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At least 1,099 records · Page 61

Oxidative coupling of methane (OCM) conversion into C 2 products through a CO 2 /O 2 co-transport membrane reactor

Oxidative coupling of methane (OCM), which transforms CH 4 into C 2 products (C 2 H 6 and C 2 H 4 ) with molecular O 2 as the oxidant, is one of the most studied direct methane conversions (DMCs). However, a major technical hurdle to the OCM process is to achieve high CH 4 conversion at high C 2 (C 2 H 6 and C 2 H 4 ) selectivity. One rudimentary cause for this “tradeoff” behavior is the high chemical reactivity of the products (C 2 H 6 or C 2 H 4 ), which can be re-oxidized by O 2 . To overcome this thermodynamic challenge, minimizing the oxidizing power of the oxidant and lowering the local oxygen partial pressure are keys. Here, In this work, we demonstrate a new membrane reactor that capture CO 2 /O 2 from a flue gas and uses it for OCM conversion. The results show that the co-captured CO 2 /O 2 mixture converts CH 4 into C 2 H 6 in the presence of a 2%Mn–5%Na 2 WO 4 /SiO 2 catalyst, followed by thermal cracking of C 2 H 6 into C 2 H 4 and H 2 . The presence of CO 2 decreases the local partial pressure of O 2 , thus reducing the propensity of C 2 -products re-oxidation and leading to a higher C 2 selectivity. We show that a small button-type membrane reactor can achieve 12% C 2 yield with ~57% C 2 -selectivity using a diluted CH 4 -Ar mixture as the feedstock. We expect higher C 2 yield with tubular plug-flow membrane reactors in the future. We also highlight the unique advantage of the membrane reactor in intensifying CO 2 capture from both flue gas and OCM purification process into one single step.

42 ENGINEERING↗

Testing of Alternative Materials for Advanced Suit Bladders

Several candidate advanced pressure bladder membrane materials have been developed for NASA Johnson Space Center by DSM Biomedical for selective permeability of carbon dioxide and water vapor. These materials were elasthane and two other formulations of thermoplastic polyether polyurethane. Each material was tested in two thicknesses for permeability to carbon dioxide, oxygen and water vapor. Although oxygen leaks through the suit bladder would amount to only about 60 cc/hr in a full size suit, significant amounts of carbon dioxide would not be rejected by the system to justify its use. While the ratio of carbon dioxide to oxygen permeability is about 48 to 1, this is offset by the small partial pressure of carbon dioxide in acceptable breathing atmospheres of the suit. Humidity management remains a possible use of the membranes depending on the degree to which the water permeability is inhibited by cations in the sweat. Tests are underway to explore cation fouling from sweat.

Bue, Grant↗

Fabrication and Scale-up of Polybenzimidazole (PBI) Membrane Based System for Precombustion-Based Capture of Carbon Dioxide

The primary objectives of this project are to (1) demonstrate the performance and fabrication of a technically and economically viable pre-combustion-based CO 2 capture system based on the high temperature stability and permeance of PBI membranes, (2) optimize a plan for integration of PBI capture system into an IGCC plant and (3) develop a commercialization plan that addresses technical issues and business issues to outline a clear path for technology transfer of the PBI membrane technology. This report describes research conducted from April 1, 2007 to March 30, 2012 and focused on achieving the above objectives. PBI-based hollow fibers have been fabricated at kilometer lengths and bundled as modules at a bench-scale level for the separation of CO 2 from H 2 at high temperatures and pressures. Long term stability of these fibers has been demonstrated with a relatively high H 2 /CO 2 selectivity (35 to 50) and H 2 permeance (80 GPU) at temperatures exceeding 225°C. Membrane performance simulations and systems analysis of an IGCC system incorporating a PBI hollow fiber membrane modules have demonstrated that the cost of electricity for CO 2 capture (<10%) using such a high temperature separator. When the cost of transporting, storing, and monitoring the CO 2 is accounted for, the increase in the COE is only 14.4%.

