聚糠醇炭分子筛膜的制备及O_2/N_2分离性能研究

以草酸为催化剂将糠醇单体直接聚合成所需黏度的聚糠醇液体作为涂膜液,仅需一步涂覆便可在价格低廉的煤基炭管支撑体上制备出高性能的聚糠醇炭分子筛膜.聚糠醇炭分子筛膜的热解过程、微观形貌和分离性能分别采用热重分析、扫描电镜以及O2、N2渗透实验进行表征.实验结果表明制备出的聚糠醇炭分子筛膜表面均匀且无缺陷.聚糠醇在热解过程中最终转化成具有超微孔的乱层石墨微晶结构.热解温度升高导致了起分离作用的有效超微孔尺寸的减小,进而表现出O2、N2的渗透速率逐渐降低,O2/N2的选择性逐渐增大的趋势.不同热解温度下制备的炭分子筛膜的O2渗透性和O2/N2选择性之间关系均超出了传统聚合物膜的Robeson上限.     

CO_2捕集炭膜的前驱体结构设计及性能

从分子结构设计出发,合成了一系列新型刚性、高自由体积的聚酰亚胺炭膜前驱体,并制备了炭膜.采用热重分析(TGA)、傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)和高分辨透射电子显微镜(HRTEM)研究了不同聚酰亚胺前驱体的热分解特性及在热解炭化过程中化学结构、微结构的变化规律;测试了所制备炭膜的气体分离性能.结果表明,前驱体的自由体积分数显著影响炭膜的气体分离性能;聚合物结构越具刚性,自由体积越大,所得炭膜结构越疏松,极微孔道尺寸越大,越有利于气体分子在炭膜极微孔道中的渗透、扩散与传输.其中,刚性大体积基团芴基、酚酞cardo基团和六氟异丙基的引入能有效破坏分子链间的堆积,提高聚合物的自由体积,所形成炭膜的结构较疏松,均表现出优异的气体渗透性和分离选择性,超越了Robeson上限,解决了传统炭膜气体渗透性能低的问题.特别是采用羟基官能化聚酰亚胺前驱体制备的炭膜在保持较高气体分离选择性的同时,CO_2气体的渗透性高达24770 Barrer(1 Barrer≈7.5×10-18m2·s-1·Pa-1),可实现对CO_2的有效分离和捕集,展现出良好的商业化应用前景.     

酸和CTAB对聚糠醇膜形貌的影响

本文采用静态界面聚合法,首次成功地制备出不同形貌的聚糠醇(PFA)膜,用SEM、TEM及TG-DTA等对其形貌、结构进行了表征。结果表明:通过改变催化剂酸的种类及表面活性剂(CTAB)用量可得到不同形貌的聚糠醇膜。该法具有合成条件温和、易于控制、能一步合成大量不同形貌的聚糠醇膜等众多优点。     

聚酰亚胺多孔碳膜的制备及其表征和应用

以乙醇为溶剂,采用溶胶-凝胶法制备了二氧化硅微球.首先由二甲基乙酰胺(DMAc)、4,4—二氨基二苯醚及均苯四甲酸二酐(PMDA)得到聚酰胺酸;再以二氧化硅微球作为模板剂,经亚胺化聚酰胺酸得到聚酰亚胺复合膜;复合膜经浸渍脱模板、高温炭化后得到多孔碳膜.采用扫描电镜观察了多孔碳膜的微结构;同时考察了碳膜的机械稳定性及其对催化剂的担载性能.结果表明,所制备的碳膜具有良好的结构多孔性和机械稳定性;其比表面积为377 m2.g-1,总的孔体积约为0.097 cm3.g-1.与此同时,多孔碳膜对金属Pt催化剂和葡萄糖氧化酶具有良好的吸附作用和担载性能.     

不同溶剂对聚醚砜酮基炭膜结构及气体分离性能的影响

为考察不同溶剂对聚醚砜酮(PPESK)炭膜结构和性能的影响,以PPESK为前驱体,分别以NMP,CHCl3,C2H2Cl4,DMAc为溶剂制备气体分离炭膜。并采用红外光谱、热重分析、X射线衍射和气体渗透等测试手段对所制膜的化学结构、炭膜的微结构和气体的分离性能进行了表征。结果表明,溶剂的溶度参数、沸点、挥发性以及原膜中溶剂的含量等导致所制备聚合物膜形成不同的化学结构,改变它在预氧化和炭化过程的结构变化规律,使形成炭膜表现出不同的炭结构、孔隙结构和表观柔韧性,最终影响炭膜的气体渗透性和分离选择性。     

