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At least 253 records · Page 14

Oxidation of glucose to glycolic acid using oxygen and pyrolyzed spent Li-ion battery electrode material as catalyst

A search for non-noble catalysts for biomass processing led to the discovery that pyrolyzed electrode coating of spent Li-ion batteries can be used as an excellent catalyst for oxidation of D-glucose to glycolic acid. New no/low-cost catalyst was prepared by pyrolyzing black electrode coatings of 18,650 Li-ion cells from a spent DELL 1525 laptop battery at 600 ºC. Catalyst was characterized using SEM, EDX and X-ray and was shown to contain lithium nickel manganese cobalt oxide (Li a Ni b Mn c Co d O e ) on carbon with Ni: Mn: Co 4.12: 2.10: 1.50. Here, the catalytic activity of this material was evaluated for oxidation of D-glucose in aq. NaOH and water; glycolic, tartaric, malic, succinic and 2-hydroxybutaric acid were identified as key degradation products. The highest glycolic acid yield of 94% was obtained for oxidation of D-glucose under 3.4 Atm. oxygen, 120 °C, 2.0 h in 0.5 M aq. NaOH using 10 g catalyst/mol glucose.

25 ENERGY STORAGE↗

Electronic Structure and Spin Correlations in Novel Magnetic Structures

The research has advanced understanding of the interrelation between the crystal structure and magnetism in several materials which are or can be of interest for the development of improved, specialized or more cost-effective permanent magnets, as well as in selected materials for biomedical and catalytic applications. Fundamental aspects of ferromagnetism were investigated for Mn-Ge, Co-V and Co-Ge nanoclusters and for melt-spun Co-Sn alloys. New solution-chemistry synthesis methods were designed and tested for Fe-Pt, Fe3C and Fe3O4 nanoparticles. Off-stoichiometric Laves phases in the Fe-Si-Zr, Fe-Nb and Fe-Ta systems, as well as Fe5(Si,Ge)B2 compounds were assessed as new rare-earth-free permanent magnet materials; all except the Fe-Si-Zr Laves phases were found to be promising enough to merit a further exploration. A new method for manufacturing rare-earth-free magnets based on the MnBi compound was developed; by purposely avoiding oxidation-sensitive fine single-crystalline powders, the new method yields magnets with a 50% larger energy storage capacity. Studies of rare-earth-lean permanent-magnet materials (lean compared to the currently predominant Nd-Fe-B materials) were focused on the tetragonal compound of the ThMn12 structure type and included both discovery and characterization of new formulations and exploration of new fabrication/processing techniques. Among the most significant achievements were successful preparation of a vanadium-lean SmFe11V compound, the first observation of thermomechanically induced texture in nanocrystalline Sm(Fe,V)12 alloys, and a breakthrough reduction-diffusion synthesis of Sm1-xZrx(Fe0.8Co0.2)11.2Ti0.8 single-crystal particles with a coercivity as high as 12.6 kOe. Several experiments aimed at improvement of the Nd-Fe-B magnet have also been undertaken including a five-fold increase of the coercivity through a grain-boundary diffusion treatment of a Nd10Fe84B6 nanocrystalline alloy.

36 MATERIALS SCIENCE↗

Synthesis and Evaluation of Cu@ZnO Core@Shell Nanowires for Use in the Carbon Dioxide Thermal Reduction Reaction

Copper-based core@shell nanomaterials are of interest for the catalytic hydrogenation of carbon dioxide toward value-added products. In this context, we have developed a facile, microwave-based procedure for the reliable and reproducible synthesis of Cu@ZnO core@shell nanowires. A systematic assessment of the effect of rationally varying various reaction conditions on this protocol was completed in order to better evaluate the growth process of these core–shell motifs. We determined that among different reaction parameters, it was the critical role of reaction time which enabled the quantitatively reliable growth of external shells with tunable thicknesses of up to 20 nm. As a demonstration of the material’s practical viability, catalytic testing was subsequently performed for the reverse water–gas shift reaction (CO 2 + H 2 → CO + H 2 O), with the evolution of the process followed with in situ X-ray diffraction and X-ray absorption spectroscopy in order to probe structural changes and gauge stability. These tests found the catalysts to be effective at converting CO 2 to CO, with notable stability detected in the shell layer and no observed alloying between copper and zinc. Furthermore, our studies support the idea that the Cu–ZnO and CuO x –ZnO interfaces are essential for the effective activation of CO 2 and H 2 .

