A LaCl3-based lithium superionic conductor compatible with lithium metal.

Inorganic superionic conductors possess high ionic conductivity and excellent thermal stability but their poor interfacial compatibility with lithium metal electrodes precludes application in all-solid-state lithium metal batteries1,2. Here we report a LaCl3-based lithium superionic conductor possessing excellent interfacial compatibility with lithium metal electrodes. In contrast to a Li3MCl6 (M = Y, In, Sc and Ho) electrolyte lattice3-6, the UCl3-type LaCl3 lattice has large, one-dimensional channels for rapid Li+ conduction, interconnected by La vacancies via Ta doping and resulting in a three-dimensional Li+ migration network. The optimized Li0.388Ta0.238La0.475Cl3 electrolyte exhibits Li+ conductivity of 3.02 mS cm-1 at 30 °C and a low activation energy of 0.197 eV. It also generates a gradient interfacial passivation layer to stabilize the Li metal electrode for long-term cycling of a Li-Li symmetric cell (1 mAh cm-2) for more than 5,000 h. When directly coupled with an uncoated LiNi0.5Co0.2Mn0.3O2 cathode and bare Li metal anode, the Li0.388Ta0.238La0.475Cl3 electrolyte enables a solid battery to run for more than 100 cycles with a cutoff voltage of 4.35 V and areal capacity of more than 1 mAh cm-2. We also demonstrate rapid Li+ conduction in lanthanide metal chlorides (LnCl3; Ln = La, Ce, Nd, Sm and Gd), suggesting that the LnCl3 solid electrolyte system could provide further developments in conductivity and utility.

Dimensional and Doping Engineering of Chiral Perovskites with Enhanced Spin Selectivity for Green Emissive Spin Light-Emitting Diodes.

Chiral perovskites play a pivotal role in spintronics and optoelectronic systems attributed to their chiral-induced spin selectivity (CISS) effect. Specifically, they allow for spin-polarized charge transport in spin light-emitting diodes (LEDs), yielding circularly polarized electroluminescence at room temperature without external magnetic fields. However, chiral lead bromide-based perovskites have yet to achieve high-performance green emissive spin-LEDs, owing to limited CISS effects and charge transport. Herein, we employ dimensional regulation and Sn2+-doping to optimize chiral bromide-based perovskite architecture for green emissive spin-LEDs. The optimized (PEA)x(S/R-PRDA)2-xSn0.1Pb0.9Br4 chiral perovskite film exhibits an enhanced CISS effect, higher hole mobility, and better energy level alignment with the emissive layer. These improvements allow us to fabricate green emissive spin-LEDs with an external quantum efficiency (EQE) of 5.7% and an asymmetry factor |gCP-EL| of 1.1 × 10-3. This work highlights the importance of tailored perovskite architectures and doping strategies in advancing spintronics for optoelectronic applications.

α-BaF2 Nanoparticle Substrate-Enabled γ-CsPbI3 Heteroepitaxial Growth for Efficient and Bright Deep-Red Light-Emitting Diodes.

All-inorganic CsPbI3 perovskite is attractive for deep-red light-emitting diodes (LEDs) because of its excellent carrier mobility, high color purity, and solution processability. However, the high phase transition energy barrier of optically active CsPbI3 black phase hinders the fabrication of efficient and bright LEDs. Here, we report a novel α-BaF2 nanoparticle substrate-promoted solution-processable heteroepitaxial growth to overcome this hindrance and obtain high-quality optically active γ-CsPbI3 thin films, achieving efficient and bright deep-red LEDs. We unravel that the highly exposed planes on the α-BaF2 nanoparticle-based heteroepitaxial growth substrate have a 99.5% lattice matching degree with the (110) planes of γ-CsPbI3. This ultrahigh lattice matching degree initiates solution-processed interfacial strain-free epitaxial growth of low-defect and highly oriented γ-CsPbI3 thin films on the substrate. The obtained γ-CsPbI3 thin films are uniform, smooth, and highly luminescent, based on which we fabricate efficient and bright deep-red LEDs with a high peak external quantum efficiency of 14.1% and a record luminance of 1325 cd m-2.

Spectrally Stable and Efficient Pure Red CsPbI3 Quantum Dot Light-Emitting Diodes Enabled by Sequential Ligand Post-Treatment Strategy.

