Copper-Catalyzed [3 + 2] Annulation of O-Acyl Oximes with 4-Sulfonamidophenols for the Synthesis of 5-Sulfonamidoindoles and 2-Amido-5-sulfonamidobenzofuran-3(2H)-ones.

A copper-catalyzed [3 + 2] annulation of O-acyl oximes with 4-sulfonamidophenols is developed. The advantage of this method lies in the concurrent double activation of two substrates to form nucleophilic enamines and electrophilic quinone monoimines. The substituent on the α-carbon of O-acyl oxime determines two different reaction pathways, thereby leading to the selective generation of 5-sulfonamidoindoles and 2-amido-5-sulfonamidobenzofuran-3(2H)-ones.

Cost-Effective Rechargeable Magnesium Battery Based on a Fluorinated Alkoxyaluminate Electrolyte and a Carbonyl Polymer Cathode.

Rechargeable magnesium batteries (RMBs) are one of the most promising "post-lithium" battery technologies, but the electrochemical performance is still far from expectation due to the sluggish reaction kinetics of divalent Mg2+ ions. Herein, we report a low-cost, high-performance Mg-organic battery based on the combination of a fluorinated alkoxyaluminate electrolyte and a carbonyl polymer cathode material. First, the one-pot synthesized Mg[Al(HFIP)4]2 (HFIP = hexafluoro-2-propanol) is proved superior to the Mg[B(HFIP)4]2 analogue in both Mg anode compatibility and electrochemical window, as the electrolyte salt in the G2-DME (G2 = diethylene glycol dimethyl ether; DME = 1,2-dimethoxyethane) mixture solvent. Second, a simple wet grinding method is proposed to effectively improve the dispersion uniformity of the poly(benzoquinone-pyrrole) (PBQPy) active material in the cathode. Third, the elaborate Mg-PBQPy battery exhibits superior electrochemical performance within 0.4-3.0 V, including a high reversible capacity of 197 mA h g-1, a high average discharge voltage of 1.6 V, and a high capacity retention of 71% after 500 cycles. Finally, based on various electrochemical analysis and ex situ characterization results, we propose a general microscopic structure evolution model to reveal the electrochemical behaviors of carbonyl polymer cathode in RMBs, including the swelling of polymer active material, trapping of Mg2+ ions, and reversible redox reaction.

Facile Synthesis of Diazaanthraquinone Dimers as High-Capacity Organic Cathode Materials for Rechargeable Lithium Batteries.

Organic cathode materials (OCMs) have tremendous potential to construct sustainable and highly efficient batteries beyond conventional Li-ion batteries. Thereinto, quinone/pyrazine hybrids show significant advantages in material availability, energy density, and cycling stability. Herein, we propose a facile method to synthesize quinone/pyrazine hybrids, i.e., the condensation reaction between ortho-diamine and bromoacetyl groups. Based on it, we have successfully synthesized three 1,4-diazaanthraquinone (DAAQ) dimers, including 2,2'-bi(1,4-diazaanthraquinone) (BDAAQ) with an exceptional theoretical capacity of 512 mAh g-1 based on the eight-electron reaction. It can be fully utilized in Li batteries in a wide voltage range of 0.8-3.8 V, at the cost of inferior cycling stability. In an optimal voltage range of 1.4-3.8 V, BDAAQ exhibits one of the best comprehensive electrochemical performances for small-molecule OCMs, including a high specific capacity of 366 mAh g-1, an average discharge voltage of 2.26 V, as well as a respectable capacity retention of 59% after 500 cycles. Moreover, the in-depth investigations reveal the redox reaction mechanisms based on C═O and C═N groups as well as the capacity fading mechanisms based on dissolution-redeposition behaviors. In brief, this work provides an instructive synthesis method and mechanism understanding of high-performance OCMs based on a quinone/pyrazine hybrid structure.

A Dual-Functional Perovskite-Based Photodetector and Memristor for Visual Memory.

