Low-temperature formation and characterization of Cu2O nanoparticles in the binary gold alloys

Thermal analyses, using differential scanning calorimetry (DSC) and dilatometry, reveal an important anomaly at low temperature for Au-25 wt.% Cu composition after homogenization at 700°C during 2 hours under vacuum followed by heating up to 160°C before water quenching. This anomaly has been already observed and not explained. Surface characterization, using scanning electron microscopy (SEM), atomic force microscopy (AFM), and scanning tunneling microscopy (STM), exhibits a specific topography, consisting of a nanostructured surface. The precipitates of nanostructured particles are homogeneously scattered all over the surface for this 18-carat gold alloy. Moreover, X-ray photoelectron spectroscopy (XPS) shows that the composition of the observed particles corresponds to cuprous oxide phase (Cu₂O). The formation of such material can be explained by the diffusion of copper atoms from the lattice to the surface at 160°C. Pulsed radio-frequency glow discharge optical emission spectroscopy (RF GD-OES) further proves the proposed Cu₂O formation through a diffusion process. The appearance of such cuprous oxide nanoparticles on the Au-Cu alloy surface explains the low-temperature DSC and dilatometry anomaly and affects directly the surface electrical resistance at low temperature. These results might open a large gate for new ideas to investigate in catalytic, electronic, and antimicrobial activities.     

镍催化环丁酮肟酯与芳基锌试剂的Negishi偶联反应

发展了一种镍催化环丁酮肟酯和芳基锌试剂之间Negishi偶联的方法.镍既作为亚胺自由基的引发剂,也作为芳基锌试剂与烷基自由基偶联反应的催化剂在反应中起作用.本方法可避免使用剧毒的氰化物,且具有很广的底物适应性和官能团兼容性,因此可能是一种具有潜在吸引力的高效合成烷基腈类化合物的新策略.初步的机理研究显示,该反应极可能经历自由基历程.     

Novel palladium nanoparticles supported on β‐cyclodextrin@graphene oxide as magnetically recyclable catalyst for Suzuki–Miyaura cross‐coupling reaction with two different approaches in bio‐based solvents

A novel nanocatalyst was designed and prepared. Initially, the surface of magnetic graphene oxide (M‐GO) was modified using thionyl chloride, tris(hydroxymethyl)aminomethane and acryloyl chloride as linkers which provide reactive C═C bonds for the polymerization of vinylic monomers. Separately, β‐cyclodextrin (β‐CD) was treated with acryloyl chloride to provide a modified β‐CD. Then, in the presence methylenebisacrylamide as a cross‐linker, monomers of modified β‐CD and acrylamide were polymerized on the surface of the pre‐prepared M‐GO. Finally, palladium acetate and sodium borohydride were added to this composite to afford supported palladium nanoparticles. This fabricated nanocomposite was fully characterized using various techniques. The efficiency of this easily separable and reusable heterogeneous catalyst was successfully examined in Suzuki–Miyaura cross‐coupling reactions of aryl halides and boronic acid as well as in modified Suzuki–Miyaura cross‐coupling reactions of N‐acylsuccinimides and boronic acid in green media. The results showed that the nanocatalyst was efficient in coupling reactions for direct formation of the corresponding biphenyl as well as benzophenone derivatives in green media based on bio‐based solvents. In addition, the nanocatalyst was easily separable, using an external magnet, and could be reused several times without significant loss of activity under the optimum reaction conditions.     

Extended phase diagram of La1-xCaxMnO3 by interfacial engineering

The interfacial enhanced ferromagnetism in maganite/ruthenate system is regarded as a promising path to broaden the potential of oxide-based electronic device applications. Here, we systematically studied the physical properties of LaLa_1-xCa_xMnO₃/SrRuO₃ superlattices and compared them with the LaLa_1-xCa_xMnO₃ thin films and bulk compounds. The LaLa_1-xCa_xMnO₃/SrRuO₃ superlattices exhibit significant enhancement of Curie temperature (T_C) beyond the corresponding thin films and bulks. Based on these results, we constructed an extended phase diagram of LaLa_1-xCa_xMnO₃ under interfacial engineering. We considered the interfacial charge transfer and structural proximity effects as the origin of the interface-induced high T_C. The structural characterizations revealed a pronounced increase of B-O-B bond angle, which could be the main driving force for the high T_C in the superlattices. Our work inspires a deeper understanding of the collective effects of interfacial charge transfer and structural proximity on the physical properties of oxide heterostructures.     

