Two-Dimensional MFI-Type Zeolite Flow Battery Membranes

Vanadium flow battery (VFB) is one of the most reliable stationary electrochemical energy-storage technologies, and a membrane with high vanadium resistance and proton conductivity is essential for manufacturing high-performance VFBs. In this study, a two-dimensional (2D) MFI-type zeolite membrane was fabricated from zeolite nanosheet modules, which displayed excellent vanadium resistance (0.07 mmol L⁻¹ h⁻¹) and proton conductivity (0.16 S cm⁻¹), yielding a coulombic efficiency of 93.9 %, a voltage efficiency of 87.6 %, and an energy efficiency of 82.3 % at 40 mA cm⁻². The self-discharge period of a VFB equipped with 2D MFI-type zeolite membrane increased up to 116.2 h, which was significantly longer than that of the commercial perfluorinated sulfonate membrane (45.9 h). Furthermore, the corresponding battery performance remained stable over 1000 cycles (>1500 h) at 80 mA cm⁻². These findings demonstrate that 2D MFI-type membranes are promising ion-conductive membranes applicable for stationary electrochemical energy-storage devices.     

钯合金膜分离纯化氢同位素的研究进展

钯合金膜因其具有优异的透氢性能及良好的化学和热稳定性,已被广泛应用于氢同位素的分离纯化领域。而PdAg和PdY合金膜在众多钯合金膜中透氢性能出色备受关注。本文比较了PdAg、PdY等多元钯合金膜的透氢性能及抗中毒情况,总结了PdAg复合膜的制备方法及透氢选择性,重点介绍了钯合金膜分离氢同位素的研究进展,并对钯合金膜的未来研究方向进行展望。     

膜分离与分离膜

本文扼要阐述了膜分离技术的基本原理、特点、内容及其近５０年来的进展和在工业上的广泛应用,系统地叙述了目前应用最广泛的有机高分子膜的。文章分析了今后膜分离的发展动向并简要介绍了我国的有关情况。     

Energy Application of Graphene Based Membrane: Hydrogen Separation

Hydrogen gas (H₂) is a viable energy carrier that has the potential to replace the traditional fossil fuels and contribute to achieving zero net emissions, making it an attractive option for a hydrogen-based society. However, current H₂ purification technologies are often limited by high energy consumption, and as a result, there is a growing demand for alternative techniques that offer higher H₂ purity and energy efficiency. Membrane separation has emerged as a promising approach for obtaining high-purity H₂ gas with low energy consumption. Nevertheless, despite years of development, commercial polymeric membranes have limited performance, prompting researchers to explore alternative materials. In this context, carbon-based membranes, specifically graphene-based nanomaterials, have gained significant attention as potential membrane materials due to their unique properties. In this review, we provide a comprehensive overview of carbon-based membranes for H₂ gas separation, fabrication of the membrane, and its characterization, including their advantages and limitations. We also explore the current technological challenges and suggest insights into future research directions, highlighting potential ways to improve graphene-based membranes performance for H₂ separations.     

CO2／CH4分离膜及沸石填料影响渗透过程的研究

报导了甲基硅橡胶和纤维素（ＣＡ、ＣＴＡ、ＥＣ）膜对ＣＯ２、ＣＨ４的选择透气性能，并讨论了沸石作为填料所引起的分子筛作用的气体渗透过程。甲基硅橡胶的气体渗透系数最高，而选择性最低，且不受填料沸石的影响。纤维素膜的气体选择性较大，渗透系数可以通过沸石的加人而明显增加。特别是沸石１３Ｘ．沸石３Ａ、４Ａ、５Ａ在ＥＣ膜中对气体分子筛作用，改变了气体原有的渗透过程，提高了选择性。使用Ａｒｒｈｅｎｉｕｓ公式计算出ＥＣ－沸石３Ａ膜的气体渗透活化能。     

Synthesis Optimization of SSZ-13 Zeolite Membranes by Dual Templates for N2/NO2 Separation

