多孔石墨烯分离CH4/CO2的分子动力学模拟

采用分子动力学方法模拟CH₄/CO₂混合气体在多孔石墨烯分离膜中的分离过程, 分析了3 种纳米孔功能化修饰(N/H 修饰、全H修饰和N/―CH₃修饰)对分离过程的影响规律. 模拟结果表明气体分子会在石墨烯表面形成吸附层, CO₂分子的吸附强度高于CH₄分子. 纳米孔的功能化修饰不仅减小了纳米孔的可渗透面积, 还通过影响纳米孔边缘原子的电荷分布提高了气体分子的吸附强度, 进而影响了混合气体分子在多孔石墨烯分离膜中的渗透性和选择性. CO₂分子在多孔石墨烯中的渗透率能达到10⁶ GPU (1 GPU=3.35×10^-10 mol·s^-1·m^-2·Pa^-1), 远远高于传统的聚合物分离膜. 研究表明多孔石墨烯分离膜在天然气处理、CO₂捕获等工业气体分离过程中具有广泛的应用前景.     

气体分子在二维石墨烯纳米孔中的选择性渗透特性（英文）

二维石墨烯纳米孔中气体分子的选择性渗透对多孔石墨烯分离膜非常重要。本文采用分子动力学方法研究了气体分子在氮氢修饰石墨烯纳米孔中的渗透特性,从分子的大小和结构、纳米孔的构型以及分子与石墨烯之间的作用强度等角度阐明了分子出现选择性渗透的原因。结果表明,不同分子的渗透率不同,即H_2O H_2S CO_2 N_2 CH_4。渗透率跟分子的质量和直径以及分子在石墨烯表面上的吸附密度有关;根据气体分子动理学理论,渗透率跟分子质量成反比关系;而分子在石墨烯表面上的高吸附密度对渗透起促进作用。对于H_2O和CH4分子,分子直径起主导作用;H_2O分子直径最小,其渗透率最大;同理,CH_4分子的渗透率最小。对于H_2S和CO_2分子,H_2S分子的直径较大,但其与石墨烯之间的作用强度较大(吸附密度较高),导致渗透率较高;对于CO_2和N_2分子,CO_2分子的直径较小,并且与石墨烯之间的作用强度较大,渗透率较高。同时发现,分子在纳米孔中的渗透使得其在石墨烯表面的密度分布极不均匀。纳米孔左右两侧的功能化氮原子使CH_4分子容易从孔两侧区域穿过,而其它分子由于直径较小在纳米孔中心区域穿过的概率最大。分子与石墨烯之间的作用越强,导致分子在石墨烯表面区域内停留的时间越长,最终使其在渗透纳米孔的过程中所经历的时间越长。本文所采用的氮氢修饰石墨烯纳米孔中,分子渗透速率达到~10~(-3)mol·s~(-1)·m~(-2)·Pa~(-1),并且其它分子相对于CH_4分子的选择性也很高,说明基于该类型纳米孔的多孔石墨烯分离膜在天然气处理等工业气体分离领域具有很好的应用前景。     

理论空燃比天然气汽车尾气中H2O和O2对CH4与NO反应的影响

共沉淀法制备CeZrYLa+LaAl 复合氧化物载体, 等体积浸渍法制备了Pt 催化剂, 用于研究理论空燃比天然气汽车(NGVs)尾气净化反应中CH₄与NO的反应规律. 并考察了10% (体积分数, φ)H₂O和计量比O₂对CO₂存在时的CH₄+NO反应的影响. 结果表明: 对于不同条件下的NO+CH₄反应, 主要生成N₂和CO₂, 高温区有CO生成. 低温区无O₂时可以生成N₂O, 有O₂时可以生成NO₂; 添加10% (φ)的H₂O后, CH₄ 转化活性降低, NO转化活性基本不变, 这是由于H₂O减弱了CH₄与CO₂的重整反应, 但是对CH₄与NO的反应基本没有影响; 添加计量比的O₂后, CH₄转化活性提高, 而NO转化活性降低, 这是由于O₂和NO之间存在竞争吸附, CH₄被O₂氧化为主要反应, 从而减弱了NO的转化; 同时添加计量比的O₂和10% (φ) H₂O, CH₄与CO₂的重整反应受到抑制,CH₄与NO的反应、甲烷蒸汽重整反应和甲烷被O₂氧化反应同时发生, CH₄和NO的转化活性均提高.     