Metal halide perovskites are promising semiconductors for next-generation light-emitting diodes (LEDs) due to their high luminance, excellent color purity, and handily tunable band gap. However, it remains a great challenge to develop perovskite LEDs (PeLEDs) with pure red emission at the wavelength of 630 nm. Herein, we report a spectrally stable and efficient pure red PeLED by employing sequential ligand post-treated CsPbI3 quantum dots (QDs). The synthesized CsPbI3 QDs with a size of ∼5 nm are treated in sequential steps using the ligands of 1-hydroxy-3-phenylpropan-2-aminium iodide (HPAI) and tributylsulfonium iodide (TBSI), respectively. The CsPbI3 QD films exhibit improved optoelectronic properties, which enables the fabrication of a pure red PeLED with a peak external quantum efficiency (EQE) of 6.4% and a stable EL emission centered at the wavelength of 630 nm. Our reported sequential ligand post-treatment strategy opens a new route to improve the stability and efficiency of PeLEDs based on QDs.

Thermochromic Phosphors Based on One-Dimensional Ionic Copper-Iodine Chains Showing Solid-State Photoluminescence Efficiency Exceeding 99 .

Thermochromic phosphors are intriguing materials for realizing thermochromic behaviors of light-emitting diodes. Here a highly luminescent and stable thermochromic phosphor based on one-dimensional Cu4 I6 (4-dimethylamino-1-ethylpyridinium)2 is reported. This unique ionic copper-iodine chain-based hybrid exhibits near-unity photoluminescence efficiency owing to the through-space charge-transfer character of relevant electronic transitions. More importantly, an alternative mechanism of thermochromic phosphorescence was unraveled, supported by a first principles simulation of concerted copper atom migration in the copper-iodine chain. Furthermore, we successfully fabricate a bright thermochromic light-emitting diode using this Cu4 I6 (4-dimethylamino-1-ethylpyridinium)2 thermochromic phosphor. Our reported flexible ionic copper-iodine chain-based thermochromic luminescent material represents a new type of cost-effective functional phosphor.

Blow-Spinning Enabled Precise Doping and Coating for Improving High-Voltage Lithium Cobalt Oxide Cathode Performance.

Lithium cobalt oxide (LiCoO2) possesses an attractive theoretical specific capacity (274 mAh g-1) and high discharge voltage (∼4.2 V vs Li+/Li). However, only a half of the theoretical capacity of LiCoO2 is available in commercialized lithium ion batteries because of the intrinsic structural instability and detrimental interface of LiCoO2 at the charging voltage over 4.2 V. Here, a facile blow-spinning synthetic method is developed to realize precise doping and simultaneous self-assembly coating of LiCoO2 particles, achieving a record performance among present LiCoO2 cathodes. Owing to the spatial confinement effect of microfibers fabricated by blow-spinning, homogeneously Mn and La doped in the LiCoO2 host and uniformly Li-Ti-O segregated at the LiCoO2 surface can be realized in every batch of samples. It is demonstrated that the Mn and La codoping can suspend the intrinsic instability and increase the Li+ diffusivity of the LiCoO2 host, and the Ti-based coating can stabilize the interface of LiCoO2 particles at the charging voltage up to 4.5 V. As a result, the obtained comodified LiCoO2 cathode shows the best rate performance (1.85 mAh cm-2 at 2C) and longest cycling stability under an areal capacity of 2.04 mAh cm-2 (83% capacity retention over 300 cycles at 0.3C), in comparison to previously reported LiCoO2 cathodes.

{Regularity of Gaseous Product Release During Direct Coal Liquefaction Residue Pyrolysis Process].

