Photoredox‐Catalyzed Isomerization of Highly Substituted Allylic Alcohols by C−H Bond Activation

Photoredox‐catalyzed isomerization of γ‐carbonyl‐substituted allylic alcohols to their corresponding carbonyl compounds was achieved for the first time by C?H bond activation. This catalytic redox‐neutral process resulted in the synthesis of 1,4‐dicarbonyl compounds. Notably, allylic alcohols bearing tetrasubstituted olefins can also be transformed into their corresponding carbonyl compounds. Density functional theory calculations show that the carbonyl group at the γ‐position of allylic alcohols are beneficial to the formation of their corresponding allylic alcohol radicals with high vertical electron affinity, which contributes to the completion of the photoredox catalytic cycle.     

In Situ Electropolymerization Enables Ultrafast Long Cycle Life and High‐Voltage Organic Cathodes for Lithium Batteries

Organic cathode materials have attracted extensive attention because of their diverse structures, facile synthesis, and environmental friendliness. However, they often suffer from insufficient cycling stability caused by the dissolution problem, poor rate performance, and low voltages. An in situ electropolymerization method was developed to stabilize and enhance organic cathodes for lithium batteries. 4,4′,4′′‐Tris(carbazol‐9‐yl)‐triphenylamine (TCTA) was employed because carbazole groups can be polymerized under an electric field and they may serve as high‐voltage redox‐active centers. The electropolymerized TCTA electrodes demonstrated excellent electrochemical performance with a high discharge voltage of 3.95 V, ultrafast rate capability of 20 A g^?1, and a long cycle life of 5000 cycles. Our findings provide a new strategy to address the dissolution issue and they explore the molecular design of organic electrode materials for use in rechargeable batteries.     

高氯废水化学需氧量分析方法综述

对高氯废水化学需氧量分析方法进行归纳和综述。常用的高氯废水化学需氧量分析方法有氯气校正容量法、降氯密闭消解分光光度法以及高温氧化总有机碳系数换算法等。其中氯气校正容量法操控要求较高,分析耗时较长,不适用于大批量样品同步分析;降氯密闭消解分光光度法灵敏度高,但在降氯过程中增加了重金属盐硫酸汞的用量,分析成本较高,易产生二次污染,且对样品的均质性要求较高;高温氧化总有机碳系数换算法操作便捷、抗干扰能力强,但是换算系数易随不同来源、不同组分的样品发生波动,数据可比性需要通过实验验证。经过梳理归纳,明确各种分析方法的特点和适用范围,为研究人员选择合适的分析方法或进一步开展相关的方法研究提供参考。     

高效液相色谱–串联质谱法同时测定土壤中8种杀菌剂残留

建立高效液相色谱-串联质谱法同时测定土壤中戊唑醇、腈菌唑、腈苯唑、氟硅唑、三唑酮、丙环唑、烯唑醇、苯醚甲环唑8种杀菌剂残留量的方法。采用QuEChERS样品前处理方法对土壤样品进行提取、净化和富集,用电喷雾离子源、正负离子扫描,以多反应监测(MRM)模式进行定性和定量分析。在优化的实验条件下,8种杀菌剂的质量浓度在0.01~0.50 mg/L范围内与色谱峰面积均成良好的线性关系,相关系数均大于0.995,方法检出限为0.005~0.010 mg/kg。样品平均加标回收率为85.6%~102.2%,测定结果的相对标准偏差为4.6%~13.2%(n=5)。该方法操作简便,灵敏度和准确度高,满足土壤中戊唑醇等8种杀菌剂残留量的测定要求。     

