《无机及分析化学》是机电工程类专业的基础课程,对专业课程学习起着重要的衔接作用.针对该专业学生的学科背景复杂、基础知识差异大等情况,授课方式与化学专业有所区别.结合课程组教学实际情况,从整合教学内容"为什么学"、改进教学方法"学什么"、培养学生兴趣"怎么学"等方面对课程的教学过程进行了思考探索.通过教学效果验证,教学思考探索可以从一定程度上有效解决"痛点"问题.

基于非化学类专业"大学化学"课程授课过程中的"痛点"问题进行教学改革创新.阐述了教学理念、教学内容、教学方法等方面的创新措施.结果表明,教学改革创新可以从一定程度上解决本课程的"痛点"问题,教学效果有所改善,学生的主观能动性明显提升.

Using dimethyl sulfoxide as the solvent,hybrid HMX containing different proportions of nano-aluminum and nano silicon combustibles have been fabricated by ultrasonic assisted spray recrystallization.The thermal performance of the prepared particles has been characterized by X-ray diffraction (XRD) and differential scanning calorimetry (DSC).The thermal decomposition properties of the mixed particles with different proportions of nano-combustible agents have been studied using Kissinger method.The results show that compared with the pristine HMX,the activation energy Ea,activation entropy △S,activation enthalpy △H,and activation free energy △G of the modified HMX by 20％ of nano-aluminum combustibles have been decreased by 26.07 kJ/mol,19.23 kJ/mol,26.09 kJ/mol and 11.75 kJ/mol,respectively.As the content of nano-combustible agents increases,the catalytic effect becomes more and more obvious.In addition,in the same proportion,the nano-aluminum combustible agent has a better catalytic effect than the nano-silicon combustible agent.That is,the nano-combustible agent can increase the reaction rate of HMX at high temperature and has obvious catalytic effect on the thermal decomposition of HMX.

The composites of zirconium phosphide with graphene (ZrP@rGO) were synthesized via a hydrothermal process with zirconium phosphide (ZrP) and graphene oxide (GO) as raw materials, and characterized by XRD, SEM, N-2-adsorption-desorption and TEM measurements. The obtained ZrP@rGO composites were found to exhibit apparent activity in the elimination of nitric oxide (NO) via facile redox reactions, and the elimination dynamics was evaluated within the context of various important experimental parameters, such as reaction temperature and ammonia gas concentration. At a fixed amount of ZrP@rGO composites, an increasing amount of NO would be eliminated with increasing reaction temperature, and complete conversion of NO to N-2 could be reached in the range of 650 to 800 degrees C. The addition of NH3 also facilitated NO elimination at a fixed reaction temperature. Furthermore, as of the products of the elimination reaction, zirconia (ZrO2) powders are biocompatible material, red phosphorus can be used as chemical material, and the N-2 might be collected and used as a protective gas or other purposes.

基于大工程背景,在实验项目设计、教学目标确定、教学方法和考核方式改革等方面,对基础化学实验教学进行了一系列改革,旨在对接专业实验和实训,一以贯之地递进式培养学生的工程意识和创新能力.

The chemical mechanisms of protonated diamines-catalyzed decarboxylation of oxaloacetic acid anions in water solutions have been studied by using density functional theory. The calculated results show that the activated Gibbs free energy of the decarboxylation step is the highest in the whole diamine-catalytic processes for OA2-, and protonated ethylenediamine (ENH+) is the best catalyst of the five diamines, which is consistent with the study of Thalji et al. However, for OA-, different with OA2-, the dehydration step is the rate-determining one except 1,3-diaminopropane, and protonated 1,4- diaminobutane is the best catalyst of the five catalysts. The results also indicate that the second amino group participates in the reaction as the proton acceptor or proton donor, and it assists in decarboxylation by hydrogen bonds, decreasing the active Gibbs free energy barrier of the whole catalytic process. These results provide insight into the precise catalytic mechanism of several enzymes whose reactions are known to proceed via an imine intermediate.

本科毕业论文是高校教学计划的重要组成部分,也是实现培养方案的重大载体,文章对目前毕业论文出现的问题进行了剖析,并对与实验室开放模式结合进行了探索,这样既可以提高学生的综合素质进而提高毕业论文的质量,同时又促进了实验室管理水平的提高.

介绍了自催化在合成/分解材料中的应用, 对材料的合成/分解自催化性能进行分析研究来说明最近的研究进展.

在回顾原油破乳剂的发展历程的基础上，通过改头、换尾、加骨、扩链、接枝、交联和复配等措施来对原油破乳剂修饰改性以合成新型破乳剂，特别详细地介绍了由丙二醇作为起始剂和设计一种新型的TA头(酚胺醛树脂头)链接环氧乙烷、环氧丙烷破乳剂的合成过程，最后再分别和TDI交联，并进行现场试验。用中国石化胜利油田有限公司孤岛采油厂的原油进行性能检测，最终生产出适合孤岛采油厂-联合站原油的高效专用新型破乳剂。达到加药量少、脱水速度快、脱水率高、污水清、界面清的效果，以满足工业需求。

运用密度泛函理论(DFT)的B3LYP方法,在6-311++G(d,p)基组水平上,采用CPCM模型对水溶剂条件下4种卤代羧酸和4种羰基(氰基)羧酸在无催化剂及水催化条件下的脱羧反应机理进行了研究.结果表明,在卤代羧酸的脱羧反应中,水催化时反应比无催化剂参与时容易,其中CCl3COOH (A)和CF3COOH (C)脱羧(H2O催化)所需克服的能垒分别为192.60、210.33 kJ/mol,与Belsky等的实验结果基本一致.而对于4种羰基(氰基)羧酸,无水参与时脱羧主要经六元环过渡态进行,反应的活化能分别为300.01 (CH3COCOOH)、160.02(CNCH2COOH)、94.01 (CHOCH2COOH)、105.26 (NH2COCH2COOH) kJ/mol,比H2O催化时反应的活化能低.