High-silica SSZ-13 zeolite membranes are promising in industrial separations of light gases and continuous membranes are highly demanded for better separation performances. Herein, pure-phase, continuous and thin SSZ-13 zeolite membranes were synthesized using dual templates of N,N,N-trimethtyl-1-adamantammonium hydroxide(TMAdaOH) and tetraethylammonium hydroxide(TEAOH). Systematical investigations of TMAdaOH/TEAOH ratios and their concentrations show that TMAdaOH acts as the main structure-directing agent in the formation of the SSZ-13 zeolite. TMAdaOH cooperatively plays with TEAOH in promoting the SSZ-13 crystal intergrowth to form a continuous polycrystalline membrane. Additionally, appropriate introduction of TEAOH is able to adjust the membrane thickness to the crystal-comparable size of ca. 2.0 μm. The SSZ-13 membranes are further applied for N₂/NO₂separation, which is firstly reported on zeolite membranes. The gas permeation results show that the SSZ-13 membrane synthesized by the dual-template approach exhibits selective separation of N₂ over NO₂ with N₂/NO₂ separation factor of 7.6 and N₂ permeance of 1.66×10^-8 mol·m^-2·s^-1·Pa^-1.     

取向晶种法制备沸石分子筛膜研究进展

近年来沸石分子筛膜因在分离、 催化、 传感和防腐等研究领域具有重要的应用价值而引起广泛关注. 其中, 具有优先取向微观结构的沸石分子筛膜由于能够显著降低客体分子在膜内的扩散路径并减少膜内的晶间界缺陷密度, 成为膜分离学科的研究重点. 本文以b-轴取向MFI沸石分子筛膜为主线, 综述了国内外制备取向沸石分子筛膜的最新研究进展; 详细介绍了取向晶种法制膜工艺, 侧重总结了MFI沸石纳米片合成、 b-轴取向沸石晶种单层制备以及二次生长调控等方面的研究成果; 在深入探讨各类取向沸石分子筛膜制备策略的基础上, 分析探讨了其中存在的关键问题与解决措施, 最后对取向沸石分子筛膜的发展方向进行了展望.     

金属有机骨架薄膜用于小分子和离子的高效分离

综述了近几年金属有机骨架（MOF）薄膜在小分子和离子高效分离应用中的研究进展.MOF膜材料因具有结晶度良好、结构可设计、孔径可调和可功能化等特点,在分离领域展现出极大的潜在应用价值而受到广泛关注.鉴于近年来MOF膜材料在分离领域取得的巨大进展,对这一领域的前沿进展进行及时系统的总结,并对未来的发展趋势进行展望,具有重要的学术价值,也为科研工作者对MOF膜材料的研究提供了参考.本文首先总结了MOF膜的4种制备方法,包括LBL自组装法（液相外延和Langmuir-Blodgett沉积）、真空制备法（化学气相沉积和原子层沉积）、电化学沉积法和粉末沉积法;而后,详述了MOF膜在气体分离、液体分离及离子/质子传导等方面的应用;最后,总结了MOF膜材料领域当前存在的挑战及潜在解决途径,并对该领域的未来发展方向进行了展望.     

氢气在Na-MAZ和Li-MAZ沸石原子簇上的吸附

采用基于密度泛函理论(DFT)的广义梯度近似(GGA)/PBE(Perdew-Burke-Ernzerhof)交换相关泛函和双数值基加p极化(DNP)基组对氢气分子在Na-MAZ和Li-MAZ沸石原子簇上的吸附进行了研究, 计算得到吸附复合物的平衡几何结构参数、振动频率以及吸附能等数据. 结果表明: MAZ沸石中存在四个稳定的吸附位点, 分别为SI′、SI″、SII′和SII″位点; 氢气分子在Na-MAZ沸石的SII″位点吸附时最稳定, 而在Li-MAZ沸石中, 氢气分子处于SI″和SII″位点时最稳定. 吸附能越大, 氢气分子键长越长, 振动频率减少也越多. Li-MAZ沸石对氢气的吸附能力要明显强于Na-MAZ沸石的吸附能力, 理论上Li-MAZ沸石具有更高的氢气储量, 可能是一种潜在的储氢材料.     

表面修饰的有机-无机杂化微孔SiO2膜的制备及氢气分离性能

采用苯基三乙氧基硅烷(PTES)和1,2-双(三乙氧基硅基)乙烷(BTESE)为前驱体, 通过溶胶-凝胶法制备了苯基修饰的有机-无机杂化SiO2 膜材料. 通过N2吸附、视频光学接触角测量、热重分析和红外光谱对膜材料的孔结构和疏水性能进行了表征, 并深入研究了膜材料的氢气渗透和分离性能. 结果表明, 修饰后的膜材料具有微孔结构, 孔径集中分布在0.4~0.6 nm. 在温度为40 ℃, 湿度为70%~80%的水热环境下陈化30 d后, 膜材料仍保持微孔结构. 苯基修饰后膜材料具有疏水性, 当n(PTES)/n(BTESE)=0.6时, 膜材料对水的接触角达到(125±0.4)°. 氢气在膜材料中的输运遵循活化扩散机理, 300 ℃时, 膜材料的H2渗透率达到8.71×10-7mol·m-2·Pa-1·s-1, H2/CO2的理想分离系数达到5.53.     

