Engineered Transport in Microporous Materials and Membranes for Clean Energy Technologies

Many forward‐looking clean‐energy technologies hinge on the development of scalable and efficient membrane‐based separations. Ongoing investment in the basic research of microporous materials is beginning to pay dividends in membrane technology maturation. Specifically, improvements in membrane selectivity, permeability, and durability are being leveraged for more efficient carbon capture, desalination, and energy storage, and the market adoption of membranes in those areas appears to be on the horizon. Herein, an overview of the microporous materials chemistry driving advanced membrane development, the clean‐energy separations employing them, and the theoretical underpinnings tying membrane performance to membrane structure across multiple length scales is provided. The interplay of pore architecture and chemistry for a given set of analytes emerges as a critical design consideration dictating mass transport outcomes. Opportunities and outstanding challenges in the field are also discussed, including high‐flux 2D molecular‐sieving membranes, phase‐change adsorbents as performance‐enhancing components in composite membranes, and the need for quantitative metrologies for understanding mass transport in heterophasic materials and in micropores with unusual chemical interactions with analytes of interest.     

Design and Fabrication of Ceramic Catalytic Membrane Reactors for Green Chemical Engineering Applications

Catalytic membrane reactors (CMRs), which synergistically carry out separations and reactions, are expected to become a green and sustainable technology in chemical engineering. The use of ceramic membranes in CMRs is being widely considered because it permits reactions and separations to be carried out under harsh conditions in terms of both temperature and the chemical environment. This article presents the two most important types of CMRs: those based on dense mixed-conducting membranes for gas separation, and those based on porous ceramic membranes for heterogeneous catalytic processes. New developments in and innovative uses of both types of CMRs over the last decade are presented, along with an overview of our recent work in this field. Membrane reactor design, fabrication, and applications related to energy and environmental areas are highlighted. First, the configuration of membranes and membrane reactors are introduced for each of type of membrane reactor. Next, taking typical catalytic reactions as model systems, the design and optimization of CMRs are illustrated. Finally, challenges and difficulties in the process of industrializing the two types of CMRs are addressed, and a view of the future is outlined.     

In situ synthesis of catalytic metal nanoparticle-PDMS membranes by thermal decomposition process

Nanoparticles of various transition elements such as palladium, iron, and nickel were synthesized in situ in the polydimethylsiloxane (PDMS) matrix by thermal decomposition of their corresponding acetylacetonate salts. Various complementary techniques such as XRD, TEM and XPS were used to characterize the nanoparticles formed in the polymer matrix. This synthesis route results in relatively monodisperse nanoparticles with a narrow particle size distribution. In addition, the composite films are pore-free and mechanically stable, making them attractive for a range of applications. Palladium-PDMS membranes can be used as catalytic membrane reactors and show enhanced catalytic activity in ethylene hydrogenation.     

Solvent-Less Vapor-Phase Fabrication of Membranes for Sustainable Separation Processes

Sustainable processes for purifying water, capturing carbon, producing biofuels, operating fuel cells, and performing energy-efficient industrial separations will require next-generation membranes. Solvent-less fabrication for membranes not only eliminates potential environmental issues with organic solvents, but also solves the swelling problems that occur with delicate polymer substrates. Furthermore, the activation procedures often required for synthesizing microporous materials such as metal–organic frameworks (MOFs) can be reduced when solvent-less vapor-phase approaches are employed. This perspective covers several vacuum deposition processes, including initiated chemical vapor deposition (iCVD), initiated plasma-enhanced chemical vapor deposition (iPECVD), solvent-less vapor deposition followed by in situ polymerization (SLIP), atomic layer deposition (ALD), and molecular layer deposition (MLD). These solvent-less vapor-phase methods are powerful in creating ultrathin selective layers for thin-film composite membranes and advantageous in conformally coating nanoscale pores for the precise modification of pore size and internal functionalities. The resulting membranes have shown promising performance for gas separation, nanofiltration, desalination, and water/oil separation. Further development of novel membrane materials and the scaling up of high-throughput reactors for solvent-less vapor-phase processes are necessary in order to make a real impact on the chemical industry in the future.     

Fusion of enveloped virus nanoparticles with polyelectrolyte-supported lipid membranes for the design of bio/nonbio interfaces

Fusion of lipid-enveloped viruses with endosomal membranes triggered by low pH in the endosome is a key step in the course of viral infection. This ubiquitous mechanism can be used to integrate functional nanoparticles of viral origin into composite materials consisting of a polyelectrolyte multilayer with an adsorbed lipid membrane in a natural and biomimetic way. Polyelectrolyte multilayers as the support for the lipid membrane are a versatile means to combine the biological functions of the viral surface with the multiplicity of polyelectrolyte borne functions into a novel bio/nonbio composite material.     