The imitation of human visual memory demands the multifunctional integration of light sensors similar to the eyes, and image memory, similar to the brain. Although humans have already implemented electronic devices with visual memory functions, these devices require a combination of various components and logical circuits. However, the combination of visual perception and high-performance information storage capabilities into a single device to achieve visual memory remains challenging. In this study, inspired by the function of human visual memory, a dual-functional perovskite-based photodetector (PD) and memristor are designed to realize visual perception and memory capacities. As a PD, it realizes an ultrahigh self-powered responsivity of 276 mA W-1 , a high detectivity of 4.7 × 1011  Jones (530 nm; light intensities, 2.34 mW cm-2 ), and a high rectification ratio of ≈100 (±2 V). As a memristor, an ultrahigh on/off ratio (≈105 ), an ultralow power consumption of 3 × 10-11  W, a low setting voltage (0.15 V), and a long retention time (>7000 s) are realized. Moreover, the dual-functional device has the capacity to perceive and remember light paths and store data with good cyclic stability. This device exhibits perceptual and cyclic erasable memory functions, which provides new opportunities for mimicking human visual memory in future multifunctional applications.

Copper-catalyzed [3+2] annulation of O-acyl ketoximes with 2-aryl malonates for the synthesis of 3-aryl-4-pyrrolin-2-ones.

A copper-catalyzed [3+2] annulation of O-acyl ketoximes with 2-aryl malonates for the concise synthesis of 3-aryl-4-pyrrolin-2-ones has been developed. The advantage of this method lies in the use of O-acyl oximes as an internal oxidant to generate the nucleophilic enamines and electrophilic p-quinone methides concurrently. The subsequent nucleophilic addition undergoes selectively on the α-C of malonates.

Copper-Catalyzed Annulation of O-Acyl Oximes with Cyclic 1,3-Diones for the Synthesis of 7,8-Dihydroindolizin-5(6H)-ones and Cyclohexanone-Fused Furans.

A copper-catalyzed annulation of O-acyl oximes with cyclic 1,3-diones has been developed for the concise synthesis of 7,8-dihydroindolizin-5(6H)-ones and cyclohexanone-fused furans through the substituent-controlled selective radical coupling process. 2-Alkyl cyclic 1,3-diones undergo C-C radical coupling, while 2-unsubstituted cyclic 1,3-diones undergo C-O radical coupling.

Constructing Extended π-Conjugated Molecules with o-Quinone Groups as High-Energy Organic Cathode Materials.

Although organic cathode materials with sustainability and structural designability have great potential for rechargeable lithium batteries, the dissolution issue presents a huge challenge to meet the demands of cycling stability and energy density simultaneously. Herein, we have designed and successfully synthesized two novel small-molecule organic cathode materials (SMOCMs) by the same innovative route, namely 7,14-diazabenzo[a]tetracene-5,6,8,13-tetraone (DABTTO) and 7,9,16,18-tetraazadibenzo[a,l]pentacene-5,6,8,14,15,17-hexaone (TADBPHO). The integrated p-quinone, o-quinone, and pyrazine groups provide these SMOCMs with attractive theoretical capacities of 473 and 568 mAh g-1 based on 6- and 10-electron reactions, respectively, which were almost fully utilized within 0.8-3.8 V vs Li+/Li. The extended aromatic nucleus of TADBPHO makes it much less soluble than DABTTO and thus able to achieve the highest level of cycling stability (66% @ 500th cycle) for SMOCMs in addition to the exceptional energy density (364 mAh g-1 × 2.56 V = 932 Wh kg-1) within 1.5-3.8 V. In addition to the excellent electrochemical performance, the redox reaction and capacity fading mechanisms have been also investigated in detail. The novel approach to construct extended π-conjugated molecules with o-quinone groups is enlightening for the development of high-energy and stable OCMs for future efficient and sustainable energy storage devices.

Revisiting the Structure and Electrochemical Performance of Poly(o-phenylenediamine) as an Organic Cathode Material.

Poly(o-phenylenediamine) (PoPDA) has been recognized as a low-cost electroactive organic material and studied as a cathode for aqueous zinc batteries or as an anode for nonaqueous lithium batteries. However, there remains a lot of confusion about its synthesis, structure, and electrochemical application. Especially, the previously studied PoPDA samples were mostly synthesized at room temperature, which were proved by us to be just a dimer, that is, 2,3-diaminophenazine (DAPZ). By various characterization methods including elemental analysis and mass spectrometry, we verified that the product synthesized at high temperature, PoPDA-H, was a polymer based on DAPZ as the structural repeat unit and with some imperfect substitutes (OH and NH3+CH3COO-). Based on the reversible redox reaction of phenazine units and the stable polymer structure within 1.3-3.8 V vs Li+/Li, PoPDA-H was more appropriate to be applied as a cathode rather than as an anode for lithium batteries. It achieved a high energy density of 490 Wh kg-1 (2.12 V × 231 mAh g-1) at 50 mA g-1 and a high cycling stability (79%@1000th cycle) at 500 mA g-1, both of which were comparable to previously reported expensive pyrazine- and carbonyl-based polymers. This work clarifies many misunderstandings of PoPDA, which is important to its further development toward practical application in energy-storage devices.

