Gas-Sensing Activity of Amorphous Copper Oxide Porous Nanosheets

In this paper, the gas-sensing properties of copper oxide porous nanosheets in amorphous and highly crystalline states were comparatively investigated on the premise of almost the same specific surface area, morphology and size. Unexpectedly, the results show that amorphous copper oxide porous nanosheets have much better gas sensing properties than highly crystalline copper oxide to a serious of volatile organic compounds, and the lowest detection limit (LOD) of the amorphous copper oxide porous nanosheets to methanal is even up to 10 ppb. By contrast, the LOD of the highly crystalline copper oxide porous nanosheets to methanal is 95 ppb. Experiments prove that the oxygen vacancies contained in the amorphous copper oxide porous nanosheets play a key role in improving gas sensitivity, which greatly improve the chemical activity of the materials, especially for the adsorption of molecules containing oxygen-groups such as methanal and oxygen.     

Real-time phase measurement and correction of dynamic multimode beam using a single spatial light modulator

In this Letter,a novel system for adaptively correcting the phase of a dynamic multimode beam is proposed.While using merely one spatial light modulator,the phase measurement of the first-order diffraction pattern and the correction of the zeroth diffraction order are simultaneously realized.The real-time experimental result is obtained at a control rate of 10 Hz.The power-in-the-bucket value is improved from 38.5%to 61.8%,even with fundamental mode content that is consistently below 30%.To the best of our knowledge,this is the first implementation of real-time adaptive correction of the entire multimode beam.     

Effects of intramolecular hydrogen bonds on phosphorescence emission: A theoretical perspective

Importing intramolecular hydrogen bond in phosphorescent transition metal complexes has been considered one of the excellent approaches to improve the electroluminescence performance of organic light-emitting diodes in real applications. However, the relationships between such H-bond structure and phosphorescent properties have not been theoretically revealed yet. In this study, two types of intramolecular hydrogen bonds are introduced into the two classes of traditional materials, that is, Pt(II) and Ir(III) complexes ( 1a and 2a ) to completely elucidate their influence on the structures and properties by comparing with the original phosphors ( 1b and 2b ) using density functional theory/time-dependent density functional theory for the first time. A comprehensive analysis of the geometric structures, molecular orbitals, and luminescence properties (including phosphorescence emission wavelengths and radiative and nonradiative decay processes) has been carried out. Our theoretical model highlights that complexes 1a and 2a embedded with H-bonds significantly promote the phosphorescence emission band blue-shifted and restrict molecular deformations compared with the corresponding 1b and 2b , which can provide helpful guidance to regulate and design several aspects of highly efficient blue phosphorescent emitters.     

Optimizing the monomer structure of polyhedral oligomeric silsesquioxane for ion transport in hybrid organic–inorganic block copolymers

Poly(ethylene oxide)-b-polyhedral oligomeric silsesquioxane (PEO–POSS) mixed with lithium bis(trifluoromethanesulfonyl)imide salt is a nanostructured hybrid organic–inorganic block copolymer electrolyte that may enable lithium metal batteries. The synthesis and characteristics of three PEO–POSS block copolymer electrolytes which only differ by their POSS silica cage substituents (ethyl, isobutyl, and isooctyl) is reported. Changing the POSS monomer structure results in differences in both thermodynamics and ion transport. All three neat polymers exhibit lamellar morphologies. Adding salt results in the formation of a disordered window which closes and gives way to lamellae at higher salt concentrations. The width of disordered window decreases with increasing length of the POSS alkyl chain substituent from ethyl to isobutyl and is absent in the isooctyl sample. Rheological measurements demonstrate good mechanical rigidity when compared with similar all-organic block copolymers. While salt diffusion coefficient and current ratio are unaffected by substituent length, ionic conductivity increases as the length of the alkyl chain substituent decreases: the ethyl substituent is optimal for ion transport. This is surprising because conventional wisdom suggests that ion transport occurs primarily in the PEO-rich domains, that is, ion transport should be unaffected by substituent length after accounting for the minor change in conducting phase volume fraction. © 2020 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2020 © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 363–371     

A simple sol–gel hydrothermal method for the synthesis of defective TiO2 nanocrystals with excellent visible-light photocatalytic activity

Research on Chemical Intermediates - Defective TiO2 nanocrystals (D-TiO2) were synthesized by a simple, mild and green sol–gel hydrothermal method. The as-prepared sample possesses a high...     

