Benson基团加和法对气相色谱保留值规律的研究

应用Ｂｅｎｓｏｎ基团加和法，对脂肪醇、醛、酮和酯几类有机化合物的分子结构与气相色谱保留值间的关系进行了研究，对部分化合物气相色谱保留值的预测结果表明，这几类化合物的气相色谱保留值具有很好的基团加和性，预测值与实验值吻合很好。     

三种钢基疏水表面微观形貌的分形特征及其对润湿性的影响

采用化学刻蚀与低表面能物质修饰相结合的方法,通过调控刻蚀时间在304不锈钢、X80管线钢和45#钢表面构造不同的微观形貌;借助扫描电子显微镜采集不同材料表面的微观形貌,并采用接触角测量仪测量其润湿性能;应用Matlab软件编程计算分形参数.结果表明,3种材料构造的疏水表面均具有分形特征,且最佳刻蚀时间为30 min,此时多重分形谱子集维数最大值最靠左,对应的奇异性指数最小,表征表面微观形貌的分形维数也达到最大值;分形维数与接触角线性拟合效果优良,接触角随分形维数的增大而增大.     

水介质对紫外光固化丙酸酯材料表面性能的影响

将含有探针组分的光敏树脂分别在水中、空气中进行紫外光固化,并对固化材料的表面性能进行了研究.固化膜的表面能测定表明,水中固化的材料表面能大于在空气中固化的材料.X射线光电子能谱(X-ray photoelectron spec-troscopy,XPS)分析表明,探针组分在不同固化介质中的运动方式不同;固化过程中组分的不同迁移、基团翻转最终导致了固化膜表面性能的差别.     

粗糙PTFE涂层表面结构对乙醇/水混合溶液润湿性的影响

以具有粗糙结构的超疏水的聚四氟乙烯(PTFE)涂层为基体, 研究具有不同表面张力的乙醇/水混合溶液在表面的润湿. 通过空气分率的计算并进行液滴受力分析. 结果表明, 随着表面张力的降低, 乙醇/水混合溶液逐渐填满涂层表面的粗糙结构, 当表面张力大于约28 mN·m-1时, 溶液首先填满表面上的条纹状结构; 当表面张力小于约28 mN·m-1时, 溶液填满表面上的乳突状结构. 当条纹状结构被填满时, 粗糙表面空气分率下降很小, 溶液不能润湿PTFE涂层表面;当乳突状结构被填满时, 粗糙表面空气分率迅速下降,溶液能够润湿PTFE涂层.     

荧光探针法研究连接基团对双子型阳离子表面活性剂聚集行为的影响

利用荧光探针法和表面张力法测定了新型双子型阳离子表面活性剂的临界胶团浓度(cmc)、最低表面张力(γ_cmc)、胶团微极性和胶团聚集数(N_agg),探讨了连接基团对此类表面活性剂在水溶液中聚集行为的影响.结果表明,当连接基团增长时,cmc和胶团微极性增加,γ_cmc增大,N_agg减少,表面活性降低,在溶液中自发形成胶团的能力减弱.     

活性炭表面基团的调变对Ru/AC氨合成催化剂的影响

通过硝酸处理的方法对活性炭表面基团进行了调控,研究了活性炭表面基团的数量对负载钌基氨合成催化剂的影响。运用N2物理吸附、CO化学吸附、Boehm滴定法和质量滴定法等分析手段对催化剂进行了表征。结果表明,随着预处理硝酸浓度的增加,活性炭表面含氧基团的数量线性增加,等电点逐渐减小,而催化剂的活性先增加后减小,钌的分散度也呈现相同的规律。当硝酸浓度达到4.6mol/L时,活性炭表面总含氧基团量为1.21mmol/g,钌的分散度和催化剂的活性都是最佳。适量的含氧基团对提高钌的分散度是有利的,但过量的含氧基团并不能进一步提高钌的分散度,催化剂的合成氨活性和载体表面的含氧基团数量不是线性增加的关系。     

Gemini表面活性剂联接基团对合成硅基介孔材料结构的影响

考察了Gemini表面活性剂不同联接基团对介孔结构的影响, 通过改变联接基团碳链的长度和在联接基团中加入苯基和羟基改变链的柔性和亲水性, 可改变表面活性剂在两相界面的头基面积和电荷分布, 形成不同的表面活性剂溶液结构, 并通过自组装过程控制生成不同介孔材料的孔结构. 当联接基团链长为4~8个碳时, 得到六方相孔道结构, 而当碳链长度增加为10~12个碳时, 形成立方相孔道结构, 其中以GEM16-6-16为模板, 形成了高度有序的MCM-41, 以GEM16-12-16为模板, 则得到高度有序的MCM-48. GEM16-3(OH)-16可合成出层状结构, 但有序性较低. GEM16-(1-Ar-1)-16的cmc较低, 在水溶液中溶解度极低, 当加入共溶剂乙醇时, 得到了空心球结构.     