The pyrolysis characteristic of direct coal liquefaction residue (DCLR) was studied with thermo-gravimetric analyzer (TG) coupled with Fourier transform infrared spectrometry (FTIR), which is used to discuss the emitted regulation of gaseous product during pyrolysis process. This research shows that the weight loss process of DCLR can be divided into three stages: the first is before the temperature of 405.10 ℃; stage from 405.10 to 523.83 ℃ which is mainly pyrolysis of high boiling point of oil and asphaltene et al, and the total weight loss of DCLR can up to 40.27% when the temperature reaches 478.45 ℃, meanwhile the mass loss rate is maximum; after 523.83 ℃, the weight loss curve becomes gentle and the total weight loss of DCLR reaches 50.55% , which is due to the secondary cracking of residue and decomposition of mineral matter. The emitted process of gaseous product can be divided into three stages too: the first is the generation of H2O and CO2, the second stage mainly emitted CO2,CH4,CO,H2O and a small quantity of SO2, in which plenty of tar is generated from 458.4 to 791.9 ℃, the final stage mainly generated CO2, CO and H2O. CO2 mainly emitted owing to the cracking of oxygenheterocycle and OCO or other oxygen-containing groups, CO emitted due to cracking of ether and oxygenheterocycle, and CH4 generated as a result of cracking of aliphatic hydrocarbon.

[Study on the Spectrum Research on the Process of Oil Shale Pyrolysis].

Spectral analysis is an important and unique advantageous method for the analysis of matter's structure and composition. Aiming to discuss the change characteristic and evolution mechanism of mineral structure of oil shale, kerogen and sime-coke from oil shale pyrolysis under different temperature, the oil shale sample was obtained from Yaojie located in Gansu province, and the oil shale after pyrolysis experiments and acid washing were investigated and analyzed in detail withpolarizing microscope, Fourier transform spectroscopy (FTIR), X-Ray diffraction (XRD) and scanning electron microscope (SEM). The result shows that the mainly minerals of oil shale include quartz, clay and pyrite; kerogen is randomly distributed as mainly strip-shaped or blocky in inorganic minerals. The metamorphic degree of kerogen is higher, and rich in aliphatic structures and aromatic structures. Experiments of oil shale pyrolysis(temperature: 300～1 000 ℃, heating rate: 10 ℃·min-1) with temperature increasing, the composition of mineral begins to dissolve, kaolinite turning into metakaolinite with dehydration at 300 ℃, clay minerals such as kaolinite and montmorillonite completely turn into metakaolinite at 650 ℃. The silica-alumina spinel and amorphous SiO2, generated from the decomposition of metakaolinite at 1 000 ℃, and the amorphous SiO2, tends to react with iron mineral to form relative low melting point mixture on the semi-coke surfaces, such as FeO­Al2O3­SiO2. kerogen break down with increasing temperature, the infrared spectra intensity of C­H band of aliphatic and aromatic is reduced, while the intensity of C­C band aromatic is increased, and more carbonaceous residue as gully-shaped that remains in the mineral matrix after pyrolysis. These results are important for both the study of structure evolution of kerogen and minerals on the process of oil shale pyrolysis and will benefit for the subsequent processing and utilization of shale oil resource.

[Characterizing Structural Composition of Dissolved and Particulate Organic Matter from Sediment Pore Water in a Urban River Using Excitation-Emission Matrix Fluorescence with Self-Organizing Map].

Excitation-emission matrix (EEM) fluorescence with self-organizing map was applied to characterize structural composition and spatial distribution of dissolved (DOM) and particulate (POM) organic matter from sediment pore water in a typical urban river. Ten sediment pore water samples were collected from the mainstream of Baitabuhe River in Shenyang City of northeast China, along a human impact gradient, i. e. river source, rural and urban regions. DOM and POM were extracted from the pore water, and their EEM fluorescence spectra were measured. ƒ450/500 of DOM ranged from 1.82 to 1.91, indicating that DOM is mainly from microbial source; ƒ450/500 of POM ranged from 1.42 to 1.68, suggesting that POM derived from land. Four components were identified from DOM and POM fractions by self-organizing map, which included tyrosine-like, tryptophan-like, fulvic-like and humic-like matters. Tyrosine-like originated from fresh and less-degraded material with a high potential for oxida- tion, which was considered as representative components of DOM and POM. Tryptophan-like was associated with microbial byproduct-like material, and can indicate microbial activities. The abundance sum of all components in DOM is roughly 2 times more than that in POM. The mean relative abundance of tyrosine-like was more than 50%, while tryptophan-like was about 18.6%-23.1%. Abundance of fulvic-like was much more than that of humic-like, but they were only a small proportion of organic matter fractions. Based on principal component analysis, the characteristics of DOM and POM distinctly were distributed along river source, rural region and urban region, proving that the river was deeply influenced by human activity.

