La_xSr_(1-x)FeO_3催化剂的制备及其催化还原SO_2性能的研究

采用柠檬酸配合溶胶凝胶法制备了不同La、Sr比例的La_xSr_(1-x)FeO_3催化剂样品,通过X射线衍射(XRD)、比表面积测定(BET)、CO-程序升温还原(CO-TPR)、SO2-程序升温脱附(SO2-TPD)、O2-程序升温脱附(O2-TPD)的方法对催化剂的结构和物理化学性质进行了表征.综合表征结果分析,通过柠檬酸配合法成功制得了具有典型钙钛矿结构的LaxSr1-xFe O3系列复合氧化物;在La Fe O3的结构中A位(La)掺杂替换少量的Sr,可以增大催化剂的比表面积、提高氧化物结构中氧空位的数量、促进反应气体在催化剂中完成反应,大大提升了SO2的催化还原转化效率.实验结果表明,当x为0.8时,CO催化还原SO2的转化率最高,在空速为24 000 m L/(g·h),温度600℃时,转化率达到95%,取得了良好的催化效果.     

不同制备方法的Mn-Ce催化剂低温SCR性能研究

采用新型共沉淀法、浸渍法以及沉淀沉积法制备基于Mn-Ce的催化剂. 对比60～160 ℃温度区间内三种方法制备的催化剂的低温选择性催化还原NO性能. 运用X射线衍射(XRD)、比表面积(BET)、程序升温脱附(NH₃-TPD)、程序升温还原(H₂-TPR)等对催化剂的形貌与性质进行了表征. 实验结果表明, 共沉淀法制备的Mn-Ce/TiO₂有更好的低温催化还原NO活性. 影响沉淀法低温催化还原NO活性的主要因素是催化剂的表面积、活性组分的分布以及Mn与Ti之间的内在作用.     

铁锰复合氧化物的氧化还原沉淀法制备及其表征

分别采用氧化还原沉淀法和常规共沉淀法制备得到铁锰复合氧化物, 并对样品进行了 Ｘ射线衍射、 Ｂ Ｅ Ｔ比表面积、程序升温还原的初步表征和比较． 结果表明, 与常规共沉淀法制备的样品相比较, 采用氧化还原沉淀法制备的铁锰复合氧化物具有粒径较小、较大的比表面积、铁锰互溶性好、铁锰物种之间的相互作用较强等特点． 作为一种较为新颖的催化剂制备方法, 氧化还原沉淀法利用在高低价可变金属离子之间发生氧化还原反应的同时使之沉淀, 不利于各相单独形成微晶, 有利于不同金属离子的均匀混合． 此种方法对制备高比表面积、含变价过渡金属离子的各类复合氧化物催化剂有其独到之处．     

La2-xSrxNiO4体系还原性能考察及La1.7Sr0.3NiO4还原机理的研究

合成了四方晶系K_2NiF_4结构的La_(2-x)Sr_xNiO_4(0.0≤x≤1.0)系列复合氧化物。用多晶XRD技术测定其晶胞参数; 用程序升温还原(TPR)技术研究了它们的还原性能。结果发现系列样品的最高还原峰温随组成(x)的变化次序和晶胞参数a的变化次序相反, 而与c的变化次序相同。利用TPR和XRD技术考察了La_(1.7)Sr_(0.3)NiO_4的还原机理, 发现此样品TPR图中前两个还原峰主要对应于Ni~(3+)还原成Ni~(2+)离子的过程, 同时轴比率c/a的计算也间接佐证了这一点; 并将最高还原峰归属于结构的破坏峰。     

NiO-MoO_3/γ-Al_2O_3催化剂硫化过程研究

利用TPR(程序升温还原)、TPS(程序升温硫化)及恒温还原硫化技术研究了实验室制备的NiO-MoO_3/γ-Al_2O_3催化剂在不同硫化剂(H_2S、CS_2)硫化过程中的反应情形。实验结果表明,H_2S容易硫化氧化态样品,而CS_2/H_2容易硫化还原态样品。提出了还原硫化反应机理——H_2S可以直接通过S—O交换硫化样品,CS_2/H_2需要被加氢生成H_2S,再以后者硫化样品。CS_2/H_2的硫化过程是先还原后硫化。提出了以CS_2/H_2作硫化剂的硫化程序。     

