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At least 631 records · Page 35

Cylindrical C 96 Fullertubes: A Highly Active Metal-Free O 2 -Reduction Electrocatalyst

A new isolation protocol was recently reported for highly purified metallic Fullertubes D 5h -C 90 , D 3d -C 96 , and D 5d -C 100 , which exhibit unique electronic features. Here, we report the oxygen reduction electrocatalytic behavior of C 60 , C 70 (spheroidal fullerenes), and C 90 , C 96 , and C 100 (tubular fullerenes) using a combination of experimental and theoretical approaches. C 96 (a metal-free catalyst) displayed remarkable oxygen reduction reaction (ORR) activity, with an onset potential of 0.85 V and a halfway potential of 0.75 V, which are close to the state-of-the-art Pt/C benchmark catalyst values. Here we achieved an excellent power density of 0.75 W cm −2 using C 96 as a modified cathode in a proton-exchange membrane fuel cell, comparable to other recently reported efficient metal-free catalysts. Combined band structure (experimentally calculated) and free-energy (DFT) investigations show that both favorable energy-level alignment active catalytic sites on the carbon cage are responsible for the superior activity of C 96 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid-state polymer magnesium supercapacitor

Here, the present article focuses on the development of a highly ion-conductive, solvent-free, solid-state polymer electrolyte membrane (PEM) via photopolymerization of polyethylene glycol diacrylate (PEGDA) network from its homogeneous melt mixtures containing succinonitrile (SCN) plasticizer and magnesium bis(trifluoromethane sulfonyl) imide Mg(TFSI) 2 salt. The above solid-state Mg-PEM exhibits a Helmholtz electric double-layer capacitor (EDLC) behavior in its supercapacitive symmetric carbonaceous electrode configuration. The electrochemical stability for this PEM membrane (20/40/40 PEGDA/SCN/Mg (TFSI) 2 ) was found to be approximately 3 V from linear sweep voltammetry with a specific capacitance of about 44 F/g from cyclic voltammetry and an energy density of approximately 17 Wh/kg in the 0–2 V range from the constant current density (CCD) experiment. Of particular interest is its excellent capacity retention of over 11,200 cycles, thus tested with the Coulombic efficiency of over 87%. Moreover, the energy density after extensive cycling for 11,200 has increased to approximately 56 Wh/kg at 10 mV/s in the potential range of 0–3 V relative to 17 Wh/kg in the potential range of 0–2 V at the same scan rate, attesting the excellent electrochemical stability and long life of the present Mg-PEM supercapacitor.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Genome-wide fitness profiling reveals molecular mechanisms that bacteria use to interact with Trichoderma atroviride exometabolites

Trichoderma spp. are ubiquitous rhizosphere fungi capable of producing several classes of secondary metabolites that can modify the dynamics of the plant-associated microbiome. However, the bacterial-fungal mechanisms that mediate these interactions have not been fully characterized. Here, a random barcode transposon-site sequencing (RB-TnSeq) approach was employed to identify bacterial genes important for fitness in the presence of Trichoderma atroviride exudates. We selected three rhizosphere bacteria with RB-TnSeq mutant libraries that can promote plant growth: the nitrogen fixers Klebsiella michiganensis M5aI and Herbaspirillum seropedicae SmR1, and Pseudomonas simiae WCS417. As a non-rhizosphere species, Pseudomonas putida KT2440 was also included. From the RB-TnSeq data, nitrogen-fixing bacteria competed mainly for iron and required the siderophore transport system TonB/ExbB for optimal fitness in the presence of T . atroviride exudates. In contrast, P . simiae and P . putida were highly dependent on mechanisms associated with membrane lipid modification that are required for resistance to cationic antimicrobial peptides (CAMPs). A mutant in the Hog1-MAP kinase (Δ tmk 3) gene of T . atroviride showed altered expression patterns of many nonribosomal peptide synthetase (NRPS) biosynthetic gene clusters with potential antibiotic activity. In contrast to exudates from wild-type T . atroviride , bacterial mutants containing lesions in genes associated with resistance to antibiotics did not show fitness defects when RB-TnSeq libraries were exposed to exudates from the Δ tmk3 mutant. Unexpectedly, exudates from wild-type T . atroviride and the Δ tmk 3 mutant rescued purine auxotrophic mutants of H . seropedicae , K . michiganensis and P . simiae . Metabolomic analysis on exudates from wild-type T . atroviride and the Δ tmk 3 mutant showed that both strains excrete purines and complex metabolites; functional Tmk3 is required to produce some of these metabolites. This study highlights the complex interplay between Trichoderma -metabolites and soil bacteria, revealing both beneficial and antagonistic effects, and underscoring the intricate and multifaceted nature of this relationship.

