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Rechargeable lithium-oxygen (Li-O2) batteries are the next generation energy storage devices due to their ultrahigh theoretical capacity. Redox mediators (RMs) are widely used as a homogenous electrocatalyst in non-aqueous Li-O2 batteries to enhance their discharge capacity and reduce charge overpotential. However, the shuttle effect of RMs in the electrolyte solution usually leads to corrosion of the Li metal anode and uneven Li deposition on the anode surface, resulting in unwanted consumption of electrocatalysts and deterioration of the cells. It is therefore necessary to take some measures to prevent the shuttle effect of RMs and fully utilize the soluble electrocatalysts. Herein, we summarize the strategies to suppress the RM shuttle effect reported in recent years, including electrolyte additives, protective separators and electrode modification. The mechanisms of these strategies are analyzed and their corresponding requirements are discussed. The electrochemical properties of Li-O2 batteries with different strategies are summarized and compared. The challenges and perspectives on preventing the shuttle effect of RMs are described for future study. This review provides guidance for achieving shuttle-free redox mediation and for designing Li-O2 cells with a long cycle life, high energy efficiency and highly reversible electrochemical reactions.

Temperature-dependent X-ray absorption near-edge structures, X-ray linear dichroism (XLD) and extended X-ray absorption fine structure (EXAFS) spectroscopic techniques were used to investigate the valence state, preferred orbital and local atomic structure that significantly affect the electrical and magnetic properties of a single crystal of YBaCuFeO5 (YBCFO). An onset of increase of resistivity at ~180 K, followed by a rapid increase at/below 125 K, is observed. An antiferromagnetic (AFM)-like transition is close to the temperature at which the resistivity starts to increase in the ab-plane and is also observed with strong anisotropy between the ab-plane and the c-axis. The XLD spectra at the Fe L3,2-edge revealed a change in Fe 3d eg holes from the preferential $${\bf{3}}{{\boldsymbol{d}}}_{{{\bf{x}}}^{{\bf{2}}}{\boldsymbol{-}}{{\bf{y}}}^{{\bf{2}}}}$$3dx2−y2 orbital at high temperature (300–150 K) to the $${\bf{3}}{{\boldsymbol{d}}}_{{{\bf{3}}{\bf{z}}}^{{\bf{2}}}{\boldsymbol{-}}{{\bf{r}}}^{{\bf{2}}}}$$3d3z2−r2 orbital at/below 125 K. The analysis of the Fe K-edge EXAFS data of YBCFO further revealed an unusual increase in the Debye-Waller factor of the nearest-neighbor Fe-O bond length at/below 125 K, suggesting phonon-softening behavior, resulting in the breaking of lattice symmetry, particularly in the ab-plane of Fe-related square pyramids. These findings demonstrate a close correlation between electrical resistivity and coupling of the preferred Fe 3d orbital with lattice distortion of a single crystal of YBCFO.

In work, (002) oriented flower-like Bi2O2CO3(BOC) composites are synthesized by a facile chemical route and carbon quantum dots (CQDs) are modified on their surfaces through a hydrothermal method. The synthesized samples (CQD/BOC) are characterized by X-ray diffraction (XRD), SEM, X-ray photoelectron spectroscopy (XPS), UV-Vis diffuser reflectances (DRS), BET and TEM/HRTEM. The morphologies of CQD/BOC composites are the flower-like shapes, the irregular flaky structures and the fine spherical particles of CQDs attached. Photocatalytic performances were investigated in terms of removing gaseous toluene at a concentration of 94.3ppm in air, with the assistance of CQD/BOC under artificial irradiation. Our results show that CQDs modified (002) oriented Bi2O2CO3 exhibits good photocatalytic activity for toluene decomposition, which can be attributed to the enhanced efficient charge separation. A certain ratio composite photocatalyst (BOC-CQD-15) shows a toluene removal rate of 96.62% in three hours, as well as great stability. CO2 was verified to be the primary product. The oriented flower-like Bi2O2CO3 with carbon quantum dots on the surface shows great potential in the field of solar driven air purification.