富氮多级孔炭材料的制备及其吸附分离CO2的性能

使用新型含氮聚合物席夫碱为炭源, SBA-15为模板,通过纳米铸型法原位合成微孔-中孔-大孔串联的多级孔富氮炭材料.材料的比表面积为752 m²·g^-1,孔容0.79 cm³·g^-1; X光电子能谱分析表明炭材料中的氮含量高达7.85%(w).将所制备的多孔炭材料应用于CO₂的吸附分离,发现炭材料的微孔发挥主导作用,表面氮掺杂发挥辅助作用.在两者的协同作用下, CO₂吸附量在常压、273 K下可达97 cm³·g^-1, CO₂/N₂和CO₂/CH₄的分离比(摩尔比)分别为7.0和3.2,低压亨利吸附选择性分别为23.3和4.2.采用Toth模型对单组分平衡吸附进行拟合,并根据理想溶液吸附理论(IAST)预测双组分CO₂/N₂和CO₂/CH₄混合气体的分离选择性分别为40和18.     

O2/CO2气氛下CO2和H2O气化反应对煤及煤焦燃烧特性的影响

利用热天平对比研究了大同煤及煤焦在O₂/N₂、O₂/CO₂和O₂/H₂O/CO₂中的燃烧行为,探讨CO₂和H₂O气化反应对其富氧燃烧特性的影响。结果表明,在5%氧气浓度下,煤粉在O₂/N₂、O₂/CO₂和O₂/H₂O/CO₂中的燃烧速率按顺序依次降低。氧气浓度降低到2%,由于CO₂和H₂O气化反应的作用,煤粉在高温区的整体反应速率按顺序依次增大。当氧气浓度为5%时,煤焦在O₂/CO₂中的燃烧速率要低于O₂/N₂中的燃烧速率,但燃烧反应推迟后气化反应的参与使得煤焦在O₂/H₂O/CO₂中的整体反应速率显著升高。当氧气浓度降低到2%后,随着温度的升高,在CO₂气化反应的作用下,煤焦在O₂/CO₂中的整体反应速率逐渐高于O₂/N₂中的燃烧速率。在O₂/H₂O/CO₂中,由于H₂O在共气化中起主要作用,煤焦在O₂/H₂O/CO₂高温区的整体反应速率进一步升高。动力学分析表明,在5%氧浓度时,煤焦在O₂/N₂、O₂/CO₂和O₂/H₂O/CO₂中的表观活化能依次升高。随着氧气浓度的降低,在不同反应气氛中的表观活化能均有所下降。     

煤炭解耦燃烧过程N迁移与转化Ⅱ:单组分气相化学反应实验

在理想平推流反应器中进行了模拟热解气对模拟烟气中NO、N₂O的还原实验研究,考察了反应温度、过剩空气系数λ、热解气中CH₄、CO、H₂、NH₃浓度、烟气中NO、N₂O浓度变化对NO、N₂O出口浓度的影响。实验结果表明,当模拟热解气仅含其中一种气体时,在反应温度973~1 223 K时热解气中CH₄、CO、H₂基本不与NO发生反应,当λ小于或等于1.0时可降低N₂O浓度0%~30%;热解气中NH₃可降低NO 10%~60%,但NH₃不与N₂O发生反应。     

通过实验和理论验证Pt0/SrTiO3-δ复合催化剂双反应路径促进CO2还原(英文)

在以H₂O为质子源的光催化二氧化碳还原反应(CO₂RR)过程中,光解H₂O产氢气(H₂)被认为是一个竞争反应.因此,光催化CO₂RR过程需要抑制H₂的产生,以提高碳氢产物的选择性和产率.以CO₂和H₂为反应物的逆水气变换反应(RWGS)是常见的CO₂加氢反应,在较高的温度和催化剂作用下生成CO和H₂O.目前,光催化CO₂RR研究主要聚焦于产物的选择性,而有关光解H₂O产生的还原性气体H₂在光热效应的促进下成为CO₂RR中新的质子源研究较少.光热催化是一种新的高效催化反应方式,在反应过程中需要光照和加热.光照能够促进半导体光生载流子的激发,热效应则能降低反应物分子的活化势垒,并能够促进中间产物的表面迁移以及生成物的脱附.利用光热催化热力学和动力学上的有利条件,为以H₂     