表面含氧基团对AuCl3-CuCl2/C双组分非汞催化剂催化性能的影响

采用HNO₃氧化及在He气氛围经不同温度焙烧处理椰壳活性炭, 以此活性炭为载体, 通过浸渍法制得AuCl₃-CuCl₂/C双组分非汞催化剂, 并用于乙炔氢氯化反应评价. 结果表明, 分别以HNO₃处理、 未处理和400 ℃焙烧处理活性炭为载体的催化剂乙炔转化率最高分别可达98%, 96%和90%; 而以700和1000 ℃焙烧的活性炭为载体的催化剂反应4 h后乙炔转化率急剧下降为30%. 考察了活性炭表面的含氧基团(尤其是羟基)对Au基催化剂的催化性能的影响.     

CuO调配SnO2表面用于碳烟颗粒燃烧:单层分散阈值效应对催化性能的影响

柴油发动机由于具有良好的动力和经济性等优势而得到广泛的应用,但排放的尾气中碳烟颗粒物(PM)却给人类健康和环境带来了严重的危害.目前PM污染的治理引起了广大科研工作者的关注.催化燃烧成为PM污染消除技术中最有效的方法.金属氧化物负载到载体上时,通常会出现单层分散现象,其单层分散容量可以通过XRD, XPS和Raman等外推法测定.此外,当负载体系用作某种反应的催化剂时,往往会表现出单层分散阈值效应,即阈值附近的催化剂通常具有较高的活性和选择性等.目前单层分散理论已被广泛接受,成为设计高性能催化材料的重要指导思想.在过去八年本课题组将SnO_2基催化材料用于多种环保和能源反应,并系统地探究了其催化性能.结果表明, SnO_2含有丰富的表面活泼氧和晶格氧,且热稳定性高,是一种优良的催化剂载体.基于单层分散理论,为获得更实用的PM燃烧催化剂,我们利用浸渍法设计制备了系列不同Cu O负载量的Cu O/SnO_2催化剂,并使用XRD, XPS, Raman, TEM, STEM-mapping,H2-TPR, soot-TPR和O2-TPD等手段深入研究了其构效关系.利用XRD和XPS外推法测得的Cu O高度分散在SnO_2载体表面,其单层分散阈值为2.09 mmol100m~(-2),即相当于4.8%CuO负载量.低于该负载量时, CuO以亚单层分散态存在;而高于该负载量时,形成的Cu O微晶和单层分散态的Cu O共存.在单层分散阈值之前,催化剂的碳烟燃烧活性随Cu O负载量的升高而上升;进一步提高CuO负载量对其活性无明显的影响.Raman结果表明,在单层分散阈值之前, CuO负载到SnO_2载体上可有效形成表面活泼氧中心,且其含量随Cu O负载量升高而增加;进一步提高Cu O负载量则对其含量无明显改变.因此,Cu O/SnO_2催化剂用于碳烟颗粒燃烧具有明显的阈值效应.以上结果表明,表面活泼氧中心含量是决定该催化剂活性的主要因素.     

碳的热处理对PEMFC氧电极性能的影响

氧还原反应;碳黑;碳的热处理对PEMFC氧电极性能的影响;聚合物燃料电池;氧电极     

Experimental investigation on wetting mechanism for coal dust with different metamorphic degree based on infrared spectrum and 13C-NMR

Respirable coal dust accounts for heart and respiratory diseases of coal miners such as asthma, pneumoconiosis, and black lung disease. What is more, coal dust explosion seriously affects coal mine safety production and coal miners' life safety. Generally, dust suppressants are commonly applied in coal mines. However, current dust suppressants are not working effectively. To develop a better dust suppressant, we attempt to explore the factors affecting the wettability of coal dust under different metamorphic levels from the essence of coal dust wetting mechanism in this paper. Specifically, we use Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) to reveal the microstructure of coal from two aspects of functional group and carbon skeleton structure and obtain the micro information of the surface functional group types, quantity, and carbon structure of coal with different degrees of metamorphism, as well as the change rule of functional group of coal sample with coal rank and the law of carbon increase and deoxidization of coal metamorphism. After that, we acquired the structural parameters of coal by the NMR experiments and fitted the quantitative mathematical relationship between the microstructure parameters and wettability of coal through SPSS and ORIGIN software. Finally, this paper constructs an evaluation model for the influencing factors of coal dust wettability, explains the influence degree of different coal dust structure on coal dust wettability, improves the coal dust wettability mechanism, and provides more quantitative research ideas and methods for the control of coal dust.     

