Study of the Phase Transformation of Single Particles of Ga2O3 by UV‐Raman Spectroscopy and High‐Resolution TEM

By taking advantage of UV‐Raman spectroscopy and high‐resolution TEM (HRTEM), combined with the focused ion beam (FIB) technique, the transformation from GaOOH into α‐Ga₂O₃ and then into β‐Ga₂O₃ was followed. We found that the stepwise transformations took place from the surface region before developing into the bulk of single particles without particle agglomeration and growth. During the transformation from GaOOH into α‐Ga₂O₃, the elimination of water vapor through the dehydroxylation of GaOOH resulted in the formation of micropores in the single particles, whilst maintaining their particle size. For the phase transformation from α‐Ga₂O₃ into β‐Ga₂O₃, the nucleation of β‐Ga₂O₃ was found to occur at the surface defects and this process could be retarded by occupying these defects with a small amount of La₂O₃. By finely controlling the process of the phase transformation, the β‐Ga₂O₃ domains gradually developed from the surface into the bulk of the single particles without particle agglomeration. Therefore, the surface structure of the α‐Ga₂O₃ single particles can be easily tuned and a particle with an α@β core–shell phase structure has been obtained.     

Synthesis and Morphology Control of AM‐6 Nanofibers with Tailored ‐V‐O‐V‐ Intermediates

Microporous vanadosilicates with octahedral VO₆ and tetrahedral SiO₄ units, better known as AM‐6, have been hydrothermally synthesized with different morphologies by controlling the Na/K molar ratio of the initial gel mixtures. The morphology of the AM‐6 materials changed from bulky cube to nanofiber aggregates as the Na/K molar ratio decreased from 1.9 to 0.2. Raman spectroscopy revealed that the VO₃^? intermediate species plays an important role in the formation of the nanofiber morphology. The orientation of ‐V‐O‐V‐ chains in nanofiber aggregates was examined by confocal polarized micro‐Raman spectroscopy. It was found that these aggregates are assemblies of short ‐V‐O‐V‐ chains perpendicular to the axis of nanofibers. The obtained AM‐6 nanofibers greatly increase the exposed proportion of V? O terminals, and thus improve the catalytic performance.     

Dynamic analysis on metal selenide electrodeposition

Based on the basic principles of kinetics and some reasonable assumptions about the electrodeposition process, a dynamic model for metal selenide electrodeposition (kink site selected model) was constructed. This model is of universal significance in realizing the compositional prediction and dynamic behavior analysis of deposited films for different main salt concentration ratios and was applied to the ternary Cu–In–Se system. For CuInSe₂ electrodeposition, in the Cu–Se system, the co-deposition of Cu and Se can be carried out within a large range of main salt concentration ratio; in the Cu–In system, the mole fraction of Cu in deposited thin films is always higher than that of Cu²⁺ in electrolyte, while in the In–Se system, the co-deposition of In and Se can be achieved only when the In³⁺ concentration is much higher than the H₂SeO₃ concentration. As for the compositional estimation of CuInSe₂, the predictive results of our dynamic model agree well with the experimental data. It is then found that by correcting the difference of kink site selectivity constants caused by the change of deposition potential, the error of the predictive results can be reduced.     

Synthesis and Characterization of Ag8(Ge1−x,Snx)(S6−y,Sey) Colloidal Nanocrystals

A facile colloidal approach to synthesize Ag₈(Ge_1?x,Sn_x)(S_6?y,Se_y) nanocrystals (NCs) in a highly controlled way across the entire compositional ranges (0≤x≤1, 0≤y≤6) has been developed. The NCs exhibit a uniform size distribution, highly crystalline structure, over 1 g scalable synthesis, and tunable band gaps in the range of 0.88–1.45 eV by varying their chemical compositions. The Ag₈GeS₆ NCs with a band gap of approximately 1.45 eV were employed as a model light harvester to assess their applicability in solar cells by a full solution‐processing device, yielding an efficiency of 0.28 % under AM1.5 illumination, demonstrating their application potential in solar energy utilization.     

A Deadly Organometallic Luminescent Probe: Anticancer Activity of a ReI Bisquinoline Complex

