Synthesis and Structures of Arene Ruthenium (II)–NHC Complexes: Efficient Catalytic α‐alkylation of ketones via Hydrogen Auto Transfer Reaction

A panel of six new arene Ru (II)‐NHC complexes 2a‐f , (NHC = 1,3‐diethyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1a , 1,3‐dicyclohexylmethyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1b and 1,3‐dibenzyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1c ) were synthesized from the transmetallation reaction of Ag‐NHC with [(η⁶‐arene)RuCl₂]₂ and characterized. The ruthenium (II)‐NHC complexes 2a‐f were developed as effective catalysts for α‐alkylation of ketones and synthesis of bioactive quinoline using primary/amino alcohols as coupling partners respectively. The reactions were performed with 0.5 mol% catalyst load in 8 h under aerobic condition and the maximum yield was up to 96%. Besides, the different alkyl wingtips on NHC and arene moieties were studied to differentiate the catalytic robustness of the complexes in the transformations.     

“Four-component” assembly of polyaromatic 4H-cyclopenta[b]thiophene structures based on GaCl3-promoted reaction of styrylmalonates with 5-phenylthiophene-2-carbaldehyde

New “four-component” self-assembly of polyaromatic thiophene structures based on styrylmalonates and 5-phenylthiophene-2-carbaldehyde has been developed. This process is promoted by GaCl₃ and involves two [2?+?3]-annulation steps on the CHO-groups and para-substitution into one Ph-ring. The main feature of discovered process is a high diastereoselectivity with a significant increase in molecular complexity. The resulting polyaromatic structures containing two thiophene moieties in each structure have intense color and strong absorption in a near UV spectral region with absorption maxima in the range of 257–360?nm.     

Unveiling the Layer‐Dependent Catalytic Activity of PtSe2 Atomic Crystals for the Hydrogen Evolution Reaction

Two‐dimensional (2D) PtSe₂ shows the most prominent layer‐dependent electrical properties among various 2D materials and high catalytic activity for hydrogen evolution reaction (HER), and therefore, it is an ideal material for exploring the structure–activity correlations in 2D systems. Here, starting with the synthesis of single‐crystalline 2D PtSe₂ with a controlled number of layers and probing the HER catalytic activity of individual flakes in micro electrochemical cells, we investigated the layer‐dependent HER catalytic activity of 2D PtSe₂ from both theoretical and experimental perspectives. We clearly demonstrated how the number of layers affects the number of active sites, the electronic structures, and electrical properties of 2D PtSe₂ flakes and thus alters their catalytic performance for HER. Our results also highlight the importance of efficient electron transfer in achieving optimum activity for ultrathin electrocatalysts. Our studies greatly enrich our understanding of the structure–activity correlations for 2D catalysts and provide new insight for the design and synthesis of ultrathin catalysts with high activity.     

Study of nano‐Cu/SiO2 catalysts for highly selective hydrogenation of acetophenone

Hydrogenation of acetophenone over nano‐Cu/SiO₂ catalysts was investigated. The catalysts, prepared by a liquid precipitation method using various precipitating agents, were characterized using low‐temperature nitrogen adsorption, X‐ray diffraction, temperature‐programmed desorption of ammonia, hydrogen temperature‐programmed reduction, transmission electron microscopy and X‐ray photoelectron spectroscopy. It was found that the catalysts prepared by a homogeneous precipitation method had better activity and stability than those prepared by a co‐precipitation method. The catalyst prepared using urea as precipitating agent had well‐dispersed copper species, high surface area and abundant pore structure. The catalytic performance and mechanism of the Cu/SiO₂ catalysts were further studied. It was found that the activity and stability of the catalysts could be improved by adjusting the proportion of Cu⁺/(Cu⁺ + Cu⁰). The sample prepared using urea as precipitating agent presented higher activity and selectivity. Also, the catalyst prepared using urea maintained a high catalytic performance while being continuously used for 150 h under the optimal reaction conditions.     

Polymer nanoparticles with a sensitive CO2‐responsive hydrophilic/hydrophobic surface

Poly(methyl methacrylate) (PMMA) nanoparticles with a sensitive CO₂‐responsive hydrophilic/hydrophobic surface that confers controlled dispersion and aggregation in water were prepared by emulsion polymerization at 50 °C under CO₂ bubbling using amphiphilic diblock copolymers of 2‐dimethylaminoethyl methacrylate (DMAEMA) and N‐isopropyl acrylamide (NIPAAm) as an emulsifier. The amphiphilicity of the hydrophobic–hydrophilic diblock copolymer at 50 °C was triggered by CO₂ bubbling in water and enabled the copolymer to serve as an emulsifier. The resulting PMMA nanoparticles were spherical, approximately 100 nm in diameter and exhibited sensitive CO₂/N₂‐responsive dispersion/aggregation in water. Using copolymers with a longer PNIPAAm block length as an emulsifier resulted in smaller particles. A higher concentration of copolymer emulsifier led to particles with a stickier surface. Given its simple preparation and reversible CO₂‐triggered amphiphilic behavior, this newly developed block copolymer emulsifier offers a highly efficient route toward the fabrication of sensitive CO₂‐stimuli responsive polymeric nanoparticle dispersions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2149–2156     

