Current Issue http://sioc-journal.cn/Jwk_hxxb EN-US http://sioc-journal.cn/Jwk_hxxb/EN/0567-7351/current.shtml http://sioc-journal.cn/Jwk_hxxb 0567-7351 http://sioc-journal.cn/Jwk_hxxb/EN/10.6023/A22090408 Bridged isoquinoline derivatives play an important role in various bioactive molecules. The cascade dearomatizative annulation of isoquinolinium salts with bis-nucleophiles is a straightforward strategy to construct bridged isoquinoline skeletons because isoquinolinium ions have two electrophilic sites. However, the reported examples only focused on the synthesis of 1,3-bridged cyclic skeletons. In the previous work, it was reported the first synthesis of 1,4-bridged dihydroisoquinolin-3-ones from isoquinolinium salts and 4-hydroxycoumarins. When cyclic 1,3-diketones were used instead of 4-hydroxycoumarins, isoquinoline-1,3,4(2H)-triones, instead of the expected 1,4-bridged dihydroisoquinolin-3-ones, were unexpectedly yielded. Experimental evidence by high resolution mass spectroscopy supports that the generation of isoquinoline-1,3,4(2H)-triones was initiated via an O-nucleophilic substitution of the cyclic 1,3-diketone, followed by an elimination of the 2-bromo-cyclic 1,3-diketone to give intermediate 4-bromoisoquinolin-3(2H)-one, which subsequently underwent dual hydrolyses and aerobic oxidations. Based on this mechanism, the O-nucleophilic substitution of cyclic 1,3-diketones was successfully inhibited by the addition of a catalytic amount of trifluoromethanesulfonic acid (TfOH). The desired 1,4-bridged dihydroisoquinolin-3-ones were then obtained. This method provides a facile access to 1,4-bridged isoquinoline skeletons under mild reaction conditions (33 examples). The general procedure is as following: under an argon atmosphere, a 5 mL Schlenk flask was charged with isoquinolinium salt 6 (0.2 mmol), phenyliodine(III) diacetate (0.6 mmol), KBr (0.2 mmol), H₂O (3.6 μL), and dry dichloroethane (2 mL). The mixture was continually stirred at room temperature until 6 was consumed as indicated by thin-layer chromatography (TLC). TfOH (5 μL) and cyclic 1,3-diketone 7 (0.4 mmol) were sequentially added. The reaction mixture was heated at 50 ℃ in the oil bath until the intermediate was consumed as indicated by TLC, then cooled to room temperature, diluted with water (5 mL), and extracted with ethyl acetate (5 mL×3). The combined organic layer was washed with brine, dried over Na₂SO₄, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel (petroleum ether/EtOAc as the eluent) to give the 1,4-bridged product 8.

]]> http://sioc-journal.cn/Jwk_hxxb/EN/10.6023/A22090399 Counterfeiting is a growing global problem, which could be effectively curbed by developing novel anti- counterfeiting materials. Responsive photonic crystals (RPCs) are one kind of promising materials for anti-counterfeiting because of their vivid rainbow effect and stimulus responsive discoloration performance. In addition to RPCs, photoluminescence materials with intrinsic emission color, can also be used for anti-counterfeiting. As one of the most common photoluminescence materials, quantum dots (QDs) exhibit narrow emission width, saturated color, and tunable emission due to the quantum confinement effect. Despite RPCs and QDs with tunable colors have shown great potential for anti-counterfeiting and information encryption, most of their color variations are actuated by a single mode, which hinders their advanced applications. In this paper, taking advantage of the dynamic continuous magnetochromic property of Fe₃O₄@SiO₂ (M) superparamagnetic colloids in organic solvents and the photoluminescence behavior of CdTe quantum dots (CdTe QDs) under the excitation of UV light, a M/QDs/EG/PDMS composite film with multimodal color-switching function for anti-counterfeiting was fabricated by encapsulating ethylene glycol (EG) droplets containing M colloids and CdTe QDs in elastomeric polydimethylsiloxane (PDMS). The internal structure, optical and mechanical properties were characterized by optical microscope, fiber optical spectrometer, fluorescence spectrometer, digital camera and tensile testing machine. The results showed that the composite film exhibited bright structural color instantaneously under application of a magnetic field. The diffraction wavelength of the composite film displayed a continuous red or blue shift with the decrease or increase of the magnetic field intensity, and the red or blue shifting range could reach 145 nm. Moreover, the composite film could emit bright fluorescence under the excitation of UV light and exhibited good photoluminescence function. In addition, the composite film showed good elasticity and the percentage of breaking elongation of the film could reach 132%, which provides a foundation for the application of anti-counterfeiting by attaching on the surface of different materials. Furthermore, through the patterned design, a patterned anti-counterfeiting film with rapid response to color change, reversible pattern hiding, and various color changes can be prepared, which is conducive to its application in the field of information encryption and advanced anti-counterfeiting.

