Atomic-scale imaging of ytterbium ions in lead halide perovskites.

Lanthanide-doped lead halide perovskites have demonstrated great potential for photoelectric applications. However, there is a long-standing controversy about the existence of lanthanide ions, e.g., whether the doping of Ln3+ is successful or not; the substituting sites of Ln3+ in lead halide perovskites are unclear. We directly identify the doped Yb3+ in CsPbCl3 perovskites by using the state-of-the-art transmission electron microscopy and three-dimensional atom probe tomography at atomic scale. Different from the previous assumptions and/or results, we evidence that Yb3+ simultaneously replace Pb2+ and occupy the lattice interstitial sites. Furthermore, we directly observe the cluster phenomenon of CsPbCl3 single crystal at near atomic scale. Density functional theory modeling further confirms and explains the mechanisms of our findings. Our findings thus provide an atomic-level understanding of the doping mechanism in perovskites and will stimulate a further thinking of the doping effect on the performance of perovskites.

The microstrain-accompanied structural phase transition from h-MoO3 to α-MoO3 investigated by in situ X-ray diffraction.

In situ X-ray diffraction indicates that the structural phase transition from h-MoO3 to α-MoO3 is a first-order transition with a phase transition temperature range of 378.5-443.1 °C. The linear coefficients of thermal expansion of h-MoO3 are strongly anisotropic, that is, αa=b = 72.87 × 10-6 K-1 and αc = -19.44 × 10-6 K-1. In the h-MoO3 phase, water molecules are located at the (0 0 0.25) site inside the MoO6 octahedra tunnel that is formed by six MoO6 corner-sharing octahedron zigzag chains. With increasing temperature, the release of water molecules from the octahedra tunnel causes the octahedra chains to shrink and the octahedra tunnel to expand. When the phase transition occurs, the anomalous expansion of the MoO6 octahedra tunnel ruptures the Mo-O2 bonds, forming individual MoO6 octahedron zigzag chains that then share corners to generate octahedron layers in the ⟨100⟩α direction. The octahedron layers are bonded by van der Waals interactions in the ⟨010⟩α direction, crystalizing into the α-MoO3 structure.

Sodium doping in brookite TiO2 enhances its photocatalytic activity.

We report in this work that sodium doping of brookite TiO2 effectively enhances its photocatalytic activity, which becomes three times higher than that of the quasi-spherical brookite TiO2. The results demonstrated that the sodium-doped brookite Na x Ti1- x O2 can be stable up to 500 °C. At 600°C, the sodium in the brookite precipitates in the form of Na2CO3, and above 700 °C, the brookite Na x Ti1- x O2 transforms into Na2Ti6O13 by a twinning process with the orientation relationship of [1-2-3]Matrix//[1-23]Twins and (-2-10)Matrix//(1-1-1)Twins. The differences in the ionic radius and the electronegativity between Na and Ti destroy the local atomic arrangement of the brookite structure and produce microstructures such as the core-shell structure, local lattice distortion, interstitial atoms, and atomic vacancies, which are critical to its excellent photocatalytic activity.

Efficient pollutant degradation under ultraviolet to near-infrared light irradiation and dark condition using CuSe nanosheets: Mechanistic insight into degradation.

The hydrothermally prepared two-dimensional copper selenide nanosheets (2D CuSe NSs) have been employed for the first time to degrade rhodamine B (RhB) in the presence of hydrogen peroxide (H2O2) under ultraviolet to near-infrared (NIR) light irradiation and dark condition. The experimental measurements demonstrate that 99.7% RhB is degraded under NIR light irradiation for 120 min. Moreover, the experimental tests clearly demonstrate that the 2D CuSe NSs display excellent ability to degrade RhB under dark condition. The different degradation mechanisms under the light irradiation and dark condition have been revealed by the experimental tests through the investigation of H2O2 role and the evaluation of hydroxyl radicals (•OH) and H2O2 concentration during the degradation reaction. Under light irradiation, the H2O2 traps the photogenerated electrons of the CuSe to generate •OH and hydroxide ion (OH-), and the holes react with OH- to produce •OH, making RhB to be degraded efficiently. Under dark conduction, the 2D CuSe NSs react with H2O2 to exhibit Fenton-like process to degrade RhB with a degradation rate of 90.0% within 120 min. This work opens a pathway for developing nanostructures with full-solar-responsive and strong near-infrared photocatalytic activity as well as Fenton-like reaction to efficiently degrade pollutants under light irradiation and dark condition.

