i氨合成催化剂的研究进展*

高稳定性、高活性、低成本的氨合成催化剂的研究已成为新的研究热点。本文从载体的制备和改性方法、钌活性组分还原与负载、助剂的机理及其作用等方面简要地介绍了氧化物负载钌催化剂的最新研究进展,此外,结合密度泛函理论的计算和实验研究成果,介绍了合金型催化剂特别是熔铁型合金催化剂、氮化物金属合金体系及负载型多金属氨合成催化剂的研究现状,指出了氧化物负载钌催化剂及合金型催化剂研究存在的一些问题并展望了氨合成催化剂的发展前景。     

硫酸盐型厌氧氨氧化性能的研究

研究了自养条件下硫酸盐型厌氧氨氧化的性能．试验表明,在无氧条件下,SO4^2-和NH4^＋化学性质稳定,两者间不发生化学反应．在厌氧反应器中接种厌氧消化污泥,经过三年多的连续驯化,可使厌氧反应器发生硫酸盐型厌氧氨氧化（NH4^＋-N和SO4^2-S同时减少）．在高基质浓度下,NH4＋-N和5042-浓度平均降低71．67和56．82mg．L^-1．硫酸盐型厌氧氨氧化的标准吉布斯自由能变化较小,反应可以发生,但不易进行．高基质浓度和低氧化还原电位对该反应有促进作用．     

贵金属钌基催化剂合成及应用研究进展

钌催化剂是近年来新兴的贵金属催化剂,其负载型催化剂具有节约成本、可回收利用、催化性能优异等优势,受到研究人员的广泛关注。本文对负载型钌基催化剂在氨合成反应、加氢反应、氧化反应的合成及应用进行了综述,主要阐述了反应过程中的载体与助剂、制备方法和催化性能,并对当前反应中存在的问题进行归纳和总结,最后提出负载型钌基催化剂现阶段亟需解决的问题以及对未来的主要发展趋势进行了展望。     

非异氰酸酯法合成脂肪族热塑性聚氨酯及其性能研究

利用二氨酯二醇氨酯交换的非异氰酸酯法合成高分子量的脂肪族热塑性聚氨酯.以己二氨酯二醇(BHCH)的自缩聚,合成了Mn为29200的聚己二氨酯(PBHCH),其熔点为154.31℃,拉伸强度为28.41MPa,断裂伸长率为3.91%;利用己内酰胺与乙醇胺的共聚合成了同时带有端氨基及端羟基的尼龙-6低聚物,并与己内酯反应转化为端羟基尼龙-6低聚体,经与BHCH在170℃常压反应4 h及180℃减压反应6.5 h,获得了数种带有短尼龙-6段的酰胺型聚氨酯(s-PAUs),红外、核磁、GPC、广角X-射线衍射、DSC、TGA和力学性能表征表明,此类s-PAUs的Mn在26000以上、熔点在123.85~170.89℃之间、拉伸强度达28.53 MPa、断裂伸长率达299.0%.     

短波近红外过程分析仪的研制与应用

本文介绍一种短波近红外(700～1100nm)过程分析仪的研制与应用。仪器在722型单光束光栅分光光度计的基础上研制成,包括光源、光栅单色器、硅探测器、信号放大、A/D转换、8位单片微型计算机、数码显示和RS-232C串行通讯接口等几部分,它具有光谱扫描、串行通讯及分析结果预测功能。仪器校正采用PLS(偏最小二乘)回归法。在应用方面,根据氨水在短波红外区的吸收光谱,利用所研制的仪器实现了氨浓度的非破坏性分析,对于氨浓度为0～13.5mol/L的试样,预测标准差(SEP)为0.116mol/L。     

准1-1型对峙反应的双谱解析法

根据准１－１型对峙反应的积分动力学方程和热动力学基本理论,建立了一种新的热动力学研究法－－准１－１型对峙反应的双谱解析法。利用该法分别研究了１５℃和２５℃下硝基乙烷与氨在准１－１型条件下质子转移反应的热动力学。     

稀土元素—氨三乙酸—氨基酸混配型配合物的研究

为探索多元体系中稀土离子与氨基酸的配位作用,本文在25℃和0.15mol/dm~3(NPCl)离子强度条件下,用pH电位法测定了稀土—氨三乙酸分别与蛋氨酸、丝氨酸生成混配型配合物的稳定常数。讨论了上述混配型配合物稳定常数随稀土原子序数的变化规律以及钇的位置。     

