巧用逻辑思维方式 讲活无机元素化学——以铜族元素的教学为例

针对铜族元素的知识特点,以逻辑思维方式精心设计教学过程,引导学生深刻剖析元素化学中物质结构和物质性质等方面间的逻辑关系,从而实现通过课堂教学培养学生思维能力、尤其是逻辑思维能力的目的。详细分析了铜族元素知识体系的教学方法,为元素化学的教学改革展示了一种范例。     

关于氮族元素教学改革的几点建议

Based on the knowledge characteristics of the chapter on nitrogen group elements, and combined with the teaching experience of our excellent video open course, this paper has probed the teaching reform of inorganic elements chemistry from the following aspects:using the principle of chemistry to explain the structure and properties of substances, designing problems to guide students to think and cultivate their learning ability, instructing students to be good at inducing the changing laws of material properties, paying attention to the relationship between the elements and compounds and practices of production and life. It aims to guide students to learn, memorize and master the knowledge of element chemistry effectively, and improve the quality of classroom teaching.     

元素化学“课程思政”教学设计与实践——以碳族元素为例

以碳族元素教学为例,介绍了元素化学“课程思政”教学设计与实践。深入挖掘课程蕴含的思想政治教育元素,充分发挥课程承载的思想政治教育功能,将科技前沿、唯物辩证法与科学认识论、爱国主义精神、生态文明思想、新时代中国“双碳”故事、化学元素发现史和科学伦理道德教育等有机融入课程内容设置和课堂教学等环节中,培养学生的创新精神、科学思维、爱国情怀、生态文明思想、探究精神、职业道德观等,实现“知识传授”和“价值引领”同步提升。     

Cl-对Zn-Fe族元素二元合金共沉积的催化作用

在氯化物电解液中以定电量（10C.cm^-2),恒温40℃电沉积Zn-Fe族元素二元合成,沉积产物用原子吸收光谱分析,根据分析结果,作出相应的电流效率、百分含量及部分极化曲线,镀层形貌采用扫描电镜（SEM）观察,发现：Zn-Fe族元素合金的共沉积为异常共沉积,Cl^-对铁族元素有催化作用,随着Cl^-浓度的增加,降低了铁族元素的过电位,促进铁族元素金属的沉积。     

氧族元素间共价单键参与的无机反应机理

结合一些热力学数据和动力学过程,运用亲电和亲核的概念,初步阐释了一些O―O键、S―S键参与的氧化还原反应的机理,并利用Gaussian09程序的计算对一些已有的机理和猜想进行了验证,以此说明无机反应机理的一些规律。     

ⅢA族元素取代杂多钨酸盐的合成及性质

报道了ⅢＡ族元素的ＸＷ１１（Ｘ＝Ｚｎ,Ｇａ,Ｔｉ,Ｚｒ）杂多化合物的合成,通过元素分析、红外光谱、紫外光谱、极谱和循环伏安、＾１８３Ｗ和＾２７Ａｌ核磁共振波谱对合成化合物的结构和性质进行了表征。     

锌、铜元素与优生优育

郑州市第一人民医院对185例分娩前健康孕妇与足月正常新生儿作发锌、铜测定，其中85人作血清锌、铜测定，10月后随访62例母婴发锌、铜含量．以探讨微量元素锌、铜与优生优育的关系。     

铜族金属与完整及氮掺杂石墨烯的相互作用

基于广义梯度密度泛函理论和周期平板模型,研究了铜族金属单原子和双原子簇与完整及氮掺杂石墨烯的结合情况.结果表明,氮掺杂后石墨烯的电子结构特性由半金属性变为金属性;铜族金属在完整及石墨型氮掺杂石墨烯上的吸附较弱,结合能约为0.5eV,而在吡啶型氮掺杂和吡咯型氮掺杂石墨烯上有较强的化学吸附,结合能一般大于1eV;吡咯型氮掺杂后的构型不稳定,金属原子及簇与包含该结构的石墨烯衬底作用时会使其向吡啶型氮掺杂转变,并最终得到基于吡啶型氮掺杂的稳定吸附构型.Mulliken电荷布居分析显示,吸附在吡啶型氮掺杂石墨烯上的金属单原子与金属双原子簇带电性质相反.态密度及轨道分析表明,Cu与吡啶型氮掺杂石墨烯空位处留有悬挂键的三个原子成键,而Au与其中两个C原子成键.     