甲烷自热重整制氢的热力学和动力学分析

对甲烷自热重整进行了系统的热力学分析,并采用预混合层流模型结合甲烷氧化、蒸汽重整、干重整机理对反应过程进行了动力学分析。结果表明,甲烷自热重整的平衡产物及其浓度主要受温度、O₂/CH₄、H₂O/CH₄的影响;压力影响不是十分明显,主要影响达到平衡的速度。在715℃~730℃、压力0.7MPa~1.0MPa,控制O₂/CH₄在0.60~0.70、H₂O/CH₄在3.15~3.25,可以得到H₂>68%、CO<10%的产物气,积炭率接近于0。动力学分析表明,自热重整过程分为两个主要阶段进行,在起始阶段主要发生甲烷氧化反应,产物主要为H₂O和CO₂;第二阶段以甲烷蒸汽重整反应为主,伴随水气变换反应（WGS）和微弱的干重整,H_2、CO和CO₂为主要产物。调节初始水浓度可以控制快速氧化阶段反应速率,避免“热点”出现,抑制CO的生成。     

互穿结构及混合配体对金属-有机骨架材料分离性能的影响

在以前的工作中, 我们利用蒙特卡洛和分子动力学模拟计算了具有互穿性结构及混合配体的金属-有机骨架材料(metal-organic frameworks, MOFs)分离CH₄/H₂的吸附选择性及扩散选择性. 研究了材料的互穿结构及混合配体对材料用于分离CH₄/H₂性能的影响. 在本工作中, 我们将以前的工作进行了扩展, 详细研究了材料的互穿结构及混合配体对材料用于分离CO₂/CH₄, CO₂/N₂和CO₂/H₂等含有CO₂的气体混合物性能的影响. 此外, 为了进一步阐明材料的结构对于其分离性能的影响, 我们亦研究了材料用于分离CH₄/H₂及CH₄/N₂. 从我们的结果可以看出, 相比无互穿结构的MOFs材料, 具有互穿结构的MOFs材料对所研究的所有混合气体的渗透选择性明显提高. 这是因为具有互穿结构的MOFs材料对混合气体的吸附选择性明显高于无互穿结构的MOFs材料. 结果表明, 如果将材料作为膜用于气体混合物分离, 使材料产生互穿结构是提高材料分离性能的一个很好的策略.     

MFI型分子膜的制备与H2S/CH4分离性能

采用二次生长法在多孔α-Al₂O₃载体上制备MFI型（ZSM-5和silicate-1）分子筛膜;通过XRD和SEM检测,证明所合成的分子筛膜为致密、交联和无取向的MFI型分子筛膜,厚度为5 μm;单组分气体渗透实验检测中,所制备样品膜的N₂渗透量均小于10^-11 mol/（m²·s·Pa）,可认为其无缺陷;同时,考察了样品分子筛膜对H₂S/CH₄混合气的分离效果,在渗透压分别为0.3和0.5 MPa时,silicate-1分子筛膜的H₂S/CH₄的分离因子分别为1.99和4.44,而ZSM-5分子筛膜的CH₄/H₂S的分离因子分别为6.71和12.85。     

基于静电效应的石墨烯纳米孔选择性渗透特性

Two-dimensional graphene nanopores have proved to be a very effective molecular sieve with ultra-high molecular permeance due to the atomic thickness of graphene sheets. The mechanism of graphene nanopores for molecular sieving is generally the size-sieving effect of different molecules. However, high-selective molecular separation is difficult to realize based only on the size-sieving effect. Therefore, graphene nanopore-based membranes usually present high permeance but a moderate selectivity, such that the separation performance cannot far exceed those of traditional separation membranes. In this study, the effects of charges on graphene surfaces on the selective permeation of CO₂/N₂ mixtures through a graphene nanopore is studied using molecular dynamics simulations; its purpose to realize electrostatic effect-based selective molecular permeation through graphene nanopores and find a promising method to improve the selectivity of molecular separation. The simulation results show that graphene nanopores with negative charges have higher CO₂ permeance and lower N₂ permeance and, thus, present a high selectivity for the separation of the CO₂/N₂ mixtures. The graphene nanopore with positive charges, however, does not improve the selectivity. The electrostatic effect-based selectivity of graphene nanopores is related to the different molecular adsorption abilities on the graphene surface with charges. For negative charges, the adsorption ability of CO₂ molecules increases and the number of permeated molecules via surface mechanism increases and the experience time during the permeation process also increases; ultimately the CO₂ permeance increases with increasing the charge density. For the molecules permeated through the surface mechanism, they are firstly adsorbed onto the graphene surface and then diffuse to the pore region for the ultimate permeation; thus, their experience time is longer than that of the molecules permeated through a direct mechanism. Therefore, a longer experience time means a more significant contribution of the surface flux to the total flux. At high surface charge densities, the contribution of surface flux is dominated and thus the experience time is longer. For CO₂ molecules, the permeation rates increase with increasing the surface charge density. Namely, a higher experience time corresponds to a higher permeation rate for CO₂ molecules. A decrease of N₂ permeance with increasing the charge density is correlated to the increasing CO₂ permeance via the inhibition effects of non-permeating components on the permeation of permeating components. For positive charges, the adsorption abilities of CO₂ and N₂ molecules have no obvious variation with the charge density and their permeance is constant; therefore, the graphene nanopore still has no electrostatic effect-based selectivity.     