Toward Understanding the Enhanced Pseudocapacitive Storage in 3D SnS/MXene Architectures Enabled by Engineered Surface Reactions

The optimization of three-dimensional (3D) MXene-based electrodes with desired electrochemical performances is highly demanded. Here, a precursor-guided strategy is reported for fabricating the 3D SnS/MXene architecture with tiny SnS nanocrystals (≈5 nm in size) covalently decorated on the wrinkled Ti₃C₂T_x nanosheets through Ti−S bonds (denoted as SnS/Ti₃C₂T_x-O). The formation of Ti−S bonds between SnS and Ti₃C₂T_x was confirmed by extended X-ray absorption fine structure (EXAFS). Rather than bulky SnS plates decorated on Ti₃C₂T_x (SnS/Ti₃C₂T_x-H) by one-step hydrothermal sulfidation followed by post annealing, this SnS/Ti₃C₂T_x-O presents size-dependent structural and dynamic properties. The as-formed 3D hierarchical structure can provide short ion-diffusion pathways and electron transport distances because of the more accessible surface sites. In addition, benefiting from the tiny SnS nanocrystals that can effectively improve Na⁺ diffusion and suppress structural variation upon charge/discharge processes, the as-obtained SnS/Ti₃C₂T_x-O can generate pseudocapacitance-dominated storage behavior enabled by engineered surface reactions. As predicted, this electrode exhibits an enhanced Na storage capacity of 565 mAh g⁻¹ at 0.1 A g⁻¹ after 75 cycles, outperforming SnS/Ti₃C₂T_x-H (336 mAh g⁻¹), SnS (212 mAh g⁻¹), and Ti₃C₂T_x (104 mAh g⁻¹) electrodes.     

pH-Dependent Slipping and Exfoliation of Layered Covalent Organic Framework

Layered/two-dimensional covalent organic frameworks (2D COF) are crystalline porous materials composed of light elements linked by strong covalent bonds. Interlayer force is one of the main factors directing the formation of a stacked layer structure, which plays a vital role in the stability, crystallinity, and porosity of layered COFs. The as-developed new way to modulate the interlayer force of imine-linked 2D TAPB-PDA-COF (TAPB = 1,3,5-tris(4-aminophenyl)benzene, PDA = terephthaldehyde) by only adjusting the pH of the solution. At alkaline and neutral pH, the pore size of the COF decreases from 34 Å due to the turbostratic effect. Under highly acidic conditions (pH 1), TAPB-PDA-COF shows a faster and stronger turbostratic effect, thus causing the 2D structure to exfoliate. This yields bulk quantities of an exfoliated few/single-layer 2D COF, which was well dispersed and displayed a clear Tyndall effect (TE). Furthermore, nanopipette-based electrochemical testing also confirms the slipping of layers with increase towards acidic pH. A model of pH-dependent layer slipping of TAPB-PDA-COF was proposed. This controllable pH-dependent change in the layer structure may open a new door for potential applications in controlled gas adsorption/desorption and drug loading/releasing.     

Cyclic Bis-alkylidene Complexes of Titanium and Zirconium: Synthesis,Characterization, and Reaction

Transition-metal alkylidenes have exhibited wide applications in organometallic chemistry and synthetic organic chemistry, however, cyclic Schrock-carbene-like bis-alkylidenes of group 4 metals with a four-electron donor from an alkylidene have not been reported. Herein, the synthesis and characterization of five-membered cyclic bis-alkylidenes of titanium ( 4 a , b ) and zirconium ( 5 a , b ) are reported, as the first well-defined group 4 metallacyclopentatrienes, by two-electron reduction of their corresponding titana- and zirconacyclopentadienes. DFT analyses of 4 a show a four-electron donor (σ-donation and π-donation) from an alkylidene carbon to the metal center. The reaction of 4 a with N,N′-diisopropylcarbodiimide (DIC) leads to the [2+2]-cycloaddition product 6 . Compound 4 a reacted with CO, affording the oxycyclopentadienyl titanium complex 7 . These reactivities demonstrate the multiple metal–carbon bond character. The reactions of 4 a or 5 a with cyclooctatetraene (COT) or azobenzene afforded sandwich titanium complex 8 or diphenylhydrazine-coordinated zirconacyclopentadiene 9 , respectively, which exhibit two-electron reductive ability.