Phase Modulating of Cu–Ni Nanowires Enables Active and Stable Electrocatalysts for the Methanol Oxidation Reaction

The design and development of non-noble metal alternatives with superior performance and promising long-term stability that is comparable or even better than those of noble-metal-based catalysts is a significant challenge. Here, we report the thermal-induced phase engineering of non-noble-metal-based nanowires with superior electrochemical activity and stability for the methanol oxidation reaction (MOR) under alkaline conditions. The optimized Cu–Ni nanowires deliver an unprecedented mass activity of 425 mA mg⁻¹, which is 4.3 times higher than that of the untreated one. Detailed catalytic investigations show that the enhanced performance is due to the large active area, the increased number of active sites (NiOOH), and fast methanol electrooxidation kinetics. In addition, the generated hollow feature in the nanowires provides a unique void space to release the volume expansion, where the activity can be maintained for 5 h without a distinct activity decay. The present work emphasizes the importance of precisely phase modulating of nanomaterials for the design of non-noble metal electrocatalysts towards the MOR, which opens up a new pathway for the design of cost-effective electrocatalysts with promising activity and long-term stability.     

Topological and Steric Constraints to Stabilize Heteroleptic Copper(I) Complexes Combining Phenanthroline Ligands and Phosphines

Heteroleptic copper(I) complexes combining phenanthroline derivatives (NN) and chelating bisphosphine ligands (PP) are an important class of luminescent materials for various applications. Although thermodynamically stable, [Cu(NN)(PP)]⁺ derivatives are also kinetically unstable. As a result, a dynamic ligand-exchange reaction is often observed in solution, leading to a dynamic mixture of heteroleptic and homoleptic complexes. To prevent the formation of the homoleptic species, macrocyclic phenanthroline ligands have been used for the preparation of [Cu(NN)(PP)]⁺ pseudorotaxanes. The topological constraint resulting from the macrocyclic structure of the NN ligand drives the thermodynamic equilibrium towards the exclusive formation of the heteroleptic complex as long as the macrocycle is large and flexible enough to allow for the threading of the PP ligand. Conversely, when the threading is prevented by steric constraints, unprecedented copper(I) complexes with a trigonal coordination geometry are obtained. These results are summarized in the present concept article.     

Catalytic Generation and Chemoselective Transfer of Nucleophilic Hydrides from Dihydrogen

Copper(I)–N-heterocyclic-carbene (NHC) complexes enabled the catalytic generation of nucleophilic hydrides from dihydrogen (H₂) and their subsequent transfer to allylic chlorides. The highly chemoselective catalyst displayed no concomitant hydrogenation reactivity; in fact, the terminal double bond formed in the hydride transfer remained intact. Switching to deuterium gas (D₂) allowed for regioselective monodeuteration with excellent isotope incorporation.     

零维到三维结构中三核铜自旋阻挫簇单元的磁构关系和反对称交换

量子自旋液体是最近几年刚被人们证实除铁磁体、反铁磁体之外的第三种磁性类型,因其有望解释高温超导的运行机制、改变计算机硬盘信息存储方式而在物理、材料等领域备受关注。自旋阻挫作为量子自旋液体的最小单元可能是解开量子自旋液体诸多问题的钥匙,所以在磁学、电学研究领域再一次成为人们研究的热点。基于文献报道的三核铜配合物[Cu3(μ3-OH)(μ-OPz)3(NO3)2(H2O)2]·CH3OH(1),我们合成了三维金属有机框架配合物{[Ag(HOPz)Cu3(μ3-OH)(NO3)3(OPz)2Ag(NO3)]·6H2O}n(2)(HOPz=甲基(2-吡嗪基)酮肟),并从自旋阻挫的角度对二者磁性质进行对比和详细分析。磁化率数据表明自旋间有很强的反铁磁相互作用和反对称交换。通过包含各向同性和反对称交换的哈密顿算符对两者磁学数据进行拟合并研究其磁构关系,所获最佳拟合参数为:配合物1:Jav=-426 cm^-1,g⊥=1.83,g∥=2.00;配合物2:Jav=-401 cm^-1,g⊥=1.85,g∥=2.00。     

Can a Procedure for the Growth of Single-layer Graphene on Copper be used in Different Chemical Vapor Deposition Reactors?

