钠硼解石碳化机理的研究

采用Ｃａ（２＋）选择电极，ｐＨ电极和电导电极对钠硼解石水溶液碳化过程进行跟踪测定。实验结果表明：反应分二步进行，反应最终结果是钠硼解石完全分解，硼全部进入溶液并大部分以Ｈ３ＢＯ３的形式存在，同时考察了温度，气流量对钠硼解石水溶液碳化结果的影响。根据碳化机理，提出了较佳的碳化条件。     

Manganese‐Catalyzed Dehydrogenative [4+2] Annulation of N?H Imines and Alkynes by C?H/N?H Activation

Described herein is a manganese‐catalyzed dehydrogenative [4+2] annulation of N H imines and alkynes, a reaction providing highly atom‐economical access to diverse isoquinolines. This transformation represents the first example of manganese‐catalyzed C H activation of imines; the stoichiometric variant of the cyclomanganation was reported in 1971. The redox neutral reaction produces H₂ as the major byproduct and eliminates the need for any oxidants, external ligands, or additives, thus standing out from known isoquinoline synthesis by transition‐metal‐catalyzed C H activation. Mechanistic studies revealed the five‐membered manganacycle and manganese hydride species as key reaction intermediates in the catalytic cycle.     

Isoquinoline skeleton synthesis via chelation-assisted C−H activation

Transition-metal-catalyzed isoquinoline synthesis that profits from the strategy of chelation-assisted C−H activation has flourished over the past decade. By virtue of the directed C−H bond cleavage of imines, amines, amidines, oximes, hydroximoyl halides, hydrazones, or azines, diverse isoquinoline derivatives have been accessed from alkynes, conjugated dienes, or diazo compounds under the catalysis of rhodium, ruthenium, palladium, nickel, or manganese. This digest summarizes the annulation reactions via chelation-assisted C−H activation leading to isoquinolines, isoquinolinium salts, or isoquinoline N-oxides.     

囊泡状二氧化硅的合成及油气吸附性能

以正硅酸四甲酯(TMOS)为硅源,P123(EO20PO70EO20)为表面活性剂,在p H=6的磷酸缓冲体系中制备了囊泡状二氧化硅材料.利用乙醇萃取脱除模板剂P123,电镜观测结果表明所得二氧化硅具有大孔囊泡结构,N2吸附结果表明其具有高比表面积和大孔容.通过Boehm滴定法确定了硅羟基数量与吸水率呈正相关.用囊泡状二氧化硅材料与商业化活性炭(AC)和硅胶(SG)对水蒸气、正己烷和油气进行静态吸附.在自建的动态正己烷吸附装置上用对囊泡状二氧化硅材料和商业化AC和SG对正己烷进行动态吸附.吸附结果表明,囊泡状二氧化硅材料的静/动态吸附容量和稳定性都远高于商业化活性炭和硅胶.     

中空碳纳米球的制备及VOCs吸附性能

首先, 在碱性条件下, 不使用表面活性剂, 采用St?ber小球法以正硅酸四乙酯(TEOS)和正硅酸四丙酯(TPOS)为硅源, 生成初级氧化硅球形颗粒; 然后, 使酚醛树脂(间苯二酚和甲醛)与球形氧化硅的羟基共缩合形成酚醛树脂-氧化硅复合材料; 最后, 经高温碳化和酸蚀获得了空心碳纳米球(HCNSs). 通过调节TEOS/TPOS的摩尔比获得了一系列具有良好的单分散性且粒径、 壁厚可调节的HCNSs, 其粒径和壁厚分别在280~430 nm和15~63 nm的范围内. 仅以TPOS为硅源时合成的HCNS-0/4具有较大的粒径(426 nm)和壁厚(63 nm)、 较高的比表面积(1216 m²/g)和孔容(0.508 cm³/g), 并且具有较大的挥发性有机化合物(VOCs)吸附性能, 其正己烷、 甲苯和油气的静态吸附容量分别为2.02, 1.42和0.926 g/g, 正己烷和甲苯的动态吸附容量分别为2.01 g/g和1.37 g/g, 均远高于商业化活性炭.     

Manganese‐Catalyzed Dehydrogenative [4+2] Annulation of NH Imines and Alkynes by CH/NH Activation

Described herein is a manganese‐catalyzed dehydrogenative [4+2] annulation of N? H imines and alkynes, a reaction providing highly atom‐economical access to diverse isoquinolines. This transformation represents the first example of manganese‐catalyzed C? H activation of imines; the stoichiometric variant of the cyclomanganation was reported in 1971. The redox neutral reaction produces H₂ as the major byproduct and eliminates the need for any oxidants, external ligands, or additives, thus standing out from known isoquinoline synthesis by transition‐metal‐catalyzed C? H activation. Mechanistic studies revealed the five‐membered manganacycle and manganese hydride species as key reaction intermediates in the catalytic cycle.     

锰催化的C?C键生成反应研究进展

迄今为止,贵金属(铑、钯、钌等)在过渡金属催化的碳碳键生成反应中发挥着主导作用,然而使用廉价金属催化剂更符合可持续发展的要求。锰是地壳中含量排第三位的过渡金属,价格便宜,环境危害性小,有潜力成为贵金属催化剂的替代品并发挥其自身独特的反应性。尽管锰参与的当量反应有大量文献报道,目前锰催化的反应尤其是碳碳键生成反应的发展还不成熟,如何实现高效的催化循环是锰催化领域面临的主要难题之一。本文对锰催化的付-克烷基化反应、格氏试剂的酰化反应、偶联反应、碳金属化反应、自由基反应和碳氢键活化反应进行了综述。     

Chemical‐Reductant‐Free Electrochemical Deuteration Reaction using Deuterium Oxide

We report a method for the electrochemical deuteration of α,β‐unsaturated carbonyl compounds under catalyst‐ and external‐reductant‐free conditions, with deuteration rates as high as 99 % and yields up to 91 % in 2 h. The use of graphite felt for both the cathode and the anode was key to ensuring chemoselectivity and high deuterium incorporation under neutral conditions without the need for an external reductant. This method has a number of advantages over previously reported deuteration reactions that use stoichiometric metallic reductants. Mechanistic experiments showed that O₂ evolution at the anode not only eliminates the need for an external reductant but also regulates the pH of the reaction mixture, keeping it approximately neutral.     

基于高斯曲率极值点的桥梁结构损伤识别方法

目前中小桥梁日常安全巡检存在对检查人员依赖性高、缺乏可量化的科学依据等不足.针对这些问题,本文提出了一种利用高斯曲率极值点对结构进行损伤识别的方法.将桥面视为受弯弹性薄板,根据弹性薄板的弯曲理论得到了在荷载作用下结构刚度变化与桥面弯曲程度(高斯曲率)的理论关系,并由此推导了高斯曲率对结构刚度损伤的敏感程度公式.通过有限...     

以系列三维立体投影实验为例谈大学物理实验中的创新型人才培养

创新能力是本世纪的核心竞争力,其关键是创新型人才的培养,这为理工类高校的实验教学提出了新的挑战.目前高校中的以学生为主体,教师为主导的大学生创新实验项目的实施是解决此挑战的有效途径之一.以笔者承担的系列三维立体投影物理实验的大学生创新实验项目为例,探讨了大学物理实验中的创新型人才培养模式.通过循序渐进的实验过程,引导学生自主搭建实验装置和编写控制程序,有效培养了学生的创新和实践能力,为高校实验教学改革提供了参考.