Electrochemical sensing of H2O2 using cobalt oxide modified TiO2 nanotubes

Cobalt oxide (Co₃O₄) modified anatase titanium dioxide nanotubes (ATNTs) have been investigated for the electrochemical sensing of hydrogen peroxide (H₂O₂). ATNTs have been synthesized by a two-step anodization process. ATNTs were then modified with Co₃O₄ employing chemical bath deposition method. The structure and morphology of ATNTs and their modification with Co₃O₄ has been confirmed by X-ray diffraction by scanning electron microscopy. H₂O₂ sensing has been studied in 0.1 M PBS solution, by cyclic voltammetry and amperometry. Variation in the peak positions and current densities was observed with addition of H₂O₂ for Co₃O₄ modified ATNTs. Sensitivity and limit of detection improved with modification of ATNTs with Co₃O₄ with precursor concentration up to 0.8 M. However, at higher precursor concentrations sensitivity and limit of detection toward H₂O₂ deteriorated. Co₃O₄ Modified ATNTS using 0.8 M precursor concentration are comparatively more suitable for H₂O₂ sensing applications due to the optimum formation of Co₃O₄/ATNTs heterojunctions.     

Lithium–Lanthanide Bimetallic Metal–Organic Frameworks towards Negative Electrode Materials for Lithium-Ion Batteries

Novel lithium–lanthanide (Ln: cerium and praseodymium) bimetallic coordination polymers with formulas C₁₀H₂LnLiO₈ (Ln: Ce (CeLipma) and Pr (PrLipma)) and C₁₀H₃CeO₈ (Cepma) were prepared through a simple hydrothermal method. The three compounds were characterized by means of FTIR spectroscopy, X-ray diffraction, single-crystal X-ray diffraction, SEM, TEM, and X-ray photoelectron spectroscopy. The results of structural refinement show that they belong to triclinic symmetry and P space group with cerium (or praseodymium) and lithium cations, forming coordination bonds to oxygen atoms from different pyromellitic acid molecules, and leading to the construction of 3D structures. It is interesting to note that the frameworks exclude any coordination water and lattice water. As an electrode material for lithium-ion batteries, CeLipma exhibits a maximum capacity of 800.5 mAh g⁻¹ and a retention of 91.4 % after 50 cycles at a current density of 100 mA g⁻¹. The favorable electrochemical properties of the lanthanide coordination polymers show potential application prospects in the field of electrode materials.     

Boosting Conjugate Addition to Nitroolefins Using Lithium Tetraorganozincates: Synthetic Strategies and Structural Insights

We report the first transition metal catalyst- and ligand-free conjugate addition of lithium tetraorganozincates (R₄ZnLi₂) to nitroolefins. Displaying enhanced nucleophilicity combined with unique chemoselectivity and functional group tolerance, homoleptic aliphatic and aromatic R₄ZnLi₂ provide access to valuable nitroalkanes in up to 98 % yield under mild conditions (0 °C) and short reaction time (30 min). This is particularly remarkable when employing β-nitroacrylates and β-nitroenones, where despite the presence of other electrophilic groups, selective 1,4 addition to the C=C is preferred. Structural and spectroscopic studies confirmed the formation of tetraorganozincate species in solution, the nature of which has been a long debated issue, and allowed to unveil the key role played by donor additives on the aggregation and structure of these reagents. Thus, while chelating N,N,N’,N’-tetramethylethylenediamine (TMEDA) and (R,R)-N,N,N’,N’-tetramethyl-1,2-diaminocyclohexane (TMCDA) favour the formation of contacted-ion pair zincates, macrocyclic Lewis donor 12-crown-4 triggers an immediate disproportionation process of Et₄ZnLi₂ into equimolar amounts of solvent-separated Et₃ZnLi and EtLi.     

半导体纳米复合材料的制备及其光电催化CO2还原

本实验通过模拟植物光合作用,设计制备了新颖的光电联合催化池3D-ZnO/Ni BiVO4/FTO,用电化学沉积法制备了泡沫镍负载的ZnO纳米棒光电阴极和BiVO4光电阳极,以0.1 mol·L^−1 KHCO3水溶液作为电解质,1 mmol·L^−1曙红Y为光敏剂,在−0.6 V硅太阳电池的电压下光电催化还原CO2得到了乙醇、乙酸和甲醇,总产率22.5μmol·L^−1·h^−1·cm^−2。实现了将太阳能贮存为化学能并减少了空气中的CO2,加深了学生对绿色化学和植物Calvin循环机理的理解。