基于压力的速率方程的应用

通过具体实例说明对于气相反应,使用基于压力的速率方程解题比使用基于浓度的速率方程更直接﹑更简便。总结了具有简单级数的反应的基于压力的速率方程及其特征。     

基于Matlab的二元共聚合反应的竞聚率的求解

以直线交叉法为依据,根据最小二乘原理,采用Matlab GUI工具设计了一款用于计算二元共聚合反应竞聚率的图形用户程序。与传统的求解竞聚率方法相比,该图形用户程序具有设计原理简单、计算快捷的特点;同时程序提供界面简洁、交互友好的数据输入平台,实用性强。实际应用表明:采用该款图形用户程序所测得的数据与微机动态搜索法、Tidwell-Mortimer法相近,而比采用斜率截距法计算竞聚率的最小差方和更小,并且也避免了采用斜率截距法由于所用方程的非对称性造成的计算结果的不一致性。     

基于环糊精的新材料的研究进展

从纳米粒子、水凝胶、纤维材料和环糊精高分子等方面介绍了近年来以环糊精为基础研制的新材料的研究进展。目前以环糊精为基础的纳米粒子材料有核壳结构的纳米粒子、环糊精的化学接枝与共聚、环糊精与无机非金属材料的复合和含环糊精的囊泡材料;以环糊精为基础的凝胶材料有水凝胶和有机凝胶两种材料;此外还有以环糊精为基础的纤维材料、环糊精高...     

某些助剂对明胶的凝胶强度的影响的研究

众所周知,物理力学性能是照相明胶的一种很重要的属性。在各种彩色及黑白胶片都面向高温快速加工发展的今天,这种属性就显得更为重要。提高胶片的物理力学性能,一方面要从提高明胶本身的胶冻强度着手,例如减少明胶中溶胶组份(分子量小、冷水中溶解度高),提高明胶中的α和β组份的相对含量,减少分子量过大的组份等等。     

酯的水解实验的改进

该文对现行的高中化学 (试验修订本 )第二册中关于乙酸乙酯水解实验的不足之处进行了分析,并提出了改进的方法,对其实验内容和实验效果进行了讨论。     

体毛的化学和头发的保护

本文介绍了体毛结构和功能的一般化学基础,讨论了毛发的化学特征如氨基酸及微量元素的组成和应用依据,研究了护发的化学方法。作为皮肤附属器官的体毛,特别是头发,除一般的美容化妆外,近10多年来还由于人体微量元素研究的进展而引起人们的重视。曾多次召开过国际人发研究学术讨论会[1],国际原子能研究机构（IAEA）还在全球范围内收集了人发数据,并发布了人发标样（IAEA-HH-1）,我国也研制了类似的标准物。在各种病因诊断、法医学研究中,头发分析是重要项目。而在日常消费新潮中,青年人也常把相当多的精力和金钱投放在发型的美化上。因此体毛的化学和头发的保护问题,日益成为化学与生活联系的重要渠道,其社会意义已不容忽视。本文尝试就毛发的结构、功能、组成及可能的病交的化学基础和有关化妆的化学信息作一简介。     

色彩斑斓的自然,五颜六色的化学

通过介绍菠菜中色素的提取分离及紫甘蓝中花青素的提取两个实验,揭示大自然色彩背后的化学奥秘,并介绍了两个实验作为科普实验项目在化学科普活动中展示和互动的效果及特点。     

一氧化碳的发现与燃素说的终结

考察一氧化碳的发现过程可知,这不仅是一种化学物质的发现史,也是燃素说的兴衰史。笃信燃素说的英国科学家普里斯特利首先在实验室制取并研究了它,称之为重可燃空气。相信氧化学说的英国化学家克鲁克香克用实验证明了它是一氧化碳,使当时的科学家大都皈依氧化学说,从而终结了燃素说。这段历史让人们认识到创新的理论思维对于科学研究的重要意义。     