二维材料膜在气体分离领域的最新研究进展

Two-dimensional (2D) materials, led by graphene, have emerged as nano-building blocks to develop high-performance membranes. The atom-level thickness of nanosheets makes a membrane as thin as possible, thereby minimizing the transport resistance and maximizing the permeation flux. Meanwhile, the sieving channels can be precisely manipulated within sub-nanometer size for molecular separation, such as gas separation. For instance, graphene oxide (GO) channels with an interlayer height of about 0.4 nm assembled by external forces exhibited excellent H₂/CO₂ sieving performance compared to commercial membranes. Cross-linking was also employed to fabricate ultrathin (< 20 nm) GO-facilitated transport membranes for efficient CO₂ capture. A borate-crosslinked membrane exhibited a high CO₂ permeance of 650 GPU (gas permeation unit), and a CO₂/CH₄ selectivity of 75, which is currently the best performance reported for GO-based composite membranes. The CO₂-facilitated transport membrane with piperazine as the carrier also exhibited excellent separation performance under simulated flue gas conditions with CO₂ permeance of 1020 GPU and CO₂/N₂ selectivity as high as 680. In addition, metal-organic frameworks (MOFs) with layered structures, if successfully exfoliated, can serve as diverse sources for MOF nanosheets that can be fabricated into high-performance membranes. It is challenging to maintain the structural and morphological integrity of nanosheets. Poly[Zn₂(benzimidazole)₄] (Zn₂(bim)₄) was firstly exfoliated into 1-nm-thick nanosheets and assembled into ultrathin membranes possessing both high permeance and excellent molecular sieving properties for H₂/CO₂ separation. Interestingly, reversed thermo-switchable molecular sieving was also demonstrated in membranes composed of 2D MOF nanosheets. Besides, researchers employed layered double hydroxides (LDHs) to prepare molecular-sieving membranes via in situ growth, and the as-prepared membranes showed a remarkable selectivity of ~80 for H₂-CH₄ mixture. They concluded that the amount of CO₂ in the precursor solution contributed to LDH membranes with various preferred orientations and thicknesses. Apart from these 2D materials, MXenes also show great potential in selective gas permeation. Lamellar stacked MXene membranes with aligned and regular sub-nanometer channels exhibited excellent gas separation performance. Moreover, our ultrathin (20 nm) MXene nanofilms showed outstanding molecular sieving property for the preferential transport of H₂, with H₂ permeance as high as 1584 GPU and H₂/CO₂ selectivity of 27. The originally H₂-selective MXene membranes could be transformed into membranes selectively permeating CO₂ by chemical tuning of the MXene nanochannels. This paper briefly reviews the latest groundbreaking studies in 2D-material membranes for gas separation, with a focus on sub-nanometer 2D channels, exfoliation of 2D nanosheets with structural integrity, and tunable gas transport property. Challenges, in terms of the mass production of 2D nanosheets, scale-up of lab-level membranes and a thorough understanding of the transport mechanism, and the potential of 2D-material membranes for wide implementation are briefly discussed.     

Gas permeation characteristics of a hydrogen selective supported silica membrane

A highly hydrogen permeable silica membrane, referred to as Nanosil, was obtained by chemical vapor deposition of a thin SiO₂ layer on a porous Vycor glass support. This composite membrane showed good permeance (10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹) for the small gas molecules (He, Ne, and H₂) at 873 K with high selectivity (10⁴) over other larger gas molecules (CO₂, CO, and CH₄). The characteristics of gas transport on the Vycor and Nanosil membrane were investigated with several gas diffusion models. The experimental gas permeation data on Vycor glass could be explained by the occurrence of Knudsen diffusion in parallel with surface diffusion. The permeance of the small gas molecules (He, Ne, and H₂) on the Nanosil membrane was activated, and increased as temperature increased. However, this permeance was limited at high temperature because of the limited permeance on the Vycor support. The gas permeance on the deposited silica layer was obtained by applying a series analysis of gas permeation on the combined silica layer and Vycor support composite system. The order of permeance through the silica layer was He>H₂>Ne which was the same as that through vitreous silica glass, but occurred with lower activation energies. The order of permeation of these small gas molecules did not follow either mass or molecular size but could be explained using a statistical gas permeance model.     

