Unprecedentedly Low CO2 Transport through Vertically Aligned, Conical Silicon Nanotube Membranes.

Nanotube membranes could show significantly enhanced permeance and selectivity for gas separations. Up until now, studies have primarily focused on applying carbon nanotubes to membranes to achieve ultrafast mass transport. Here, we report the first preparation of silicon nanotube (SiNT) membranes via a template-assisted method and investigate the gas transport behavior through these SiNT membranes using single- and mixed-gas permeation experiments. The SiNT membranes consist of conical cylinder-shaped nanotubes vertically aligned on a porous silicon wafer substrate. The diameter of the SiNT pore mouths are 10 and 30 nm, and the average inner diameter of the tube body is 80 nm. Interestingly, among the gases tested, we found an unprecedentedly low CO2 permeance through the SiNT membranes in single-gas permeation experiments, exceeding the theoretical Knudsen selectivity toward small gases/CO2 separation. This behavior was caused by the reduction of CO2 permeability through the blocking effect of CO2 adsorbed in the narrow pore channels of the SiNT cone regions, indicating that CO2 molecules have a high affinity to the native silicon oxide layer (∼2 nm) that is formed on the inner walls of SiNTs. SiNT membranes also exhibited enhanced gas permeance and water flux as compared to classic theoretical models and, as such, may prove useful as a new type of nanotube material for use in membrane applications.

Defect Engineering in Metal-Organic Frameworks Towards Advanced Mixed Matrix Membranes for Efficient Propylene/Propane Separation.

Highly permselective and durable membrane materials have been sought for energy-efficient C3 H6 /C3 H8 separation. Mixed-matrix membranes (MMMs) comprising a polymer matrix and metal-organic frameworks (MOFs) are promising candidates for this application; however, rational matching of filler-matrix is challenging and their separation performances need to be further improved. Here, we propose a novel strategy of "defect engineering" in MOFs as an additional degree of freedom to design advanced MMMs. MMMs incorporated with defect-engineered MOFs exhibit exceptionally high C3 H6 permeability and maintained C3 H6 /C3 H8 selectivity, especially with enhanced stability under industrial mixed-gas conditions. The gas transport, sorption, and material characterizations reveal that the defect sites in MOFs provide the resulting MMMs with not only ultrafast diffusion pathways but also favorable C3 H6 sorption by forming complexation with unsaturated open metal sites, confirmed by in situ FT-IR studies. Most importantly, the concept is also valid for different polymer matrices and gas pairs, demonstrating its versatile potential in other fields.

Graphene-based membranes: status and prospects.

Recently, graphene-based membranes have been extensively studied, represented by two distinct research directions: (i) creating pores in graphene basal plane and (ii) engineering nanochannels in graphene layers. Most simulation results predict that porous graphene membranes can be much more selective and permeable than current existing membranes, also evidenced by some experimental results for gas separation and desalination. In addition, graphene oxide has been widely investigated in layered membranes with two-dimensional nanochannels, showing very intriguing separation properties. This review will cover state-of-the-art of graphene-based membranes, and also provide a material guideline on future research directions suitable for practical membrane applications.

Origin of CO2-philic Sorption by Graphene Oxide Layered Nanosheets and Their Derivatives.

Graphene oxide (GO) is a promising 2D material for adsorbents and membranes, in particular, for the CO2 separation process. However, CO2 diffusion and sorption in GO and its layered structures are still not well understood because of its heterogeneous structure. Here we report CO2 sorption in GO and its derivatives (e.g., reduced GO (rGO)) in powders and films. These CO2 sorption behaviors reveal that GO is highly CO2-philic via complex CO2-functional-group-surface interactions, as compared with graphite and rGOs. Even in highly interlocked, lamellar GO films, CO2 molecules above a certain threshold pressure can diffuse into GO interlayers, causing GO films to swell and leading to dramatic increases in CO2 sorption. Intercalated water in GO interlayers can be removed by preferential CO2 sorption without any changes in the GO chemical structure. This finding helps to explain the origin of CO2 affinity with GO and has implications for preparing anhydrous GO assemblies for various applications.

Understanding Gas Transport Behavior through Few-Layer Graphene Oxide Membranes Controlled by Tortuosity and Interlayer Spacing.

Here, we elucidate the gas transport behavior through few-layer graphene oxide membranes (FGOMs) that have a systematically controlled diffusion pathway, including tortuosity and channel width. The obtained unusual gas permeation order (especially, CH4 > O2 > N2) of the FGOM provides strong evidence that gas molecules can indeed penetrate through the empty voids created by horizontally assembled GO, which allows selective gas transport features. These unique transport features of the FGOM originate from its continuously connected channel structure, which is an analogue of an ultrapermeable glassy polymer with extremely large free volumes in dense films. Furthermore, variation of the channel width in the range of 0.50-0.55 nm leads to notable changes in the gas permeance orders related to CH4, indicating that there is a transition region for switching the gas transport mechanism between a molecular sieving character and the solution-diffusion model.

High-performance CO2-philic graphene oxide membranes under wet-conditions.

Ultrathin graphene oxide (GO) (<5 nm) membranes were prepared by spin-casting onto microporous polymeric support membranes. GO membranes exhibited a highly CO2 permeable character, which is suitable for CO2 separation. In the presence of water vapour, high CO2 selectivity (e.g., CO2/H2, CO2/N2, and CO2/CH4) was achieved by enhanced CO2 sorption.

Selective gas transport through few-layered graphene and graphene oxide membranes.

Graphene is a distinct two-dimensional material that offers a wide range of opportunities for membrane applications because of ultimate thinness, flexibility, chemical stability, and mechanical strength. We demonstrate that few- and several-layered graphene and graphene oxide (GO) sheets can be engineered to exhibit the desired gas separation characteristics. Selective gas diffusion can be achieved by controlling gas flow channels and pores via different stacking methods. For layered (3- to 10-nanometer) GO membranes, tunable gas transport behavior was strongly dependent on the degree of interlocking within the GO stacking structure. High carbon dioxide/nitrogen selectivity was achieved by well-interlocked GO membranes in high relative humidity, which is most suitable for postcombustion carbon dioxide capture processes, including a humidified feed stream.