36 MATERIALS SCIENCE↗

Advances in Colloidal InP-Based Quantum Dots for Photocatalytic Hydrogen Evolution

Photocatalytic materials for hydrogen generation are typically categorized into UV-absorbing metal oxides and visible-range semiconductors such as chalcogenides or perovskites, which often incorporate toxic elements. To address environmental concerns of the latter group, indium phosphide (InP)-based quantum dots (QDs) have recently emerged as a less toxic alternative. These nanocrystals (NCs) benefit from a broadband and tunable absorption spectrum, which is well matched for solar photochemistry, and offer suitable electronic characteristics to drive photoinduced charge separation. This perspective provides a comprehensive summary of the recent advancements in developing InP-based NCs with a focus on photocatalytic hydrogen production. We discuss synthetic strategies that enhance the catalytic activity of these materials and highlight key challenges that must be addressed to enhance their performance. Finally, we explore future research directions aimed at improving photocatalytic efficiency and integrating InP-based QDs into practical solar-to-fuel conversion systems.

Hydrogen↗

Locally Engineering and Interrogating the Photoelectrochemical Behavior of Defects in Transition Metal Dichalcogenides

Transition metal dichalcogenides (TMDs) are attractive materials for a variety of applications in solar energy conversion and electrocatalysis, due to their favorable optical and electrical properties and their unique two-dimensional structures which facilitate the fabrication of wide-area, ultrathin layers. Unfortunately, the basal planes which make up the majority of these materials are relatively inert, and thus a great deal of effort has been directed to engineering favorable, catalytically active defects into these materials. In this paper, we demonstrate how probe-based electrochemical techniques can be employed as multifunctional tools for locally modifying TMD materials and probing the electrochemical behavior of the resulting defects. Scanning Electrochemical Cell Microscopy (SECCM) was employed to locally anodize exfoliated p-type WSe 2 nanosheets, creating hole-like defects within individual basal planes in a highly controllable fashion. Photoelectrochemical SECCM imaging was then employed to characterize the chemical behavior of these engineered defects, revealing significantly enhanced activity toward the Hydrogen Evolution Reaction (HER). Atomic force microscopy studies are presented which suggest these enhancements result from an increased density of monolayer-high step features within the anodized defects. Analysis of the SECCM data in the context of finite element simulations revealed that these enhancements increased with increasing anodization time, with local kinetic rates over 2 orders of magnitude higher than unaltered basal planes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computationally aided, entropy-driven synthesis of highly efficient and durable multi-elemental alloy catalysts

Multi-elemental alloy nanoparticles (MEA-NPs) hold great promise for catalyst discovery in a virtually unlimited compositional space. However, rational and controllable synthesize of these intrinsically complex structures remains a challenge. Here, we report the computationally aided, entropy-driven design and synthesis of highly efficient and durable catalyst MEA-NPs. The computational strategy includes prescreening of millions of compositions, prediction of alloy formation by density functional theory calculations, and examination of structural stability by a hybrid Monte Carlo and molecular dynamics method. Selected compositions can be efficiently and rapidly synthesized at high temperature (e.g., 1500 K, 0.5 s) with excellent thermal stability. We applied these MEA-NPs for catalytic NH 3 decomposition and observed outstanding performance due to the synergistic effect of multi-elemental mixing, their small size, and the alloy phase. We anticipate that the computationally aided rational design and rapid synthesis of MEA-NPs are broadly applicable for various catalytic reactions and will accelerate material discovery.

