高比表面积PAN-ACF的吸附与孔结构解析

以KOH为活化剂制备了比表面积大于2000m^2/g的高比表面积PAN基活性炭毡（ACF）,以液氦为吸附介质在77．4K测试PAN－ACF吸附等温线,并对其孔结构进行了表征。采用BET法计算比表面积,t-plot法,Horvath-Kawazoe,Dubinin-Radushkevich方程以及密度函数理论（DFT0表征孔结构。研究表明即使比表面积超过3000m^2/g时,PAN－ACF的孔分布仍然很窄,并且含有大量的分子筛型孔,以金子克美等人提出多段吸附机理为依据,采用DR方程对PAN－ACF三段吸附过程所对应的E^0,x进行了计算。结果认为低压段的负偏离在一定程度上是由于吸附较强的微孔与表面官能团共同作用的结果,并非完全由于活化扩散引起,以上分析方法的表征结果具有较好的一致性,为PAN－ACF的吸附性能与孔结构提供了准确的信息。     

CO_2直接活化法制备PAN基活性炭纤维及其对苯系气体吸附性能的研究

以聚丙烯腈(PAN)预氧丝为原料,采用CO_2直接活化法,制备了PAN基活性炭纤维,并通过液压成型方式将PAN基活性炭纤维制成滤材。通过氮吸附、SEM和XPS对制得的PAN基活性炭纤维进行表征。利用自搭建的吸附性能测试系统,将PAN基滤材和以相同成型方法制成的粘胶基滤材进行苯、甲苯的吸附测试。结果表明,自制的PAN基活性炭纤维比表面积为860m2/g,总孔容积为0.361m3/g,最可几孔径为0.62nm,官能团为羟基、醚基、羧基、酯基和类吡啶基团。PAN基滤材单位表面积对苯和甲苯的饱和吸附量均大于粘胶基滤材,其吸附活性位比粘胶基滤材多,更适合用来吸附苯系污染物。     

新型炭／T型分子筛复合膜材料的设计、制备及应用

以聚酰胺酸为有机前驱，两种不同形貌的T型分子筛为杂化物经高温热解制备了新型的炭／T型分子筛复合膜材料。利用TG、XRD、SEM等分析手段对所制备的复合膜的微结构进行了研究。结果表明，T型分子筛在炭相中分散良好，其晶体结构在热解过程中没有被破坏，同时形成了稳定的无机，无机复合结构。单组分气体（CO2，O2，N2和CH4）以及混合气体（CO2／CH4，O2／N2）的渗透实验表明，分子筛减小了气体分子在膜中的扩散阻力从而大大提高了复合膜对气体分子的渗透能力，其中，复合膜对CO2和O2渗透系数可达1302Barrer[1Barrer=1×10^-10cm^3（STP）·cm／cm^2·s·cmHg]和334Barrer，同时CO2／CH4混合气体分离系数达到62，O2／N2分离系数达到8左右。这些数据表明该复合膜是一种可实现大规模二氧化碳以及空气分离的理想膜材料。     

负载含银介孔分子筛活性碳纤维的制备与性能

将CAF加入由以十二胺，正硅酸乙酯，乙醇，水等组成的介孔分子筛（MS）合成反应液中制备负载MS的活性碳纤维（ACF－MS），MS含量由反应液中ACF的含量确定，通过真空浸渍和热分解使ACF－MS载银，载成新型净水材料－负载含银介孔分子筛的活性碳纤维（ACF－MS（Ag)），银含量由浸渍时间控制，在流动水的冲刷下ACF－MS（Ag)样品中的银含量缓慢下降，下降速率随着水流速和样品含银量的增加而增加，与ACF（Ag）相比，ACF－MS（Ag)的耐水冲刷性能显著提高。     

KOH二次活化制备富含中孔的PAN—ACF

以水蒸汽活化的聚丙腈基活性炭纤维（PAN－ACF）为原料,研究了KOH二次活化对PAN－ACF纳米孔隙结构发展过程的影响。以氮吸附等温线为基础,根据微孔填充理论,采用αs-plot和DFT等方法研究了二次活化PAN－ACF的纳米微结构。结果表明：在实验考察范围内,经过二次活化后PAN－ACF的比表面积和孔容积增加,尤其中孔容积增加显著,约占总孔容积的50％,活化过程中不出现大孔。     