01 COAL, LIGNITE, AND PEAT↗

Poly(aryl piperidinium) membranes and ionomers for hydroxide exchange membrane fuel cells

One promising approach to reduce the cost of fuel cell systems is to develop hydroxide exchange membrane fuel cells (HEMFCs), which open up the possibility of platinum-group-metal-free catalysts and low-cost bipolar plates. However, scalable alkaline polyelectrolytes (hydroxide exchange membranes and hydroxide exchange ionomers), a key component of HEMFCs, with desired properties are currently unavailable, which presents a major barrier to the development of HEMFCs. Here we show hydroxide exchange membranes and hydroxide exchange ionomers based on poly(aryl piperidinium) (PAP) that simultaneously possess adequate ionic conductivity, chemical stability, mechanical robustness, gas separation and selective solubility. Here, these properties originate from the combination of the piperidinium cation and the rigid ether-bond-free aryl backbone. A low-Pt membrane electrode assembly with a Ag-based cathode using PAP materials showed an excellent peak power density of 920 mW cm -2 and operated stably at a constant current density of 500 mA cm -2 for 300 h with H 2 /CO 2 -free air at 95 °C.

25 ENERGY STORAGE↗

Toward Rapid Actinium-225 Purification via Membrane Adsorbers with Covalently Tethered Diglycolamide Ligands

Extractive diglycolamide (DGA) resins are used in several state-of-the-art techniques for purifying 225 Ac, a promising radiometal for targeted alpha therapy. Unfortunately, separation processes that rely on resins are often limited to slow flow rates, high elution volumes, and long processing times. Membrane adsorbers functionalized with DGA ligands are an alternative separation material that may overcome these challenges. This work presents (1) the synthesis of an aminated tetrahexyldiglycolamide ligand, (2) the covalent tethering of the ligand to electrospun poly(vinylbenzyl chloride) fiber mats, and (3) the adsorption and desorption of La(III) and 225 Ac. Chemical and physical characterization supports the covalent tethering of the ligand to the fiber mat, as well as the preservation of the fiber surface area and porosity after functionalization. Equilibrium adsorption experiments were performed with stable La(III) and radioactive 225 Ac. Trends in affinity are consistent between commercial resins and the synthesized membrane adsorbers; however, the Langmuir constants and the maximum binding capacity of the membrane adsorbers were generally lower than the resins. Despite these differences, the modeled selectivity for an equimolar solution of La(III)/ 225 Ac in 10 M nitric acid is 57. Furthermore, 225 Ac is rapidly desorbed from the fibers in 10 M nitric acid (<20 min). The La(III)/ 225 Ac selectivity and rapid 225 Ac desorption indicate this class of materials is promising for rapid radioanalytical separations.

07 ISOTOPE AND RADIATION SOURCES↗

Bulk-like and Interfacial Water Dynamics in Nafion Fuel Cell Membranes Investigated with Ultrafast Nonlinear IR Spectroscopy

The water confined in the hydrophilic domains of Nafion fuel cell membranes is central to its primary function of ion transport. Water dynamics are intimately linked to proton transfer and are sensitive to the structural features and length scales of confinement. Here, ultrafast polarization-selective pump-probe and two-dimensional infrared vibrational echo (2D IR) experiments were performed on fully hydrated Nafion membranes with sodium counterions to explicate the water dynamics. Like aerosol-OT reverse micelles (AOT RMs), the water dynamics in Nafion are attributed to bulk-like core water in the central region of the hydrophilic domains and much slower interfacial water. Population and orientational dynamics of water in Nafion are slowed by polymer confinement. Comparison of the observed dynamics to those of AOT RMs helps identify local interactions between water and sulfonate anions at the interface and among water molecules in the core. This comparison also demonstrates that the well-known spherical cluster morphology of Nafion is not appropriate. Spectral diffusion of the interfacial water, which arises from structural dynamics, was obtained from the 2D IR experiments taking the core water to have dynamics similar to bulk water. Like the orientational dynamics, spectral diffusion was found to be much slower at the interface compared to bulk water. Together, the dynamics indicate slow reorganization of weakly hydrogen-bonded water molecules at the interface of Nafion. We report these results provide insights into proton transport mechanisms in fuel cell membranes, and more generally, water dynamics near the interface of confining systems.

