Copper-Catalyzed Aerobic Oxidation for the Amination of Benzoxazole Under Air

A practical copper-catalyzed aerobic oxidation for the amination of benzoxazole with secondary amine has been discovered. This reaction has proved to be effective to a variety of amines with lower catalyst loading amount, and only oxygen in air is required to facilitate this transformation. A copper-catalyzed/amine-induced ring opening of the benzoxazole and recyclization mechanism was also proposed.     

氯化铜参与的制备对称二硫化合物的新方法

报道了在正丁基锂和氯化铜条件下氧化硫醇生成对称的二硫化合物的新方法.所实施的十个例子都具有很高的产率.     

Copper as a Robust and Transparent Electrocatalyst for Water Oxidation

Copper metal is in theory a viable oxidative electrocatalyst based on surface oxidation to Cu^III and/or Cu^IV, but its use in water oxidation has been impeded by anodic corrosion. The in situ formation of an efficient interfacial oxygen‐evolving Cu catalyst from Cu^II in concentrated carbonate solutions is presented. The catalyst necessitates use of dissolved Cu^II and accesses the higher oxidation states prior to decompostion to form an active surface film, which is limited by solution conditions. This observation and restriction led to the exploration of ways to use surface‐protected Cu metal as a robust electrocatalyst for water oxidation. Formation of a compact film of CuO on Cu surface prevents anodic corrosion and results in sustained catalytic water oxidation. The Cu/CuO surface stabilization was also applied to Cu nanowire films, which are transparent and flexible electrocatalysts for water oxidation and are an attractive alternative to ITO‐supported catalysts for photoelectrochemical applications.     

2-取代苯并噁唑衍生物的合成及生物活性

疏基苯并噁唑;2-取代苯并噁唑衍生物的合成及生物活性     

Borate Buffer as a Key Player in Cu-Based Homogeneous Electrocatalytic Water Oxidation

Borate buffer was found to have both structural and functional roles within a low-cost tri-copper electrocatalyst for homogeneous water oxidation that exhibits a high turnover frequency of 310 s⁻¹. The borate buffer was shown to facilitate the catalytic activity by both bridging the three Cu ions and participating in O−O bond formation. Phosphate and acetate buffers did not show such roles, making borate a unique player in this catalytic system.     

多金属氧酸盐催化的水氧化研究进展

氢气以其清洁无污染、燃烧值高等优点成为未来最具潜力的可再生能源之一,而清洁生产氢气的最佳选择之一即为裂解水. 利用太阳能模拟光合作用实现水的全分解产生氢气和氧气是目前最为理想的能源转化方式,并且已经引起了众多研究者的关注. 水分解的半反应之一--水氧化反应由于其过程复杂,一直是制约水分解的瓶颈. 所以寻找高效、稳定的水氧化催化剂便成为了突破该瓶颈的关键. 多金属氧酸盐是一类以前过渡金属氧簇为基本单元形成的多金属氧簇化合物. 由于多金属氧酸盐在物理、化学性质方面具有无法比拟的特性,使得其在催化、药物、纳米科技和材料科学等方面已被广泛地应用. 多金属氧酸盐的全无机配体可很好地抵御水氧化反应的强氧化性环境,故将其作为水氧化催化剂越来越引起研究者们的注意,并且已有多种多金属氧酸盐被设计为水氧化催化剂. 本文详细介绍了各种不同过渡金属取代的多金属氧酸盐水氧化催化剂的研究进展.     

On-Demand Synthesis of H2O2 by Water Oxidation for Sustainable Resource Production and Organic Pollutant Degradation

H₂O₂ is a versatile and environmentally friendly chemical involved in water treatment, such as advanced oxidation processes. Anthraquinone oxidation is widely used for large-scale production of H₂O₂, which requires significant energy input and periodic replacement of the carrier molecule. H₂O₂ production should be customized considering the specific usage scenario. Electrochemical synthesis of H₂O₂ can be adopted as alternatives to traditional method, which avoids concentration, transportation, and storage processes. Herein, we identified Bi₂WO₆:Mo as a low-cost and high-selectivity choice from a series of Bi-based oxides for H₂O₂ generation via two-electron water oxidation reaction. It can continuously provide H₂O₂ for in situ degradation of persistent pollutants in aqueous solution. Clean energy from H₂ can also be produced at the cathode. This kind of water splitting producing sustainable resources of H₂O₂ and H₂ is an advance in environmental treatment and energy science.     

Straightforward Oxidation of a Copper Substrate Produces an Underwater Superoleophobic Mesh for Oil/Water Separation

A superhydrophilic and underwater superoleophobic Cu(OH)₂‐covered mesh with micro‐ and nanoscale hierarchical composite structures is successfully fabricated through a one‐step chemical oxidation of a smooth‐copper mesh. Such mesh, without any further modification, can selectively separate water from oil/water mixtures with high separation efficiency, and possess excellent stability even after 60 uses. This method provides a simple, low‐cost, and scalable strategy for the purification of oily wastewater.     