Effect of oxygen-containing functional groups on the wettability of coal through DFT and MD simulation

To investigate the wettability of different oxygen-containing functional group (OFG) surfaces, graphite substrates were used as a model for coal adsorbents. The substrates were modified with COOH, OH, CO, and OCH₃. The adsorption-diffusion behavior of H₂O molecules/water droplets on different OFG surfaces was investigated using molecular dynamics (MD) simulations with frontier orbital energy difference as a metric for different surface wettability degrees in quantum chemical analysis. The results indicated that the frontier orbital energy difference of the H₂O molecule was 3.480, 3.491, 3.631, and 3.680 eV for PhCOOH, PhOH, PhCO, and PhOCH₃, respectively. In addition, the equilibrium contact angle, interaction energy, and number of hydrogen bonds after the adsorption equilibrium of water droplets for COOH, OH, CO, and OCH₃ surfaces were 22.34°, ?5.03 kcal/mol, and 652; –23.72°, ?4.19 kcal/mol, and 450; 68.01°, ?0.79 kcal/ mol, and 61; 90.51°, ?0.50 kcal/mol, and 28, respectively. The smaller the energy difference between the frontier orbitals of the H₂O molecule and the OFG, the smaller the equilibrium contact angle between the water droplet and the OFG surface, the more hydrogen bonds were formed, and the larger the absolute value of the interaction energy, the better the wettability of the surface of the OFG. The order of wettability of the different OFG surfaces was COOH > OH > CO > OCH₃, which is consistent with the radial distribution function and the analysis results for the extended area, etc. The results of density functional theory (DFT) calculations and MD simulations exhibited identical patterns, indicating the reasonableness of the simulations. This study may serve as a reference for the suppression of hydrophilicity in low-order coal and the enhancement of the flotation effect.     

东胜长焰煤热解含氧官能团结构演化的13C-NMR和FT-IR分析

以东胜煤田色拉一号井田2号煤层长焰煤为研究对象,利用浮沉离心法富集其镜质组。基于工业分析、元素分析、¹³C-NMR、FT-IR、谱图分峰拟合技术和化学分析测试,求取镜煤及一系列热解煤含氧官能团结构与含量参数,从不同角度研究了含氧官能团的分布规律与演化特点。镜煤中羧基、羰基含量分别为8.91~10.90 mol/kg、1.61~1.79 mol/kg,随热解温度升高羧基显著减少。热解作用促使以端基形式连接在脂肪链或脂肪环结构氧上的甲基和亚甲基首先脱去,且在温度高于350 ℃后基本稳定。氧在热解过程赋存状态的变化是芳香体系与脂肪体系相互竞争的结果,510 ℃热解煤中芳香类氧和脂肪类氧的含量分别为7.49、3.45 mol/kg。羟基的演化过程与热解过程中氧的赋存状态密切相关。随着热解过程的进行,在热解温度低于440 ℃时,各种羟基含量均减少,热解过程对于大分子网络的破坏干扰了各种氢键作用,而羟基π作用则暂时增强,至510 ℃时各种氢键含量均降为最低。东胜长焰煤中含氧官能团化学活性顺序为:[COOH]>[R-O]>[Ar-O-Ar,Ar-O-C,C-O-C]>[C=O]。镜煤非活性醚键含量为0.68 mol/kg,活性醚键为0.48 mol/kg,主要为非活性醚键。     

Evolution of the composition and structure of PAN carbon fiber during preoxidation

Using scanning electronic microscope, X-ray diffraction analysis, PYR-GCMS and IR etc., we studied the evolving process of the composition and structure of PAN carbon fiber during preoxidation. In the initial stage of preoxidation, PAN filament tows disappear and become semi-thaw. At first, reactions happen between the copolymers and esters disappear. The molecules annularly crosslink and the index of cyclation slowly increases. It is easy to fix the structure and form defects during the initial and the medium stages, which are most reactive. More traction is advised in these stages to minimize the structural deficiencies. In the medium stage of preoxidation, the fiber was reshaped into new sheet stacks and gradually changed to sheet sectors, and this structure tends to be stable in the final stage. Induced by acid and ester copolymer, PAN fiber forms a very stable cycle structure in the final stage. Besides, monomer, dimmer and trimer obviously decrease. In the final stage of the preoxidation, there exi     