本文对高校化学化工专业开放性实验室建设中存在的组织问题进行了探讨，以本科生导师制为组织单元，通过实验内容优化、重视实验教学主体和实验管理模式改革等具体方法和措施，把本科生导师制与开放性实验室建设有机结合到了一起。实践证明，这种结合模式提高了化学化工专业学生工业分析实验的教学质量，取得了良好的效果。实践证明，与本科生导师制的有机结合是建设开放性实验室的一个有效组织模式。

The decarboxylation mechanism of oxaloacetic acid aided with ethylenediamine or without any catalyst is investigated employing Density Functional Theory (DFT). DFT calculations for both the gas phase and in water solution indicate a stepwise mechanism for each of the steps of the reactions. In the catalyzed mechanism, the dehydration of carbinolamine (IM1) is via a seven-membered ring transition structure (TS5), which is consistent with the structure proposed by Thalji, et al. The decarboxylation of the imine (IM6) is the rate determining step with an energy barrier of 16.46 kcal/mol, lower than the reaction without any catalysts or catalyzed with ions.

Opening of college professional laboratory for the students is the necessity of training applied professional talents with initiative spirit.Combined with the concrete practice of opening laboratory of applied chemistry speciality in Binzhou University,some practices on progressive training of creative thinking,practical ability and the ability of self management etc are discussed based on the open platform of professional laboratory.

Oval-plate-like, sphere-like, bundle-like and plate-like copper oxide (CuO) nanostructures were prepared by hydrothermal method using Cu(CH3COO)2·H2O and NaOH as the reagents in the absence of any surfactants or templates. The morphology and structure of CuO nanostructures could be easily tailored by adjusting the amount of NaOH. The catalytic activity of the as-prepared CuO nanostructures was demonstrated by catalytic oxidation of methylene blue (MB) in presence of hydrogen peroxide (H2O2). The oval-plate-like CuO exhibited better catalytic activity and which was mainly attributed to the larger specific surface area.

The ethylenediamine-catalyzed decarboxylation mechanism of oxaloacetic acid is studied by Density Functional Theory (DFT) both in gas phase and in water solutions. The decarboxylation without any catalyst is also investigated in order to evaluate the functions of proton and ethylenediamine. The catalyzed mechanisms of oxaloacetic acid proposed by Leussing et al. are confirmed by our calculations. The calculated results show that the dehydration of IM4 is the rate-determining step for the whole catalytic process, agreeing with the conclusions drawn by Thalji et al. And the energy barrier for the decarboxylation of IM6 is only 6.48 kcal/mol, much lower than the reaction without any catalysts or catalyzed with ions. (C) 2013 Elsevier B.V. All rights reserved.

Density Function Theory (DFT) B3LYP method was employed to study the mechanism about three kinds of decarboxylation (without catalyst, with the assistance of H2O, or with the assistance of H3O+) of benzothiophene-2-carboxylic acid with the 6-311++G(d, p) basis sets. The potential energy of the decarboxylation of benzothiophene-2-carboxylic acid at the condition without any catalyst or aided with H2O was calculated to be 249.1 kJ·mol-1 and 246.5 kJ·mol-1, respectively. When aided with H3O+, the reaction mainly through theα-protonated of the thiophene ring, the hydration of the carboxyl group and the breaking of the C-C bond. The reaction was controlled by the hydration of the carboxyl group, the energy barrier was 177.6 kJ·mol-1, and the activation energy of the rupture of C-C bond was only 32.8 kJ·mol-1. Which suggest that the decarboxylation of benzothiophene-2-carboxylic acid may be catalyzed effectively by H3O+.

A rapid and efficient method for the synthesis of 1,3,5-triarylpent-2-ene-1,5-diones is described based on a low-cost and environmentally benign KF/Al2O3 and PEG-400 co-catalyst catalyst via open-ring reactions of 2,4,6-triarylpyrylium salts compounds under microwave irradiation conditions. The advantage of this method is satisfactory yields, short reaction time and the use of a cheaper, milder, and efficient catalyst. Finally, twelve alpha, beta- unsaturated diones have been obtained in good to excellent yields by this procedure.

AbstractA simple and environmentally benign synthesis of title compounds (III) is presented.

The enthalpies of dilution of D-sorbitol in water and sodium halide aqueous solutions had been determined by isothermal flow-mix microcalorimetry at 293.15K,303.15K,308.15K,and 318.15K.Experiential equations of apparent enthalpies of dilution varying with the concentration of D-sorbitol had been established from the experimental data in terms of the improved McMillan-Mayer theory,and enthalpic interaction coefficients(h2,h3,and h4),pairwise entropic interaction coefficient s2 and pairwise Gibbs free energy interaction coefficient g2 obtained.The values of h2 had been discussed in the light of solute-solute and solute-solvent interactions.The results indicated that,the values of h2 increased as raising temperature in pure water and the sodium halide aqueous solutions;and it shows quite well linear dependence on temperature,so s2 is a constant in the experimental range of temperature.

An environmentally rapid and benign protocol for the synthesis of 4-aryl-1,4-dihydropyridines compounds using VB1 as a catalyst under microwave irradiation and solvent-free conditions has been achieved. The procedure is operationally simple, giving good to high product yield.