UnitCell Tools, a package to determine unit-cell parameters from a single electron diffraction pattern.

Electron diffraction techniques in transmission electron microscopy (TEM) have been successfully employed for determining the unit-cell parameters of crystal phases, albeit they exhibit a limited accuracy compared with X-ray or neutron diffraction, and they often involve a tedious measurement procedure. Here, a new package for determining unit-cell parameters from a single electron diffraction pattern has been developed. The essence of the package is to reconstruct a 3D reciprocal primitive cell from a single electron diffraction pattern containing both zero-order Laue zone and high-order Laue zone reflections. Subsequently, the primitive cell can be reduced to the Niggli cell which, in turn, can be converted into the unit cell. Using both simulated and experimental patterns, we detail the working procedure and address some effects of experimental conditions (diffraction distortions, misorientation of the zone axis and the use of high-index zone axis) on the robustness and accuracy of the software developed. The feasibility of unit-cell determination of the TiO2 nanorod using this package is also demonstrated. Should the parallel-beam, nano-beam and convergent-beam modes of the TEM be used flexibly, the software can determine unit-cell parameters of unknown-structure crystallites (typically >50 nm).

The intercalation of 1,10-phenanthroline into layered NiPS3via iron dopant seeding.

Using 2% percent of iron dopants as reaction active sites yields a series of single crystals of 1,10-phenanthroline intercalated NiPS3, via a solution reaction with aniline chloride, not possible by a direct reaction. Experimental magnetic susceptibility measurements demonstrate that 1,10-phenanthroline intercalation suppresses the anti-ferromagnetism ordering at around 150 K in Fe0.02Ni0.98PS3, and gives rise to a ferrimagnetic phase transition at a temperature around 75 K. An intercalation mechanism is proposed for the reaction, and this dopant seeding method provides a new approach for intercalation into layered materials.

Direct observation of oxygen-vacancy formation and structural changes in Bi2WO6 nanoflakes induced by electron irradiation.

The prominent role of oxygen vacancies in the photocatalytic performance of bismuth tungsten oxides is well recognized, while the underlying formation mechanisms remain poorly understood. Here, we use the transmission electron microscopy to investigate the formation of oxygen vacancies and the structural evolution of Bi2WO6 under in situ electron irradiation. Our experimental results reveal that under 200 keV electron irradiation, the breaking of relatively weak Bi-O bonds leads to the formation of oxygen vacancies in Bi2WO6. With prolonged electron irradiation, the reduced Bi cations tend to form Bi clusters on the nanoflake surfaces, and the oxygen atoms are released from the nanoflakes, while the W-O networks reconstruct to form WO3. A possible mechanism that accounts for the observed processes of Bi cluster formation and oxygen release under energetic electron irradiation is also discussed.

Heterogeneous p-n Junction CdS/Cu2O Nanorod Arrays: Synthesis and Superior Visible-Light-Driven Photoelectrochemical Performance for Hydrogen Evolution.

Heterogeneous p-n junction CdS/Cu2O nanorod arrays have been fabricated by using a facile successive ionic-layer adsorption and reaction process to grow Cu2O nanoparticles on the surface of ordered CdS nanorod arrays. The heterogeneous p-n junction nanorod arrays exhibit superior photoelectrochemical performance for hydrogen (H2) generation and high stability under visible-light irradiation. The highest photocurrent density achieved by heterogeneous nanorod array photoelectrode is 4.2 mA cm-2 in a sacrificial Na2S and Na2SO3 mixture electrolyte solution at 0 V versus Ag/AgCl, which is 4 times higher than that of a pure CdS nanorod array photoelectrode. In addition, the heterogeneous nanorod array photoelectrode achieves an incident photon conversion efficiency value of 40.5% at 470 nm. The photocatalytic hydrogen generation rate of the heterogeneous nanorod array photoelectrode reaches up to 161.2 µmol h-1, around 3-fold increase compared to that of a bare CdS photoelectrode. Furthermore, the heterogeneous p-n junction CdS/Cu2O nanorod arrays show an excellent stability under long light illumination of 7200 s. The improved photoelectrochemical performance, photocatalytic activity, and excellent stability of the heterogeneous nanorod array photoelectrode resulted from the efficient separation of photoinduced electron-hole pairs, which is achieved by the synergistic effects of CdS, Cu2O, p-n junction, and an inner electric field in the photoelectrode. The present work provides a new strategy to fabricate a heterogeneous photoelectrode. This facile strategy is expected to be utilized to fabricate electrodes of other materials for highly efficient solar-driven water splitting application.