59 BASIC BIOLOGICAL SCIENCES↗

Pure-Water-Fed Forward-Bias Bipolar Membrane CO 2 Electrolyzer

Coupling renewable electricity to reduce carbon dioxide (CO 2 ) electrochemically into carbon feedstocks offers a promising pathway to produce chemical fuels sustainably. While there has been success in developing materials and theory for CO 2 reduction, the widespread deployment of CO 2 electrolyzers has been hindered by challenges in the reactor design and operational stability due to CO 2 crossover and (bi)carbonate salt precipitation. Herein, we design asymmetrical bipolar membranes assembled into a zero-gap CO 2 electrolyzer fed with pure water, solving both challenges. By investigating and optimizing the anion-exchangelayer thickness, cathode differential pressure, and cell temperature, the forward-bias bipolar membrane CO 2 electrolyzer achieves a CO faradic efficiency over 80% with a partial current density over 200 mA cm –2 at less than 3.0 V with negligible CO 2 crossover. In addition, this electrolyzer achieves 0.61 and 2.1 mV h –1 decay rates at 150 and 300 mA cm –2 for 200 and 100 h, respectively. Postmortem analysis indicates that the deterioration of catalyst/polymer– electrolyte interfaces resulted from catalyst structural change, and ionomer degradation at reductive potential shows the decay mechanism. Furthermore, all these results point to the future research direction and show a promising pathway to deploy CO 2 electrolyzers at scale for industrial applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing the electrical double layer by operando X‐ray photoelectron spectroscopy through a graphene‐carbon nanotube composite window

Abstract The electrical double layer is known to spontaneously form at the electrode‐electrolyte interface, impacting many important chemical and physical processes as well as applications including electrocatalysis, electroorganic synthesis, nanomaterial preparation, energy storage, and even emulsion stabilization. However, it has been challenging to study this fundamental phenomenon at the molecular level because the electrical double layer is deeply “buried” by the bulk electrolyte solution. Here, we report a quantitative probing of the electrical double layer of ionic liquids from the solid side of a photoelectron‐transparent graphene‐carbon nanotube hybrid membrane electrode using X‐ray photoelectron spectroscopy. The membrane window is ultrathin (1‐1.5 nm), large (~1 cm 2 ), and robust, enabling a tight seal of the electrolyte and quantitative measurement with excellent photoelectron signals. By operando monitoring the population changes of cations and anions in response to the applied electrical potentials, we experimentally resolve the chemical structure and dynamics of the electrical double layer, which corroborate results from molecular dynamics simulations. image

Wang, Peng↗

New directions and principles for solvent extraction for recovery of lithium from aqueous brines and mineral leachates: A brief review