36 MATERIALS SCIENCE↗

Graphite crystals in catalytically-graphitized glass-like carbon

Catalytic graphitization of glass-like carbon leads to enhanced growth of micro-sized graphitic crystals with unusual shapes of wires, filaments, tubes, rods, whiskers, and spirals. Similar particles with axial symmetry are also found in pure glass-like carbon heat-treated at high temperatures. Nonetheless, the presence of a graphitization catalyst, Si in this case, in the heat-treatment process supports the transformation of porous, disordered carbon structure towards the graphitic atomic order and the formation of manifold peculiar polyhedral wires and particles of geometry distinct from the plate-like shape typical for conventional graphite. In contrast to conventional carbon nanotubes and fibers, the graphene layers are stacked perpendicular to the tube axis, while the size of the most common tube fibers can reach up to 10 μm in diameter and 100 μm in length. X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopy, small-angle X-ray scattering combined with complementary techniques have been used to characterize the structure of the glass-like carbon derived from furfuryl alcohol catalytically-graphitized using Si particles at 3000 °C. Finally, since control of graphite shape is vital to achieving the level of performance required in contemporary applications, the obtained results demonstrate that the catalytic graphitization method may be employed to produce filamentous graphite crystals.

36 MATERIALS SCIENCE↗

Iridium metallene oxide for acidic oxygen evolution catalysis

Exploring new materials is essential in the field of material science. Especially, searching for optimal materials with utmost atomic utilization, ideal activities and desirable stability for catalytic applications requires smart design of materials’ structures. Herein, we report iridium metallene oxide: 1 T phase-iridium dioxide (IrO 2 ) by a synthetic strategy combining mechanochemistry and thermal treatment in a strong alkaline medium. This material demonstrates high activity for oxygen evolution reaction with a low overpotential of 197 millivolt in acidic electrolyte at 10 milliamperes per geometric square centimeter (mA cm geo –2 ). Together, it achieves high turnover frequencies of 4.2 s UPD –1 (3.0 s BET –1 ) at 1.50 V vs. reversible hydrogen electrode. Furthermore, 1T-IrO 2 also shows little degradation after 126 hours chronopotentiometry measurement under the high current density of 250 mA cm geo –2 in proton exchange membrane device. Theoretical calculations reveal that the active site of Ir in 1T-IrO 2 provides an optimal free energy uphill in *OH formation, leading to the enhanced performance. The discovery of this 1T-metallene oxide material will provide new opportunities for catalysis and other applications.

36 MATERIALS SCIENCE↗

Two-dimensional forms of robust CO 2 reduction photocatalysts

Photoelectrocatalysts that use sunlight to power the CO 2 reduction reaction will be crucial for carbon-neutral power and energy-efficient industrial processes. Scalable photoelectrocatalysts must satisfy a stringent set of criteria, such as stability under operating conditions, product selectivity, and efficient light absorption. Two-dimensional materials can offer high specific surface area, tunability, and potential for heterostructuring, providing a fresh landscape of candidate catalysts. From a set of promising bulk CO 2 reduction photoelectrocatalysts, we screen for candidate monolayers of these materials, then study their catalytic feasibility and suitability. For stable monolayer candidates, we verify the presence of visible-light band gaps, check that band edges can support CO 2 reduction, determine exciton binding energies, and compute surface reactivity. We find visible light absorption for SiAs, ZnTe, and ZnSe monolayers, and that due to a lack of binding, CO selectivity is possible. We thus identify SiAs, ZnTe, and ZnSe monolayers as targets for further investigation, expanding the chemical space for CO 2 photoreduction candidates.

36 MATERIALS SCIENCE↗

Innovative SCR Materials and System for Low Temperature - CRADA 350 (Abstract)

The aim of this CRADA is focused on providing a new enabling SCR catalyst system that will function at very high efficiency to attain the most demanding emissions regulations and thereby facilitate the market introduction of advanced powertrains that will support domestic energy independence and security. Future powertrains, that will be significantly more efficient than currently available technologies, will be needed by automotive manufacturers to meet rapidly increasing CAFE and GHG standards. However, these powertrains cannot enter into the US light duty vehicle market unless they are coupled with an aftertreatment system that will sufficiently remediate tailpipe emissions to meet EPA Tier III and California SULEV emissions standards. The low temperature exhaust associated with these powertrains is especially challenging for any current aftertreatment technology to meet these standards. The key focus of this CRADA is to further develop newly invented materials for the selective catalytic reduction (SCR) of NOx by ammonia (NH3) that show promise for significantly reducing ‘light-off’ temperatures compared to current commercial catalysts. Specifically, the goal of the proposed work is to achieve ‘light-off’ of NH3 SCR at 150 ºC in order to realize conversion efficiencies of 90% at these low temperatures. This will enable deployment of lean combustion powertrains with significantly increased fuel efficiencies but lower exhaust temperatures. To accomplish this overall goal, it will be essential to also identify an appropriate NH3 supply strategy for the SCR aftertreatment device that can controllably deliver NH3 at these low temperatures.