Layer-structured Bi2O2CO3 is a novel photocatalyst for eliminating environmental pollutants. In this work, Bi2O2CO3 nanosheets were synthesized by hydrothermal methods, followed by annealing in nitrogen. (002) oriented Bi2O2CO3 nanosheets were obtained and characterized by XRD, SEM, XPS, BET and UV-Vis diffuse reflectance spectra. Photocatalytic properties were investigated by toluene removal in air, with the assistant of Bi2O2CO3 nanosheets under artificial irradiation. Our results show that Bi2O2CO3 annealed in nitrogen exhibited high full-light-driven photocatalytic activity for toluene photocatalytic decomposition, which may be ascribed to facet orientation evolution during the annealing process and enhanced efficient charge separation. The sample annealed at 150&deg, C for 8 h (BOC-150-8h) showed high stability and the highest toluene removal rate, which was up to99%. The final degradation products were detected by gas chromatography&ndash, mass spectrometer (GC-MS) and CO2 was verified to be the primary product. Photocatalytic mineralization of toluene in air over Bi2O2CO3 was proposed. This work may provide a foundation for application of annealedBi2O2CO3 in indoor air purification.

This investigation reports on anisotropy in the magnetic interaction, lattice-orbital coupling and degree of phonon softening in single crystal Ni3TeO6 (NTO) using temperature- and polarization-dependent X-ray absorption spectroscopic techniques. The magnetic field-cooled and zero-field-cooled measurements and temperature-dependent Ni L3,2-edge X-ray magnetic circular dichroism spectra of NTO reveal a weak Ni-Ni ferromagnetic interaction close to ~60 K (TSO: temperature of the onset of spin ordering) with a net alignment of Ni spins (the uncompensated components of the Ni moments) along the crystallographic c-axis, which is absent from the ab-plane. Below the Néel temperature, TN~ 52 K, NTO is stable in the antiferromagnetic state with its spin axis parallel to the c-axis. The Ni L3,2-edge X-ray linear dichroism results indicate that above TSO, the Ni 3d eg electrons preferentially occupy the out-of-plane 3d3z2−r2 orbitals and switch to the in-plane 3dx2−y2 orbitals below TSO. The inherent distortion of the NiO6 octahedra and anisotropic nearest-neighbor Ni-O bond lengths between the c-axis and the ab-plane of NTO, followed by anomalous Debye-Waller factors and orbital-lattice in conjunction with spin-phonon couplings, stabilize the occupied out-of-plane (3d3z2−r2) and in-plane (3dx2−y2) Ni eg orbitals above and below TSO, respectively.

Cuprous based chalcogenides have attracted intensive research interest due to the potential applications in solar energy conversion. However, typical fabrications of these compounds are often carried out under severe conditions, such as inert gas protection, high vacuum, and/or extreme high temperature. Here we reported a one-pot process for cuprous based chalcogenides synthesis in aqueous solution. A strategy for BiCuSO nanosheets fabrication without toxic chemicals or rigorous reagents at pretty low temperatures under an ambient atmosphere was established, with the practicality of morphology controlling and the compatibility of multifarious precursors. Platelike BiCuSO with a thickness range from several to hundreds nanometers are fabricated by adjusting the alkali concentration, reaction time, and temperature. The positive effect of alkali hydroxide concentration is proposed cautiously based on the experimental results. The photocatalytic activities of BiCuSO nanosheet under UV, visible, and near-infrared irradiation were also investigated. BiCuSO obtained at room temperature with a thickness of 4.5 nm showed the most impressive efficiency to decompose organic contaminants. Our research presented a new way for cuprous sulfides fabrication, and might open up a new vista for large-scale synthesis of cuprous based materials as promising broadband spectrum light-absorbing materials.

We report a novel composite graphene oxide (GO)/NiFe2O4/TiO2 nanorod arrays (NRAs) prepared by calcinating and dipping, TiO2 NRAs were prepared via hydrothermal method. XRD, SEM, XPS, and PL, show that GO/NiFe2O4/TiO2 NRAs have been successfully synthesized having enhanced photocatalytic performance. Furthermore, the optimal degradation conditions of unsymmetrical dimethylhydrazine (UDMH) using the catalyst were obtained by orthogonal and single-factor experiment. Moreover, the possible photocatalytic mechanism is briefly discussed; under visible light, electrons and holes excited from NiFe2O4 can be effectively separated due to the band energy matching between NiFe2O4 and TiO2. In addition, photogenerated electrons can quickly migrate to GO owing to the conduction band, as the position of NiFe2O4 is more negative than the Fermi level of GO. The electrons and holes were well separated so that they can efficiently participate in the degradation of UDMH, resulting in enhancement of photocatalytic activity.