Gas transport property of polyallylamine–poly(vinyl alcohol)/polysulfone composite membranes

Polyallylamine (PAAm) was synthesized by free radical polymerization and characterized by Fourier transform infrared resonance (FT-IR) spectroscopy, hydrogen nuclear magnetic resonance (¹H NMR) spectroscopy and differential scanning calorimetry (DSC). The composite membranes were prepared by using PAAm–poly(vinyl alcohol) (PVA) blend polymer as the separation layer and polysulfone (PSF) ultrafiltration membranes as the support layer. The surface and cross-section morphology of the membrane was inspected by environmental scanning electron microscopy (ESEM). The gas transport property of the membranes, including gas permeance, flux and selectivity, were investigated by using pure CO₂, N₂, CH₄ gases and CO₂/N₂ gas mixture (20 vol% CO₂ and 80 vol% N₂) and CO₂/CH₄ gas mixture (10 vol% CO₂ and 90 vol% CH₄). The plots of gas permeance or flux versus feed gas pressure imply that CO₂ permeation through the membranes follows facilitated transport mechanism whereas N₂ and CH₄ permeation follows solution–diffusion mechanism. Effect of PAAm content in the separation layer on gas transport property was investigated by measuring the membranes with 0–50 wt% PAAm content. With increasing PAAm content, gas permeance increases initially, reaches a maximum, and then decreases gradually. For CO₂/N₂ gas mixture, the membranes with 10 wt% PAAm content show the highest CO₂ permeance of about 1.80 × 10⁻⁵ cm³ (STP) cm⁻² s⁻¹ KPa⁻¹ and CO₂/N₂ selectivity of 80 at 0.1 MPa feed gas pressure. For CO₂/CH₄ gas mixture, the membranes with 20 wt% PAAm content display the highest CO₂ permeance of about 1.95 × 10⁻⁵ cm³ (STP) cm⁻² s⁻¹ KPa⁻¹ and CO₂/CH₄ selectivity of 58 at 0.1 MPa feed gas pressure. In order to explore the possible reason of gas permeance varying with PAAm content, the crystallinity of PVA and PAAm–PVA blend polymers was measured by X-ray diffraction (XRD) spectra. The experimental results show an inverse relationship between crystallinity and gas permeance, e.g., a minimum crystallinity and a maximum CO₂ permeance are obtained at 20 wt% PAAm content, indicating that the possibility of increasing CO₂ permeance with PAAm content due to the increase of carrier concentration could be weakened by the increase of crystallinity.     

Novel CO2 selectively permeating membranes containing PETEDA dendrimer

Pentaerythrityl tetraethylenediamine (PETEDA) dendrimer was synthesized from pentaerythrityl tetrabromide and ethylenediamine. Its molecular structure was characterized by elemental analysis, Fourier transform infrared resonance (FT-IR) and hydrogen nuclear magnetic resonance (¹H NMR) spectroscopy. The composite membranes for selectively permeating CO₂ were prepared by using PETEDA-PVA blend polymer as the active layer and polyethersulfone (PES) ultrafiltration membrane as the support layer and their permselectivity was tested by pure CO₂ and CH₄ gases and the gas mixture containing 10 vol.% CO₂ and 90 vol.% CH₄, respectively. For pure gases, the membrane containing 78.6 wt% PETEDA and 21.4 wt% PVA in the blend has a CO₂ permeance of 8.14 × 10⁻⁵ cm³ (STP) cm⁻² s⁻¹ cmHg⁻¹ and CO₂/CH₄ selectivity of 52 at 143.5 cmHg feed gas pressure. While feed gas pressure is 991.2 cmHg, CO₂ permeance reaches 3.56 × 10⁻⁵ cm³ (STP) cm⁻² s⁻¹ cmHg⁻¹ and CO₂/CH₄ selectivity is 19. For the gas mixture, the membrane has a CO₂ permeance of 6.94 × 10⁻⁵ cm³ (STP) cm⁻² s⁻¹ cmHg⁻¹ with a CO₂/CH₄ selectivity of 33 at 188.5 cmHg feed gas pressure, and a CO₂ permeance of 3.29 × 10⁻⁵ cm³ (STP) cm⁻² s⁻¹ cmHg⁻¹ with a CO₂/CH₄ selectivity of 7.5 at a higher feed gas pressure of 1164 cmHg. A possible gas transport mechanism in the composite membranes is proposed by investigating the permeating behavior of pure gases and the gas mixture and analyzing possible reactions between CO₂/CH₄ gases and the PETEDA-PVA blend polymer. The effect of PETEDA content in the blend polymer on permselectivity of the composite membranes was investigated, presenting that CO₂ permeance and CO₂/CH₄ selectivity increase and CH₄ permeance decreases, respectively with PETEDA content. This is explained by that with increasing PETEDA content, the carrier content increases, and the crystallinity and free volume of the PETEDA-PVA blend decrease that were confirmed by the experimental results of X-ray diffraction spectra (XRD) and positron annihilation lifetime spectroscopy (PALS).     