36 MATERIALS SCIENCE↗

Presentation of gas-phase-reactant-accessible single-rhodium-atom catalysts for CO oxidation, via MOF confinement of an Anderson polyoxometalate

Geometric or electronic confinement of guests within nanoporous hosts holds promise for imparting catalytic functionality, including single-metal-atom catalytic functionality, to existing materials. When the nanoporous host is a metal–organic framework (MOF), single-metal-ion catalysts have typically been installed by grafting to an open site on an inorganic node, with the node effectively becoming the support for the catalyst. This approach, however, imposes compositional constraints, as the node not only needs to be receptive to grafting, but also must be capable of stabilizing the framework against solvent evacuation, chemical exposure, and heating. Here, we show that disk-like, Anderson polyoxometalate clusters (RhMo 6 O 24 n- and Mo 7 O 24 m- ; POMs) can be confined in pore-specific and orientation-specific fashion within the hierarchically porous, Zr(IV)-based MOF, NU1K. Self-limiting loading of one cluster per pore, and associated nano-confinement, serve to isolate each POM and prevent consolidation caused by sintering. Additionally, the oriented confinement serves to expose individual rhodium atoms to candidate gas-phase reactants, while enabling the rhodium atom to employ a well-defined oxy-molybdenum cluster, rather than a MOF node, as a support. Synchrotron-based difference-electron-density maps and differential pair-distribution-function analyses of scattered X-rays establish cluster siting and orientation and confirm isolation. Nanoconfined (i.e., MOF- and POM-confined) single-rhodium(III)-atoms are catalytically competent for an illustrative gas-phase reaction, CO oxidation by O 2 , with the MOF-isolated POM enormously outperforming nonporous, MOF-free, solid (NH 4 ) 3 [H 6 RhMo 6 O 24 ]·6H 2 O. This paper highlights the value of MOF-based nano-confinement and oriented isolation of planar POMs as a means of uniformly presenting and stabilizing potent single-metal-atom catalysts, in reactant-accessible form, on well-defined supports.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Critical Assessment of Electronic Structure Descriptors for Predicting Perovskite Catalytic Properties

The discovery and design of materials which can efficiently catalyze the oxygen reduction and evolution reactions at reduced temperatures is important for facilitating the widespread adoption of fuel cell and electrolyzer technologies. Numerous studies have produced correlations between catalytic properties, such as oxygen surface exchange or electrode area specific resistance (ASR), and properties of the catalyst material. However, correlations have historically been limited in scope (e.g., using only a few materials or at a single temperature) and it has been difficult to provide detailed assessments of their robustness. Here, in this study, we assess the ability of the O p-band center electronic structure descriptor, obtained from density functional theory (DFT) calculations, to correlate with oxygen surface exchange rates, diffusivities, and area specific resistances for a large database of perovskite oxide catalytic properties. By data mining the literature, we obtain 747 catalytic property value data points spanning 299 unique perovskite compositions from 313 studies. We assess linear correlations of each property with the O p-band center and find generally modest correlations that are qualitatively useful (prediction mean absolute errors of about 0.5 log units are typical), where the correlations are improved at higher temperatures (e.g., 800 °C vs. 500 °C) and significantly improve when considering fits to the subset of materials which have multiple independent measurements. These findings suggest that the spread of property data is significantly influenced by experimental uncertainty, and subsequent measurements of additional materials will likely improve the O p-band center correlations.