We report a simple mechanochemical ball milling method for synthesizing monodisperse CuS quantum dots (QDs) with sizes as small as sub-5 nm. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV–vis spectroscopy. The CuS QDs exhibited excellent visible-light-driven photocatalytic activity and stability for degradation of Rodanmine B aqueous solution as Fenton-like reagents. Our study opens the opportunity to low-cost and facile synthesis of QDs in large scale for future industrial applications.

Bi1-xSmxFe1-yMnyO3 (BSFMO, x = 0.0, 0.05; y = 0.0, 0.05, 0.10, 0.15, 0.20, 0.25) nanoparticles were synthesized by using double solvent sol–gel method. Photocatalytic activity was investigated under UV and visible-light illumination. The structural, morphological, and optical properties were analyzed by X-ray diffraction, scanning electron microscopy, and UV-vis spectroscopy respectively. The crystallite size of BiFeO3 (BFO) decreases from (57.3–17.2 nm) with the increase in Sm and Mn-doping concentration. The surface morphology shows that the pure and Sm-doped BFO nanoparticles are irregular in shape but changes to spherical shape after Mn-doping up to 25%. The band-gap engineering of BFO nanoparticles is achieved by co-doping of Sm and Mn. The band-gap of BFO could be tuned successfully from 2.08–1.45 eV, which may be due to the distortion induced in Fe-O octahedron and the rearrangement of molecular orbitals. These results give rise to enhanced photocatalytic activity by degradation of organic dyes (MB, CR, and MV) under the visible-light illumination.

Pure perovskite BiFeO3, sillenite Bi2Fe4O9, and BiFeO3/Bi2Fe4O9 were synthesized facilely by controlling the precursor Bi/Fe ion ratio through a hydrothermal method. The phase composition, morphology, optical properties, and photocatalytic activity of as-prepared samples were investigated in detail. Our results indicate that the morphology and properties of products strongly dependent on the precursor Bi/Fe ion ratio. Photocatalysis of Congo Red reveals that sillenite Bi2Fe4O9 shows superior activity to perovskite BiFeO3, and BiFeO3/Bi2Fe4O9 exhibited higher activity with 71.45% degradation rate in 90 min. It provides an easy and efficient way to tune the composition and photocatalytic activity of Bi-based oxides.

Energy band engineering and the nature of surface/interface of a semiconductor play a significant role in searching high efficiency photocatalysts. Actually, the active facets, morphology controlling, especially the exposed facets modulation of photocatalysts during preparation are very desirable. In order to achieve high photocatalytic performance, intrinsic mechanism of such anisotropic properties should be fully considered. In this review, we mainly emphasis on the latest research developments of several extensively investigated photocatalysts and their anisotropic photocatalytic properties, as well as the correlation between effective masses anisotropy and photocatalytic properties. It will be helpful to understand the photocatalytic mechanism and promote rational development of photocatalyst for wide applications.

High efficiency photocatalyst Bi2O2(CO3)1−xSx was synthesized conveniently with chemical bath precipitation using Bi2O2CO3 as the precursor. The microstructures of the samples are systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and UV-Vis spectroscopy; the optical and photocatalytic properties are carefully tested as well. The content of S, which was tuned through the controlling of the precipitation process, was verified to have an intense effect over the photocatalytic properties. A nearly saturated S ratio and the best photocatalytic performance were observed in specimens with the most S content. Our study reveals that, with negligible influence of the morphology and crystal structure, Bi2O2(CO3)1−xSx possessed a broadened optical absorption regionfromultraviolet to visible light, and enhanced photocatalytic activity in comparison to precursor Bi2O2CO3 in photocatalytic degradation of Congo Red aqueous solution.

The danger of toxic organic pollutants in both aquatic and air environments calls for high-efficiency purification material. Herein, layered bismuth copper oxychalcogenides, BiCuSO, nanosheets of high photocatalytic activity were introduced to the PVDF (Polyvinylidene Fluoride). The fibrous membranes provide an easy, efficient, and recyclable way to purify organic pollutant. The physical and photophysical properties of the BiCuSO and its polymer composite were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), ultraviolet-visible diffuse reflection spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), electron spin resonance (EPR). Photocatalysis of Congo Red reveals that the BiCuSO/PVDF shows a superior photocatalytic activity of a 55% degradation rate in 70 min at visible light. The high photocatalytic activity is attributed to the exposed active {101} facets and the triple vacant associates V B i ‴ V O • • V B i ‴ . By engineering the intrinsic defects on the surface of bismuth oxysulfide, high solar-driven photocatalytic activity can be approached. The successful fabrication of the bismuth oxysulfide and its polymer nanocomposites provides an easy and general approach for high-performance purification materials for various applications.