微孔碳分子筛表面含氧基团对H_2O_2催化分解的动力学影响

多孔碳的表面含氧官能团对其吸附及催化性能的影响受到越来越多的关注[1-2],表面含氧基团对活性炭催化醇脱水[3]、乙苯脱氢[4]、O2还原为过氧化氢[5]、Fe(II)与O2氧化反应[6]已有报道.     

昭通褐煤的热解提质及其对气化反应性能的影响

为了对储量相对丰富的昭通褐煤进行合理有效的分级转化利用,采用固定床程序升温热解的方法研究了不同温度下煤的热解行为,借助GC-MS和拉曼光谱对所得焦油和煤焦进行了表征分析,并在850℃下对不同热解温度制得的煤焦进行了水蒸气等温气化特性评价。结果表明,热解温度为700℃时,热解气体有效组分(H_2、CO、CH_4)的累积物质的量占总释放量的70%,此温度下热解气低位热值增长速率最快(以500℃下热解气低位热值为基准计算,其值为90%);酚类化合物在500-700℃大量生成析出,而温度高于700℃时,酚类化合物的分解反应加剧。不同热解温度下所制煤焦的表观气化反应速率随热解温度的升高不断降低,气化产物中CO_2与CO的物质的量逐渐升高,700℃热解制得的煤焦在水蒸气气氛下气化所得合成气中有效组分H_2与CO的比率最高。     

光催化制氢中助催化剂表面氢氧复合反应的抑制

在光催化分解水产氢的过程中,Pt等助催化剂在催化产生氢的同时也会诱导催化氢气和氧气重新复合为水的逆反应,严重降低了悬浮体系光催化全分解水产氢的效率。本文综述了近年来在逆反应抑制方面的研究进展,总结和对比分析了各种抑制逆反应策略的特点,并对这些方法的应用于悬浮体系光催化全分解水制氢的前景进行了展望。     

显微镜图像分析研究非相容高密度聚乙烯/尼龙1010共混体系熔体动态过程中相结构的形成与发展

讨论了非相容高密度聚乙烯,尼龙1010共混体系在熔融混炼过程中相结构的形成与发展.应用在线连续采样方法,获得共混过程中体系不同时刻的样品,应用扫描电子显微镜观察并得到共混物相结构的显微图像.用图像处理和图估计方法求得了体系分散相平均粒径和粒径分布宽度,讨论了平均粒径和分布宽度随混炼时间的变化.结果表明,共混物相结构的变化主要发生在混炼初期,即混炼两分钟以前,之后平均粒径和分布宽度趋于平稳,保持在一定数值范围内.引入分性概念,应用测度法计算了体系的分形维数,表明体系相结构的变化具有自相似性,分形维数的变化与体系的均匀性有关.同时,研究了混炼温度和混炼设备的转速(剪切速率)与体系分散相平均粒径、分布宽度和分形维数等结构参数的关系.     

Adsorption of acetonitrile and its reaction with oxygen on TiO2-supported Au — Rh bimetallic catalysts

The adsorption of acetonitrile and its surface reactions with oxygen on TiO₂-supported Au — Rh bimetallic catalysts were studied by FTIR and mass spectrometry at 300–673 K. The band due to CH₃CN on Lewis acid centres shifted to lower wavenumbers with the increase of the Rh content, which shows that the strength of Lewis acid sites weakens with the increase of the Rh content of the catalysts. CH₃CN, on the other hand, dissociates producing CN_(a) species. From the shift to higher wavenumbers of the band due to CN_(a), strengthening of the C — N bond with increasing Rh content has been established. During the heat treatments of the adsorbed CH₃CN layer, methylamine (CH₃NH₂) was detected in the gas phase, the amount of which depended on the composition of the catalysts. Dehydrogenation of the adsorbed acetonitrile also depends on the Rh content: the higher the Rh content of the sample, the lower the temperature of the first appearance of gaseous H₂, and the higher the amount of H₂ evolved. The presence of gaseous oxygen affects the formation of isocyanate (NCO) surface species only on 1% Au/TiO₂ and on 1% (0.75Au–0.25Rh)/TiO₂ catalysts.