地球的内部可能是湿润的

在地球的低层地幔下 ,可能存在着比现在的海洋还要多 4倍的水 ,这是日本工业大学的Ｍ .Ｍｕｒａｋａｍｉ和他的同事们最近估测出来的。日本地球科学家们利用了一种多功能钻探仪 ,通过对 3种据信包含低层地幔中在高温高压下生成的主要矿物组成的分析后 ,得到了这个结论。这 3种矿物是 :Ｍｇ ｐｅｒｏｖｓｋｉｔｅ ,Ｃａ ｐｅｒｏｖｓｋｉｔｅ和Ｍａｇｎｅｓｉｏｗ櫣ｓｔｉｔｅ。再利用ＳＩＭＳ对矿物中溶解的氢的含量进行测量 ,矿物学家认为氢是水的标记。发现这3种矿物的含水量都相当可观 ,大约在 0 .2 %至 0 .4 %(重量比率 )之间。用红外…     

基于钯催化的Catellani反应的Rhazinal的高效全合成

Rhazinal是Rhazinilam家族中的一员,其家族都含有一个因环张力而形成的吡咯-苯胺手性轴,一个高张力的九元内酰胺,一个全碳季碳手性中心以及[3.4]并环结构.Rhazinilam被发现是一个很好的多种癌细胞的抑制剂,具有诱导和促进微管蛋白的聚合、防止解聚、稳定微管的作用.自其被分离之后得到了有机和生物有机化学家的广泛重视,至今已有多个其家族成员的全合成的报道.中国科学技术大学化学系顾振华小组将Pd催化的Catellani反应首次成     

可见光诱导提升Pt/g-C3N4纳米片甲酸氧化性能的研究

以半导体材料类石墨氮化碳纳米片(g-C₃N₄纳米片)为载体,通过微波-多元醇法构筑了Pt/g-C₃N₄纳米片催化剂. 通过TEM、XRD、XPS、紫外-可见吸收光谱等方法对Pt/g-C₃N₄纳米片催化剂的粒径尺寸、组成、结构、光学等性质进行分析. 通过对比可见光照和暗室条件下的甲酸电氧化活性,Pt/g-C₃N₄纳米片催化剂在可见光照射下展现出良好的催化性能. 该性能的提高一方面可能是由于g-C₃N₄纳米片在可见光照射下加速了电子从Pt转移给g-C₃N₄纳米片,Pt处于“电子匮乏”状态,可削弱CO与Pt之间的化学键能,减弱CO在Pt表面的吸附能力,促进了CO的氧化,提高了催化剂抗中毒能力;另一方面,g-C₃N₄纳米片在光照条件下分离出的空穴可有效氧化甲酸分子,提高甲酸氧化活性. 因此,可见光条件下可有效提高Pt/g-C₃N₄纳米片催化剂甲酸催化氧化活性,这为直接甲酸燃料电池的发展提供了新思路.     

石墨相氮化碳负载磷钨酸杂化材料的制备及其氧化脱硫催化性能

以1-丁基-3-甲基咪唑溴离子液体([Bmim]Br)、磷钨酸(H_3PW_(12)O_(40))和g-C_3N_4为原料,采用原位沉淀法合成了负载型[Bmim]_3PW_(12)O_(40)/g-C_3N_4催化剂(BPWO/g-C_3N_4)。通过XRD、FT-IR、UV-vis、氮气吸附、TEM和XPS等手段对催化剂的形貌和结构进行了表征,并以二苯并噻吩(DBT)的正庚烷溶液为模拟油、过氧化氢为氧化剂,考察了各组分负载量、催化剂用量、氧/硫物质的量比(O/S)和反应温度变量等对其氧化脱硫效果的影响。结果表明,BPWO/g-C_3N_4具有Keggin型杂多阴离子结构特征,BPWO (20%)/g-C_3N_4催化剂具有最优的对DBT的氧化脱硫性能,在50℃、O/S物质的量比为6.0的条件下反应180 min,可以完全氧化浓度为800μg/g的含DBT模拟油。同时,该BPWO/g-C_3N_4催化剂具有良好的重复使用性能,循环使用八次后其对DBT的氧化活性没有明显降低。     