Increasing demand for lithium for manufacturing of batteries is fueling the unprecedented search for improved recovery and alternative sources. Wider source distribution, lower energy consumption, and greater sustainability make extraction of lithium from brines, both natural and process-derived, an attractive alternative to mineral ores. Solvent extraction, used industrially for production of metals, salts, and pharmaceuticals, has been investigated as a methodology for lithium recovery for several decades. However, industrial application of solvent extraction for lithium recovery has so far been limited. In contrast, direct lithium extraction using adsorbents based on inorganic minerals has rapidly advanced from research to commercialization. A comparison of solvent extraction processes to adsorption highlights these issues and explains the preference for adsorbents. Although the application of solvent extraction has been criticized for use of large amounts of acid, alkali, and organic solvents, steady progress has been made to improve its potential for industrial lithium production, spurred on generally by the advantages of solvent extraction in selectivity and throughput. Previously developed beta-diketone, organophosphate, and crown ether ligands are being adapted and improved. Their novel use with ionic liquids, deep eutectic solvents, and membrane technologies promises to expand capabilities for extraction of lithium from dilute aqueous sources while improving sustainability. Possibilities for further discovery and innovation abound. In this review, we provide a unique perspective from the field of solvent extraction starting with fundamentals such as ion-transfer theory and apply them to understanding lithium selectivity and extraction behavior. In conclusion, the results are cast in the light of the practical realities of developing economical solvent extraction processes.

Brine↗

Solvent Processing and Ionic Liquid-Enabled Long-Range Vertical Ordering in Block Copolymer Films with Enhanced Film Stability

Rapid and reliable processing methods for forming ordered block copolymer (BCP) materials with low defect density in a thin film geometry are required for many nanotechnology applications. Vertically aligned BCP structures, in particular, have applications ranging from nanolithography for electronics and photonics to nanoporous membranes for water remediation and novel batteries for flexible electronics. However, the attainment of nearly complete vertical orientational order of the BCP ordered phase remains challenging. Solvent-based techniques, such as direct immersion annealing (DIA) and solvent vapor annealing (SVA), have immense potential for these applications of BCP films, as it allows for tuning of their thermodynamic, structural, and chain mobility driven kinetic properties. We first demonstrate that DIA, using a judicious choice of binary solvent mixtures along with a relatively hydrophobic ionic liquid (IL), induces the rapid vertical ordering in polystyrene-b-polymethylmethacrylate (PS-PMMA) block copolymer in lamellar films. The IL establishes synergy to the binary solvent mixture of toluene and heptane to 1 create a near-neutral solvent environment for attaining the vertical microstructure of the BCP. Next, we show that IL can suppress the de-wetting of the PS-PMMA films to achieve long-range order using SVA in cylindrical films for long annealing times. Both vertical and horizontal morphology is attained in these films by selecting different solvent environments. Furthermore, attaining enhanced vertical and horizontal BCP structure with long-range defect-free order by tuning solvent quality and using additives like IL can render them useful for many nanotech applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydration-Controlled Proton Transport in Respiratory Complex I

Proton pumping by respiratory complex I is one essential element for generating the proton motive force that drives ATP synthesis in mitochondria. Although it is understood that electrons from NADH reduce ubiquinone at the peripheral arm and that four protons are transferred in the membrane domain, the mechanism by which this redox reaction initiates proton translocation remains unclear. A lateral pathway linking the quinone binding site to the membrane domain via ND1, ND3, and ND4L subunits has been proposed as a possible initial path of an excess proton. However, experimental structures indicate that the hydration connectivity between D66 ND3 and E34 ND4L is comparatively weaker than in neighboring segments, suggesting a potential regulatory point for proton transfer. Using multiscale reactive molecular dynamics (MS-RMD) and a water wire connectivity metric, we directly simulate proton transport through this region as coupled to the hydration by water molecules. Our results reveal that proton transfer is thermodynamically feasible when transient hydration aligns with the presence of an excess proton, revealing the strong coupling between hydration and proton transfer (PT) in this region of Complex I. These findings support a model where proton injection enhances local hydration, dynamically opening the pathway for proton transfer and regulating the onset of proton pumping in Complex I.