25 ENERGY STORAGE↗

Creation of Polymer Datasets with Targeted Backbones for Screening of High-Performance Membranes for Gas Separation

A simple approach was developed to computationally construct a polymer dataset by combining simplified molecular-input line-entry system (SMILES) strings of a targeted polymer backbone and a variety of molecular fragments. This method was used to create 14 polymer datasets by combining seven polymer backbones and molecules from two large molecular datasets (MOSES and QM9). Polymer backbones that were studied include four polydimethylsiloxane (PDMS) based backbones, poly(ethylene oxide) (PEO), poly(allyl glycidyl ether) (PAGE), and polyphosphazene (PPZ). The generated polymer datasets can be used for various cheminformatics tasks, including high-throughput screening for gas permeability and selectivity. This study utilized machine learning (ML) models to screen the polymers for CO2/CH4 and CO2/N2 gas separation using membranes. Several polymers of interest were identified. Here the results highlight that employing an ML model fitted to polymer selectivities leads to higher accuracy in predicting polymer selectivity compared to using the ratio of predicted permeabilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solar Sail Loads, Dynamics, and Membrane Studies

While a number of solar sail missions have been proposed recently, these missions have not been selected for flight validation. Although the reasons for non-selection are varied, principal among them is the lack of subsystem integration and ground testing. This paper presents some early results from a large-scale ground testing program for integrated solar sail systems. In this series of tests, a 10 meter solar sail tested is subjected to dynamic excitation both in ambient atmospheric and vacuum conditions. Laser vibrometry is used to determine resonant frequencies and deformation shapes. The results include some low-order sail modes which only can be seen in vacuum, pointing to the necessity of testing in that environment.

Slade, K. N.↗

Improvement of General Electric’s Chilled Ammonia Process with the use of Membrane Technology

General Electric Environmental Control Solutions (formerly Alstom Power Environmental Control Systems) set out to complete the Phase 1 award requirements for a Phase II renewal application for their project selected under DOE-FOA-0001190 “Small and Large Scale Pilots for Reducing the Cost of CO 2 Capture and Compression”. The project focus was to implement several improvement concepts utilizing membrane technology at the recipient’s Chilled Ammonia Process (CAP) CO 2 capture large-scale pilot plant. The goal was to lower the overall cost of technology. During the development of costs for the preliminary techno-economic assessment (TEA), it became clear that the capital and operating costs of this concept were not economically attractive. All work related to a Phase II renewal application at that point was halted as GE made the decision not to submit a Phase II renewal application. Discussions with DOE resulted in a path towards useful information produced from the design and cost work already completed on the project. With the reverse osmosis (RO) unit providing most of the cost issues, GE would provide a sensitivity analysis of the RO unit with respect to project cost. This information would be included with the Techno-Economic Analysis along with the Technology Gap Analysis.

20 FOSSIL-FUELED POWER PLANTS↗

Pyrazine-Fused Porous Graphitic Framework-Based Mixed Matrix Membranes for Enhanced Gas Separations

Membrane-based separations can mitigate the capital- and energy-intensive challenges associated with traditional thermally driven processes. To further push the boundary of gas separations, mixed matrix membranes (MMMs) have been extensively exploited; however, identifying an optimal nanofiller to boost the separation performance of MMMs beyond Robeson permeability-selectivity upper bounds remains an ongoing challenge. In this study, a new class of MMMs based on pyrazine-fused crystalline porous graphitic frameworks (PGFs) is reported. At a loading of 6 wt % PGFs, the MMMs surpass the current H 2 /CH 4 Robeson upper bound, ideally suited for applications such as H 2 regeneration. In addition, the fabricated MMMs exhibit appealing CO 2 separation performance, closely approaching the current Robeson upper bounds for CO 2 separation. Compared with the pristine polymeric membranes, the PGF-based MMMs display a record-high enhancement of gas permeability over 120% while maintaining intrinsic gas selectivities. Highlighting the crucial role of the crystallinity of nanofillers, this study demonstrates a facile and effective approach in formulating high-performance MMMs, complementing state-of-the-art membrane formation processes. The design principles open the door to energy-efficient separations of gas mixtures with enhanced productivity compatible with the current membrane manufacturing.

36 MATERIALS SCIENCE↗

Interfacial Engineering of Supported Liquid Membranes by Vapor Cross-Linking for Enhanced Separation of Carbon Dioxide