沉积Ag纳米层改善定型相变复合纤维膜的传热性能

以癸酸(CA)、月桂酸(LA)和肉豆蔻酸(MA)为原料制备了新型的脂肪酸三元低共熔物(CA-LA-MA),并将其作为固-液相变材料,以沉积2 h银(Ag)纳米颗粒的静电纺聚丙烯腈(PAN)纳米纤维膜为支撑材料,通过物理吸附法制备了新型的CA-LA-MA/PAN和CA-LA-MA/PAN/Ag定型相变复合纤维膜。研究了磁控溅射Ag纳米层对定型相变复合纤维传热性能的影响。结果表明,沉积Ag纳米层后定型相变复合纤维膜的储热和放热时间分别缩短了31%和25%。制备的CA-LA-MA/PAN/Ag定型相变复合纤维膜的融化温度和结晶温度分别为19.87℃和11.63℃,融化焓值和结晶焓值分别为123.1 kJ/kg和121.5 kJ/kg。     

燃料电池用质子交换膜的研究进展

对燃料电池用质子交换膜的研究进展进行了简要的概述,特别是从膜材料角度分类．较详细的介绍了全氟化质子交换膜,部分氟化质子交换膜,接枝、交联、共混型质子交换膜等的特性及最新的研究状况,并对其发展前景进行了探讨．     

优先渗透CO_2的TS-1/C杂化功能炭膜的制备研究

以PMDA-ODA型聚酰胺酸为原料,通过掺杂钛硅分子筛(TS-1)制备气体分离用杂化功能炭膜.系统考察了钛硅分子筛(TS-1)掺杂量、炭化温度等因素对功能炭膜气体渗透性和分离性能的影响,利用FT-IR、XRD、TG和TEM等分析手段对TS-1/C杂化原膜及其在不同温度下炭化的炭膜结构和性能进行表征.结果表明:掺杂钛硅分子筛(TS-1)可大幅提高炭膜对CO2的渗透性能;当掺杂质量分数为20%,炭化温度为600℃时,CO2、H2、O2、N2、CH4的渗透系数分别可达9 087Barrer、8 111Barrer、2 017Barrer、426Barrer和357Barrer;当炭化温度为700℃以上时,功能炭膜对各气体的渗透性急剧降低,气体分离性大幅提高.     

Continuous Covalent Organic Frameworks Membranes: From Preparation Strategies to Applications

Covalent organic frameworks (COFs) are porous crystalline polymeric materials formed by the covalent bonding of organic units. The abundant organic units library gives the COFs species diversity, easily tuned pore channels, and pore sizes. In addition, the periodic arrangement of organic units endows COFs regular and highly connected pore channels, which has led to the rapid development of COFs in membrane separations. Continuous defect-free and high crystallinity of COF membranes is the key to their application in separations, which is the most important issue to be addressed in the research. This review article describes the linkage types of covalent bonds, synthesis methods, and pore size regulation strategies of COFs materials. Further, the preparation strategies of continuous COFs membranes are highlighted, including layer-by-layer (LBL) stacking, in situ growth, interfacial polymerization (IP), and solvent casting. The applications in separation fields of continuous COFs membranes are also discussed, including gas separation, water treatment, organic solvent nanofiltration, ion conduction, and energy battery membranes. Finally, the research results are summarized and the future prospect for the development of COFs membranes are outlined. More attention may be paid to the large-scale preparation of COFs membranes and the development of conductive COFs membranes in future research.     

Antifouling ultrafiltration membranes via post-fabrication grafting of biocidal nanomaterials

Ultrafiltration (UF) membranes perform critical pre-treatment functions in advanced water treatment processes. In operational systems, however, biofouling decreases membrane performance and increases the frequency and cost of chemical cleaning. The present work demonstrates a novel technique for covalently or ionically tethering antimicrobial nanoparticles to the surface of UF membranes. Silver nanoparticles (AgNPs) encapsulated in positively charged polyethyleneimine (PEI) were reacted with an oxygen plasma modified polysulfone UF membrane with and without 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) present. The nucleophilic primary amines of the PEI react with the electrophilic carboxyl groups on the UF membrane surface to form electrostatic and covalent bonds. The irreversible modification process imparts significant antimicrobial activity to the membrane surface. Post-synthesis functionalization methods, such as the one presented here, maximize the density of nanomaterials at the membrane surface and may provide a more efficient route for fabricating diverse array of reactive nanocomposite membranes.     