Chemical structure↗

CP26 is not involved in qE- or qZ-type non-photochemical quenching in Arabidopsis

CP26 is a monomeric minor light-harvesting complex of Photosystem II (LHCII) protein located at the interface between LHCII trimers and the PSII core in thylakoid membranes. Previous studies have proposed that CP26 plays a role in non-photochemical quenching (NPQ) in addition to light harvesting. Here, we utilized biophysical and pharmacological approaches to investigate this role using single- and higher-order Arabidopsis (Arabidopsis thaliana) cp26 mutants, examining its relationship to known NPQ regulators (Photosystem II subunit S, PsbS, violaxanthin de-epoxidase, and the pH gradient across the thylakoid membrane). cp26 mutants showed significantly reduced maximum PSII quantum efficiencies (F v /F m ) in darkness, indicating a constitutively quenched state, further confirmed by fluorescence lifetime measurements. Destabilized PSII-LHCII supercomplexes observed in native gel electrophoresis and tighter PSII supercomplex packing were potential causes, with no other antenna proteins capable of rescuing this phenotype. In addition, the cp26 mutants exhibited altered NPQ capacity—modest in single mutants but substantial in double mutants—independent of PsbS and violaxanthin de-epoxidase. Together, these results show that CP26 is not involved in qE or qZ but may primarily play an indirect role in apparent NPQ responses via PSII-LHCII supercomplex organization.

Walter, Julia [University of Cambridge (United Kin↗

Defect Repair of Polyelectrolyte Bilayers Using SDS: The Action of Micelles Versus Monomers

Defects within single, double, and triple polyelectrolyte bilayers derived from poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethyammonium chloride) (PDDA) have been repaired using aqueous solutions of sodium dodecyl sulfate (SDS), as evidenced by a reduction in their permeability and an increase in their permeation selectivity. In contrast to the use of monomer solutions of SDS, which were moderately effective in repairing only double and triple bilayers, micellar solutions proved highly effective for all three assemblies. Here, evidence for intact micelles or micellar fragments being deposited on the surface of single bilayers of PSS/PDDA has been obtained from a combination of atomic force microscopy, X-ray photoelectron spectroscopy, ellipsometry, and contact angle measurements. Observed CO 2 permeances of ca. 200 GPU and CO 2 /N 2 selectivities of ca. 30 for SDS-repaired, single bilayers of PSS/PDDA suggest that further development of such assemblies could have the practical potential for the separation of CO 2 from N 2 in the flue gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Temporal performance indicators for an integrated pilot-scale membrane distillation-concentrated solar power/photovoltaic system

Management of concentrate streams in inland applications has uncertain long-term environmental impacts. This study investigates an intensified solar-energy capture desalination system that integrates membrane distillation (MD) with a hybrid concentrated solar power (CSP)/photovoltaic (PV) collector to realize self-sustained zero-waste discharge for effective management of concentrate streams in inland and off-grid applications. The demonstration-scale CSP/PV system can produce up to 178 kWh of thermal energy and 4 kWh of electrical energy per day. The thermal and electrical energy from the CSP/PV system is directly supplied to the air gap MD (AGMD) pilot-scale system producing up to 288 L of distilled water per day. Experiments were performed on the hybrid AGMD-CSP/PV system to evaluate system performance under various operating conditions including AGMD and CSP flow rates, CSP system pre-heating, and AGMD vacuum pressure. Experimental results indicate that doubling the AGMD flow rate results in a 119% increase in thermal energy utilization and a 71% increase in distillate production. Compared to the winter months, operating the system in summer months when direct normal irradiance (DNI) is highest results in nearly double the distillate production (88 L in winter and 168 L in summer) and nearly three times the amount of thermal energy consumption (15 kWh in winter and 43 kWh in summer). Operating with vacuum resulted in a 34% increase in distillate production and allowing the thermal storage reservoir to preheat in the winter resulted in a 61% increase in distillate production. Altogether, experimental results highlight the tradeoff between distillate production and thermal and electrical energy production and consumption under various environmental conditions and the potential for AGMD-CSP/PV to be a stand-alone desalination system.