具有不对称孔道结构的小介孔二氧化硅粒子的合成及其高分子杂化膜的构建

利用手性阴离子酸表面活性剂, 采用软模板法制备了具有不对称孔道结构的小介孔二氧化硅(SiO₂)粒子. 将小介孔SiO₂粒子引入聚偏四氟乙烯(PVDF)和聚酰亚胺(PI)中构建了两种有机/无机杂化膜. 利用傅里叶变换红外光谱(FTIR)、 透射电子显微镜(TEM)、 扫描电子显微镜(SEM)和比表面积分析等表征了小介孔SiO₂粒子和有机/无机杂化膜的微结构, 并通过超滤实验和气体渗透实验分别考察两种杂化膜的性能. 研究结果表明, 表面含有大量亲水基团的小介孔SiO₂粒子具有规则有序排列的孔道结构, 该孔道结构呈现螺旋扭曲和不对称性. 构建的两种有机/无机杂化膜的极性显著提升, 进而有效增强了PVDF杂化膜的膜通量和抗污染性能及PI杂化膜对CO₂气体的分离性能, 克服了高分子膜的博弈效应(Trade-off效应). 另外, SiO₂的小介孔孔道还可以在PI杂化膜中引入优先通过CO₂分子的限域传质通道, 加速了CO₂气体在杂化膜中扩散. 但过多小介孔SiO₂粒子的加入导致其在高分子基质中团聚, 削弱杂化膜的极性和亲水性, 从而降低了两种杂化膜的分离性能.     

溶胶凝胶法合成聚酰亚胺二氧化钛杂化膜

溶胶凝胶法制备了负载型聚酰亚胺 二氧化钛杂化膜 ,采用扫描电镜、红外光谱、TG DTA、压汞法和气体渗透性能测试装置对膜材料的表面形貌、表面结构、热性能、孔径分布和气体渗透性能进行了表征 .结果表明 ,杂化膜材料形成了有机相包裹无机相的交联结构 ;聚酰亚胺与二氧化钛粒子形成了新型键联结构 ;其热分解温度随二氧化钛含量的增加而降低 ,在 4 5 0℃以下热稳定性优于聚酰亚胺膜材料 ;平均孔径随二氧化钛含量增大而增大 ,孔径分布趋于弥散 ;N2 、H2 和CO2 在膜内渗透由Knudsen扩散控制 ,H2 O N2 分离因子均大于Knudsen扩散值 ,表现出良好的亲水性 .     

化学气相沉积聚合制备羧基取代聚对亚苯基二亚甲基及其性能研究

用化学气相沉积(CVD)聚合法制备了羧基取代聚对亚苯基二亚甲基(PPX-carb)膜,采用FTIR和元素分析的方法证实了其化学结构.对膜溶解性和抗化学氧化性能的研究表明PPX-carb膜仍具有优异的耐溶剂性和抗化学氧化性能.对PPX-carb膜热性能的研究表明羧基的引入使得膜的玻璃化转变温度降低,室温柔性增强,动态力学阻尼性能增大,与聚对亚苯基二亚甲基(PPX)相比引入了羧基的PPX-carb热稳定性有所下降,热降解起始温度比PPX低,但主链降解温度比PPX反而高出约80℃.此外,羧基的引入使得膜的亲水性能大幅度提高,水汽渗透性能也有所提高.     

膜相渗透原位化学聚合法制备PAn/CA复合透膜

采用膜相渗透原位化学聚合法,使苯胺(An)原位化学聚合于醋酸纤维素(CA)基体膜的微孔壁中,得到均匀分布的PAn/CA复合导电透膜.通过研究聚合反应条件对复合透膜的导电性能和CO₂/O₂表观分离性能的影响,获得了制备性能较优的PAn/CA复合导电透膜的适宜条件.结果表明,采用膜相渗透化学原位聚合法制备的PAn/CA复合导电透膜,平均孔径明显变小,孔径分布变窄,具有优于CA基体膜的微孔结构形态.     