光催化TiO_2复合分离膜的制备技术

纳米TiO2复合分离膜集过滤、光催化降解、自清洁、防垢、提高膜通量等功能于一体,能有效解决传统膜分离系统存在的膜污染和膜通量衰减的问题,对发展新型的膜分离技术、开发纳米光催化新材料,以及在节水减排和中水回用等方面具有重要的应用价值。TiO2复合分离膜涉及TiO2纳米晶的合成和固载化工艺、多孔陶瓷载体的选择、烧结工艺及复合膜的稳定性。本文对目前国内外使用的TiO2复合分离膜的各种制备工艺和方法进行了归纳、总结和分析,并对其今后的发展和应用提供了建议。     

渗透汽化分离有机物

用不同的方法制备了几种分离有机物的膜，如CA/PAN、PVA/PAN的复合膜，以及含金属离子载体的PVA膜，这些膜是复合膜或非对称膜．测量了膜材料(CA和PVA—Me^n )的吸附特性并评价了其性能．结果表明，CA和CTA膜以及几种复合膜适于分离MTBE/MeOH，修正的溶解-扩散模型可成功地估算MTBE／MeOH透过CA膜的渗透汽化分离性能．从初步吸附试验看，含金属离子载体的PVA膜对分离苯／环乙烷体系可能是一好的候选膜．     

Fabrication of nanocomposite membranes from nanofibers and nanoparticles for protection against chemical warfare stimulants

Nanoparticles of MgO were synthesized by Aero gel method. These MgO nanoparticles were then mixed with various polymer solutions (poly(vinyl chloride) (PVC), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF copolymer), polysulfone (PSU)) and then subjected to electrospinning to produce nanocomposite membranes. The hydrolysis of paraoxon, a never agent stimulant, in presence of these membranes was studied using UV. The order of the reactivity of the membranes are found to be PVC-MgO < PVDF < PSU < PVDF-MgO < PSU-MgO. After selecting PSU as the supportive candidate, relative rates of hydrolysis were compared for nanoparticles or charcoal with nanocomposite membranes. The order is as follows; Charcoal (1) < PSU-Al₂O₃ (1.5) < PSU-MgO (2.1) < Al₂O₃ nanoparticles (2.8) < MgO nanoparticles (5.4). The amount of hydrolysis of PSU-MgO composite membrane was 60% less when compared to MgO nanoparticles as such usage. The loading percentage of MgO into nanofiber is 35 %. The fabricated composite membrane (containing 5% MgO) was tested for chemical warfare agent stimulant, paraoxon, and found to be about 2 times more reactive than currently used charcoal.     

Ultraselective Carbon Molecular Sieve Membranes with Tailored Synergistic Sorption Selective Properties

Membrane‐based separations can reduce the energy consumption and the CO₂ footprint of large‐scale fluid separations, which are traditionally practiced by energy‐intensive thermally driven processes. Here, a new type of membrane structure based on nanoporous carbon is reported, which, according to this study, is best referred to as carbon/carbon mixed‐matrix (CCMM) membranes. The CCMM membranes are formed by high‐temperature (up to 900 °C) pyrolysis of polyimide precursor hollow‐fiber membranes. Unprecedentedly high permselectivities are seen in CCMM membranes for CO₂/CH₄, N₂/CH₄, He/CH₄, and H₂/CH₄ separations. Analysis of permeation data suggests that the ultrahigh selectivities result from substantially increased sorption selectivities, which is hypothetically owing to the formation of ultraselective micropores that selectively exclude the bulkier CH₄ molecules. With tunable sorption selectivities, the CCMM membranes outperform flexible polymer membranes and traditional rigid molecular‐sieve membranes. The capability to increase sorption selectivities is a powerful tool to leverage diffusion selectivities, and has opened the door to many challenging and economically important fluid separations that require ultrafine differentiation of closely sized molecules.     

A review of advanced proton-conducting materials for hydrogen separation

This paper provides a comprehensive overview of developments and recent trends in H₂ separation technology that uses dense proton–electron conducting ceramic materials and their associated membranes. Various proton–electron conducting materials and their associated membranes are summarized and classified into several important categories, such as Ni-composite proton-conducting materials, as well as tungstate-based, BaPrO₃-based, LaGaO₃-based, and niobate/tantalite composite metal oxide-based ceramic materials/membranes. Various membrane designs, including asymmetric ceramic membranes (supported and self-supported) and surface-modified membranes, are also reviewed. Several important properties of ceramic materials and membranes, such as proton and electron conductivity and performance (i.e., H₂ transport flux and lifetime stability), are also discussed. To highlight the technical progress in this area, all possible ceramic materials and associated membranes are summarized, along with their properties and performance, to help readers quickly locate the information they are looking for. Based on this review, several challenges hindering the maturation of this technology are analyzed in depth, and possible research directions for overcoming these challenges are suggested.     