Structural Channels and Atomic-Cluster Insertion in CsxBi4Te6 (1 ≤ x ≤ 1.25) As Observed by Aberration-Corrected Scanning Transmission Electron Microscopy.

Microstructural analyses based on aberration-corrected scanning transmission electron microscopy (STEM) observations demonstrate that low-dimensional CsxBi4Te6 materials, known to be a novel thermoelectric and superconducting system, contain notable structural channels that go directly along the b axis, which can be partially filled by atom clusters depending on the thermal treatment process. We successfully prepared two series of CsxBi4Te6 single-crystalline samples using two different sintering processes. The CsxBi4Te6 samples prepared using an air-quenching method show superconductivity at approximately 4 K, while the CsxBi4Te6 with the same nominal compositions prepared by slowly cooling are nonsuperconductors. Moreover, atomic structural investigations of typical samples reveal that the structural channels are often empty in superconducting materials; thus, we can represent the superconducting phase as Cs1-yBi4Te6 with considering the point defects in the Cs layers. In addition, the channels in the nonsuperconducting crystals are commonly partially occupied by triplet Bi clusters. Moreover, the average structures for these two phases are also different in their monoclinic angles (ß), which are estimated to be 102.3° for superconductors and 100.5° for nonsuperconductors.

Electromagnetic Property and Tunable Microwave Absorption of 3D Nets from Nickel Chains at Elevated Temperature.

We fabricated the nickel chains by a facile wet chemical method. The morphology of nickel chains were tailored by adjusting the amount of PVP during the synthesis process. Both the complex permittivity and permeability of the three-dimensional (3D) nets constructed by nickel chains present strong dependences on temperature in the frequency range of 8.2-12.4 GHz and temperature range of 323-573 K. The peaks in imaginary component of permittivity and permeability mainly derive from interfacial polarizations and resonances, devoting to dielectric and magnetic loss, respectively. The effect from both dielectric and magnetism contribute to enhancing the microwave absorption. The maximum absorption value of the 3D nickel chain nets is approximately -50 dB at 8.8 GHz and 373 K with a thickness of 1.8 mm, and the bandwidth less than -10 dB almost covers the whole investigated frequency band. These are encouraging findings, which provide the potential advantages of magnetic transition metal-based materials for microwave absorption application at elevated temperature.

Multiscale Assembly of Grape-Like Ferroferric Oxide and Carbon Nanotubes: A Smart Absorber Prototype Varying Temperature to Tune Intensities.

Ideal electromagnetic attenuation material should not only shield the electromagnetic interference but also need strong absorption. Lightweight microwave absorber with thermal stability and high efficiency is a highly sought-after goal of researchers. Tuning microwave absorption to meet the harsh requirements of thermal environments has been a great challenge. Here, grape-like Fe3O4-multiwalled carbon nanotubes (MWCNTs) are synthesized, which have unique multiscale-assembled morphology, relatively uniform size, good crystallinity, high magnetization, and favorable superparamagnetism. The Fe3O4-MWCNTs is proven to be a smart microwave-absorber prototype with tunable high intensities in double belts in the temperature range of 323-473 K and X band. Maximum absorption in two absorbing belts can be simultaneously tuned from ∼-10 to ∼-15 dB and from ∼-16 to ∼-25 dB by varying temperature, respectively. The belt for reflection loss ≤-20 dB can almost cover the X band at 323 K. The tunable microwave absorption is attributed to effective impedance matching, benefiting from abundant interfacial polarizations and increased magnetic loss resulting from the grape-like Fe3O4 nanocrystals. Temperature adjusts the impedance matching by changing both the dielectric and magnetic loss. The special assembly of MWCNTs and magnetic loss nanocrystals provides an effective pathway to realize excellent absorbers at elevated temperature.