30 DIRECT ENERGY CONVERSION↗

Design Study for Bio-Oil Production from Biomass Using a Dual Fluidized-Bed Reactor

To evaluate the re-design and reconfiguration of a dual-fluidized bed (DFB) gasification system into a recirculating pyrolysis reactor, Computation Fluid Dynamic (CFD) simulations of the system were conducted. The Barracuda Virtual Reactor® computational particle fluid dynamic code was used to perform simulations of the pyrolysis process. Modeling of the chemical reaction kinetics for both gas phase and solid particle phase were included. The recirculating pyrolysis reactor shown in Fig. 1a is based on a bubbling-bed biomass pyrolyzer and a riser combustor to convert the remaining char. The operational differences in the re-configuration of the DFB gasification system into a recirculating pyrolysis system for the production of bio-oil are (1) replacement of a low-surface area inert bed material with a high-surface-area bed material that has acidic properties to provide catalytic activity for the production of bio-oil with reduced oxygen content, (2) lower temperature and residence time for bio-oil production from pyrolysis, (3) replacement of the fluidization gas in the bubbling bed pyrolyzer from steam to nitrogen, and (4) the reduction of pyrolyzer freeboard volume. The bed material used for catalytic pyrolysis is Sasol 300 (300-micron dia., bulk density 0.94 kg/l, and surface area 130 m2/g) and is a theta-alumina with mild acidity. This is in comparison with previous standard bed material Carbo HSP (430-micron dia., bulk density 2.01 kg/l, and surface area 0.03 m2/g) used for gasification. For bio-oil production, pyrolysis in the bubbling bed requires temperatures in the range of 550 C in comparison with gasification temperatures near 850 C. To attain this lower temperature requires management of the energy mass balances, with control of the bed material recirculation rate between bubbling bed pyrolyzer and riser combustor, the introduction of a nitrogen purge in the pyrolyzer, and adjusting the pressure balance between the two vessels. To extract bio-oil from the pyrolysis reactor with a snorkel, two different freeboard configurations were evaluated. In Fig. 1 b the existing high freeboard configuration is shown and in Fig. 1 c the reduced freeboard design is presented. The introduction of a nitrogen purge for the high free board configuration provided the highest bio-oil production from the CFD simulations. To decrease the bed-material circulation rate, primary and secondary air on the combustor side were reduced, and the pressure on the combustor was slightly increased. A portion of the biomass and bio-oil was observed to be transported to the combustor, leading to a smaller pyrolysis yield. The control of the pyrolyzer temperature is performed by controlling the circulation rate. Good fluidization of the bubbling bed and cascade PID control are required to keep the temperature from oscillating due to large time delay experienced when changing primary and secondary air. (a) (b) (c) Figure 1. (a) Dual Fluidized Bed pyrolysis system configuration, (b) mole fraction of nonpolar biooil in high freeboard configuration, and (c) mole fraction of nonpolar bio-oil in low freeboard configuration with nitrogen purge introduced in both configurations.

BASIC BIOLOGICAL SCIENCES,BIOMASS FUELS↗

Perovskite evolution on La modified Mn 1.5 Co 1.5 O 4 spinel through thermal ageing with enhanced oxidation activity: Is sintering always an issue?

Non-precious metal oxides have great potential in catalytic deep oxidation of emitted hydrocarbons to help address various environmental pollution concerns. However, sintering issue is a stumbling block in practical application upon long-term high-temperature operation or thermal shock experience. Herein, La was applied to modify Mn 1.5 Co 1.5 O 4 spinel to get a highly active oxidation catalyst with exceptional stability against high-temperature thermal ageing treatment. With thermal ageing at 750 °C for 100 h, the La modified Mn–Co composite reached 90 % conversion in toluene oxidation at 265 °C under the high WHSV of 120,000 mL g -1 h -1 , while this value increased to 312 °C over blank Mn–Co spinel. The addition of La not only inhibited the growth of spinel nanocrystals, but also brought about perovskite formation through sintering, generating perovskite-spinel interfaces, thus enhancing both activity and stability. Meanwhile, the La modified Mn–Co spinel exhibited superior performance in presence of water or sulfur dioxide after thermal ageing treatment. In conclusion, this work offers a versatile strategy to design anti-sintering and active oxidation nanocatalysts based on non-precious metal oxides for industrial applications.