The photophysical properties of [Re(CO)₃(L ‐N₃)]Br (L ‐N₃=2‐azido‐N,N‐bis[(quinolin‐2‐yl)methyl]ethanamine), which could not be localized in cancer cells by fluorescence microscopy, have been revisited in order to evaluate its use as a luminescent probe in a biological environment. The Re^I complex displays concentration‐dependent residual fluorescence besides the expected phosphorescence, and the nature of the emitting excited states have been evaluated by DFT and time‐dependent (TD) DFT methods. The results show that fluorescence occurs from a ¹LC/MLCT state, whereas phosphorescence mainly stems from a ³LC state, in contrast to previous assignments. We found that our luminescent probe, [Re(CO)₃(L ‐N₃)]Br, exhibits an interesting cytotoxic activity in the low micromolar range in various cancer cell lines. Several biochemical assays were performed to unveil the cytotoxic mechanism of the organometallic Re^I bisquinoline complex. [Re(CO)₃(L ‐N₃)]Br was found to be stable in human plasma indicating that [Re(CO)₃(L ‐N₃)]Br itself and not a decomposition product is responsible for the observed cytotoxicity. Addition of [Re(CO)₃(L ‐N₃)]Br to MCF‐7 breast cancer cells grown on a biosensor chip micro‐bioreactor immediately led to reduced cellular respiration and increased glycolysis, indicating a large shift in cellular metabolism and inhibition of mitochondrial activity. Further analysis of respiration of isolated mitochondria clearly showed that mitochondrial respiratory activity was a direct target of [Re(CO)₃(L ‐N₃)]Br and involved two modes of action, namely increased respiration at lower concentrations, potentially through increased proton transport through the inner mitochondrial membrane, and efficient blocking of respiration at higher concentrations. Thus, we believe that the direct targeting of mitochondria in cells by [Re(CO)₃(L ‐N₃)]Br is responsible for the anticancer activity.     

Highly Enantioselective Catalytic System for Asymmetric Copolymerization of Carbon Dioxide and Cyclohexene Oxide

A new ligand can be easily prepared, and its intramolecular dinuclear zinc complexes act as a high performance catalyst for the asymmetric alternating copolymerization of cyclohexene oxide and CO₂ under very mild conditions (1 atm CO₂, room temperature), affording completely alternating polycarbonates with up to 93.8 % enantiomeric excess (ee) and 98 % yield. A high M_n value of 28 600 and a relatively narrow polydispersity (M_w/M_n ratio) of 1.43 were also achieved.     

Two-dimensional Molecular Phase Transition of Alkylated-TDPB on Au(111) and Cu(111) Surfaces

The derivatives of aromatic cores bearing alkyl chains with different lengths are of potential interest in on-surface chemistry, and thus have been widely investigated both at liquid-solid interfaces and in vacuum. Here, we report on the structural evaluation of self-assembled 1,3,5-tri(4-dodecylphenyl)benzene(TDPB) molecules with increased molecular coverages on both Au(111) and Cu(111) surfaces. As observed on Au(111), rhombic and herringbone structures emerge successively depending on surface coverage. In the case of Cu(111), the same process of phase conversion is also observed, but with two distinct structures. In comparison, the self-assembled structures on Au(111) surface are packed more densely than that on Cu(111) surface under the same preparation conditions. This may fundamentally result from the higher adsorption energy of TDPB molecules on Cu(111), restricting their adjustment to optimize a thermodynamically favorable molecular packing.     

Understanding energetic disorder in electron-deficient-core-based non-fullerene solar cells

Recent advances in material design for organic solar cells(OSCs) are primarily focused on developing near-infrared nonfullerene acceptors, typically A-DA′D-A type acceptors(where A abbreviates an electron-withdrawing moiety and D, an electron-donor moiety), to achieve high external quantum efficiency while maintaining low voltage loss. However, the charge transport is still constrained by unfavorable molecular conformations, resulting in high energetic disorder and limiting the device performance. Here, a facile design strategy is reported by introducing the "wing"(alkyl chains) at the terminal of the DA′D central core of the A-DA′D-A type acceptor to achieve a favorable and ordered molecular orientation and therefore facilitate charge carrier transport. Benefitting from the reduced disorder, the electron mobilities could be significantly enhanced for the"wing"-containing molecules. By carefully changing the length of alkyl chains, the mobility of acceptor has been tuned to match with that of donor, leading to a minimized charge imbalance factor and a high fill factor(FF). We further provide useful design strategies for highly efficient OSCs with high FF.     

Magnetron sputtering deposition of silicon nitride on polyimide separator for high-temperature lithium-ion batteries

To date,lithium-ion batteries are becoming increasingly significant in the application of portable devices and electrical vehicles,and revolutionary progress in theoretical research and industrial application has been achieved.However,the commercial polyolefin separators with unsatisfying electrolytes affinity and poor thermal stability have extremely restricted the further application of lithium-ion batteries,especially in the high-temperature fields.In this work,magnetron sputtering deposition technique is employed to modify the commercial polyimide separator by coating silicon nitride on both sides.Magnetron sputtering deposition modified polyimide(MSD-PI)composite separator shows high thermal stability and ionic conductivity.More importantly,compared with the cells using Celgard separator,the cells with MSD-PI separator exhibit superior electrochemical performance,especially long-term cycle performance under high temperature environment,owing to the high thermal conductivity of surface Si3 N4 particles.Hence,lithium-ion batteries with MSD-PI separator are capable of improving thermal safety and capacity retention,which demonstrates that magnetron sputtering deposition technique could be regarded as a promising strategy to develop advanced organic/inorganic composite separators for high-temperature lithium-ion batteries.