MxCo3O4/g-C3N4 Derived from Bimetallic MOFs/g-C3N4 Composites for Styrene Epoxidation by Synergistic Photothermal Catalysis

Although metal-organic frameworks(MOFs) have been widely reported as precursors for obtaining various porous materials in recent years, the limited MOF types and monofunctional active site of MOF-based catalysts remain to be hard to crack. Herein, bimetallic MOFs, MCo-ZIFs stabilized by graphitized carbon nitride(g-C₃N₄) and their pyrolytic M_xCo₃O₄/g-C₃N₄ hybrids(M=Zn, Cu, Fe, Ni) have been designedly synthesized. The obtained M_xCo₃O₄/g-C₃N₄ hybrids display synergistic photothermal effect from both M_xCo₃O₄ and g-C₃N₄ under visible light irradiation. Significantly, the solution temperature can be heated from room temperature(20℃) to 66℃ after 40 min irradiation. Therefore, the catalytic activity of M_xCo₃O₄/g-C₃N₄ exceeds those of most reported catalysts under mild reaction conditions. The optimal Zn_xCo₃O₄/g-C₃N₄ catalyst realizes 96% conversion and 75% selectivity toward styrene oxide within 20 min. Incredibly, the Cu_xCo₃O₄/g-C₃N₄ could achieve up to 89% selectivity toward styrene oxide. To our knowledge, this is the first report about the novel photothermal effect of ZIFs-derived metal oxides.     

类石墨烯C3N4纳米片光催化分解水制氢中的量子限域效应

从层状化合物获得的纳米片是一类新型纳米结构材料,这种二维各向异性的纳米甚至亚纳米级的材料具有独特的物理化学性能,其中最好的一个例证就是从石墨烯C₃N₄到石墨烯C₃N₄纳米片的转变。通过高温氧化热刻蚀方法将体相g-C₃N₄剥离成g-C₃N₄纳米片,应用于染料敏化可见光分解水产氢,表现出了较体相g-C₃N₄高于2.6倍的产氢速率。通过X射线衍射（XRD）、傅里叶变换红外（FTIR）光谱、扫描电子显微镜（SEM）、Brunauer-Emmett-Teller（BET）、荧光光谱和光电化学等表征研究了g-C₃N₄纳米片的结构及曙红（EY）和g-C₃N₄纳米片之间的电子迁移过程。热剥离后的g-C₃N₄纳米片具有较高的比表面积,不仅可以更为有效地吸附染料分子,还因其量子限域效应大大增强了光生电荷的分离效率和电子转移效率,改善了电子沿平面方向的传输能力以及光生载流子的寿命,从而显著提高g-C₃N₄纳米片的光催化产氢活性。     

In situ Carbon Modification of g-C3N4 from Urea co-Crystal with Enhanced Photocatalytic Activity Towards Degradation of Organic Dyes Under Visible Light

An in situ strategy was introduced for synthesizing carbon modified graphitic carbon nitride(g-C₃N₄) by using urea/4-aminobenzoic acid(PABA) co-crystal(PABA@Urea) as precursor materials. Via co-calcination of the PABA co-former and the urea in PABA@Urea co-crystals, C guest species were generated and compounded into g-C₃N₄ matrix in situ by replacing the lattice N of the carbon nitride and forming carbon dots onto its layer surface. The carbon modification dramatically enhanced visible-light harvesting and charge carrier separation. Therefore, visible light photo-catalytic oxidation of methylene blue(MB) pollution in water over the carbon modified g-C₃N₄(C/g-C₃N₄) was notably improved. Up to 99% of methylene blue(MB) was eliminated within 60 min by the optimal sample prepared from the PABA@Urea co-crystal with a PABA content of 0.1%(mass ratio), faster than the degradation rate over bare g-C₃N₄. The present study demonstrates a new way to boost up the photocatalysis performance of g-C₃N₄, which holds great potential concerning the degradation of organic dyes from water.     