14 SOLAR ENERGY↗

Internally cooled membrane-based absorber for dehumidification and water heating: Validated model and simulation study

This report presents a comprehensive model for advanced membrane-based absorber components accounting for three separate fluid streams, one of them providing internal cooling, with complex flow patterns. The model was implemented with various liquid desiccants and their properties (including LiCl, CaCl 2 , and [emim][OMS] ionic liquid [IL]). The model has been validated using data from two laboratory prototype absorbers, one with CaCl 2 as the working fluid and one with an IL as the working fluid. Entropy analysis was further carried out to verify the model and understand effect of internal cooling on the entropy variation of three fluid streams. The developed model and codes are expected to enable detailed configuration optimization and provide in-depth understanding of three-fluid heat and mass exchanger (HMX) performance. The paper also describes parametric studies of the HMX components in utilizing the latent heat removed in space cooling to heat water and numerically explores the unique benefit of its application in a semi-open absorption heat pump water heater. The results show that a single three-fluid HMX has the potential to achieve simultaneous dehumidification and water heating efficiently at cost effectiveness, particularly in hot and humid climates.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Mechano-chemical understanding of NaSICON for aqueous redox-flow batteries

Redox-flow batteries utilizing a sodium superionic conductor (NaSICON) can be cost-effective systems for grid energy storage by combining high sodium selectivity with reliance on abundant, low-cost elements. However, improving membrane toughness while maintaining a sufficiently thin membrane for ion conduction is needed. Addressing this issue requires deeper insight into the mechanical properties of NaSICON, its interactions with aqueous chemistries, and the chemo-mechanical degradation mechanisms that arise at the intersection of these phenomena. Here, we provide a framework for understanding these problems, strategies to address them, and highlight the potential of unconventional sintering and thin-film fabrication to optimize the performance of NaSICON in practical flow cells.

Grid energy storage↗

Probing Heterogeneous Degradation of Catalyst in PEM Fuel Cells under Realistic Automotive Conditions with Multi-Modal Techniques

The heterogeneity of polymer electrolyte fuel cell catalyst degradation is studied under varied relative humidity and types of feed gas. Accelerated stress tests (ASTs) are performed on four membrane electrode assemblies (MEAs) under wet and dry conditions in an air or nitrogen environment for 30 000 square voltage cycles. The largest electrochemically active area loss is observed for MEA under wet conditions in a nitrogen gas environment AST due to constant upper potential limit of 0.95 V and significant water content. The mean Pt particle size is larger for the ASTs under wet conditions compared to dry conditions, and the Pt particle size under land is generally larger than under the channel. Observations from ASTs in both conditions and gas environments indicate that water content promotes Pt particle size growth. ASTs under wet conditions and an air environment show the largest difference in Pt particle size growth for inlet versus outlet and channel versus land, which can be attributed to larger water content at outlet and under land compared to inlet and under channel. From X-ray fluorescence experiments Pt particle size increase is a local phenomenon as Pt loading remains relatively uniform across the MEA.

25 ENERGY STORAGE↗

Differentiated mouse kidney tubuloids as a novel in vitro model to study collecting duct physiology

Kidney tubuloids are cell models that are derived from human or mouse renal epithelial cells and show high similarities with their in vivo counterparts. Tubuloids grow polarized in 3D, allow for long-term expansion, and represent multiple segments of the nephron, as shown by their gene expression pattern. In addition, human tubuloids form tight, functional barriers and have been succesfully used for drug testing. Our knowledge of mouse tubuloids, on the other hand, is only minimal. In this study, we further characterized mouse tubuloids and differentiated them towards the collecting duct, which led to a significant upregulation of collecting duct-specific mRNAs of genes and protein expression, including the water channel AQP2 and the sodium channel ENaC. Differentiation resulted in polarized expression of collecting duct water channels AQP2 and AQP3. Also, a physiological response to desmopressin and forskolin stimulation by translocation of AQP2 to the apical membrane was demonstrated. Furthermore, amiloride-sensitive ENaC-mediated sodium uptake was shown in differentiated tubuloids using radioactive tracer sodium. This study demonstrates that mouse tubuloids can be differentiated towards the collecting duct and exhibit collecting duct-specific function. This illustrates the potential use of mouse kidney tubuloids as novel in vitro models to study (patho)physiology of kidney diseases.