Modification strategies of lead halide perovskite nanocrystals for efficient and stable LEDs.

Lead halide perovskite nanocrystals (PNCs) hold immense promise in high-performance light-emitting diodes (LEDs) for future high-definition displays. Their adjustable bandgaps, vivid colors, and good carrier mobility are key factors that make them a potential game-changer. However, to fully harness their potential, the efficiency and long-term stability of PNCs-based light-emitting diodes (PNC-LEDs) must be enhanced. Recent material research results have shed light on the leading cause of performance decline in PNC-LEDs, which is ionic migration linked to surface defects and grain boundary imperfections. This review aims to present recent advancements in the modification strategies of PNCs, focusing on obtaining high-quality PNCs for LEDs. The PNC modification strategies are first summarized, including crystal structure regulation, nanocrystal size tuning, ligand exchange, and surface passivation. Then, the effects of these material design aspects on LED device performances, such as efficiency, brightness, and stability, are presented. Based on the efficient modification strategies, we propose promising material design insights for efficient and stable PNC-LEDs.

Short-branched alkyl sulfobetaine-passivated CsPbBr3 nanocrystals for efficient green light emitting diodes.

Inorganic cesium lead bromide nanocrystals (CsPbBr3 NCs) hold promising prospects for high performance green light-emitting diodes (LEDs) due to their exceptional color purity and high luminescence efficiency. However, the common ligands employed for passivating these indispensable NCs, such as long-chain organic ligands like oleic acid and oleylamine (OA/OAm), display highly dynamic binding and electronic insulating issues, thereby resulting in a low efficiency of the as-fabricated LEDs. Herein, we report a new zwitterionic short-branched alkyl sulfobetaine ligand, namely trioctyl(propyl-3-sulfonate) ammonium betaine (TOAB), to in situ passivate CsPbBr3 NCs via a feasible one-step solution synthesis, enabling efficiency improvement of CsPbBr3 NC-based LEDs. The zwitterionic TOAB ligand not only strengthened the surface passivation of CsPbBr3 NCs with a high photoluminescence quantum yield (PLQY) of 97%, but also enhanced the carrier transport in the fabricated CsPbBr3 NC thin films due to the short-branched alkyl design. Consequently, CsPbBr3 NCs passivated with TOAB achieved a green LED with an external quantum efficiency (EQE) of 7.3% and a maximum luminance of 5716 cd m-2, surpassing those of LEDs based on insulating long-chain ligand-passivated NCs. Our work provides an effective surface passivation ligand design to enhance the performance of CsPbBr3 NC-based LEDs.

[Iron-based Bimetallic Catalysts for Persulfate Activation to Remove Antibiotics in Water: A Review].

In recent years, antibiotic residues are commonly detected in a variety of water bodies, causing serious threat to water ecosystems and human health. The removal of antibiotic contaminants from water based on the advanced oxidation process of activated persulfate has become a hot research topic due to its strong oxidative properties, high selectivity, and wide pH applicability range. Iron-based bimetallic materials with low cost, high stability, and excellent catalytic performance can effectively activate persulfate, which makes up for the defects of being a single iron activator, such as easy deactivation, low efficiency, and producing secondary pollution easily. Three typical Fe-based bimetallic catalysts, namely spinel ferrite, Fe-based layered double hydroxides, and Fe-based Prussian blue analogues, were investigated and analyzed for their activation of persulfate for antibiotic degradation. Several intrinsic mechanisms of persulfate activation by Fe-based bimetallic catalysts are systematically discussed, including the generation of free radicals, singlet oxygen, and high-valent metals; the process of electron transfer; and the direct oxidation process of persulfate. Finally, the general degradation pathways of four typical antibiotics, including fluoroquinolones, sulfonamides, tetracyclines, and ß-lactam antibiotics, are summarized to act as a reference for future studies on the application of Fe-based bimetallic catalysts and their modifications, derivatives, and complexes in the activating technology of persulfate.

Efficient degradation of semi-coking wastewater in three-dimensional electro-Fenton by CuFe2O4 heterocatalyst.