σ2 Hessian方程的Pogorelov型C2 内估计及应用

提出利用拉格朗日乘子法重新证明σ2算子的最优凹性,并定义了一个凸锥Γ3?=λ=(λ1,λ2,?,λn)∈Rn:σ1(λ)>0,σ2(λ|i)>0,1≤i≤n。利用σ2算子的最优凹性，给出了σ2Hessian方程Pogorelov型C2内估计，进而证明了σ2(D2u(x))=1,x∈Rn的满足二次多项式增长条件的Γ3?-凸整解为二次多项式。     

Impregnated copper ferrite on mesoporous graphitic carbon nitride: An efficient and reusable catalyst for promoting ligand‐free click synthesis of diverse 1,2,3‐triazoles and tetrazoles

Magnetic CuFe₂O₄/g‐C₃N₄ hybrids were synthesized through a facile method and their catalytic performances were evaluated in click chemistry for the first time. The structural and morphological characterization of prepared materials was carried out by different techniques such as X‐ray diffraction, high‐resolution transmission electron microscopy, field emission scanning electron microscopy, Fourier infrared spectroscopy, vibrating sample magnetometry, thermogravimetric analysis, and N₂ adsorption–desorption analysis (Brunauer–Emmett–Teller surface area). The utilization of magnetic CuFe₂O₄/g‐C₃N₄ enabled superior performance in the one‐pot azide–alkyne cycloaddition reaction in water using alkyl halides and epoxides as azide precursors without the need of any additional agents. The present system is broad in scope and especially practical for the synthesis of macrocyclic triazoles and also tetrazoles. In addition, the catalytic system highly fulfills the demands of “green click chemistry” with its convenient conditions, especially easy access to a variety of significant products in low catalyst loading and simple work‐up and isolation procedure.     

Oxidative dehydrogenation of n-octane over a vanadium–magnesium oxide catalyst: Influence of the gas hourly space velocity

Oxidative dehydrogenation (ODH) of n-octane was carried out over a vanadium–magnesium oxide catalyst in a continuous flow fixed bed reactor. The catalyst was characterized by ICP–OES, powder XRD and SEM. The catalytic tests were carried out at different gas hourly space velocities (GHSVs), viz. 4000, 6000, 8000, and 10,000 h^?1. The best selectivity for octenes was obtained at the GHSV of 8000 h^?1, while that for C8 aromatics was attained at the GHSV of 6000 h^?1 at high temperatures (500 and 550 °C). The catalytic testing at the GHSV of 10,000 h^?1 showed the lowest activity, while that at the GHSV of 4000 h^?1 consistently showed the lowest ODH selectivity. Generally, the best ODH performance was obtained by the catalytic testing at the GHSVs of 6000 and 8000 h^?1. No phasic changes were observed after the catalytic testing.     

甲烷-二氧化碳重整制合成气与现代分析技术应用于探究性化工专业实验的设计与探索

以甲烷-二氧化碳重整制合成气为实例，设计探究性实验，将合成气的制备和现代分析技术应用于化工专业实验的教学实践中以提高学生的创新和实践能力。实验包括催化剂的制备，催化剂的性能评价和催化剂的表征等3大部分。采用工业最常用的浸渍法制备含有不同助剂的Ni/X/γ-Al2O3（X为Co，Fe，MgO，CeO2）催化剂，以甲烷-二氧化碳重整反应评价其催化性能，并采用XRD、H2-TPR、BET和TG对催化剂的微观结构进行表征。结合催化剂的性能评价结果和表征结果，探讨不同助剂对镍基催化剂性能的改善效果及机制。通过开设该实验，可以让学生了解化工学科的前沿知识以及现代分析技术的基本原理和用途，掌握专业的实验操作、数据处理和谱图绘制方法，提高学生的专业素养和综合能力。     

Synthesis,crystal structure and magnetic properties of a new tri‐nuclear iron (II,III) complex,a precursor for the preparation of superparamagnetic Fe3O4 nanoparticles applicable in the removal of Cd2+

This study reports the structural and spectroscopic characterization of a novel metal organic compound formulated as [Fe (bpy)₃] [Fe (dipic)₂]₂.7H₂O ( 1 ) (dipic = pyridine‐2,6‐dicarboxylate and bpy = 2,2^′‐bipyridine). 1 was investigated by elemental analysis, FT‐IR spectroscopy, powder X‐ray diffraction and single crystal X‐ray diffraction (SC‐XRD), which revealed a triclinic structure of expected composition. Thermal degradation of 1 was also investigated. Complex 1 was used as a precursor to prepare superparamagnetic nanoparticles of Fe₃O₄ by thermal analysis. The obtained Fe₃O₄ was characterized by Fourier transformed infrared spectroscopy (FT‐IR), powder X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Fe₃O₄ nanoparticles were used as a nano‐adsorbent to remove Cd²⁺ from water at room temperature. The results showed that this nano‐adsorbent is effective in removing Cd²⁺ from contaminated water sources, and that the maximal effectivity of adsorption occurs at pH = 6. Magnetic measurements of complex 1 and Fe₃O₄ nanoparticles at room temperature revealed paramagnetic and superparamagnetic behavior, respectively.