]]> http://sioc-journal.cn/Jwk_hxxb/EN/10.6023/A22070304 Photocatalysts play an important role in industrial wastewater treatment. So far, the photocatalysts of photo- Fenton degradation of water pollutants include metal-organic frameworks, two-dimensional layered hydroxides, and transition metal oxides. Among them, transition metal oxides have become a research hotspot because of their easy availability of metal ions, stability and non-toxicity during degradation. In particular, ferric oxide (Fe₂O₃) has the advantages of wide visible light absorption range, good optical response and high thermodynamic stability, which is considered to be a promising semiconductor photocatalyst. Herein, in this work, Fe₂O₃ of two morphologies, flakes (namely 300-Fe₂O₃ and 400-Fe₂O₃) and spheres (namely 500-Fe₂O₃ and 600-Fe₂O₃) were obtained by calcinating sheet-like iron-based metal-organic gel (Fe-MOG) synthesized with Fe³⁺ and 1,10-phenanthroline-2,9-dicarboxylic acid in one step at room temperature, and were used for photo-Fenton degradation of rhodamine B (Rh B). The crystal structure and optoelectronic properties of the as-prepared Fe₂O₃ were characterized by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy elemental mapping (EDS), the UV-Vis diffuse reflectance spectra (UV-Vis DRS) and electrochemical impedance spectroscopy (EIS). Among them, 400-Fe₂O₃ with carbon skeleton structure exhibited excellent electron transport performance and high photogenerated charge separation efficiency, endowing it with remarkable catalytic activity. In addition, the existence of oxygen vacancy in 400-Fe₂O₃ promoted the formation of Fe²⁺, which was the key factor to enhance the photo-Fenton activity. 400-Fe₂O₃ could photocatalytically degrade 97.5% Rh B within 60 min under neutral conditions, and the degradation efficiency was retained 85.3% after five consecutive cycles. Under visible light irradiation, a part of the photogenic electron (e^‒) generated by 400-Fe₂O₃ reacted with O₂ to generate superoxide anion radical (•O₂^‒), the other part of e^‒ reduced Fe³⁺ to Fe²⁺ in situ. Subsequently, Fe²⁺ can catalyze the decomposition of H₂O₂ into hydroxyl radicals (•OH), and participated in the photodegradation of Rh B together with •O₂^‒. This work provides a new idea for the development and design of semiconductor photocatalysts with excellent catalytic activity.

]]> http://sioc-journal.cn/Jwk_hxxb/EN/10.6023/A22080375 In order to solve the problems of low adsorption efficiency and slow precipitation rate for powdered activated carbon (PAC) in the process of removing hydrophilic organics with low molecular weight, this study successfully prepare a kind of powdered activated carbon matrix composites (PACMC) by reaction of mixed powdered activated carbon (PAC), potassium humate (HS), and polyaluminium chloride (PACl) raw materials in oily sewage as the purification adsorbent. We confirmed the micro-morphology and chemical composition of PACMC by scanning electron microscopy-X-ray energy dispersive spectroscopy (SEM-EDS) and Fourier transform infrared spectroscopy (FT-IR), certifying that PACMC was synthesized by chemical reaction of PAC, HS and PACl. PACMC has layered porous structure and functional groups, which is beneficial to the transport, diffusion and chemical adsorption of oily sewage molecules. The static adsorption experiments were carried out to investigate the adsorption properties of organic pollutants in oily sewage by PACl, PAC and PACMC respectively. The results showed that the adsorption capacity of PACMC for organic pollutants in oily sewage was 2~3 times as high as that of PAC and PACl (q_e=23.04 mg•g^‒1, C₀=300 mg•L^‒1). When the adsorption time reached 120 min, the binding of the active site on PACMC and organic pollutants in oily sewage had basically reached saturation (q_e=23.04 mg•g^‒1, C₀=300 mg•L^‒1). The pH value of the solution has a significant effect on the adsorption of organic pollutants in oily sewage by PACMC, and the best adsorption effect was observed at pH=3 (q_e=27.6 mg•g^‒1, C₀=300 mg•L^‒1). The adsorption of organic pollutants in oily sewage by PACMC can be well described by the pseudo-second-order kinetics. The kinetic fitting results revealed that the adsorption process involved several steps, where the chemical adsorption and intra-particle diffusion both played the important roles. The isothermal adsorption data were in accordance with the Dubinin-Radushkevich model, which indicated that the adsorption mechanism was chemical adsorption. Therefore, the mechanism of PACMC adsorption of oily sewage included chemical binding/chelation effect, hydrophobic effect and electrostatic adsorption effect.