单层石墨相氮化碳负载Pt4团簇吸附O2的第一性理论研究

采用第一性原理密度泛函理论结合周期性平板模型模拟研究了Pt₄团簇吸附单层石墨相氮化碳(g-C₃N₄)的几何结构和电子性质,以及氧气在其表面上的吸附行为。同时,对比分析了氧气在纯净的石墨相氮化碳和Pt₄团簇上的吸附行为。计算结果表明, Pt₄团簇吸附在3-s-三嗪环石墨相氮化碳表面,并与四个边缘氮原子成键,形成两个六元环时为最稳定构型。Pt₄团簇倾向于吸附在三嗪环石墨相氮化碳的空位并与邻近三个氮原子成键。由于Pt与N原子较强的杂化作用,以及金属与底物之间较多电子转移增强了Pt₄团簇吸附g-C₃N₄的稳定性。另外,对比分析了氧气在纯净的g-C₃N₄和金属吸附的g-C₃N₄上吸附行为,发现金属原子的加入促进了电子转移,同时拉长了O―O键长。Pt₄吸附3-s-三嗪环g-C₃N₄比Pt₄吸附三嗪环g-C₃N₄表现出微弱的优势,表现出明显的基底扭曲以及较大的吸附能。这些结果表明,化学吸附通过调节电子结构和表面性质增强催化性能的较好方法。     

通过g-C3N4担载MNi12 (Fe,Co, Cu,Zn)纳米团簇调节甲烷化

As a unique two-dimensional material, graphitic carbon nitride (g-C₃N₄) has received significant attention for its particular electronic structure and chemical performance. Its instinctive defect can provide a stable anchoring site for metals, potentially improving the surface reactivity. Ni-based catalysts are economical but their activity for CO₂ methanation is lower than that of noble metal catalysts. Ni nanoparticles (NPs) supported on a substrate can further enhance the stability and activity of catalysts. Based on the principles of strong metal-support interaction (SMSI) and the synergistic effect on an alloy, MNi₁₂/g-C₃N₄ composites as novel catalysts are expected to improve stability and catalytic performance of Ni-based catalysts. The configurations are established with core-shell structures of MNi₁₂ (M = Fe, Co, Cu, Zn) nanoparticles (NPs) supported on g-C₃N₄ in this work. In the CO₂ methanation reaction, the reactivity of CO on slab (E_CO) is a critical factor, which is relative to the catalytic activity. Thus, the catalytic reactivity of these complexes via CO adsorption were explored using density functional theory (DFT). The values of cohesive energy (E_coh) for MNi₁₂ NPs range from -39.90 eV to -34.82 eV, suggesting that the formation of these NPs is favored as per thermodynamics, and E_coh and partial density of state (PDOS) reveal that the central M atom with the less filled d-shell interacts more strongly with surface Ni atoms. Therefore, ZnNi₁₂ is the most unstable structure among all the studied alloy, and the synergistic effect is also the weakest among them. When MNi₁₂ NPs are supported on the g-C₃N₄ substrate, the binding energies (E_b) vary from -9.40 eV to -8.39 eV, indicating that g-C₃N₄ is indeed a good material for stabilizing these NPs. The PDOS analysis of pure g-C₃N₄ suggests the sp² dangling bonds of N atoms in g-C₃N₄ can stabilize these transition metal NPs. Furthermore, the results of CO adsorbed on MNi₁₂ NPs and MNi₁₂/g-C₃N₄ composites show that E_CO and d_CO reduced with the introduction of g-C₃N₄. According to the results of the analysis of the Hirshfeld charges and electrostatic potential (ESP), the reason is that CO obtains less electrons from MNi₁₂ NPs after deposition on the g-C₃N₄ substrate, which lowers the reactivity of CO on catalysts. Additionally, the deformation charge density is analyzed to investigate the interaction between the NPs and g-C₃N₄. With the introduction of g-C₃N₄, charge redistribution indicates the strong metal-support interaction, which further reduces the CO adsorption energy. In summary, MNi₁₂ supported on g-C₃N₄ exhibit not only high stability but also tunable reactivity in CO₂ methanation. These changes are beneficial for CO₂ methanation reaction.     

