding degrees, as well as CuO, via suitable chemical conversions. The Kirkendall effect determined the final hollow structure. The results in this paper provide a good example of the broadening of the scope of application of polyol synthesis route and may supply a thinking clue for the synthesis of other oxide materials.      

Unexpected luminescence enhancement of upconverting nanocrystals by cation exchange with well retained small particle size

Highly luminescent upconversion nanoparticles （UCNPs） with small sizes are highly desirable for bioapplications. A facile in situ cation exchange strategy has been developed to greatly enhance the UC luminescence of hexagonal phase NaYF4 NPs while maintaining their small particle size and shape. Via a cation exchange treatment by hot-injecting Gd3＋ precursors into the as-prepared NPs solution without pre-separation, the naked-eye visible UC emission of the NPs was enhanced about 29 times under 980 nm near infrared （NIR） excitation with unchanged particle size. The cation exchange process was further demonstrated for the case of NaYF4 nanorods （NRs）. After the cation exchange, the nanorod was broken into two NPs with stronger emission. The cation exchanged hydrophobic UCNPs were further encapSulated with poly（amino acid） and successfully applied for targeted cancer cell UC luminescence imaging.