还原热处理对铈锆铝复合氧化物性能的影响

采用共沉淀法制备铈锆铝复合氧化物(CeO2-ZrO2-Al2O3,CZA)和铈锆复合氧化物(CeO2-ZrO2,CZ),将样品分别在空气和10%H2/Ar气氛下进行热处理,利用X射线粉末衍射(XRD)、O2脉冲吸附、H2程序升温还原(H2-TPR)等手段研究了复合氧化物的结构及性能.结果表明:CZA样品经950℃还原热处理后出现CeAlO3晶相,热处理温度越高,越有利于CeAlO3物相生成.CZA储氧量(OSC)随着还原热处理温度升高逐渐增大,至900℃达到1270.3μmo·lg-1;温度继续升高,OSC减小,1100℃还原热处理后CZA的OSC仅为23.2μmo·lg-1.研究发现还原热处理中形成CeAlO3,其显著影响CZA样品的储氧性能和还原性能.     

还原温度对MoP催化剂加氢精制性能的影响

 通过程序升温还原磷钼酸盐前体的方法制备了无负载磷化钼(MoP)催化剂,并采用XRD,BET,XPS和高压连续微反技术,考察了催化剂的性质,研究了还原温度对催化剂HDN,HDS和HYD性能的影响. 结果表明,在还原温度为600～800 ℃范围内,成功制备出磷化钼催化剂. 高压连续微反结果表明,MoP的催化特性与其比表面积、还原度和表相组成有关,比表面积大、还原度适中和表相Moδ+/Pδ-比适中的磷化钼具有更高的催化活性; 650～700 ℃为最合适的还原温度,高于或低于该温度时所制备的MoP催化剂活性均大幅度下降. 在合适的条件下,MoP催化剂对噻吩HDS,吡啶HDN和环己烯HYD的转化率可分别达到94.3%,100.0%和90.3%.     

热稳定体相还原态对二氧化钛气敏应用重要性的实验证实

TiO₂ 中体相还原态与气敏性质之间的关系已有理论预测但一直未得到实验验证. 在此, 我们报道一种利用多孔无定型二氧化钛作前驱体制备含热稳定体相还原态TiO₂ 的化学方法. 紫外-可见漫反射光谱, 电子顺磁共振波谱(EPR)以及X-射线光电子能谱(XPS)证明所获材料中含有的体相还原态为热稳定的Ti³⁺离子以及捕获电子的氧缺位. O₂-程序升温脱附测量结果表明, 体相还原态的存在可以显著提升二氧化钛表面对氧分子的吸附作用. 所获得的体相还原纳米材料不仅表现出优越的对有机分子(乙醇、甲醇及丙酮)的传感性和快速响应性, 而且具有对CO 传感的良好选择性(相对于CH₄ 和H₂). 测试结果证实了TiO₂ 传感材料中体相还原态的重要性, 材料的气体传感性能与TiO₂ 表面氧气分子吸附作用密切相关.     