59 BASIC BIOLOGICAL SCIENCES↗

Nanoscopic Plugs Block Hydrogen Crossover in Submicron Thick Proton-Conducting SiO 2 Membranes for Water Electrolysis

Zero-gap electrolyzers based on submicron thick proton-conducting oxide membranes (POMs) represent a promising approach to increasing the efficiency of H 2 production from water electrolysis while moving away from conventional perfluorosulfonic acid (PFSA) membranes. A critical barrier to the commercialization of such electrolyzers is that the ultrathin nature of POMs, which is necessary to achieve low cell resistance, makes them more susceptible to defects that can lead to unacceptably high rates of H 2 crossover. Herein, we demonstrate an approach to mitigate this problem through selective deposition of carbon-containing silicon oxide (SiO x C y ) “nanoplugs” into the defects of submicron thick SiO 2 membranes using a facile electrochemically mediated deposition process. Selective deposition of nanoplugs within the defects was verified by multiple characterization techniques, while scanning electrochemical microscopy (SECM) was used to confirm selective plugging of H 2 -crossover hotspots associated with defects at identical locations. Thanks to the use of nanoplugs, the H 2 permeance of 250 nm thick SiO 2 membranes was reduced by 5 to 6 orders of magnitude compared to the unmodified atomic layer deposition (ALD) SiO 2 membranes while having negligible impact on the ionic resistance of the membrane. These plug-modified membranes also enabled safe and stable operation of a zero-gap full cell electrolysis cell, in contrast to cells lacking nanoplugs that produced anode effluent streams having H 2 concentrations near or exceeding the lower flammability limit (LFL) of H 2 . Furthermore, beyond water electrolysis, this defect-sealing strategy has the potential to be broadly implemented in other applications, such as fuel cells and flow batteries, offering a versatile solution to mitigate crossover-related performance losses.

ALD SiO2↗

Breaking the Linear Scaling Relations for the Oxygen Reduction Reaction with a Dual‐Atom Catalyst Composed of a MnFe‐Porphyrrole Aerogel

Bimetallic catalysts offer enhanced catalytic performance through synergistic interactions between the two metals, allowing them to break the linear scaling relations and reach high electrocatalytic activity. This study presents bimetallic aerogel-based catalyst synthesized as a covalent, three-dimensional framework containing neighboring iron and manganese sites. The aerogel structure provides a high surface area and porosity, facilitating an ultra-high active site density and efficient mass transport. The MnFe porphyrrole's unique structure is obtained by alternately linking Mn-porphyrin and Fe-corrole complexes. It exhibited outstanding performance with an onset potential of 0.99 V RHE . Comparative studies with a free-base Fe porphyrrole catalyst (E onset 0.97 V RHE ) revealed that while Mn incorporation led to only a slight improvement in half-cell performance, it resulted in significantly enhanced performance in anion exchange membrane fuel cell. The MnFe catalyst achieved an OCV of 0.97 V and a peak power density of 0.27 W cm −2 , outperforming the free-base Fe counterpart. Using density functional theory calculations, we show that the higher ORR activity of MnFe-porphyrrole is due to charge transfer between Mn and Fe atoms, which is absent in the reference free-base Fe-porphyrrole. These findings underscore the advantages of bimetallic catalysts in improving ORR activity and fuel cell efficiency by leveraging synergistic effects.

Aerogel↗

Engineered bacterial microcompartments: apps for programming metabolism

Bacterial Microcompartments (BMCs) are used by diverse bacteria to compartmentalize enzymatic reactions, functioning analogously to the organelles of eukaryotes. The bounding membrane and encapsulated components are composed entirely of protein, which makes them ideal targets for modification by genetic engineering. In contrast to viruses, in which generally only one protein forms the capsid, the shells of BMCs consist of a variety of shell proteins, each a potential unit of selection. Despite their differences in permeability, the shell proteins are surprisingly interchangeable. Recent developments have shown that they are also highly amenable to engineered modifications which poise them for a variety of biotechnological applications. Additionally, given their modular structure, with a module defined as a semi-autonomous functional unit, BMCs can be considered apps for programming metabolism that can be de-bugged by adaptive evolution.

59 BASIC BIOLOGICAL SCIENCES↗