炭分子筛的结构和表面性质对其吸附分离CH4/N2和CO2/N2的影响

对日本Takeda(CMS-1)、Kuraray(CMS-2)和德国BF(CMS-3)3种炭分子筛(CMS)的孔结构和表面官能团进行了表征,分析了它们对CH4/N2和CO2/N2的吸附平衡和吸附动力学分离性能,以及CMS的结构与表面性质对吸附性能的影响。结果表明,CMS-1和CMS-2可实现CH4/N2的动力学分离,还可实现N2/CO2的平衡分离;CMS-3平衡分离CH4/N2和CO2/N2的效果要优于动力学分离。孔结构是影响炭分子筛分离性能的直接因素,孔径分布的差异使CMS-1和CMS-2对CH4/N2的位阻-动力学分离效应表现得更为明显;表面含氧官能团有利于提高炭分子筛的吸附分离性能。     

H2O2改性对聚丙烯腈原丝化学结构的影响

为节省预氧化进程的能耗和时间并优化聚丙烯腈（PAN）预氧纤维的性能,用H₂O₂改性PAN原丝,使其提前环化。采用FTIR、XPS等方法表征不同处理温度获得的未改性和改性PAN原丝。结果表明:H₂O₂水溶液在60℃改性PAN原丝时,H₂O₂可引发氰基环化,末端环发生亚胺、烯胺互变异构,由此出现亚氰基、类芳香伯胺;改性温度越高,改性PAN原丝的亚氰基含量、共轭程度越大。在模拟稳定化过程中,改性PAN原丝的类芳香伯胺可在较低温度下引发相邻氰基环化。使用氨水（NH₃H₂O）作为助剂获得改性PAN原丝,与未改性PAN原丝经历相同的预氧化进程,改性后的PAN原丝能在较短时间内达到适合的预氧化程度,且PAN预氧纤维径向结构的均匀性被改善,由此获得热稳定性更高的PAN预氧纤维。      

PAN基活性炭纳米纤维的制备及其对金的吸附研究

采用静电纺丝技术,制备了聚丙烯腈纳米纤维,并以聚丙烯腈纳米纤维为前驱体,制备了PAN基活性炭纳米纤维,并对PAN基活性炭纳米纤维吸附金的性能进行了初步研究,取得了令人满意的结果。     

PAN基碳纤维原丝致密性及其孔结构研究

利用碘吸附法、扫描电子显微镜（SEM）、透射电子显微镜（TEM）和小角x射线衍射（SAXS）等测试方法对国内外企业生产的几种聚丙烯腈（PAN）基碳纤维原丝的致密性及孔结构进行了较系统的测试与研究。结果表明,各种PAN原丝内部都存在着疏松的孔结构,致使其致密性较差,且孔结构的尺寸分布不均。PAN基碳纤维原丝的结构缺陷对其性能有着重要的影响作用。     

氟化活性炭纤维对极性分子的吸附

将活性炭纤维（ACF）与氟气反应制备出氟化活性炭纤维（FACF），根据将FACF与参照试样XPS的对比，碳原子是以sp^3杂化轨道同氟原子形成共健键。αs图分析氮吸附等温线的线果表明，ACF氟化后其比表面积和微孔容积都显著降低，微孔宽度基本不变，ACF的水吸附等温线呈V型，而FACF对水的吸附量极小；FACF的微孔表面具有完美的憎水性和高稳定性，乙醇和甲醇在ACF上的吸附等温线是Ⅰ型，在FACF上接近于Ⅰ型，但吸附量显著降低。     

Application of low-temperature glassy carbon films in solid-phase microextraction.

Low-temperature glassy carbon (LTGC) films were investigated as a sorbent coating for solid-phase microextraction because of its uniquely selective adsorptive characteristics. The selectivity of these coatings is primarily controlled by shape characteristics of the solute molecule and the final processing temperature used to form the LTGC, demonstrating unique adsorptive characteristics compared to commercial phases. The LTGC films were prepared by first coating porous silica particles with a diethylnyl oligomer precursor and then heat curing at temperatures between 300 and 1000 degrees C to form the LTGC. Then, using a sol-gel process, the LTGC-coated silica particles were immobilized onto stainless steel fibers and subsequently used for headspace and liquid extractions followed by GC-FID analysis. The selectivity of the LTGC is demonstrated by the extraction of a variety of aromatic hydrocarbons as well as the taste and odor contaminants geosmin, 2-methylisoborneol, and 2,4,6-trichloroanisole commonly found in water supplies. The data show that the LTGC coating has the highest affinity for molecules with the greatest cross-sectional surface area and polarizability and that this selective mechanism increases as a function of LTGC processing temperature.     