还原温度对低温还原法制备的Ni_2P/Ti-MCM-41催化剂加氢脱硫性能的影响

以氯化镍(Ni Cl_2·6H_2O)为镍源、次磷酸铵(NH_4H_2PO_2)为磷源、Ti-MCM-41为载体,通过程序升温还原法制备了Ni_2P/Ti-M CM-41催化剂,并采用H_2-TPR、XRD、BET、XPS、TEM等手段对其结构和性质进行了表征。以二苯并噻吩(DBT)为模型化合物,考察了还原温度对Ni_2P/Ti-M CM-41催化剂的加氢脱硫(HDS)性能的影响。结果表明,程序升温还原法制备的Ni_2P/Ti-M CM-41催化剂前驱体的还原温度为318℃,比传统程序升温还原制备的Ni_2P低200℃。在350-500℃下还原得到的催化剂活性相为单一的Ni_2P相,较低的还原温度有利于形成更小粒径的磷化镍晶粒。还原温度为400℃时,制得的Ni_2P/Ti-M CM-41催化剂比表面积高、分散性最好、表面P富集少,具有最高的HDS活性;在340℃、3.0 M Pa、H_2/油体积比500、质量空速(WHSV)为2.0 h~(-1)的条件下,二苯并噻吩HDS转化率达到99.4%。     

基于还原石墨烯/纳米银复合材料的电化学传感器测定双酚A

石墨烯特有的褶皱层状结构以及银纳米粒子良好的催化性能,使其在电化学方面具有良好的应用潜能.本研究以柠檬酸钠为还原剂,通过水热反应原位制备出还原石墨烯/纳米银复合材料(rGO/AgNPs),用于修饰玻碳电极,研究了双酚A的电化学行为.循环伏安法(CV)和方波伏安法(SWV)的实验结果表明,双酚A可以在rGO/AgNPs修饰电极表面发生快速的氧化还原反应,基于此实现了对双酚A的高灵敏检测.在最优条件下,双酚A的氧化峰电流与其浓度在0.1~40.0μmol/L范围内呈良好的线性关系(r2=0.996),检出限为50.7 nmol/L(S/N=3).将其用于实际环境和塑料样品中双酚A的检测,回收率为91.7%~102.9%.     

Some Advances in the Inorganic Chemistry of Bromine

Recent advances in the chemistry of bromine and its inorganic compounds are covered under the headings of technology, properties and reactions, liquid bromine as an inorganic solvent, analysis, and new or newly studied compounds. Much of what is new is bromine chemistry is characteristic also of what is new in inorganic chemistry as a whole. That is, more detailed information about compounds and reactions is becoming available from the application of new instrumental and theoretical techniques.     

On the Synthesis of the FeMo Cofactor of Nitrogenase: Gene-Controlled in Nature versus Laboratory-Produced by Man

One of the primary challenges of chemistry is the controlled synthesis of compounds with tailor-made structures and properties. Natural products serve as inspiration in this quest, ranging from biocatalysts with optimal selectivity and activity to “inorganic materials” with exceptional properties, whose generation can be described by the term biomineralization. It is of fundamental importance to comprehend the courses of events at the interface between gene expression and the subsequent processes of epigenesis that are no longer under gene control. Chemistry has been able to achieve many goals; however, in the area of controlled syntheses of highly complex, tailor-made metal clusters, there is a lack of fundamental theories and principles. This is especially true for the fascinating metal–sulfur cluster of nitrogenase, which, in this enzyme, functions as the active center for the N₂ reduction and, so far, has eluded all attempts to be synthesized in the laboratory. To understand the biosynthesis of this cluster, information from genetics and chemistry must be combined.     

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.     

Supramolecular Inorganic Chemistry: Small Guests in Small and Large Hosts

A key reaction in the biological and material world is the controlled linking of simple (molecular) building blocks, a reaction with which one can create mesoscopic structures, which, for example, contain cavities and display specifically desired properties, but also compounds that exhibit typical solid-state structures. The best example in this context is the chemistry of host–guest interactions, which spans the entire range from three- and two-dimensional to one- and “zero-dimensional”, discrete host structures. Members of the class of multidimensional compounds have been classified as such for a long time, for example, clathrates and intercalation compounds. Thus far, however, there are no classifications for discrete inorganic host–guest compounds. The first systematic approach can be applied to novel polyoxometalates, a class of compounds which has only recently become known. Molecular recognition; tailor-made, molecular engineering; control of fragment linkage of spin organization and crystallization; cryptands and coronands as “cages” for cations, anions or anion–cation aggregates as sections of ionic lattices; anions within anions, receptors; host–guest interactions; complementarity, as well as the dialectic terms reduction and emergence are important terms and concepts of supramolecular inorganic chemistry. Of particular importance for future research is the comprehension of the mesoscopic area (molècular assemblies)—that between individual molecules and solids (“substances”)—which acts in the biological world as carrier of function and information and for which interesting material properties are expected. This area is accessible through certain variations of “controlled” self-organization processes, which can be demonstrated by using examples from the chemistry of polyoxometalates. The comprehension of the laws that rule the linking of simple polyhedra to give complex systems enables one to deal with numerous interdisciplinary areas of research: crystal physics and chemistry, heterogeneous catalysis, bioinorganic chemistry (biomineralization), and materials science. In addition, conservative self-organization processes, for example template-directed syntheses, are of importance for natural philosophy in the context of the question about the inherent properties of material systems.     