In the last decade, catalytic chemical vapor deposition (CVD) has been intensively explored for the growth of single-layer graphene (SLG). Despite the scattering of guidelines and procedures, variables such as the surface texture/chemistry of catalyst metal foils, carbon feedstock, and growth process parameters have been well-scrutinized. Still, questions remain on how best to standardize the growth procedure. The possible correlation of procedures between different CVD setups is an example. Here, two thermal CVD reactors were explored to grow graphene on Cu foil. The design of these setups was entirely distinct, one being a “showerhead” cold-wall type, whereas the other represented the popular “tubular” hot-wall type. Upon standardizing the Cu foil surface, it was possible to develop a procedure for cm²-scale SLG growth that differed only by the carrier gas flow rate used in the two reactors.     

Mononuclear and Dinuclear Copper Complexes of Tridentate Redox-active Ligands with Tunable H-bonding Donors: Structure,Spectroscopy and H+/e− Reactivity

In this research article, we describe the synthesis and characterization of mononuclear and dinuclear Cu complexes bound by a family of tridentate redox-active ligands with tunable H-bonding donors. The mononuclear Cu-anion complexes were oxidized to the corresponding “high-valent” intermediates by oxidation of the redox-active ligand. These species were capable of oxidizing phenols with weak O−H bonds via H-atom abstraction. Thermodynamic analysis of the H-atom abstractions, which included reduction potential measurements, pK_a determination and kinetic studies, revealed that modification of the anion coordinated to the Cu and changes in the H-bonding donor did not lead to major differences in the reactivity of the “high-valent” CuY complexes (Y: hydroxide, phenolate and acetate), which indicated that the tridentate ligand scaffold acts as the H⁺ and e⁻ acceptor.     

1,10-Phenanthroline: A versatile ligand to promote copper-catalyzed cascade reactions

Ligand-promoted copper-catalyzed cascade reactions have become a robust tool for the synthesis of cyclic compounds. Although numerous ligands have been developed, this review focuses on the introduction of commercially available 1,10-phenanthroline-promoted copper-catalyzed cascade reactions in recent years. Moreover, based on original articles, this review highlights product yields in the presence and absence of the ligand, and the possible mechanistic role of the ‘copper/1,10-phenanthroline’ catalytic system.     

Multi-C−C/C−N-Coupled Light-Emitting Aliphatic Terpolymers: N−H-Functionalized Fluorophore Monomers and High-Performance Applications

To circumvent costly fluorescent labeling, five nonconventional, multifunctional, intrinsically fluorescent aliphatic terpolymers ( 1 – 5 ) have been synthesized by C−C/C−N-coupled, solution polymerization of two non-emissive monomers with protrusions of fluorophore monomers generated in situ. These scalable terpolymers were suitable for sensing and high-performance exclusion of Cu^II, logic function, and bioimaging. The structures of the terpolymers, in situ attachment of fluorescent monomers, aggregation-induced enhanced emission, bioimaging ability, and super adsorption were investigated by ¹H and ¹³C NMR, EPR, FTIR, X-ray photoelectron, UV/Vis, and atomic absorption spectroscopy, thermogravimetric analysis, high-resolution transmission electron microscopy, dynamic light scattering, solid-state fluorescence, fluorescence imaging, and fluorescence lifetime measurements, as well as by isotherm, kinetics, and thermodynamic studies. The geometries and electronic structures of the fluorophores and the absorption and emission properties of the terpolymers were examined by DFT, time-dependent DFT, and natural transition orbital analyses. For 1 , 2 , and 5 , the limits of detection were determined to be 1.03×10⁻⁷, 1.65×10⁻⁷, and 1.77×10⁻⁷ m , respectively, and the maximum adsorption capacities are 1575.21, 1433.70, and 1472.21 mg g⁻¹, respectively.