]]> http://sioc-journal.cn/Jwk_hxxb/EN/10.6023/A22080380 The organic semiconducting materials feature various sources, tailorable chemical structures, low-temperature device fabrication and good compatibility with plastic substrates, largely expanding the functions and applications of electronic devices. However, electron-transporting (n-type) organic semiconductors lag far behind their hole-transporting (p-type) counterpart in terms of molecular diversity, carrier mobility as well as air stability, preventing the development in the ambipolar transistors, p-n junctions and organic complementary circuits. Amidation and imidization of aromatic systems can enhance electron affinity values significantly, thus opening up the possibility to achieve high-performance n-type organic semiconductors. The recent research progress in n-type organic small-molecule and polymeric semiconducting materials including naphthalene diimides, perylene diimides, diketopyrrolopyrroles, isoindigos and other amide/imide derivatives is summarized in this review. From the viewpoint of molecular design, we deeply discuss how the molecular structures alter molecular frontier orbital levels, intermolecular forces, aggregation structures, device stability and electrical characteristics. Finally, we address several key points for further exploration in this field.

]]> http://sioc-journal.cn/Jwk_hxxb/EN/10.6023/A22090385 Nonaqueous magnesium secondary batteries have attracted tremendous attention owing to their natural abundance, low cost, high theoretical volumetric specific capacities of 3833 mAh/cm³, and free of dendrite formation. However, the high polarity of Mg²⁺ ion results in the strong electrostatic interaction between Mg²⁺ ions and the anions of cathode materials, which makes it difficult to realize reversible insertion and de-insertion of Mg²⁺ ion in most cathode materials used in lithium ion batteries. At present, the research of cathode materials for magnesium secondary batteries is mainly focused on inorganic compounds. Unfortunately, such cathode materials suffer from problems of working at low current density, slow reaction kinetics, and complicated synthesis process. In comparison, organic electrode materials have been recognized as promising electrode materials for electrochemical energy storage systems because organic materials composed of naturally abundant chemical elements of C, H, O, N, S, etc., can be easily synthesized from renewable resources with low-cost at mild conditions. More importantly, organic materials with chemical diversity and structural flexibility can be purposefully synthesized. What’s more, the capacity, oxidation/reduction potentials, solubility, electron transfer rates, and mechanical properties can be regulated by introducing various groups or heteroatoms. Furthermore, compared to inorganic electrode materials with sluggish kinetics, organic electrode materials usually store ions through ion coordination mechanism, which is not limited by the type and size of ions and can be applied to different energy storage systems such as lithium ion batteries, sodium ion batteries, potassium ion batteries, multivalent-ion batteries, and supercapacitors. Herein, the recent progress of various organic- based materials for nonaqueous magnesium secondary batteries is summarized and the general redox mechanism is presented. Finally, the problems and challenges, resolution strategies and future development directions of organic electrode materials are briefly summarized and discussed.

]]> http://sioc-journal.cn/Jwk_hxxb/EN/10.6023/A22080362 The achievement of the “double carbon target” requires precise policy guidance and the development of alternative clean energy. In recent years, hydrogen energy has attracted more and more attention due to its rich sources, high heating value, low-carbon, and diverse application scenarios. Among the traditional hydrogen production technologies, fossil fuel hydrogen production technology is the most widely used, but the larger energy consumption and greenhouse gas emission are caused by its hydrogen production reaction process. Photocatalytic water splitting can transfer solar energy to hydrogen, which can store solar energy in the form of chemical energy. This strategy not only can utilize solar energy to generate hydrogen, but also can combine hydrogen with CO₂ to produce high-value chemicals. Moreover, this technology can reduce carbon dioxide emissions and realize the comprehensive utilization of hydrocarbon resources. The research progress of photocatalytic (PC) hydrogen production, photoelectrocatalytic (PEC) hydrogen production and photovoltaic electrocatalytic (PV-EC) hydrogen production are reviewed. The basic principles of related technologies are explained, and the key materials in hydrogen production technology are introduced. The related researches of solar to hydrogen (STH) conversion efficiency and material stability are summarized in detail during the development of three hydrogen production technologies. Finally, the key challenges and future development directions are discussed and prospected for the three solar hydrogen production technologies.

]]> http://sioc-journal.cn/Jwk_hxxb/EN/10.6023/A22080347 As an indispensable part of today's society, the research on the manufacturing and packaging process of chips is particularly important. In the conventional chip manufacturing and packaging process, physical vapor deposition, chemical vapor deposition, electroplating, hot pressing and other processes are widely used. These processes are not only complicated and expensive, but also have some disadvantages that hinder the development of chip technology. The electroless deposition process has the advantages of mild conditions, low equipment cost, simple steps, and strong conformal ability. Researchers have paid attention to and studied its application in the field of chip manufacturing and packaging. Firstly, the principle and types of chip electroless deposition, activation, pre-grafting treatment methods and key materials were introduced in this paper. Secondly, to illustrate the advantages of electroless deposition in chip manufacturing, the main process of conductive interconnection in chip manufacturing were introduced, the conventional manufacturing process and electroless deposition manufacturing process in the interconnection process in chip, 3D packaging through silicon via (TSV) process, redistribution layer, bump, and bonding process were compared. Thirdly, the research progress of electroless deposition using in in-chip including barrier layer, seed layer, gap filling, substrate, bump is summarized and discussed; the composition and function of the plating solution, mechanism of additives in super electroless deposition gap filling are also discussed. Finally, the future application of electroless plating technology in the new generation of chip manufacturing is prospected.

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