离子色谱法测定地表水氨的条件优化

基于美国Aquion ICS型离子色谱仪,优化离子色谱分析在饮用水氨检测中的应用条件,由实验结果所得的回归方程为A=0.2562ρ+0.008, 相关系数r=0.9998。在精密度检测中0.5 mg/L和10 mg/L的标准溶液所得标准偏差分别为1.130%和0.114%。在加标回收测试中加标量为1mg和2mg时,回收率在98%-102%、98%-100.1%。说明该方法总体准确度较高,可以满足检测需求。     

无铬CO高温变换催化剂的研究 Ⅱ.过渡元素对高变催化剂结构与性能的影响

通过XRD,BET和XPS表征及反应性能测定表明,铁系高变催化剂中加入的过渡元素能够进入Fe3O4晶格形成固溶体,并使催化剂的晶胞参数随着加入元素离子半径的增大而增大,晶粒度明显变小,比表面积增大,起到铬的作用,催化剂的活性和热稳定性提高.发现部分过渡元素具有富集OH-的特性,使催化剂在较低的汽/气比条件下具有较高的催化活性.研制成功的B121型无铬高变催化剂性能达到铁铬系高变催化剂的技术指标.     

光离子检测气相色谱法分离分析氨及其氧化产物

本文采用光离子化和热导池两个检测器串联,以5A钙型分子筛填充柱与Chromesorb 104+2％KOH填充柱并联方式,成功地定量分离分析了N2,O2,NO或NO_2,N_2O和NH_3的混合气体。     

Large-Sized Ammonia Clusters and Solvation Energies of the Proton in Ammonia

The absolute solvation energies (free energies and enthalpies) of the proton in ammonia are used to compute the pK_a of species embedded in ammonia. They are also used to compute the solvation energies of other ions in ammonia. Despite their importance, it is not possible to determine experimentally the solvation energies of the proton in a given solvent. We propose in this work a direct approach to compute the solvation energies of the proton in ammonia from large-sized neutral and protonated ammonia clusters. To undertake this investigation, we performed a geometry optimization of neutral and protonated ammonia 30-mer, 40-mer, and 50 mer to locate stable structures. These structures have been fully optimized at both APFD/6-31++g(d,p) and M06-2X/6-31++g(d,p) levels of theory. An infrared spectroscopic study of these structures has been provided to assess the reliability of our investigation. Using these structures, we have computed the absolute solvation free energy and the absolute solvation enthalpy of the proton in ammonia. It comes out that the absolute solvation free energy of the proton in ammonia is calculated to be −1192 kJ mol^–1, whereas the absolute solvation enthalpy is evaluated to be −1214 kJ mol^–1. © 2019 Wiley Periodicals, Inc.     

Micro Ammonia Sensor

Abstract

A micro ammonia sensor, consisting of an ISFET covered with a dry membrane which is made from nonactin and substituted poly-γ-methyl-L-glutamate (PMG) is described. The gate output voltage of the micro ammonia sensor increased with NH₄OH addition. The response time of the sensor was 2 min at 30°C, and the sensor exhibited superior selectivity for NH₄ ⁺ compared to a pH sensitive ISFET.     

用于氨氮检测的薄层氨气微传感芯片及其系统研究

设计并制备了一种具有微池薄液层结构的氨气微传感芯片,并构建了以此微传感芯片为敏感单元的氨氮检测系统,探索了使用安培型氨气微传感器检测氨氮的方法。此微传感芯片采用MEMS工艺制备,通过电化学方法在微电极表面修饰了对氨具有良好电催化氧化性能的纳米铂,提高了传感器的灵敏度。在芯片的SU-8微池中滴入微量碳酸丙烯酯(PC),形成可使氨气迅速扩散到电极表面的薄层电解液,使传感器具有较快的响应速度。使用自行设计的氨氮检测系统对氨氮进行检测,考察了氨氮检测的浓度响应特性、时间响应特性、重复性及选择性。氨氮检测系统的线性范围为0.1～5.0 mg/L;检测下限为0.1 mg/L;响应时间小于1 min;重复性偏差为4.0%。     