Supported liquid membranes (SLMs) based on ionic liquids (ILs) with not only high gas permeability and selectivity, but also high stability under high pressure, are highly desired for gas separation applications. In this paper, permeable and selective polyamide network (PN) layers are deposited on the surface of SLMs by utilizing the cross-linking reaction of trimesoyl chloride, which was pre-dispersed in the SLMs, and vapor of amine linkers. The vapor cross-linking method makes it easy to control the growth and aggregation of PN layers, owing to the significantly reduced reaction rate, and thereby ensuring the good distribution of PN layers on the surface of SLMs. With rational choice of amine linkers and optimization of vapor cross-linking conditions, the prepared sandwich-like PN@SLMs with ILs embedded homogeneously within polymeric matrices displayed much-improved CO 2 permeability and CO 2 /N 2 selectivity in relation to the pristine SLMs. Moreover, those SLMs with ILs impregnated into porous supports physically displayed improved stability under high pressure after vapor cross-linking, because the PN layers formed on the surface of SLMs help prevent the ILs from being squeezed out. Finally, this interfacial engineering strategy represents a significant advance in the surface modification of SLMs to endow them with promising applications in CO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure of Human GIVD Cytosolic Phospholipase A2 Reveals Insights into Substrate Recognition

Cytosolic phospholipases A2 (cPLA2s) consist of a family of calcium-sensitive enzymes that function to generate lipid second messengers through hydrolysis of membrane-associated glycerophospholipids. The GIVD cPLA2 (cPLA2δ) is a potential drug target for developing a selective therapeutic agent for the treatment of psoriasis. Here, we present two X-ray structures of human cPLA2δ, capturing an apo state, and in complex with a substrate-like inhibitor. Comparison of the apo and inhibitor-bound structures reveals conformational changes in a flexible cap that allows the substrate to access the relatively buried active site, providing new insight into the mechanism for substrate recognition. The cPLA2δ structure reveals an unexpected second C2 domain that was previously unrecognized from sequence alignments, placing cPLA2δ into the class of membrane-associated proteins that contain a tandem pair of C2 domains. Furthermore, our structures elucidate novel inter-domain interactions and define three potential calcium-binding sites that are likely important for regulation and activation of enzymatic activity. These findings provide novel insights into the molecular mechanisms governing cPLA2's function in signal transduction.

59 BASIC BIOLOGICAL SCIENCES↗

Enhanced biochemical sensing with high- Q transmission resonances in free-standing membrane metasurfaces

Optical metasurfaces provide solutions to label-free biochemical sensing by localizing light resonantly beyond the diffraction limit, thereby selectively enhancing light–matter interactions for improved analytical performance. However, high-Q resonances in metasurfaces are usually achieved in the reflection mode, which impedes metasurface integration into compact imaging systems. Here, we demonstrate a metasurface platform for advanced biochemical sensing based on the physics of the bound states in the continuum (BIC) and electromagnetically induced transparency (EIT) modes, which arise when two interfering resonances from a periodic pattern of tilted elliptic holes overlap both spectrally and spatially, creating a narrow transparency window in the mid-infrared spectrum. We experimentally measure these resonant peaks observed in transmission mode (Q ~ 734 at λ ~ 8.8 µm) in free-standing silicon membranes and confirm their tunability through geometric scaling. We also demonstrate the strong coupling of the BIC-EIT modes with a thinly coated PMMA film on the metasurface, characterized by a large Rabi splitting (32 cm -1 ) and biosensing of protein monolayers in transmission mode. Our new photonic platform can facilitate the integration of metasurface biochemical sensors into compact and monolithic optical systems while being compatible with scalable manufacturing, thereby clearing the way for on-site biochemical sensing in everyday applications.

Rosas, Samir [Univ. of Wisconsin, Madison, WI (Uni↗

Bacterial Efflux Pumps and Their Inhibitors

Bacterial multidrug efflux transporters have distinct molecular features and mechanisms that enable their impressive substrate polyspecificity. These transporters are involved in all physiological processes where nonspecific but active transport across membranes is critical for survival and proliferation. Importantly, efflux pumps contribute to bacterial virulence and pathogenesis, as well as the spread of antibiotic resistance in clinics. Transporters belonging to several protein superfamilies have been selected for polyspecificity by evolution and augmented with accessory proteins that extend and couple transport reactions across the inner and outer membranes of the bacterium. As a result, bacteria are equipped with diverse efflux machines that protect cells from a broad variety of toxic compounds including antibiotics and other small molecule therapeutics. The inhibition of such polyspecific biomolecular machines is a challenging task, which still awaits an efficient solution. Here, we review the molecular mechanisms of efflux pumps from Gram-negative bacteria and recent advances and challenges associated with the discovery of effective inhibitors of these pumps.