碱催化剂g-C3N4在液相反应中溶胀特性的研究

Graphitic carbon nitrides (g-C₃N₄) with different surface areas were prepared by pyrolysis using different precursors including melamine, dicyandiamide, thiourea and urea, and subsequently characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectra (FTIR), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA) and N2 adsorption. Their basicities were measured by temperature-programmed desorption of CO₂ (CO₂-TPD) and acid-base titration. The catalytic properties for the Knoevenagel condensation of benzaldehyde and malononitrile were investigated in various solvents. In non-polar toluene solution, the benzaldehyde conversions of the g-C₃N₄ catalysts were low and changed according to their respective surface areas and basicities. However, in polar ethanol solution, the benzaldehyde conversions of all catalysts were similar, and much higher than those in toluene. This could not be explained by the results obtained from either of the two conventional basicity measurements. Further experimental results proved that g-C₃N₄ catalysts swelled in polar solutions, and more basic sites were exposed on the surface of the swollen catalysts, leading to the imminent increase in catalytic activity. This was proved by the catalyst poisoning data, which showed that the g-C₃N₄ catalyst lost its activity completely in toluene by adding 40.9 mmol·g^-1 benzoic acid, while the same catalyst was still active in ethanol until the added amount exceeded 143.3 m·g^-1. Additionally, the reaction tests in various solutions showed that the swelling effect was enhanced according to the polarity of the solvent used. A similar conclusion could be reached for the Knoevenagel condensation of furfural and malononitrile in various solvents. The reusability of g-C₃N₄ catalyst in Knoevenagel condensation was also studied, which showed that g-C₃N₄ was stable in liquid-phase reactions, whose activity dropped from 74.2% to 63.8% after three regeneration processes.     

竹浆纤维素转化制低碳多元醇反应中有机氮对金属催化剂稳定性影响的研究

采用等体积浸渍法制备了一系列多孔竹炭负载的有机氮掺杂的镍钨催化剂,并将其应用于催化竹浆纤维氢解制C_2,3多元醇反应。有机氮源与催化剂前驱体中Ni²⁺络合,高温煅烧时载体表面碳、氮和金属离子相互作用后生成一定量的C₃N₄、氮化物和合金物相。通过XRD、XPS和TEM等表征手段分析了催化剂Ni-W/MBC表面物理化学性质与催化活性间的关系。结果表明,除了金属镍、氧化钨物相外,表面还含有Ni-W合金（NiWO₄为主）;金属粒子表面包围了一层石墨化C₃N₄物相。XPS分析表明,有机氮源高温分解反应后形成了C₃N₄物相。在反应条件下,15% Ni-20% W/MBC@M-0.25催化剂得到乙二醇收率为55.8%,而未添加有机氮源的催化剂15% Ni-20% W/MBC获得的乙二醇收率仅为36.9%。催化剂稳定性实验结果表明,Ni-W合金和C₃N₄物相的形成显著增强了Ni-W/MB催化剂的稳定性,延长了催化剂寿命。     

WO3/g-C3N4异质结催化剂的制备及其氧化脱硫性能

以尿素和钨酸铵为原料采用浸渍法制备了金属氧化物三氧化钨（WO₃）与石墨相氮化碳（g-C₃N₄）异质结复合材料WO₃/g-C₃N₄。采用XRD、UV-vis、SEM、PL和XPS表征手段考察了催化剂的理化性质,发现WO₃与g-C₃N₄存在较好的相互作用和电子转移,保证了WO₃/g-C₃N₄本身所具有较高的氧化脱硫活性。以WO₃/g-C₃N₄作为催化剂,过氧化氢异丙苯为氧化剂,考察其光催化氧化脱硫性能,在反应温度80℃,O/S物质的量比为3.0的反应条件下,反应180 min,二苯并噻吩（DBT）转化率可以达到72.79%。通过游离基捕获实验,发现超氧自由基（·O₂^-）、电子（e^-）、羟基自由基（·OH）起到了促进反应速率的作用,并对该体系的反应机理进行了探讨。