Practical Synthesis of Aromatic Dithiocarbamates

Oxidation-sensitive N,N-diaryl dithiocarbamates (DTCs) are synthesized in good yields by the generation of metal amide salts from N-benzoyl precursors, followed by addition of CS₂. para-Substituted diphenylamines are prepared by electrophilic aromatic substitution of diphenylbenzamide and saponification. Deacylation of electron-rich species such as bis(p-dimethylaminophenyl)benzamide is challenging because of the oxidative sensitivity of the anionic intermediate but could be achieved in good yield by using n-BuLi to generate a hemiaminal adduct, prior to acidification. The N,N-diaryl DTCs are stable as alkali salts and can be used to produce densely packed monolayers on gold surfaces.     

Two Trinuclear CuII Complexes: Effect of Phosphonate Ligand on the Magnetic Property and Electrocatalytic Reactivity for Water Oxidation

Two trinuclear copper phosphonate complexes, [Cu₃(pda)₃(tBuPO₃)]?2(Et₃NH) ( 1 ) and [Cu₃(pda)₃(PhPO₃)]?2(Et₃NH) ( 2 ), have been synthesized and investigated by a combination of X‐ray crystallography, PXRD, magneto‐ and electrochemistry, EPR, in situ UV‐vis spectroelectrochemistry and DLS. The two complexes feature almost identical crystal structures, the anions of which are both supported by pda^2? and tBuPO₃^2?/PhPO₃^2? groups, bridging three five‐coordinated Cu^II atoms to form a crown‐like structure. This is the first time that trinuclear copper phosphonate complexes have been isolated and characterized. Magnetic susceptibility measurements reveal that complexes 1 and 2 both display overall ferromagnetic characters, but with different exchange interactions between the metal ions within the two clusters. The electrocatalytic activity for water oxidation of the two complexes was preliminarily investigated, which reveals that both of the two complexes can carry out electrocatalytic water oxidation in a neutral system owing to the introduction of phosphonate ligands into the complexes, with a TOF of about 0.82 s^?1 ( 1 ) and 0.58 s^?1 ( 2 ), respectively. We propose that the presence of phosphonate ligands may affect the magnetic property and catalytic activity of the complexes.     

Synthesis of metal-doped tio2 nanotubes and their catalytic performance for low-temperature co oxidation

Summary Gold-, gold and copper-doped TiO₂ nanotubes (Au/TiO₂ NTs, Au-Cu/TiO₂ NTs) are prepared by impregnation-reduction method. The doped nanotubes are characterized by powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). Their catalytic performance for CO oxidation is also examined     

A Bio‐inspired Cu4O4 Cubane: Effective Molecular Catalysts for Electrocatalytic Water Oxidation in Aqueous Solution

Inspired by the cubic Mn₄CaO₅ cluster of natural oxygen‐evolving complex in Photosystem II, tetrametallic molecular water oxidation catalysts, especially M₄O₄ cubane‐like clusters (M=transition metals), have aroused great interest in developing highly active and robust catalysts for water oxidation. Among these M₄O₄ clusters, however, copper‐based molecular catalysts are poorly understood. Now, bio‐inspired Cu₄O₄ cubanes are presented as effective molecular catalysts for electrocatalytic water oxidation in aqueous solution (pH 12). The exceptional catalytic activity is manifested with a turnover frequency (TOF) of 267 s^?1 for [(L_Gly‐Cu)₄] at 1.70 V and 105 s^?1 for [(L_Glu‐Cu)₄] at 1.56 V. Electrochemical and spectroscopic study revealed a successive two‐electron transfer process in the Cu₄O₄ cubanes to form high‐valent Cu^III and Cu^IIIO^. intermediates during the catalysis.     

甘油作溶剂、微波促进苯并噁唑类化合物的合成

苯并噁唑类化合物在医药、化工、有机合成等方面应用广泛,其合成具有重要意义。以邻氨基苯酚与苯甲醛类化合物为原料,物质量的比为1∶1,用绿色试剂甘油做溶剂,微波加热促进合成苯并噁唑类化合物。聚焦微波功率为20W,反应温度110℃。在此条件下,以80%~91%的产率得到相应的目标产物。该方法具有溶剂无污染、反应条件温和、操作简便、产率较高、反应底物易得,反应快速简便等优点,为现有方法提供了有益和重要的补充。     

2－（4－联苯基）苯并噁唑衍生物的合成及其光学性能

合成了７种２－（４－联苯基）苯并　唑衍生物，其中５种为未知物．经元素分析、ＩＲ、ＵＶ、１ＨＮＭＲ和ＭＳ表征，并测定了上述化合物的荧光发射光谱、荧光量子产率和激光转换效率，结果发现５，７－二异丙基－２－（４－联苯基）苯并　唑的激光转换效率高，具有应用价值．