An improved X-means and isolation forest based methodology for network traffic anomaly detection.

Anomaly detection in network traffic is becoming a challenging task due to the complexity of large-scale networks and the proliferation of various social network applications. In the actual industrial environment, only recently obtained unlabelled data can be used as the training set. The accuracy of the abnormal ratio in the training set as prior knowledge has a great influence on the performance of the commonly used unsupervised algorithms. In this study, an anomaly detection algorithm based on X-means and iForest is proposed, named X-iForest, which clusters the standard Euclidean distance between the abnormal points and the normal cluster centre to achieve secondary filtering by using X-means. We compared X-iForest with seven mainstream unsupervised algorithms in terms of the AUC and anomaly detection rates. A large number of experiments showed that X-iForest has notable advantages over other algorithms and can be well applied to anomaly detection of large-scale network traffic data.

Synthesis of Anti-poisoning Spinel Mn-Co-C as Cathode Catalysts for Low-Temperature Anion Exchange Membrane Direct Ammonia Fuel Cells.

Low-temperature anion exchange membrane direct ammonia fuel cells (AEM-DAFCs) have emerged as a potential power source for transportation applications with the recognition that liquid ammonia is a carbon-free hydrogen carrier and facilitates storage, refill, and distribution. However, ammonia crossover from the cell anode to cathode can decrease the fuel efficiency, drop the voltage, and poison the cathode catalysts. In this work, the Mn-Co spinel on three different carbon supports [BP2000, Vulcan XC-72R, and multiwalled carbon nanotubes (MWCNTs)] has been successfully synthesized and demonstrated a high oxygen reduction reaction (ORR) activity with good ammonia tolerance. The structure and composition of the obtained Mn-Co-C catalysts were characterized by high-angle annular dark-field scanning transmission electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. All three catalysts exhibit superb ammonia tolerance, and Mn-Co-BP2000 demonstrates the highest ORR activity, even better than the commercial Pt-C in the presence of ammonia. When paired with the commercial PtIr-C anode, the Mn-Co-BP2000 cathode improved the peak power density of single cells from 100.1 mW cm-2 for the Pt-C cathode to 128.2 mW cm-2 under a 2 bar backpressure in both electrodes at 80 °C. All the results have manifested that Mn-Co-BP2000 is a good cathode catalyst for low-temperature AEM-DAFCs.

Ultrafast Speed, Dark Current Suppression, and Self-Powered Enhancement in TiO2-Based Ultraviolet Photodetectors by Organic Layers and Ag Nanowires Regulation.

TiO2-based photodetectors (PDs) have been hotspots in recent years for their excellent thermal stabilities and optoelectronic performance under ultraviolet (UV) light. However, the high dark current caused by defects in TiO2 films has limited the detectivity (D) of these PDs. Here, the dark current of a TiO2-based PD was effectively reduced by 3 magnitudes (from 0.1 mA to 20 nA) and D was increased to 1.2 × 1014 Jones by introducing PC71BM. The TiO2/PC71BM heterojunction also made the PD self-powered, and by further introducing an interface layer of PEDOT:PSS and finely optimizing the electrode Ag nanowires (Ag NWs), the self-powered responsivity (R) was increased to 33 mA/W. Ultrafast rise/decay times (129 ns/1 ms at -1 V and 0.06 s/<1 µs at 0 V) were achieved. This work successfully applied an organic-inorganic heterojunction, an organic interface, and Ag NWs to suppress the dark current and enhance the self-powered photocurrent/R of inorganic PDs, providing a feasible strategy in high-performance UV PDs' design.

A Co-Precursor Approach Coupled with a Supercritical Modification Method for Constructing Highly Transparent and Superhydrophobic Polymethylsilsesquioxane Aerogels.