Gas permeability in rubbery polyphosphazene membranes

The synthesis, characterization, and gas permeability of 10 new polyphosphazenes has been studied. Additionally, the first gas permeation data has been collected on hydrolytically unstable poly[bis-(chloro)phosphazene]. Gases used in this study include CO₂, CH₄, O₂, N₂, H₂, and Ar. CO₂ was the most permeable gas through any of the phosphazenes and a direct correlation between the T_g of the polymer and CO₂ transport was noted with permeability increasing with decreasing polymer T_g. To a lesser degree, permeability of all the other gases studied also yielded increases with decreasing polymer T_g. The trend observed for these new polymers was further supported by published data for other phosphazenes. Furthermore, permeability data for all gases were found to correlate to the gas condensability and the gas critical pressures, except for hydrogen, suggesting that the nature of the gas is also a significant factor for permeation through rubbery phosphazene membranes. Ideal separation factors () for the CO₂/H₂ and CO₂/CH₄ gas pairs were calculated. For CO₂/CH₄, no increase in was observed with decreasing T_g, however increases in were noted for the CO₂/H₂ pair.     

Characteristics of a zirconia composite membrane fabricated by a laser firing method

By a method of laser firing, a high zirconia containing (70%) composite membrane on porous ceramic tubing was successfully fabricated. The laser sintered composite membrane was characterized by gas separation/permeation experiments. In the separation experiment of a CO₂---CH₄ gaseous mixture, it was found that the separation factor of CH₄ over CO₂ was 1.15. In the pure gases permeation experiment, it was found that Knudsen diffusion is considered to be predominant in the permeation mechanism for pure gases H₂, He, CH₄, N₂, O₂, and CO₂, and the permeation mechanism of H₂O at lower temperature depends mainly on surface diffusion and on Knudsen diffusion at higher temperature.     

Pore size control and gas permeation kinetics of silica membranes by pyrolysis of phenyl-substituted ethoxysilanes with cross-flow through a porous support wall

A silica membrane was produced by chemical vapor deposition using tetraethoxysilane (TEOS), phenyltriethoxysilane (PTES) or diphenyldiethoxysilane (DPDES) as the Si source. Amorphous silica was deposited in the mesopores of a γ-alumina film coated on a porous -alumina tube, by evacuating the reactant through the porous wall. Hydrogen permeance at a permeation temperature of 600°C was of the order of 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹, and was not greatly dependent on the Si sources. The silica membrane produced using TEOS contained micropores permeable to both helium and hydrogen, but CO₂ and larger molecules were only slightly permeated through those mesopores which were left unplugged. The silica membrane produced from DPDES showed a single-component CO₂ permeance equivalent to that of single-component He, and CO₂/N₂ selectivity was approximately 9 at a permeation temperature of 30°C. When a mixture of CO₂ and N₂ was fed, however, CO₂ permeance decreased to the level of N₂ permeance. The H₂/N₂ selectivity, determined from single-component permeances to H₂ and N₂, was approximately 100, and these permeances remained unchanged when an equimolar mixture of H₂ and N₂ was fed. Thus, the DPDES-derived membrane possessed two types of micropores, abundant pores through which helium and hydrogen permeated and a small number of pores in which molecules of CO₂ and N₂ were permeable but not able to pass one another. Neither meso or macropores remained in the DPDES membrane.