A novel Cu1.8Se/Cu3Se2 composite photocatalyst was prepared by the simple precipitation method. This composite possesses a wide photoabsorption until the range of near-infrared light, and exhibits significantly enhanced photocatalytic activity for methyl orange degradation under visible and near-infrared light irradiation compared with bare Cu1.8Se and Cu3Se2. The mechanism of this outstanding photocatalytic behavior can be explained by the calculated energy band positions. The efficient charge separation via a phase junction of Cu1.8Se/Cu3Se2 composite would make a great contribution to its much-enhanced photocatalytic efficiency.

The majority of unsymmetrical dimethylhydrazine (UDMH) treatments produce lots of toxic by-products, among which N -Nitrosodimethylamine (NDMA) is a strong carcinogen. The compositions of the by-products are important for evaluating the treatment efficiency and understanding the UDMH degradation mechanism to achieve UDMH mineralization. The intermediate and end products of UDMH treatment with different oxidants were investigated by using a simple and fast method, solid-phase micro-extraction (SPME) in combination with gas chromatography–mass spectrometry (GC-MS). The effects of several parameters (coating fibre, salt addition, pH, sampling time and desorption time) were studied to optimize analyte recovery. The best response can be attained by the 65 µm PDMS/DVB fibre at pH 7 during 10 min after desorption of 1 min in the GC inlet. The intermediate and final oxidative products of UDMH wastewater treatment with different oxidants (O 3 , Mn 2+ /O 3 , Fe 2+ /H 2 O 2 ) were investigated. The results showed that the UDMH treatment with O 3 could lead to high yields of NDMA. Metal catalytic ozonation could largely minimize the formation of NDMA. No NDMA was observed in the final decontaminated samples after treatment with Fe 2+ /H 2 O 2 . The NDMA formation and degradation mechanism were discussed based on the intermediates. This study is expected to provide useful information for controlling NDMA formation during UDMH wastewater treatment.

BiFeO3 nanofibers doped with divalent barium have been fabricated using electrospinning technique. Phase transition from space group R3c to C222 can be observed by the Ba doping. Our results indicate that these BiFeO3 nanofibers show obvious room temperature ferromagnetic behaviors, which can be enhanced remarkably with the increment of Ba doping. Microstructure and composition analysis indicates that barium effectively affected the magnetism after doping content was more than 5% and optical properties.

Ca and Mn co-doped BiFeO3 ultrafine nanofibres were prepared with the purpose of improving magnetic and photocatalytic performances of the one-dimensional multiferroic material. Impurity phase introduced by both Bi fluctuation and Mn substitution can be suppressed by Ca doping and a space group transition from R3c to C222 can also be triggered by Bi-site doping. With co-substitution of Mn into iron site, the Ca0.15Bi0.85Mn0.05Fe0.95O3 nanofibres presented a larger saturation magnetization than the singly Ca doping samples, possibly due to the increased double exchange interation of Fe3+-O-Fe2+, strengthened by Ca and Mn. Photocatalytic degradation test witnessed a similar drop-and-rise performance with the magnetism.

Pure BiFeO3 and heterostructured BiFeO3/BiFe0.95Mn0.05O3 (5% Mn-doped BiFeO3) thin films have been prepared by a chemical deposition method. The band structures and photosensitive properties of these films have been investigated elaborately. Pure BiFeO3 films showed stable and strong response to photo illumination (open circuit potential kept −0.18 V, short circuit photocurrent density was −0.023 mA·cm−2). By Mn doping, the energy band positions shifted, resulting in a smaller band gap of BiFe0.95Mn0.05O3 layer and an internal field being built in the BiFeO3/BiFe0.95Mn0.05O3 interface. BiFeO3/BiFe0.95Mn0.05O3 and BiFe0.95Mn0.05O3 thin films demonstrated poor photo activity compared with pure BiFeO3 films, which can be explained by the fact that Mn doping brought in a large amount of defects in the BiFe0.95Mn0.05O3 layers, causing higher carrier combination and correspondingly suppressing the photo response, and this negative influence was more considerable than the positive effects provided by the band modulation.