Polymethylsilsesquioxane (PMSQ) aerogels obtained from methyltrimethoxysilane (MTMS) are well-known high-performance porous materials. Highly transparent and hydrophobic PMSQ aerogel would play an important role in transparent vacuum insulation panels. Herein, the co-precursor approach and supercritical modification method were developed to prepare the PMSQ aerogels with high transparency and superhydrophobicity. Firstly, benefiting from the introduction of tetramethoxysilane (TMOS) in the precursor, the pore structure became more uniform and the particle size was decreased. As the TMOS content increased, the light transmittance increased gradually from 54.0% to 81.2%, whereas the contact angle of water droplet decreased from 141° to 99.9°, ascribed to the increase of hydroxyl groups on the skeleton surface. Hence, the supercritical modification method utilizing hexamethyldisilazane was also introduced to enhance the hydrophobic methyl groups on the aerogel's surface. As a result, the obtained aerogels revealed superhydrophobicity with a contact angle of 155°. Meanwhile, the developed surface modification method did not lead to any significant changes in the pore structure resulting in the superhydrophobic aerogel with a high transparency of 77.2%. The proposed co-precursor approach and supercritical modification method provide a new horizon in the fabrication of highly transparent and superhydrophobic PMSQ aerogels.

Ultrasonic Remove of Particle Aggregation in Carbon Based Counter Electrodes for Dye-Sensitized Solar Cells.

Low-cost carbon materials (carbon black and graphite power) were applied as substitution of platinum (Pt) in counter electrodes (CEs) for dye-sensitized solar cells (DSSCs). Three fabrication methods, such as ball-milled, pulp-refined, and ultrasonic-crushed, were applied to remove the particle aggregation in the carbon pastes. Then the carbon based pastes were printed on fluorine-doped transparent conducting oxide (FTO) glasses, used as the CEs for DSSCs. Under illumination of 100 mW/cm2, DSSCs with ultrasonic-crushed CEs (U-CEs) show an energy conversion efficiency of 3.57%, which reach to 65.38% of that with conventional sputtered platinum CEs (5.46%). In addition, U-CEs exhibit a higher catalytic activity and a faster charge transfer rate toward the reduction of I-3 to I-.

Cobalt Salt as Efficient Dopant for Spiro-MeOTAD in Cesium-Containing Planar Perovskite Solar Cells.

The chemical doping is an effective strategy to improve the charge transport property of hole transport material (HTM). Herein, tris(2-(1H-pyrazol-1-yl)pyridine]cobalt(III) (FK102) doped 2,2,7,7-tetrakis(N, N-di-p-methoxyphenylamine)-9,9-spirobifluorene (spiro-MeOTAD) as HTM for semi-transparent cesium-containing planar perovskite solar cell (Cs0.1MA0.9PbI3) is demonstrated. Incorporating FK102 realizes efficient doping, which improves the mobility of HTM from 3.948 × 10-3 m2V-1s-1 to 2.22 × 10-2 m2V-1s-1, which is 5.6 times enhancement. As a result, the power conversion efficiency (PCE) is largely improved from 7.58% to 10.09% due to the improved hole transport and extraction.

Simulation of the tensile properties of silica aerogels: the effects of cluster structure and primary particle size.

A new two-level model is proposed to investigate the relationship between the mechanical properties and microstructure of silica aerogels. This two-level model consists of the particle-particle interaction model and the cluster structure model. The particle-particle interaction model is proposed to describe interactions between primary particles, in which the polymerization reaction between primary particles is considered. The cluster structure model represents the geometrical structure of silica aerogels, and it is established using a modified diffusion-limited colloid aggregation (DLCA) algorithm. This two-level model is used to investigate the tensile behavior of silica aerogels based on the discrete element method (DEM). The numerical results show that the primary particle size has significant effects on the elastic modulus and tensile strength of silica aerogels. Moreover, the power-law relationships between tensile properties and aerogel density are dependent on the variation of the primary particle radius with density. The present results can explain the difference among different experimental exponents to a certain extent. In comparison with experimental data within a wide density range, this two-level model provides good quantitative estimations of the elastic modulus and tensile strength of silica aerogels after the size effects of the primary particle are considered. This paper provides a fundamental understanding of the relationship between the mechanical properties and microstructure of silica aerogels. The two-level model can be extended to study the mechanical properties of other aerogels and aerogel composites.