基于方法训练的氧族元素复习

与科学知识相比,科学方法具有更大的稳定性和更普遍的适用性.特别是进行个人决策时,恰当地运用科学方法是一个人具有良好科学素养的重要标志之一.从这个意义上讲,掌握方法要比掌握知识更为重要.     

元素化学教学中关于“无机物热稳定性”的知识建构

"无机物热稳定性"是元素化学内容教与学的难点之一。本文选取代表性实例,通过分析、比较和归纳影响无机物热稳定性的根本影响因素,对其进行结构化、本源化理解,构建认识无机物热稳定性的思维导图,建立无机物热稳定性的认识模型。以"无机物热稳定性"为知识载体,探讨知识"建构式"的学习模式在元素化学教学中的应用。     

Permethylated Disila[2]metallocenophanes of Group 14 and 15 Elements

Permethylated disila[2]metallocenophanes of silicon, germanium, tin, lead, 2 a – d , (tetrelocenophanes) and antimony, 3 a , b , (pnictogenocenophanes) are described. In the case of antimony, a chloro-substituted stibonocenophane, 3 a , as well as cationic stibonocenophanium tetrachloroaluminate and tetraphenylborate salts, 3 b [X] (X=[AlCl₄], [BPh₄]), were synthesized. These represent the first examples of metallocenophanes of any Group 15 element. All compounds were studied in solution and in the solid state. Without exception the ansa-bridge exerts a strong influence on the bending angle of the two Cp-ligands. For disila[2]plumbocenophane, 2 d , its reactivity towards Group 15 halides was probed. Treatment of disila[2]plumbocenophane, 2 d , with two equivalents of phosphorus(III) chloride or arsenic(III) chloride, results in a ring-opening reaction and gives the bis(dihalopnictogenyl)-substituted products, 4 a , b .     

Homoatomic Bonding of Main Group Elements

Clusters of main group elements are not rare. On the contrary, it is becoming difficult to avoid the discovery of new substances of this type. Clusters are the natural intermediate stages between an element and its isolated atoms or ions. In the form of polycations and polyanions they offer models for the stepwise oxidation and reduction of an element and represent a bridge between the elements. The great majority of homonuclear bonded structures are already present in the solid phases of simple systems. Mobilization of these clusters as molecules represents a great challenge.     

Clinical and Allergological Biomonitoring of Occupational Hypersensitivity to Platinum Group Elements

Abstract

Platinum (Pt), palladium (Pd), rhodium (Rh) and iridium (Ir), the platinum group elements (PGEs), have been reported to induce hypersensitive reactions. The purpose of this research was to assess: (i) the PGEs level in indoor air and in biological samples (blood, urine and hair) of workers involved in the assembly of catalysers and recycling metals; (ii) the prevalence and the clinical characteristics of hypersensitivity to PGEs; (iii) the association between the environmental exposure and the levels of the xenobiotics in biological samples and the presence of PGE allergies. Airborne particles were collected by means of fixed area samplers equipped with a PM10 sampling head and by means of personal devices worn by the workers. Analyses of all the samples were performed by a sector field and a quadrupole inductively coupled plasma mass spectrometry. The highest mean level in PM10 airborne and soluble Pt percentage was found in coating department, while the highest concentrations of total Pd were found in the recycling and in the catalyst chemical departments, also confirmed by the biological data. Positive prick test reactions to PGEs were found in 17 out of the 103 workers who performed skin prick or patch tests. All of the 17 were positive to H₂PtCl₆, three out 17 also had a positive reaction to IrCl₃ and RhCl₃ and 1 also had a positive reaction to PdCl₂. No differences were observed between subjects with positive or negative skin test to PGEs on mean concentration of the metals in blood, urine and hair. The results show that Pt‐salts are important allergens in the catalyst industry and that the clinical manifestations involve the respiratory system, ocular symptoms and the skin. The concentration of PGEs in biological samples are not correlated with hypersensitivity, but the sensitivity is present only in subjects involved in production processes.     