层级多孔碳载铂催化剂的制备及可达性

层级多孔碳作为氧还原铂基催化剂载体的选择之一, 简单的旋转圆盘电极(RDE)验证此类催化剂具有较高的氧还原活性, 但几乎都缺少膜电极(MEA)性能验证, 实用性无法保证. 本文设计制备了基于聚苯胺的层级多孔碳（NHPC）载铂催化剂（Pt/NHPC850）, 研究了其氧还原活性、 MEA质子传输和氧传输特性. RDE测试研究表明, Pt/NHPC850催化剂在低I/C（离聚物与碳载体质量比）时的面积活性低于实心碳载铂催化剂（Pt/XC-72）, 但当I/C增大到与膜电极中一致时, 由于Nafion树脂对Pt催化剂的毒化作用增强, 其面积活性反而优于 Pt/XC-72. Pt/NHPC850催化剂的高Pt分散性及其优异的抗Nafion毒化性能, 使其在I/C为0.8时的质量活性为Pt/XC-72催化剂的1.34倍. MEA质子传输研究表明, 即使在高加湿条件下, Pt/NHPC850质子电阻率仍高达72.6 mΩ·cm², 为Pt/XC-72的3倍. Pt/NHPC850制备的膜电极极化曲线在500 mA/cm²电流密度下性能迅速下降, Pt/NHPC850的氧增益电压达到144.4 mV, 比Pt/XC-72高56.7 mV. 表明Pt/NHPC850膜电极的质子传输和氧传输性能较差. 对比Pt/NHPC850催化剂的RDE和MEA的测试结果, 说明以层级多孔碳为载体的铂碳催化剂虽然耐Nafion毒化能力提高, 但是质子和氧气的氧传输性较差, 此类层级多孔碳还需进一步优化其结构, 才有可能满足低铂质子交换膜燃料电池（PEMFC）的应用需求.     

Structure and properties relationships for aromatic polyimides and their derived carbon membranes: experimental and simulation approaches

The main objective of this study is to investigate the factors of the chemical structure and physical properties of rigid polyimides in determining the performance of derived carbon membranes through both the experimental and simulation methods. Four polyimides made of different dianhydrides were pyrolyzed at 550 and 800 degrees C under vacuum conditions. The resultant carbon membranes exhibit excellent gas separation performances beyond the traditional upper limit line for polymer membranes. The thermal stability and the fractional free volume (FFV) of polyimides were examined by a thermogravimetric analyzer and a density meter. The chain properties of polyimide, such as flatness, chain linearity, and mobility, were simulated using the Cerius(2) software. All above characterizations of polyimides were related to the microstructure and gas transport properties of the resultant carbon membranes. It was observed that the high FFV values and low thermal stability of polyimide produce carbon membranes with bigger pore and higher gas permeability at low pyrolysis temperatures. Therefore, polyimides with big thermally labile side groups should be preferred to prepare carbon membranes at low pyrolysis temperatures for high permeability applications. On the other side, since the flatness and in-plane orientation of precursors may lead carbon membranes to ordered structure, thus obtaining high gas selectivity, linear polyimides with more coplanar aromatic rings should be first choice to prepare carbon membranes at high pyrolysis temperatures for high selectivity applications. The location of the indan group also affects chain flatness and in-plane orientation. As a result, carbon membranes derived from the BTDA-DAI precursor have superior separation performance to those derived from Matrimid.     

The Utilization of Douglas-Fir Bark for the Production of Oxalic Acid and High Density Carbon Pellets

The production of oxalic acid by the catalytic oxidation of Douglas-fir (Psedotsuga menfiesii (Mirb) Franco) bark and subsequent pyrolysis of the residue to produce high density carbon pellets is discussed. Kinetic rate data are presented for oxalic acid production from Douglasfir bark. A maximum yield of 38 wt% oxalic acid has been obtained in 8 h at 80°C with 62.5 vol% HNO₃ and 0.5 mg V₂O₅/g of bark. Additional oxalic acid can be produced by the conversion of pyrolytic oils and tars (obtained during carbonization of the residue) to increase the total yield to 45 wt%. An economic analysis based on the current cost of oxalic acid indicates the viability of the proposed process.     

Effect of pyrolysis temperature and operating temperature on the performance of nanoporous carbon membranes

Technology designed to capture and store carbon dioxide (CO₂) will play a significant role in the near-term reduction of CO₂ emissions and is considered necessary to slow global warming. Nanoporous carbon (NPC) membranes show promise as a new generation of gas separation membranes suitable for CO₂ capture.We have made supported NPC membranes from polyfurfuryl alcohol (PFA) at various pyrolysis temperatures. Positron annihilation lifetime spectrometry (PALS) and wide angle X-ray diffraction (WAXD) results indicate that the pore size decreases whilst the porosity increases with increasing pyrolysis temperature. The membrane performance results support these findings with a significant increase in permeance being seen with increasing pyrolysis temperature, which relates to the increase in porosity.Mixed gas performance measurements also show an increase in CH₄ permeance as the operating temperature is increased from 35 to 200 °C, which can be related to an increase in the rate of diffusion. However, the selectivity decreases with increasing operating temperature due to the smaller changes in the CO₂ permeance. These smaller changes in CO₂ permeance can be related to the stronger adsorption of this gas on the carbon surface at lower operating temperatures. Interestingly, regardless of the original pyrolysis temperature, the selectivity at higher operating temperatures is similar, whereas the permeance remains related to this pyrolysis temperature.     