Semi-coking wastewater contains a rich source of toxic and refractory compounds. Three-dimensional electro-Fenton (3D/EF) process used CuFe2O4 as heterocatalyst and activated carbon (AC) as particle electrode was constructed for degrading semi-coking wastewater greenly and efficiently. CuFe2O4 nanoparticles were prepared by coprecipitation method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy disperse spectroscopy (EDS). Factors like dosage of CuFe2O4, applied voltage, dosage of AC and pH, which effect COD removal rate of semi-coking waste water were studied. The results showed that COD removal rate reached to 80.9% by 3D/EF process at the optimum condition: 4 V, 0.3 g of CuFe2O4, 1 g of AC and pH = 3. Trapping experiment suggesting that hydroxyl radical (•OH) is the main active radical. The surface composition and chemical states of the fresh and used CuFe2O4 were analyzed by XPS indicating that Fe, Cu, and O species are involved into the 3D/EF process. Additionally, anode oxidation and the adsorption and catalysis of AC are also contributed to the bleaching of semi-coking waste water. The possible mechanisms of 3D/EF for degrading semi-coking waste water by CuFe2O4 heterocatalyst were proposed.

Planar defect-free pure red perovskite light-emitting diodes via metastable phase crystallization.

Solution-processable all-inorganic CsPbI3-xBrx perovskite holds great potential for pure red light-emitting diodes. However, the widely existing defects in this mixed halide perovskite markedly limit the efficiency and stability of present light-emitting diode devices. We here identify that intragrain Ruddlesden-Popper planar defects are primary forms of such defects in the CsPbI3-xBrx thin film owing to the lattice strain caused by inhomogeneous halogen ion distribution. To eliminate these defects, we develop a stepwise metastable phase crystallization strategy to minimize the CsPbI3-xBrx perovskite lattice strain, which brings planar defect-free CsPbI3-xBrx thin film with improved radiative recombination, narrowed emission band, and enhanced spectral stability. Using these high-quality thin films, we fabricate spectrally stable pure red perovskite light-emitting diodes, showing 17.8% external quantum efficiency and 9000 candela meter-2 brightness with color coordinates required by Rec. 2020.

Comparison of the photoconversion of para-chlorophenol under simulated sunlight and UV irradiation in ice.

The photochemistry of para-chlorophenol (4-CP) was studied under simulated sunlight (lambda > 300 nm) and UV irradiation by using a 125 W high-pressure mercury lamp with or without a hard glass as light source in an ice matrix. The experiments were carried out in a photochemical cold chamber reactor at -14 to -12 degrees C. The photoconversion rate, photoproducts and photoconversion mechanism of 4-CP were all inspected and compared. The results show that the 4-CP photoconversion obeys the first order kinetic model and its photoconversion rate is highly affected by the initial concentration of 4-CP, light intensity and water quality. It is found that the conversion rate of 4-CP under UV irradiation is higher than that under simulated sunlight irradiation. The intermediate products of 4-CP were characterized by GC-MS, HPLC-ESI-MS and HPLC techniques and the possible photoconversion mechanism was proposed accordingly. It is concluded that the mechanism and photoproducts of 4-CP photolysis in ice are different from those in water, and the photoproducts and photoconversion pathways of 4-CP in ice varied with different light sources.

[Realtime analysis of volatile organic compounds in source water by membrane inlet/time-of-flight mass spectrometry].

To establish an early-warning system for source water pollution accident, a membrane inlet/time-of-flight mass spectrometry technology was applied to a series of pollution scenarios as an online monitoring method for typical volatile organic compounds such as BTEX (benzene, toluene, ethylbenzene and xylene), substituted benzenes, and halogenated aliphatic hydrocarbons. It was shown that this technology can adequately meet the requirements of realtime analysis with short response time to the target organic pollutants (30-70 s for BTEX and 30 s for halogenated aliphatic hydrocarbons) in a linear detecting range of 3-4 magnitudes; the detection limits of BTEX and chlorobenzene were less than 10 microg x L(-1). The results of 52 simulated water pollution accidents in a 30-days' continuous monitoring indicated that the monitoring system was stable with the relative standard deviation less than 5%; the accuracy was acceptable and could be reduced to within 10% by periodical calibrations. Membrane inlet/time-of-flight mass spectrometry technology was proven to be available for the remote monitoring and early-warning of source water pollution accident.