Photocatalysis is attracting enormous interest driven by the great promise of addressing current energy and environmental crises by converting solar light directly into chemical energy. However, efficiently harvesting solar energy for photocatalysis remains a pressing challenge and the charge kinetics and mechanism of the photocatalytic process is far from being well understood. Here we report a new full solar spectrum driven photocatalyst in the system of a layered oxyselenide BiCuSeO with good photocatalytic activity for degradation of organic pollutants and chemical stability under light irradiation and the photocatalytic performance of BiCuSeO can be further improved by band gap engineering with introduction of La. Our measurements and density-functional-theory calculations reveal that the effective mass and mobility of the carriers in BiCuSeO can be tuned by the La-doping, which are responsible for the tunable photocatalytic activity. Our findings may offer new perspectives for understanding the mechanism of photocatalysis through modulating the charge mobility and the effective mass of carriers and provide a guidance for designing efficient photocatalyts.

Purpose MicroRNAs (miRNAs) play an essential role in breast malignant tumor development and progression. The development of clinically validated biomarkers for primary breast cancer (BC) has remained an insurmountable task despite other advances in the field of cancer molecular biology. The objective of this study is to investigate the differential expression of miRNAs and the potential of circulating microRNAs as novel primary breast cancer biomarkers. Methods Our analyses were performed on 48 tissue and 100 serum samples of patients with primary BC and a set of 20 control samples of healthy women, respectively. The relative expression of ten candidate miRNAs (miR-106b, miR-125b, miR-17, miR-185, miR-21, miR-558, miR-625, miR-665, miR-92a, and miR-93) from the results of four bioinformatics approaches and literature curation was measured by real-time quantitative reverse transcription PCR (qRT-PCR). Results The level of miR-92a was significantly lower, while miR-21 was higher, as previous reports, in tissue and serum samples of BC than that of healthy controls (p

High efficiency photocatalyst Bi2O2(CO3)1−xSx was synthesized conveniently with chemical bath precipitation using Bi2O2CO3 as the precursor. The microstructures of the samples are systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and UV-Vis spectroscopy; the optical and photocatalytic properties are carefully tested as well. The content of S, which was tuned through the controlling of the precipitation process, was verified to have an intense effect over the photocatalytic properties. A nearly saturated S ratio and the best photocatalytic performance were observed in specimens with the most S content. Our study reveals that, with negligible influence of the morphology and crystal structure, Bi2O2(CO3)1−xSx possessed a broadened optical absorption regionfromultraviolet to visible light, and enhanced photocatalytic activity in comparison to precursor Bi2O2CO3 in photocatalytic degradation of Congo Red aqueous solution.

Single phase polycrystalline BiFeO3 thin films were grown on three different substrates via chemical solution deposition. Our results indicate that the band gap of as-prepared BiFeO3 films can be tuned (2.02–2.67 eV) by the grain size effects caused by the substrates. These BiFeO3 films show good photocatalytic properties by the degradation of Congo red solution under visible-light irradiation ( λ > 400 nm). Additionally, weak ferromagnetic behaviors can be observed at room temperature in all the films, which should be correlated to the destruction of the incommensurate cycloid spin structure of BiFeO3 phase and the coexistence of Fe3+ and Fe2+ as confirmed by X-ray photoelectron spectroscopy.

Ca-doped BiFeO3 nanofibres have been fabricated by electrospinning method. Our results indicate that phase transition from space group R3c to C222 can be observed by the Ca doping. These BiFeO3 nanofibres show obvious room temperature ferromagnetic behaviors, and saturation magnetization can be enhanced with the Ca-doping concentration increasing, which could be correlated with the variation of the ratio of Fe2+/Fe3+ valence state. The BiFeO3 nanofibres show obvious photocatalytic performance and can be improved by the Ca-doping.

In the title compound, C2H9N2+·C6H2N3O7−, the dihedral angles between the mean planes of the three nitro groups and the benzene ring are 63.5 (3), 10.5 (2) and 10.4 (2)°. In the crystal, molecules are linked by N—H...O hydrogen bonds into a two-dimensional network parallel to (001).

Low-dimensional nanostructures are a promising class of ideal high-performance candidates for energy storage and conversion owing to their unique structural, optical, and chemical properties. Low-dimensional nanostructured photocatalysts have attracted ever-growing research attention. In this review, we mainly emphasize on summarizing the 0-, 1-, and 2-dimensional nanostructured photocatalysts systematically, including their photocatalytic performance, synthesis methods, and theoretical analysis. From the viewpoint of dimension, we try to figure out the way to design more high-efficiency photocatalysts towards numerous applications in the field of solar energy conversion, hoping to promote efficient control and rational development of photocatalysts.