Combination of nanogel polyethylene glycol-polyethylenimine and 6(hydroxymethyl)-1,4-anthracenedione as an anticancer nanomedicine

Polyethylene glycol-polyethylenimine (PEG-PEI) nanogels have been used to deliver nucleic acids and oligonucleotides into cells. First, we synthesized PEG-PEI nanogels with methylene proton ratios (CH2O:CH2N) in PEG-PEI ranging from approximately 6.8:1 to 4:1 and less, as shown by 1H NMR spectra. We first synthesized various nanogels with varying ratios of CH2O:CH2N (methylene proton) in PEG-PEI as shown by 1H NMR spectra and tested their cytotoxicity using a rodent pancreatic adenocarcinoma cell line (Pan 02). We showed that the nanogel PEG-PEI with methylene proton ratio of 4:1 was strongly cytotoxic to Pan 02 cells in vitro, while the nanogel with the methylene proton ratio of 6.8:1 was not toxic. We incorporated a novel anti-cancer drug, 6-(hydroxymethyl)-1,4-anthracenedione (AQ) analogue (AQ10) into nontoxic nanogel PEG-PEI and tested the effect of AQ10 loaded nanogel PEG-PEI (AQ10-nanogel PEG-PEI) and AQ10 dissolved in DMSO on Pan 02 cell growth. The size of this AQ10-nanogel PEG-PEI was characterized using atomic force microscopy (AFM). Our studies showed that the AQ10-nanogel PEG-PEI is readily taken up by Pan 02 cells. Growth attenuation of Pan 02 cells treated with AQ10-nanogel PEG-PEI was three to four times that of cells treated with AQ10 dissolved in DMSO. These results suggest that PEG-PEI, usually used to deliver nucleic acids into cells, can also be used to deliver an insoluble small molecule anticancer drug, AQ10.     

KOH活化法制备气体分离用炭分子筛膜

选用KOH为活化剂,利用化学活化法制备炭分子筛膜,考察在热塑性酚醛树脂(PFNR)涂膜液中添加不同质量分数的KOH对炭分子筛膜的影响.结果表明,在炭化过程中,KOH的加入可促进炭分子筛膜孔径的均匀分布,使炭分子筛膜具有发达的孔隙结构.当KOH在PFNR中的添加量从0％增加到4％时,H2的渗透速率由23.68×10-10 mol·m-2·s-1·pa-1提高到28.6×10-10 mol·m-2·s-1·Pa-1;但H2/N2和H2/CH4的分离系数明显下降,分别从471.3下降到147.5、540下降到270.CO2/CH4和O2/N2的分离系数只有轻微下降.     

Temperature programmed CVD: a novel technique to investigate carbon nanotube synthesis on FeMo/MgO catalysts

In this work, it is demonstrated how a novel technique based on temperature-programmed chemical vapor deposition (TPCVD) can be used to investigate the synthesis of carbon nanotubes (CNTs) from methane on a classic catalyst FeMo(x)/MgO (x = 0.07, 0.35 and 1.00). TPCVD monitors carbon deposition by measuring H2 formed during CH4 decomposition and affords information on the different catalytic species, deactivation process, reaction kinetics and carbon yields. The obtained results showed for FeMgO catalyst a simple TPCVD peak related to the production of carbon beginning at 760 degrees C with maximum at 800 degrees C followed by a rapid deactivation resulting in a low carbon yield. The addition of Mo to Fe/MgO catalyst completely changes the TPCVD profile with the formation of a new catalytic species active at temperatures higher than 900 degrees C, which is stable and continuously decomposes CH4 to produce high carbon yields. Raman, TG/DTG, M?ssbauer, SEM, TEM, XRD and TPR analyses suggested that this active catalytic phase is likely related to Fe-Mo and Fe-Mo-C phases active to produce single wall and mainly multiwall carbon nanotubes.     

Growth and structure of TiCxNy coatings chemically vapour deposited on graphite substrates

TiCxNy coatings were grown on graphite substrates in a computer-controlled, hot-wall chemical vapour deposition (CVD) reactor, using gas mixtures of TiCl4–CH4–N2–H2 at a total pressure of 10.7 kPa (80 torr) and at a temperature of 1400 K. Growth rate, composition, morphology and crystallographic texture of the TiCxNy coatings were investigated as a function of the CH4/CH4+N2 ratio in the range 0–1 at a constant CH4+N2 flow rate of 370 standard cubic centimeters per minute (sccm). The C/C+N ratio and growth rate of the TiCxNy coatings increased with increasing CH4/CH4+N2 ratio in the gas phase. The compositions of the coatings with C/C+N ratios in the range 0–1 were found to be between the thermodynamic and the kinetic predictions. Morphology and preferred orientation of the coatings were observed to be strongly affected by the CH4/CH4+N2 ratio in the gas phase.     