分离液体的膜

本文概述了7种以高分子为膜材料、用于混合液体分离的膜分离过程,即离子交换膜与电渗析、反渗透、超滤、微孔过滤、膜萃取、渗透汽化和膜蒸馏。对其原理、高分子膜材料、应用和发展趋向作了简要介绍;并阐述了我国膜分离发展的现状和展望。     

Separation of p-xylene from multicomponent vapor mixtures using tubular MFI zeolite mmbranes

MFI zeolite membranes have been synthesized on tubular -alumina substrates to investigate the separation of p-xylene (PX) from m-xylene (MX) and o-xylene (OX) in binary, ternary, and simulated multicomponent mixtures in wide ranges of feed pressure and operating temperature. The results demonstrate that separation of PX from MX and OX through the MFI membranes relies primarily on shape-selectivity when the xylene sorption level in the zeolite is sufficiently low. For an eight-component mixture containing hydrogen, methane, benzene, toluene, ethylbenzene, PX, MX, and OX, a PX/(MX + OX) selectivity of 7.71 with a PX flux of 6.8 × 10⁻⁶ mol/(m² s) was obtained at 250 °C and atmospheric feed pressure. The addition of a small quantity of nonane to the multicomponent mixture caused drastic decreases in the fluxes of aromatic components and the PX separation factor because of the preferential adsorption of nonane in the zeolite channels. The nanoscale intercrystalline pores also caused serious decline in the PX separation factor. A new method of online membrane modification by carbonization of 1,3,5-triisopropylbenzene in the feed stream was found to be effective for reducing the intercrystalline pores and improving the PX separation.     

Inorganic Membranes for Hydrogen Separation

Hydrogen, one of the most promising energy carriers for the future, is currently produced mainly by natural gas reforming or coal gasification, where mixtures containing H₂, CO₂ and contaminants like CO, H₂S and CH₄ are obtained. Among other methods, membrane technology has received special attention due to its potential efficiency for hydrogen separation, simplicity of operation, low energy consumption, and because it is environmentally friendly. For this application, the inorganic membranes can be essentially divided into five main families: metallic and proton conducting (dense phases), and silica, zeolite and carbon molecular sieve (porous solids). Over the past 20 years, palladium-based membranes have been the most studied and implemented at industrial level; however, recent advances in other membrane types have received a great deal of attention. This article critically reviews more than 520 publications, highlighting the latest research developments on inorganic membranes for the recovery and purification of hydrogen, with emphasis on their structural characteristics, synthesis, commercial application, drawbacks and challenges. Furthermore, a large compilation of data is provided in Supplementary Material divided according to membrane type.     

NaA分子筛膜催化剂上CO和C2H4混合气的选择性氧化反应

Defect-free zeolite NaA membranes were coated onto the surface of spherical Pt/Al2O3 particles using a two-step hydrothermal method. The structure and morphology of the synthesized composite catalysts were characterized using XRD and SEM techniques, respectively. The results indicated a layer of compact and uniform NaA molecular sieve membrane with a thickness of about 20 滋m was coated on the spherical Pt/Al2O3 particles after the two-step hydrothermal synthesis. The prepared NaA membrane coated catalysts were used in the oxidation of a mixture of CO and C2H4 to study the reactant selectivity over the coated zeolite NaA membranes. Under the optimized conditions, the oxidation selectivity for CO over C2H4 on the composite catalyst was as high as 96%. The feasible application of this composite membrane coated catalyst to the selective removal of CO in the presence of C2H4 was anticipated.     