Fabrication of hybrid membrane of electrospun polycaprolactone and polyethylene oxide with shape memory property

Hybrid materials with nanostructure could exhibit a diverse range of applications as advanced functional materials. This research work, composite membranes with shape memory property based on biocompatible polycaprolactone and polyethylene oxide were successfully fabricated by using electrospinning technique. Electrospun fiber configuration is strongly related to the concentration of polymer and electric field strength. The hydrophilic property of hybrid membrane has been improved and water play a critical role in resulting lower its responsive temperature compared with dry membrane. The mechanism of shape memory PCL/PEO hybrid membrane at wet condition has been proposed.     

Plasmon hybridization reveals the interaction between individual colloidal gold nanoparticles confined in an optical potential well

The understanding of interaction forces between nanoparticles in colloidal suspension is central to a wide range of novel applications and processes in science and industry. However, few methods are available for actual characterization of such forces at the single particle level. Here we demonstrate the first measurements of colloidal interactions between two individual diffusing nanoparticles using a colorimetric assay based on plasmon hybridization, that is, strong near-field coupling between localized surface plasmon resonances. The measurements are possible because individual gold nanoparticle pairs can be loosely confined in an optical potential well created by a laser tweezers. We quantify the degree of plasmon hybridization for a large number of individual particle pairs as a function of increasing salt concentration. The data reveal a considerable heterogeneity at the single particle level but the estimated average surface separations are in excellent agreements with predictions based on the classical theory of Derjaguin, Landau, Verwey, and Overbeek.     

燃料电池用高温质子交换膜的研究进展

燃料电池是一种高效的清洁能源技术,可缓解当今社会面临的能源和环境问题。质子交换膜燃料电池是一种重要的燃料电池类型,质子交换膜是其关键组件,起到传导质子、隔绝电子和阴阳两极的反应物的作用。质子交换膜燃料电池在低温下存在许多难以解决的问题,升高工作温度可以解决这些问题。因此需要开发高温低湿度下工作的膜材料。本文综述了高温质子交换膜的主要类型、制备与改性方法和质子传导机制,指出质子导体掺杂的聚苯并咪唑(PBI)类膜材料在高温低湿度下作为质子交换膜适用的巨大潜力,并探讨了复合PBI高温质子交换膜的制备、掺杂的质子导体类型和性能提升方法。最后本文归纳了高温质子交换膜面临的挑战,并指出了该类材料未来的研究方向,如设计合成新型质子导体、改善PBI抗氧化稳定性、调控膜微观结构来提升性能和开发新型聚合物电解质。     

Engineering high-temperature stable nanocomposite materials

The low thermal stability of nanoparticles typically restricts their use in catalytic and other applications to low-?to moderate-temperature conditions. We present a novel approach to the stabilization of nanosized noble metal particles by embedding them in a high-temperature stabilized hexa-aluminate matrix. The simple 'one-pot' approach is based on a microemulsion-templated sol-gel synthesis and yields mesoporous nanocomposite materials with pure textural porosity and excellent high-temperature stability up to about 1200?°C. To our knowledge, this is the first time that metal nanoparticles have been stabilized to such high temperatures. We furthermore find that the microemulsion templating allows a tailoring of the ceramic matrix without influencing the size of the embedded Pt particle. This opens up the possibility of a true multiscale engineering of nanocomposite materials. We see these novel materials therefore not only as very promising candidates for a broad range of high-temperature catalytic applications, but generally view this versatile synthesis route as a first step towards expanding the parameter range for nanoparticle applications.     

Moving Frontiers in Transition Metal Catalysis: Synthesis,Characterization and Modeling

Nanosized transition metal particles are important materials in catalysis with a key role not only in academic research but also in many processes with industrial and societal relevance. Although small improvements in catalytic properties can lead to significant economic and environmental impacts, it is only now that knowledge‐based design of such materials is emerging, partly because the understanding of catalytic mechanisms on nanoparticle surfaces is increasingly improving. A knowledge‐based design requires bottom‐up synthesis of well‐defined model catalysts, an understanding of the catalytic nanomaterials “at work” (operando), and both a detailed understanding and a prediction by theoretical methods. This article reports on progress in colloidal synthesis of transition metal nanoparticles for preparation of model catalysts to close the materials gap between the discoveries of fundamental surface science and industrial application. The transition metal particles, however, often undergo extensive transformations when applied to the catalytic process and much progress has recently been achieved operando characterization techniques under relevant reaction conditions. They allow better understanding of size/structure–activity correlations in these systems. Moreover, the growth of computing power and the improvement of theoretical methods uncover mechanisms on nanoparticles and have recently predicted highly active particles for CO/CO₂ hydrogenation or direct H₂O₂ synthesis.