氨基络合物制备氨硼烷及放氢性能研究

以NaBH₄为硼源、氨基络合物Ni(NH₃)₆Cl₂为氨源制备高储氢容量的氨硼烷(NH₃BH₃, Ammonia Borane, AB)及其放氢性能研究. 通过XRD, FTIR, ¹¹B NMR, ICP等手段分析表征了所制备产物的组成和纯度, 在此基础上探究了原料比例、反应温度、时间和溶剂等因素对产物的影响. 同时, 对不同原料比制得氨硼烷的热解放氢性能进行了研究. 实验结果表明: 当物质的量NaBH₄∶Ni(NH₃)₆Cl₂＝2∶1经过10 h的反应, 得到了纯度非常高的氨硼烷(纯度＞99%)|以NaBH₄∶Ni(NH₃)₆Cl₂＝3∶1得到的氨硼烷, 当以2 ℃/min进行升温时, 氢气释放主要集中在第一步, 并且没有硼烷和硼嗪等杂质气体的产生. 另外, 在产物中得到了金属Ni纳米颗粒, 经洗涤干燥后其粒径大小可控制在10 nm左右, 在催化氨硼烷等材料的水解放氢方面具有潜在的应用价值.     

Catalytic Organometallic Reactions of Ammonia

Until recently, ammonia had rarely succumbed to catalytic transformations with homogeneous catalysts, and the development of such reactions that are selective for the formation of single products under mild conditions has encountered numerous challenges. However, recently developed catalysts have allowed several classes of reactions to create products with nitrogen‐containing functional groups from ammonia. These reactions include hydroaminomethylation, reductive amination, alkylation, allylic substitution, hydroamination, and cross‐coupling. This Minireview describes examples of these processes and the factors that control catalyst activity and selectivity.     

Spectrophotometric Determination of Ammonia and Nitrogen Oxides in the Reaction Products of Ammonia Oxidation

A spectrophotometric procedure is developed for the simultaneous determination of ammonia, NO, and NO₂ in the reaction products of the catalytic oxidation of ammonia under industrial conditions. Samples are taken from the reactor, and the analysis is made at 250°C. A multiple linear regression is used for the calibration. The relative standard deviation of the determination of ammonia and nitrogen oxides is no higher than 6%.     

氨的反复变色喷泉实验设计与教学思考

根据氨的一些性质,设计了氨的反复变色喷泉实验,并应用到化学教学论实验课上,获得了较好的教学效果。由此对化学教育产生了几点思考：（1）教师应利用化学实验创设生动活泼的教学情境;（2）教师应利用化学实验促进三重表征思维之间的联系;（3）教师应使化学实验教学功能最大化;（4）教师应有主动开发化学实验案例的意识;（5）教师应有亲自动手试做化学实验的行动。     

Analysis of Urea Nitrogen in the Presence of Ammonia Using an Ammonia Gas Sensitive Electrode

Abstract

This report describes a method for the determination of ammonia and urea in raw sewage samples using an Orion Ammonia Gas-Sensing Electrode. Urea is determined by potentiometrically measuring the ammonia produced following exhaustive hydrolysis by urease and subtracting the amount of ammonia present before enzymatic hydrolysis. The recovery of urea from raw sewage samples using the procedure herein described is shown to be nearly Quantitative.     

Efficient Organocatalytic Dehydrogenation of Ammonia Borane

Dehydrogenation of ammonia borane by sterically encumbered pyridones as organocatalysts is reported. With 6‐tert‐butyl‐2‐thiopyridone as the catalyst, a turnover frequency (TOF) of 88 h^?1 was achieved. Experimental mechanistic investigations, substantiated by DLPNO‐CCSD(T) computations, indicate a mechanistic scenario that commences with the protonation of a B?H bond by the mercaptopyridine form of the catalyst. The reactive intermediate formed by this initial protonation was observed by NMR spectroscopy and the molecular structure of a surrogate determined by SCXRD. An intramolecular proton transfer in this intermediate from the NH₃ group to the pyridine ring with concomitant breaking of the S?B bond regenerates the thiopyridone and closes the catalytic cycle. This step can be described as an inorganic retro‐ene reaction.     

Electrochemical Hydrogenation with Gaseous Ammonia

As a carbon‐free and sustainable fuel, ammonia serves as high‐energy‐density hydrogen‐storage material. It is important to develop new reactions able to utilize ammonia as a hydrogen source directly. Herein, we report an electrochemical hydrogenation of alkenes, alkynes, and ketones using ammonia as the hydrogen source and carbon electrodes. A variety of heterocycles and functional groups, including for example sulfide, benzyl, benzyl carbamate, and allyl carbamate were well tolerated. Fast stepwise electron transfer and proton transfer processes were proposed to account for the transformation.