NiO hierarchical nanorings on SiC: enhancing relaxation to tune microwave absorption at elevated temperature.

We fabricated NiO nanorings on SiC, a novel hierarchical architecture, by a facile two-step method. The dielectric properties depend on temperature and frequency in the range from 373 to 773 K and X band. The imaginary part and loss tangent increase more than four times and three times with increasing temperature, respectively. The architecture demonstrates multirelaxation and possesses high-efficient absorption. The reflection loss exceeds -40 dB and the bandwidth covers 85% of X band (approximately -20 dB). The synergistic effect between multirelaxation and conductance is beneficial to the microwave absorption. Our findings provide a novel and feasible strategy to tune microwave absorption.

Strong coupling of the iron-quadrupole and anion-dipole polarizations in Ba(Fe(1-x)Co(x))2As2.

We use a quantitative convergent beam electron diffraction based method to image the valence electron density distribution in Ba(Fe1-xCox)2As2. We show a remarkable increase in both the charge quadrupole of the Fe cations and the charge dipole of the arsenic anions upon Co doping from x=0 (Tc=0 K) to x=0.1 (Tc=22.5 K). Our data suggest that an unexpected electronic correlation effect, namely strong coupling of Fe orbital fluctuation and anion electronic polarization, is present in iron-based superconductors.

Reduced graphene oxides: light-weight and high-efficiency electromagnetic interference shielding at elevated temperatures.

Chemical graphitized r-GOs, as the thinnest and lightest material in the carbon family, exhibit high-efficiency electromagnetic interference (EMI) shielding at elevated temperature, attributed to the cooperation of dipole polarization and hopping conductivity. The r-GO composites show different temperature-dependent imaginary permittivities and EMI shielding performances with changing mass ratio.

p-n junction CuO/BiVO4 heterogeneous nanostructures: synthesis and highly efficient visible-light photocatalytic performance.

A new strategy via coupling a polyol route with an oxidation process has been developed to successfully synthesize p-n junction CuO/BiVO4 heterogeneous nanostructures. The experimental results reveal that the as-prepared p-n junction CuO/BiVO4 heterogeneous nanostructures exhibit much higher visible-light-driven photocatalytic activity for the degradation of model dye rhodamine B (RhB) than the pure BiVO4 nanocrystals. The photocatalytic degradation rate (C/C0) of the RhB for p-n junction CuO/BiVO4 heterogeneous nanostructures is about two times higher than that of pure BiVO4 nanocrystals. The enhanced photocatalytic efficiency is attributed to a large number of p-n junctions in CuO/BiVO4 heterogeneous nanostructures, which effectively reduces the recombination of electrons and holes by charge transfer from n-type BiVO4 to the attached p-type CuO nanoparticles. This work not only provides an efficient route to enhance the visible-light-driven photocatalytic activity of BiVO4, but also offers a new strategy for fabricating p-n junction heterogeneous nanostructure photocatalysts, which are expected to show considerable potential application in solar-driven wastewater treatment and water splitting.

Microstructure and physical properties of two charge density wave states in NbSe3 nanowires.

The whisker-like niobium triselenide (NbSe3) nanowires were synthesized using the traditional solid state reaction. X-ray diffraction experiment suggested the monoclinic structure (P2(1)/m), and crystal morphology analysis indicated that the band-like shape is the stable morphology. Two charge density wave (CDW) states were observed at around 140 K and 50 K, respectively, and the nonlinear effect was detected in the CDW states from the R-T and I-V measurements. The doped Fe atoms, as pinning centers, play an important role in the nonlinear properties of the CDW state. Electron diffraction and HRTEM experiments were carried out at different temperatures in order to investigate the structural features and their evolution. The sets of incommensurate modulation spots with modulation vector q1 - (h, k +/- 0.243, l) appeared below 145 K, and other sets of complex superstructure spots with modulation vector q2 - (h, k + 0.3, l + 1.3424), q3 - (h, k - 0.3137, 1.5685), q4 = (1/3, k, 1) and q5 = (0.5, 0.25, 0.5) were observed at [1 0 0] and [3 0 1] zone axis at about 20 K, respectively, suggesting the complex incommensurately modulated structures in this material.