Lithium Fluoride in Electrolyte for Stable and Safe Lithium-Metal Batteries.

Electrolyte engineering via fluorinated additives is promising to improve cycling stability and safety of high-energy Li-metal batteries. Here, an electrolyte is reported in a porous lithium fluoride (LiF) strategy to enable efficient carbonate electrolyte engineering for stable and safe Li-metal batteries. Unlike traditionally engineered electrolytes, the prepared electrolyte in the porous LiF nanobox exhibits nonflammability and high electrochemical performance owing to strong interactions between the electrolyte solvent molecules and numerous exposed active LiF (111) crystal planes. Via cryogenic transmission electron microscopy and X-ray photoelectron spectroscopy depth analysis, it is revealed that the electrolyte in active porous LiF nanobox involves the formation of a high-fluorine-content (>30%) solid electrolyte interphase layer, which enables very stable Li-metal anode cycling over one thousand cycles under high current density (4 mA cm-2 ). More importantly, employing the porous LiF nanobox engineered electrolyte, a Li || LiNi0.8 Co0.1 Mn0.1 O2 pouch cell is achieved with a specific energy of 380 Wh kg-1 for stable cycling over 80 cycles, representing the excellent performance of the Li-metal pouch cell using practical carbonate electrolyte. This study provides a new electrolyte engineering strategy for stable and safe Li-metal batteries.

Suppressing Auger Recombination in Cesium Lead Bromide Perovskite Nanocrystal Film for Bright Light-Emitting Diodes.

All-inorganic cesium lead halide perovskite colloidal nanocrystals are attractive for next-generation light-emitting diodes because of their high color purity, but the nonradiative Auger recombination in perovskite nanocrystal film limits the efficiency and brightness of the fabricated devices. Here, we introduce a surface-engineering process to exchange the original long-chain oleic acid/oleylamine ligands by the cerium-tributylphosphine oxide hybrid ligands to suppress nonradiative Auger recombination in CsPbBr3 NC film for bright and low-efficiency roll-off light-emitting diodes. Using ultrafast transient absorption and time-resolved photoluminescence spectroscopy, we demonstrate that the hybrid ligand passivation can efficiently remove surface trap states to enhance radiative recombination and homogenize the exciton concentration to suppress nonradiative Auger recombination in the CsPbBr3 nanocrystal thin film. Consequently, we fabricate a light-emitting diode with efficient charge injection into the CsPbBr3 nanocrystal emitting layer, achieving a pronounced improvement of electroluminescence with an external quantum efficiency from 5.5% to 9.1%. More importantly, the efficiency roll-off characteristics of high-brightness light-emitting diodes is effectively mitigated. Our reported hybrid ligand passivation suppressed Auger recombination strategy shows a great potential for fabricating high-brightness cesium lead halide perovskite light-emitting diodes.

The remediation of heavy metals contaminated sediment.

Heavy metal contamination has become a worldwide problem through disturbing the normal functions of rivers and lakes. Sediment, as the largest storage and resources of heavy metal, plays a rather important role in metal transformations. This paper provides a review on the geochemical forms, affecting factors and remediation technologies of heavy metal in sediment. The in situ remediation of sediment aims at increasing the stabilization of some metals such as the mobile and the exchangeable fractions; whereas, the ex situ remediation mainly aims at removing those potentially mobile metals, such as the Mn-oxides and the organic matter (OM) fraction. The pH and OM can directly change metals distribution in sediment; however oxidation-reduction potential (ORP), mainly through changing the pH values, indirectly alters metals distribution. Mainly ascribed to their simple operation mode, low costs and fast remediation effects, in situ remediation technologies, especially being fit for slight pollution sediment, are applied widely. However, for avoiding metal secondary pollution from sediment release, ex situ remediation should be the hot point in future research.

A fluorinated alloy-type interfacial layer enabled by metal fluoride nanoparticle modification for stabilizing Li metal anodes.

Using highly dispersed metal fluoride nanoparticles to construct a uniform fluorinated alloy type interfacial layer on the surface of Li metal anodes is realized by an ex situ solution chemical modification method. The fluorinated alloy-type interfacial layer can effectively inhibit the growth of undesirable Li dendrites while enhancing the performance of Li metal anodes.