Fabrication of Highly Oriented Ultrathin Zirconium Metal-Organic Framework Membrane from Nanosheets towards Unprecedented Gas Separation

Concurrent regulation of crystallographic orientation and thickness of zirconium metal–organic framework (Zr-MOF) membranes is challenging but promising for their performance enhancement. In this study, we pioneered the fabrication of uniform triangular-shaped, 40 nm thick UiO-66 nanosheet (NS) seeds by employing an anisotropic etching strategy. Through innovating confined counter-diffusion-assisted epitaxial growth, highly (111)-oriented 165 nm-thick UiO-66 membrane was prepared. The significant reduction in thickness and diffusion barrier in the framework endowed the membrane with unprecedented CO₂ permeance (2070 GPU) as well as high CO₂/N₂ selectivity (35.4), which surpassed the performance limits of state-of-the-art polycrystalline MOF membranes. In addition, highly (111)-oriented 180 nm-thick NH₂-UiO-66 membrane showing superb H₂/CO₂ separation performance with H₂ permeance of 1230 GPU and H₂/CO₂ selectivity of 41.3, was prepared with the above synthetic procedure.     

沸石膜的合成、表征与应用

综述了沸石膜的合成、表征及应用。沸石膜合成最常用的方法为水热合成法,并相继发展了二次生长和微波合成法。XRD、SEM、EPMA及气体渗透为表征沸石膜常用的手段。沸石膜在分离、膜反应、催化及光学材料等方面具有广阔的应用前景。最后对沸石膜的发展进行了展望。     

等离子体辅助合成分子筛膜及其催化性能的研究

首次将等离子体技术应用于分子筛膜的制备，研究了以微波等离子体处理基材表面分子筛膜前驱体辅助水热反应合成支撑β型分子筛膜．利用XRD、SEM、XPS、BET、TPD表征了分子筛膜的物相、形貌、孔结构、表面元素组成和表面酸性，并通过甲醇与异丁烯液相反应体系实验考察了分子筛膜的催化性能．结果表明，等离子体处理能有效改善分子筛膜前驱体在基材表面的分散状况，减小了分子筛膜晶体的尺度，使晶体大小均匀，形成的膜致密、牢固．与采用常规方法合成的分子筛膜相比，等离子体辅助合成的分子筛膜对甲醇与异丁烯的反应有更好的催化活件．     

层状分子筛MCM-56的合成及表征

分子筛催化剂一般具有很好的择形性 ,但较小的孔径很难用于较大分子的催化转化 .目前寻找既具有一般分子筛的酸性和稳定性 ,又具有规则的较大孔径的催化剂是石油化工研究中的迫切需要 .因此 ,如果一种材料具有可让较大有机物分子接近的类分子筛的酸性点 ,就必然会引起广泛重视 .具有特殊晶体结构的 MCM- 2 2族分子筛 [1～ 5]则符合以上要求 ,其合成与催化研究已成为分子筛催化领域中的一个热点课题 .MCM- 5 6 [6]属于 MWW结构的分子筛 ,其晶胞参数 c为 2 .5 5 nm,并且层状结构经5 4 0℃焙烧后可基本保持原状 .MCM- 5 6具有可溶胀性 ,说…     

Structure Regulation of MOF Nanosheet Membrane for Accurate H2/CO2 Separation

High-purity H₂ production accompanied with a precise decarbonization opens an avenue to approach a carbon-neutral society. Metal–organic framework nanosheet membranes provide great opportunities for an accurate and fast H₂/CO₂ separation, CO₂ leakage through the membrane interlayer galleries decided the ultimate separation accuracy. Here we introduce low dose amino side groups into the Zn₂(benzimidazolate)₄ conformation. Physisorbed CO₂ served as interlayer linkers, gently regulated and stabilized the interlayer spacing. These evoked a synergistic effect of CO₂ adsorption-assisted molecular sieving and steric hinderance, whilst exquisitely preserving apertures for high-speed H₂ transport. The optimized amino membranes set a new record for ultrathin nanosheet membranes in H₂/CO₂ separation (mixture separation factor: 1158, H₂ permeance: 1417 gas permeation unit). This strategy provides an effective way to customize ultrathin nanosheet membranes with desirable molecular sieving ability.     

高硅ZSM—5沸石填充硅橡胶膜的醇—水渗透蒸发分离性质

高硅ZSM－5沸石填充疏水性硅橡胶蓦地低浓度醇－水体度醇－水体的渗透蒸发性质的研究有明，提高沸石硅铝比，增加填充量以及进行酸处理皆有利于改善膜对醇－水的分离系数和通量。料液的成，浓度以及温度对膜的分离性质也有显著影响。