Zgurskaya, Helen↗

Highly Permeable Oligo(ethylene oxide)- co -poly(dimethylsiloxane) Membranes for Carbon Dioxide Separation

Here, a series of cross–linked, freestanding oligo(ethylene oxide)– co –(polydimethylsiloxane–norbornene) membranes with varied composition is synthesized via in situ ring–opening metathesis polymerization. These membranes show remarkably high CO 2 permeabilities (3400 Barrer) and their separation performance approaches the Robeson upper bound. The excellent permeability of these copolymer membranes provides great potential for real–world applications where enormous volumes of gases must be separated. The gas transport properties of these films are found to be directly proportional to oligo(ethylene oxide) content incorporation, which stems from the increased solubility selectivity change within the copolymer matrix. This work provides a systematic study of how gas separation performance in rubbery membranes can be enhanced by tuning the CO 2 –philicity of their constituent monomeric subunits.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer-iron oxide hybrid films for controlling electrokinetic properties

Electrokinetic phenomena at polymer-water interfaces are central to technologies for water purification, ion separations, and energy conversion, yet the ability to systematically control polymer surface charge and associated electrokinetic processes remains limited. Here, we demonstrate a simple liquid-phase infiltration (LPI) method to synthesize polymer–metal oxide hybrid films with controllable interfacial properties. Hydroxy-terminated poly(2-vinylpyridine) (P2VP-OH) brushes grafted to silicon substrates were infiltrated with iron nitrate from ethanolic solution, followed by low-temperature thermal treatment to convert the infiltrated precursor into iron oxide. Spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and thermogravimetric analysis confirmed oxide incorporation and hybrid film formation without polymer degradation. Electrokinetic measurements reveal that the hybrid films acquire the electrokinetic properties of the infiltrated oxide, with concentration-dependent streaming potentials and surface conductivities closely matching those of pure iron oxide films. These results establish metal oxide infiltration as a scalable and low-cost strategy for controlling interfacial charge in polymer surfaces. The approach introduces new materials and design parameters for tailoring ion selectivity, transport, and energy conversion, with broad implications for the development of advanced membranes, electrokinetic harvesting devices, and polymer-supported oxide electrodes.

36 MATERIALS SCIENCE↗

Vectorial Charge Transfer across Bipolar Membrane Loaded with CdS and Au Nanoparticles

Bipolar membranes (BPMs) which consist of a cation exchange layer (CEL) and anion exchange layer (AEL) are quite effective as membranes in gas phase electrolyzers. However, such membranes can also serve as a host to embed photocatalysts and electrocatalysts. By selectively exchanging cations with Cd 2+ and anions with AuCl 4 – , we were able to synthesize CdS and Au nanoparticles in CEL and AEL layers, respectively, through sequential chemical and photocatalytic reactions. Reacting Cd 2+ with thioacetamide formed the CdS nanoparticles in CEL. The photogenerated electrons from CdS were then used to reduce AuCl4– in an H-cell configuration to produce Au nanoparticles in AEL and thus prepare a photocatalytically active BPM film (referred to as a CdS/BPM/Au film). Such a concerted design of BPM allows “vectorial” electron transfer between two layers of BPM leading to its transfer to an acceptor molecule (methyl viologen) in solution. Designing photocatalytically active BPM and understanding the vectorial electron flow between two separate ion-selective layers offer new opportunities in water splitting and CO 2 reduction.

13 HYDRO ENERGY↗

Tuning the Perfluorosulfonic Acid Membrane Morphology for Vanadium Redox-Flow Batteries

The microstructure of the perfluorinated sulfonic acid proton exchange membranes such as Nafion significantly affects their transport properties and performance in a vanadium redox flow battery (VRB). In this work, Nafion membranes with various equivalent weights (EW) ranging from 1000 to 1500 are prepared and the structure-property-performance relationship is investigated. Nuclear magnetic resonance (NMR) and small-angle X-ray scattering (SAXS) studies revealed their composition and morphology variances, which lead to major differences in key transport properties related to proton conduction and vanadium ion permeation. Their performances are further characterized as VRB membranes. Based on those understanding, a new perfluorosulfonic acid membrane is designed with optimal pore geometry and thickness, leading to higher ion selectivity and lower cost compared with the widely used Nafion® 115. Excellent VRB single-cell performance (89.3% energy efficiency at 50mA∙cm-2) was achieved along with a stable cyclical capacity over prolonged cycling.

25 ENERGY STORAGE↗