基于氦离子化气相色谱法测定微量氧、氮的影响因素

探讨氦离子化气相色谱法测定样品中微量氧、氮含量的影响因素。采用控制变量法,对色谱柱温度、进样流量、进样管道环境及极化电压等因素对微量氧、氮测定结果的影响进行讨论和分析。结果表明,当色谱柱温度为25~45℃时,色谱柱对氧、氮吸附量最小;当进样流量不小于70 mL/min时,微量氧、氮测定结果受外界干扰最小;当极化电压为80~160 V时,氧、氮具有最佳的响应值;初次测定样品中微量氧、氮含量时,需使进样管道表面吸附的氧、氮处于饱和状态,以便获得理想的测定结果。讨论的结果可为氦离子化气相色谱法测定相关样品中微量氧、氮含量时提供技术参考。     

Ruthenium coordination preferences in imidazole‐containing systems revealed by electrospray ionization mass spectrometry and molecular modeling: Possible cues for the surprising stability of the Ru (III)/tris (hydroxymethyl)‐aminomethane/imidazole complexes

Ruthenium is a platinoid that exhibits a range of unique chemical properties in solution, which are exploited in a variety of applications, including luminescent probes, anticancer therapies, and artificial photosynthesis. This paper focuses on a recently demonstrated ability of this metal in its +3 oxidation state to form highly stable complexes with tris (hydroxymethyl)aminomethane (H₂NC(CH₂OH)₃, Tris‐base or T) and imidazole (Im) ligands, where a single Ru^III cation is coordinated by two molecules of each T and Im. High‐resolution electrospray ionization mass spectrometry (ESI MS) is used to characterize Ru^III complexes formed by placing a Ru^II complex [(NH₃)₅Ru^IICl]Cl in a Tris buffer under aerobic conditions. The most abundant ionic species in ESI MS represent mononuclear complexes containing an oxidized form of the metal, ie, [X_nRu^IIIT₂ – 2H]⁺, where X could be an additional T (n = 1) or NH₃ (n = 0‐2). Di‐ and tri‐metal complexes also give rise to a series of abundant ions, with the highest mass ion representing a metal complex with an empirical formula Ru₃C₂₄O₂₁N₆H₆₆ (interpreted as cyclo(T₂RuO)₃, a cyclic oxo‐bridged structure, where the coordination sphere of each metal is completed by two T ligands). The empirical formulae of the binuclear species are consistent with the structures representing acyclic fragments of cyclo(T₂RuO)₃ with addition of various combinations of ammonia and dioxygen as ligands. Addition of histidine in large molar excess to this solution results in complete disassembly of poly‐nuclear complexes and gives rise to a variety of ionic species in the ESI mass spectrum with a general formula [Ru^IIIHis_kT_m (NH₃)_n ? 2H]⁺, where k = 0 to 2, m = 0 to 3, and n = 0 to 4. Ammonia adducts are present for all observed combinations of k and m, except k = m = 2, suggesting that [His₂Ru^IIIT₂ ? 2H]⁺ represents a complex with a fully completed coordination sphere. The observed cornucopia of Ru^III complexes formed in the presence of histidine is in stark contrast to the previously reported selective reactivity of imidazole, which interacts with the metal by preserving the RuT₂ core and giving rise to a single abundant ruthenium complex (represented by [Im₂Ru^IIIT₂ ? 2H]⁺ in ESI mass spectra). Surprisingly, the behavior of a hexa‐histidine peptide (HHHHHH) is similar to that of a single imidazole, rather than a single histidine amino acid: The RuT₂ core is preserved, with the following ionic species observed in ESI mass spectra: [HHHHHH·(Ru^IIIT₂)_m ? (3m‐1)H]⁺ (m = 1‐3). The remarkable selectivity of the imidazole interaction with the Ru^IIIT₂ core is rationalized using energetic considerations at the quantum mechanical level of theory.     