卡皮克重复提取理论在无机化学教学中的应用实践

The theory of Karpicker retrieval practice is applied in the inorganic chemistry course teaching in order to improve the effect of classroom teaching of inorganic chemistry. The strategy is designed in particular for chemistry majoring undergraduates with less learning interests and poor initiatives and passions, as well as unpleasant teaching quality of professional course. Through three years of chemistry teaching practices of the theory of Karpicker retrieval practice, the results demonstrated that retrieval practice not only contributed to information encoding and information retrieve, but also improved learning results of chemical undergraduates significantly.     

以实验为情境问题的PBL教学法在元素化学教学中的应用

元素化学是无机化学课程的学习重点和讲授难点。针对元素化学内容繁杂、易学难巩固的特点,本文以铁、铜化合物实验为情境问题,在元素化学的教学中实施PBL教学方法以激发学生的学习兴趣,促进并巩固教学效果。     

软硬酸碱理论与元素的存在形式

在无机化学元素部分教学中,元素的存在形式既是该元素化学性质的重要组成部分,又决定了元素单质和化合物的制备与合成方法。运用离子的电子结构知识及化学基本原理分析元素在自然界中的存在形式,既可以加深学生对化学基本知识和基本原理的理解,又可以将元素知识形成知识链以减少记忆量。本文利用软硬酸碱理论和地球环境的基本状况来分析元素在自然界的存在形式,得到了与实际较为符合的结果,表明这是一种简单实用的思路和方法。     

无机化学多元信息化教学模式的构建与实践研究

针对现代大学生的移动阅读习惯和信息化学习需求,构建了无机化学多元信息化教学模式。介绍了构建这种教学模式所需微信公众号、微助教和QQ群作业的使用方法。初步探讨了无机化学多元信息化教学模式在教学中的实践效果,弥补了传统教学中的不足。     

一种确定氧化数的新方法

氧化数是元素的重要性质,在无机化学中应用广泛。长期以来,确定元素氧化数主要根据桐山良一和鲍林等建立的规则,这些规则对于氧化数概念在化学中的推广普及起了很大的作用,但在遇到结构复杂或未知化合物时有时仍然会出现问题。本文根据IUPAC的氧化数定义提出,氧化数完全取决于成键两原子之间的电子供需关系,元素的最高正氧化数受到其原子价层电子数的限制,而元素的最低负氧化数受到同周期稀有气体元素外层电子数与其价层电子数差值的限制,据此建立了确定元素氧化数的新方法,该方法既不需要考虑分子结构,也不依赖元素氧化数的习惯规定,符合氧化数概念提出的初衷,简便易行,例外情况少,不仅适合大学化学教学,也适合中学化学教学。     

探讨PBL教学法在无机化学元素部分教学中的应用

元素部分是无机化学教学中的难点.笔者结合自己的教学实践和教学对象,根据元素化学教学内容的特点,从问题的设定,过程中的实施、效果与评价,多媒体辅助等几方面论述了元素化学教学的实施过程与方法.经验表明,该方法能提高学生的各项能力,充分调动学生的主动性与积极性,有助于元素化学教学质量的提高.