聚醚共聚酰胺多层复合气体分离膜的制备及其分离性能

采用浸渍涂覆法,以聚醚共聚酰胺PEBA1074嵌段高分子为选择层膜材料制备具有超薄分离层的PEI/PDMS/PEBA1074/PDMS多层复合气体分离膜,探讨了操作条件对H2、N2、CH4和CO2等在多层复合膜中的渗透性能的影响.多层复合膜对极性气体具有较高的渗透通量,并且对极性/非极性气体分离体系具有较高的选择性.CO2对多层复合膜存在增塑作用,其渗透通量随操作压力的增加而增加;随着操作温度的升高,H2、N2、CH4和CO2在复合膜中的渗透通量显著增大,而CO2/非极性气体(H2、N2和CH4)的分离系数减小.气体渗透通量与温度的关系在PEO链段熔点的上下分别满足不同的Arrhenius方程.当操作温度大于PEO链段熔点温度时,气体的渗透活化能减小.     

Dicationic ion-pairing agents for the mass spectrometric determination of perchlorate

Perchlorate and other hydrophobic ions can be measured with high sensitivity and selectivity by forming a positively charged ion pair with a dicationic agent. A commercially available reagent, 1,6-bis(trimethylammonium)hexane dibromide (Br(N(CH3)3)(CH2)6(N(CH3)3)Br) allows for the determination of perchlorate by electrospray ionization mass spectrometry as the [(N(CH3)3)(CH2)6(N(CH3)3)ClO4]+ ion. Limits of detection (LODs) are better than those previously observed with custom-synthesized dicationic agents. An LOD of 20 ng/L is readily attainable with a single-quadrupole mass spectrometer.     

The enhanced adsorption of dibenzothiophene onto cerium/nickel-exchanged zeolite Y

The investigations for selective adsorption of dibenzothiophene (DBT) over Ce/Ni-loaded Y zeolites with the emphasis on the effect of Ce as a cocation in the Ni-loaded Y zeolite are carried out in an attempt to produce more effective adsorbents for the desulfurization from transportation fuels. The promotional effects of Ce and coexisting toluene in the model fuel as well as contact time and adsorbent dose on the adsorptive performance were examined. The sulfur uptake strongly depends on the amount of Ce in the zeolite structure. The sorption data is varied according to both Langmuir and Freundlich isotherm models. The maximum sorption capacity by theoretically calculation is 22.2mg/g at 25 degrees C. The Langmuir constants b=5.82 mL/mg and the Freundlich constants K=1.042 L/mg and 1/n=0.4 are evaluated. Ni/Ce-loaded Y zeolites (NiCeY) and NiY, CeY, NaY zeolites were used as adsorbents for the removal of DBT from model fuel containing 500 mg/L sulfur with 5 vol% of toluene by a batch method under ambient conditions. NiCeY exhibits higher adsorptive selectivity for DBT than NiY and CeY, indicating that NiCeY is a more effective adsorbent to remove sulfur compounds from transportation fuels.     

Optimization of (15)n detection with an atomic emission detector

Gas chromatography with atomic emission detection is a useful tool for the detection of stable isotope labels in complex samples. While papers involving the analysis of D and (13)C are numerous, little work has been done in the area of (15)N detection. For (15)N isotope detection, three reagent gases are used: H(2), O(2), and CH(4). In this work, the reagent gas flows were varied to optimize the sensitivity of (15)N detection without sacrificing isotope selectivity. The optimal gas flows determined in this work produce the following ratios of the spectral peak areas: O 725 area/He 728 area = 0.039 with only O(2) flowing; H 486 area/He 492 area = 12 with only H(2) flowing; C 496 area/He 502 area = 0.41 with O(2), H(2), and CH(4) flowing for C and no gases flowing for He. When using these gas settings, the (15)N sensitivity is increased by nearly 2 orders of magnitude relative to the manufacturer-recommended settings. It was also demonstrated that the presence of a compound in both the labeled and unlabeled forms in the same sample does not affect the response. The ratios of (15)N to (14)N in standards, calculated from calibration plots (which are linear for both isotopes), agree well with the actual values. A tobacco smoke sample containing various (15)N-labeled compounds was used to show the utility of the GC-AED for indicating which compounds in a complex sample contain the label. This sample also demonstrates the necessity for optimal sensitivity when dealing with samples containing small amounts of compounds with low incorporation levels.     

等离子体化学气相沉积金刚石膜过程中光发射谱和朗谬尔探针原位诊断

报道了利用光发射谱(OES)和朗谬尔探针对热阴极直流放电等离子体化学气相沉积金刚石薄膜的等离子体条件进行原位研究的部分结果,研究了几种过程参数变化中等离子体状态,并与金刚石膜的沉积相联系。当CH