Photoactivated Fluorescence Enhancement in F,N‐Doped Carbon Dots with Piezochromic Behavior

Photoactivation in CdSe/ZnS quantum dots (QDs) on UV/Vis light exposure improves photoluminescence (PL) and photostability. However, it was not observed in fluorescent carbon quantum dots (CDs). Now, photoactivated fluorescence enhancement in fluorine and nitrogen co‐doped carbon dots (F,N‐doped CDs) is presented. At 1.0 atm, the fluorescence intensity of F,N‐doped CDs increases with UV light irradiation (5 s–30 min), accompanied with a blue‐shift of the fluorescence emission from 586 nm to 550 nm. F,N‐doped CDs exhibit photoactivated fluorescence enhancement when exposed to UV under high pressure (0.1 GPa). F,N‐doped CDs show reversible piezochromic behavior while applying increasing pressure (1.0 atm to 9.98 GPa), showing a pressure‐triggered aggregation‐induced emission in the range 1.0 atm–0.65 GPa. The photoactivated CDs with piezochromic fluorescence enhancement broadens the versatility of CDs from ambient to high‐pressure conditions and enhances their anti‐photobleaching.     

Enabling High‐Voltage Lithium Metal Batteries by Manipulating Solvation Structure in Ester Electrolyte

Lithium metal is an ideal electrode material for future rechargeable lithium metal batteries. However, the widespread deployment of metallic lithium anode is significantly hindered by its dendritic growth and low Coulombic efficiency, especially in ester solvents. Herein, by rationally manipulating the electrolyte solvation structure with a high donor number solvent, enhancement of the solubility of lithium nitrate in an ester‐based electrolyte is successfully demonstrated, which enables high‐voltage lithium metal batteries. Remarkably, the electrolyte with a high concentration of LiNO₃ additive presents an excellent Coulombic efficiency up to 98.8 % during stable galvanostatic lithium plating/stripping cycles. A full‐cell lithium metal battery with a lithium nickel manganese cobalt oxide cathode exhibits a stable cycling performance showing limited capacity decay. This approach provides an effective electrolyte manipulation strategy to develop high‐voltage lithium metal batteries.     

Endogenous Nanoparticles Strain Perovskite Host Lattice Providing Oxygen Capacity and Driving Oxygen Exchange and CH4 Conversion to Syngas

Particles dispersed on the surface of oxide supports have enabled a wealth of applications in electrocatalysis, photocatalysis, and heterogeneous catalysis. Dispersing nanoparticles within the bulk of oxides is, however, synthetically much more challenging and therefore less explored, but could open new dimensions to control material properties analogous to substitutional doping of ions in crystal lattices. Here we demonstrate such a concept allowing extensive, controlled growth of metallic nanoparticles, at nanoscale proximity, within a perovskite oxide lattice as well as on its surface. By employing operando techniques, we show that in the emergent nanostructure, the endogenous nanoparticles and the perovskite lattice become reciprocally strained and seamlessly connected, enabling enhanced oxygen exchange. Additionally, even deeply embedded nanoparticles can reversibly exchange oxygen with a methane stream, driving its redox conversion to syngas with remarkable selectivity and long term cyclability while surface particles are present. These results not only exemplify the means to create extensive, self‐strained nanoarchitectures with enhanced oxygen transport and storage capabilities, but also demonstrate that deeply submerged, redox‐active nanoparticles could be entirely accessible to reaction environments, driving redox transformations and thus offering intriguing new alternatives to design materials underpinning several energy conversion technologies.     

Solvent‐Free Self‐Assembly for Scalable Preparation of Highly Crystalline Mesoporous Metal Oxides

Mesoporous metal oxides (MMOs) have been demonstrated great potential in various applications. Up to now, the direct synthesis of MMOs is still limited to the solvent induced inorganic‐organic self‐assembly process. Here, we develop a facile, general, and high throughput solvent‐free self‐assembly strategy to synthesize a series of MMOs including single‐component MMOs and multi‐component MMOs (e.g., doped MMOs, composite MMOs, and polymetallic oxide) with high crystallinity and remarkable porous properties by grinding and heating raw materials. Compared with the traditional solution self‐assembly process, the avoidance of solvents in this method not only greatly increases the yield of target products and synthesis efficiency, but also reduces the environmental pollution and the consumption of cost and energy. We believe the presented approach will pave a new avenue for scalable production of advanced mesoporous materials for various applications.