Effects of sulfone/ketone in poly(phthalazinone ether sulfone ketone) on the gas permeation of their derived carbon membranes

A series of copolymer, poly(phthalazinone ether sulfone ketone)s (PPESKs) with the sulfone over ketone unit (S/K) ratio varying from 20/80, 50/50 to 80/20, were used as precursors to prepare carbon membranes. The effects of chemical structure as S/K ratio of PPESKs on the microstructure and gas separation performance of their derived carbon membranes were mainly investigated. The properties of PPESKs were detected in terms of density, fractional free volume, char yield, interlayer distance and glass transition temperature. During the formation process of carbon membranes (i.e., stabilization and pyrolysis), the changes in functional groups, microstructural parameters and gas permeation were monitored by FTIR, X-ray diffraction, TEM and single gas permeation techniques. The results have shown that the microstructure and gas permeation of obtained carbon membranes are significantly affected by the S/K ratio in precursor PPESKs. Carbon membranes exhibit higher selectivity and lower permeability when prepared at low pyrolytic temperature (i.e., 650 °C and 800 °C) and from PPESKs with S/K ratio equaling 50/50, followed with 20/80 and 80/20. As for carbon membranes prepared at high pyrolytic temperature (i.e., 950 °C), the selectivity order of them is well in accordance with S/K mole ratio in precursor PPESKs: 20/80 > 50/50 > 80/20, and vice versa for permeability.     

高有机硫炼焦煤分选组分中硫的赋存形态及其热变迁行为研究

利用重介质分选法分别将两种高有机硫炼焦煤分选为密度范围不同的五个组分。采用X射线光电子能谱仪（XPS）、核磁共振波谱仪（¹³C NMR）和热解质谱联用技术（Py-MS）探究不同分选组分中硫的赋存形态及其热变迁行为。结果表明,不同分选组分中硫的分布、赋存形态及其所处化学环境存在显著差异。有机硫主要分布在低密度组分（D1）中,且以噻吩硫的形式存在;无机硫作为矿物质组分主要分布于高密度组分（D5）中。随着分选组分密度的增大,其脂肪碳的比例降低,芳香碳的比例增加,D1中硫醇、硫醚等硫化物的含量明显增加。热解过程中脂肪碳结构裂解生成的挥发分促进含硫气体的释放,进而提高了D1的脱硫效率,D5中硫的热变迁行为则主要受煤中矿物质的影响。     

Titration of oxalic acid with cerium sulphate at room temperature using ferroïn as internal indicator

Evidence is presented to show that, contrary to the statements of earlier workers, the reaction between ceric sulphate and oxalic acid is quite rapid in hydrochloric acid medium specially in the presence of iodine monochloride as catalyst. We have now found that the need for a temperature of 50° in the cerimetric titration of oxalic acid using ferroïn as indicator is not due to the sluggishness of the reaction between oxalic acid and Ce^IV (as believed by Willard and Young) but because of the slow reaction between oxidised ferroïn and oxalic acid in the presence of sulphate ion derived from eerie sulphate. Conditions have now been developed for the titration of oxalic acid with eerie sulphate at room temperature in lN hydrochloric acid medium using ferroïn as indicator, and barium ion as scavenger for sulphate ion, which latter markedly retards the reaction between oxalic acid and oxidised ferroïn, as well as that between oxalic acid and Ce^IV. The method now developed has several advantages over that prescribed by Willard and Young because it avoids the high temperature of 50°, where the ferroïn indicator is found to undergo some dissociation. It also avoids the use of the iodine monochloride catalyst.     

Chemical transformations of CO2 in trifluoroacetic acid solutions

It is established that a conversion reaction of carbon dioxide takes place at room temperature and atmospheric pressure in aqueous solutions of trifluoroacetic acid (TFA), which leads to the formation of oxalic acid and heavier polymerized products.     