Molecular Nitrides with Titanium and Group 13–15 Elements

Several heterometallic nitrido complexes were prepared by reaction of the imido–nitrido titanium complex [{Ti(η⁵‐C₅Me₅)(μ‐NH)}₃(μ₃‐N)] ( 1 ) with amido derivatives of Group 13–15 elements. Treatment of 1 with bis(trimethylsilyl)amido [M{N(SiMe₃)₂}₃] derivatives of aluminum, gallium, or indium in toluene at 150–190 °C affords the single‐cube amidoaluminum complex [{(Me₃Si)₂N}Al{(μ₃‐N)₂(μ₃‐NH)Ti₃(η⁵‐C₅Me₅)₃(μ₃‐N)}] ( 2 ) or the corner‐shared double‐cube compounds [M(μ₃‐N)₃(μ₃‐NH)₃{Ti₃(η⁵‐C₅Me₅)₃(μ₃‐N)}₂] [M=Ga ( 3 ), In ( 4 )]. Complexes 3 and 4 were also obtained by treatment of 1 with the trialkyl derivatives [M(CH₂SiMe₃)₃] (M=Ga, In) at high temperatures. The analogous reaction of 1 with [{Ga(NMe₂)₃}₂] at 110 °C leads to [{Ga(μ₃‐N)₂(μ₃‐NH)Ti₃(η⁵‐C₅Me₅)₃(μ₃‐N)}₂] ( 5 ), in which two [GaTi₃N₄] cube‐type moieties are linked through a gallium–gallium bond. Complex 1 reacts with one equivalent of germanium, tin, or lead bis(trimethylsilyl)amido derivatives [M{N(SiMe₃)₂}₂] in toluene at room temperature to give cube‐type complexes [M{(μ₃‐N)₂(μ₃‐NH)Ti₃(η⁵‐C₅Me₅)₃(μ₃‐N)}] [M=Ge ( 6 ), Sn ( 7 ), Pb ( 8 )]. Monitoring the reaction of 1 with [Sn{N(SiMe₃)₂}₂] and [Sn(C₅H₅)₂] by NMR spectroscopy allows the identification of intermediates [RSn{(μ₃‐N)(μ₃‐NH)₂Ti₃(η⁵‐C₅Me₅)₃(μ₃‐N)}] [R=N(SiMe₃)₂ ( 9 ), C₅H₅ ( 10 )] in the formation of 7 . Addition of one equivalent of the metalloligand 1 to a solution of lead derivative 8 or the treatment of 1 with a half equivalent of [Pb{N(SiMe₃)₂}₂] afford the corner‐shared double‐cube compound [Pb(μ₃‐N)₂(μ₃‐NH)₄{Ti₃(η⁵‐C₅Me₅)₃(μ₃‐N)}₂] ( 11 ). Analogous antimony and bismuth derivatives [M(μ₃‐N)₃(μ₃‐NH)₃{Ti₃(η⁵‐C₅Me₅)₃(μ₃‐N)}₂] [M=Sb ( 12 ), Bi ( 13 )] were obtained through the reaction of 1 with the tris(dimethylamido) reagents [M(NMe₂)₃]. Treatment of 1 with [AlCl₂{N(SiMe₃)₂}(OEt₂)] affords the precipitation of the singular aluminum–titanium square‐pyramidal aggregate [{{(Me₃Si)₂N}Cl₃Al₂}(μ₃‐N)(μ₃‐NH)₂{Ti₃(η⁵‐C₅Me₅)₃(μ‐Cl)(μ₃‐N)}] ( 14 ). The X‐ray crystal structures of 5 , 11 , 13 , 14 , and [AlCl{N(SiMe₃)₂}₂] were determined.     

小锍试金铂族元素富集方法

研究了降低捕集剂镍用量的小铳试金铂族元素富集方法。通过测试,比较了重约０．５ｇ、２．５ｇ、２５ｇ试金扣的酸溶时间、铂族元素（ＰＧＥ）空白值。研究证明２．５ｇ试金扣既克服了常规试金扣和微型试金扣的缺点,又保留了它们的优点。经标准物质难证,铂族元素测定值与真值相符合。     

Formazanate Complexes of Hypervalent Group 14 Elements as Precursors to Electronically Stabilized Radicals

The stability of molecular radicals containing main‐group elements usually hinges on the presence of bulky substituents that shield the reactive radical center. We describe a family of Group 14 formazanate complexes whose chemical reduction allows access to radicals that are stabilized instead by geometric and electron‐delocalization effects, specifically by the square‐pyramidal coordination geometry adopted by the Group 14 atom (Si, Ge, Sn) within the framework of the heteroatom‐rich formazanate ligands. The reduction potentials of the Si, Ge, and Sn complexes as determined by cyclic voltammetry become more negative in that order. Examination of the solid‐state structures of these complexes suggested that their electron‐accepting ability decreases with increasing size of the Group 14 atom because a larger central atom increases the nonplanarity of the ligand‐based conjugated π‐electron system of the complex. The experimental findings were supported by density‐functional calculations on the parent complexes and the corresponding radical anions.