Asymmetric silver "nanocarrot" structures: solution synthesis and their asymmetric plasmonic resonances.

Here we report the wet-chemical synthesis of asymmetric one-dimensional (1D) silver "nanocarrot" structures that exhibit mixed twins and stacking fault domains along the <111> direction. Oriented attachment is the dominant mechanism for anisotropic growth. Multipolar plasmon resonances up to fourth order were measured by optical extinction spectroscopy and electron energy-loss spectroscopy (EELS) and are in agreement with theoretical calculations. Compared with those of symmetric 1D nanostructures of similar length, the dipole modes of the nanocarrots show a clear red shift, and the EELS maps show an asymmetric distribution of the resonant plasmonic fields and a compression of the resonance node spacing toward the tail. In addition, increasing the length of the nanocarrots causes an increase in the intensity and a steady red shift of the longitudinal surface plasmon resonance peaks. The silver nanocarrots also show very high sensitivity to the refractive index of their environment (890 ± 87 nm per refractive index unit).

A facile and environmentally friendly NaCl nonaqueous ionic liquid route to prepare crystalline ß-CaSiO3 nanowires.

We described an environmentally friendly and facile NaCl nonaqueous ionic liquid route for the first time to synthesize ß-CaSiO3 nanowires. ß-CaSiO3 nanowires were prepared by annealing precursor calcium silicate hydrate (CSH) nanostructures in NaCl nonaqueous ionic liquid, in which the precursor CSH nanostructures were first prepared by a facile one-step, solid state reaction, ground with both NaCl and surfactant nonyl phenyl ether (9) (NP-9), and heated at 850 °C for 2 h. ß-CaSiO3 nanowires were characterized by XRD, TEM and HRTEM. The comparative experiments have been conducted systemically to investigate the growth mechanism of ß-CaSiO3 nanowires, and the roles of salt NaCl nonaqueous ionic liquid and NP-9 on the formation of ß-CaSiO3 nanowires. The results demonstrated that both salt NaCl nonaqueous ionic liquid and surfactant NP-9 played key roles on the formation of ß-CaSiO3 nanowires. A rational growth mechanism of ß-CaSiO3 nanowires has been proposed on the basis of experimental results.

Contribution of interlayer hybridization to the electronic structure in iron pnictides: a study of EELS and first-principles calculations.

Using electron energy loss spectroscopy (EELS) measurements and first-principles electronic structure calculations, the significant interlayer hybridization between the insulating layers (ReO or Ba) and the conducting FeAs layers was investigated in the layered iron pnictides, which is quite different from the case in the cuprate superconductors. This interlayer hybridization would result in an increase in the bandwidth near the Fermi level and interorbital charge transfer in the Fe 3d orbitals, which subsequently leads to a decrease in the Fe local moment and the modification of the Fermi surface topology. Therefore, a three-dimensional character of the electronic structure due to the interlayer hybridization is expected, as observed in previous experiments. These findings indicate that reduced dimensionality is no longer a necessary condition in the search for high-T(c) superconductors in iron pnictides.

Features of twins and stacking faults in silver nanorice and electron-beam irradiation effect.

Systematic structural characterization using high resolution transmission electron microscope (HRTEM), selected area electron diffraction (SAED) and diffractogram analysis of silver nanorice was aimed to reveal the characteristic features of twins and stacking faults, faceting effect and smoothing phenomena of outer surfaces. Nucleation, growth and crystallization of new nanocrystals, and depletion of parent nanorice was observed by the in situ TEM through electron-beam irradiation. It can be seen that the fundamental growth mechanism of the new nucleus is Ag atom diffusion or migration through carbon film supported these crystals. Twins in the as-grown nanorice is a reflection twin with {111} lattice plane as the common plane, and they are formed by 120° or 60° rotation about the reference twin lamella. Shockley partial dislocation was formed by the {111} lattice plane shifting along the <112> direction with the Burgers vector a/6 <112>. Twin faults occur in the form of adjacent twin lamellas inserted into a single atomic plane. Growth morphology analysis suggests that {111} and {001} lattice planes with the minimum surface attachment energy have a tendency to facet.