热解条件对氮杂有序介孔炭材料电催化性能的影响

氧还原反应是燃料电池及金属空气电池中极其重要的电化学反应之一,贵金属铂基催化剂被认为是最有效的氧还原反应电催化剂.然而,贵金属铂的资源稀缺以及高成本问题阻碍了相关技术的大规模应用,探索发展廉价高效的贵金属替代型催化剂是推动燃料电池发展的根本解决方案.近年来,人们在非贵金属催化剂开发方面取得了显著进展,其中新型纳米结构掺杂炭材料研究尤为活跃.氮杂有序介孔炭材料由于其高比表面积和独特的孔结构,在燃料电池技术上具有广泛的应用前景.在氮杂有序介孔炭材料的制备过程中,热解条件对炭材料组成、结构及电催化性能有着重要影响.然而,目前尚未见对氮杂炭材料制备过程中热解条件的影响进行系统研究.
　　本文采用我们发展的蒸汽化-毛细管冷凝法,以SBA-15为硬模板浸渍前驱体吡咯,制备出具有高比表面积和独特孔结构的氮杂有序介孔炭材料,系统研究了热解条件(包括热解温度、热解时间和升温速率)对炭材料组成、结构及电催化性能的影响,采用N2吸附-脱附等温线、X射线光电子能谱(XPS)及Raman光谱等方法考察了氮杂有序介孔炭材料的结构和组成,采用循环伏安法与旋转环盘电极研究了其电化学行为与氧还原反应电催化活性及选择性.
　　N2吸附-脱附等温线显示,氮杂炭材料对应IV型吸附-脱附等温线,孔径主要分布在2–10 nm,表明所制材料具有介孔结构.随着热处理温度升高,氮杂有序介孔炭材料比表面积先增加而后降低,热处理时间的延长有利于比表面积增大,但升温速率对所制炭材料比表面积没有明显影响,当升温速率为30 oC/min,900 oC焙烧3 h时,氮杂有序介孔炭材料的比表面积达到最大值888 m2/g. XPS测试结果表明,随着热处理温度升高,氮杂有序介孔炭材料中含氮基团的分解进一步加深,使N含量逐渐降低.延长热处理时间亦然,而升温速率的改变对N含量无明显影响.在热处理温度较低时(600 oC),所得材料中N主要以吡咯氮和吡啶氮的形式存在;当温度达到800 oC以上,吡咯氮转化为吡啶氮和骨架氮,且主要以骨架氮形式存在,说明氮杂有序介孔炭材料的石墨化程度逐渐升高. Raman光谱结果显示,随着热处理温度升高, ID/IG逐渐降低,进一步印证了温度对石墨化程度的影响.
　　电化学测试结果表明,随着热处理温度升高,氮杂有序介孔炭材料的氧还原反应电催化活性逐渐升高,但是当热处理温度从900 oC升至1000 oC时,氧还原反应活性增加很小;升温速率与热处理时间对氧还原反应电催化活性的影响均不明显.与商品Pt/C催化剂相比,900 oC以上所制催化剂均表现出更优异的氧还原电催化活性与选择性.由此可见,热处理温度是决定碳源热化学行为的关键因素,进而决定炭材料表面组成与结构.电化学研究结果表明,800 oC以上进行热处理碳化,所生成石墨化微晶可有效促进电子传递,降低欧姆极化损失,同时,较高的处理温度可促进骨架氮掺杂,从而构建出高效氧还原反应活性位点.因此,氮杂型炭催化剂的组成、结构与电化学性能更多地受控于热处理过程中的热力学,而非热解动力学过程.     

Pyrolysis study of Sol-gel derived TiO2 Powders: Part II. TiO2-anatase prepared by reacting titanium(IV) isopropoxide with oxalic acid

Homogeneous TiO₂ powders were obtained, via sol-gel method, hydrolysing titanium(IV) isopropoxide, previously reacted with oxalic acid in order to better control the gelling process. The characterization of the amorphous TiO₂ powders was carried out by using different techniques such as FT-IR, XRD and N2 adsorption analysis. Coupled thermogravimetric (TG) gas chromatographic (GC) and mass spectrometric (MS) analyses were performed to quantify the organic content present in the titania gel and its release during pyrolysis. A detailed semiquantitative analysis of the evolved chemical species from TG-MS data allowed to describe the chemical composition of the TiO₂ gel and the chemical rearrangements occurring in matrix during pyrolysis up to its crystallization to anatase form at 530°C. This revised version was published online in July 2006 with corrections to the Cover Date.