36 MATERIALS SCIENCE↗

Selective Oxidation and Cr Segregation in High-Entropy Oxide Thin Films

High-entropy oxides (HEOs) offer exceptional compositional flexibility and structural stability, making them promising materials for energy and catalytic applications. Here, in this study, we investigate Sr doping effects on B-site cation oxidation states, local composition, and structure in epitaxial La 1–x Sr x (Cr 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 )O 3 thin films. X-ray spectroscopies reveal that Sr doping preferentially promotes Cr oxidation from Cr 3+ to Cr 6+ , partially oxidizes Co and Ni, while leaving Mn 4+ and Fe 3+ unchanged. Atomic-resolution scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy shows pronounced Cr segregation, with depletion at the interface and enrichment at the surface, along with partial amorphization in heavily Sr-doped samples. This segregation is likely driven by oxidation-induced migration of smaller, high-valence Cr cations during growth. These findings highlight the critical interplay between charge compensation, local strain, and compositional fluctuations in HEOs, indicating that precise control over growth conditions is critical for tuning their surface composition and electronic structure toward more robust electrocatalyst design.

36 MATERIALS SCIENCE↗

Bridging Thermal Catalysis and Electrocatalysis: Catalyzing CO 2 Conversion with Carbon‐Based Materials

Abstract Understanding the differences between reactions driven by elevated temperature or electric potential remains challenging, largely due to materials incompatibilities between thermal catalytic and electrocatalytic environments. We show that Ni, N‐doped carbon (NiPACN), an electrocatalyst for the reduction of CO 2 to CO (CO 2 R), can also selectively catalyze thermal CO 2 to CO via the reverse water gas shift (RWGS) representing a direct analogy between catalytic phenomena across the two reaction environments. Advanced characterization techniques reveal that NiPACN likely facilitates RWGS on dispersed Ni sites in agreement with CO 2 R active site studies. Finally, we construct a generalized reaction driving‐force that includes temperature and potential and suggest that NiPACN could facilitate faster kinetics in CO 2 R relative to RWGS due to lower intrinsic barriers. This report motivates further studies that quantitatively link catalytic phenomena across disparate reaction environments.

Koshy, David M.↗

Bridging Thermal Catalysis and Electrocatalysis: Catalyzing CO 2 Conversion with Carbon-Based Materials

Understanding the differences between reactions driven by elevated temperature or electric potential remains challenging, largely due to materials incompatibilities between thermal catalytic and electrocatalytic environments. In this work, we show that Ni, N-doped carbon (NiPACN), an electrocatalyst for the reduction of CO 2 to CO (CO 2 R), can also selectively catalyze thermal CO 2 to CO via the reverse water gas shift (RWGS) representing a direct analogy between catalytic phenomena across the two reaction environments. Advanced characterization techniques reveal that NiPACN likely facilitates RWGS on dispersed Ni sites in agreement with CO 2 R active site studies. Finally, we construct a generalized reaction driving-force that includes temperature and potential and suggest that NiPACN could facilitate faster kinetics in CO 2 R relative to RWGS due to lower intrinsic barriers. This report motivates further studies that quantitatively link catalytic phenomena across disparate reaction environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CO 2 hydrogenation over rhodium cluster catalyst nucleated within a manganese oxide framework

Rhodium-based manganese oxide frameworks were explored as a prototype for carbon dioxide reactive capture and conversion. Three-dimensional frameworks of MnOx were utilized as support structures to isolate Rh metal centers. V, Na, and Zn were introduced as counterions to stabilize the structure and for their beneficial effect as promoters. Here, with this multicomponent catalyst, Rh active centers with MnOxs and varied counterions, we were able to selectively tune the catalytic performance of the material via the choice of counterion and structure of the host material. With cryptomelane-type tunnel manganese oxides octahedral molecular sieve (OMS2), we found that Rh-V-OMS2 was highly stable even after 48 hours on stream with a reaction rate of around 1.5x10 -4 mol CO 2 /g Rh /s, surpassing the net reactivity of other initially more active combinations. Furthermore, during CO 2 hydrogenation, in situ XAFS showed that single Rh atoms nucleated into nanoparticles/ sub-nanometer clusters with a coordination number of 5.5 or less. Our finding of the correlation between the reaction rate and particle size offers the potential for enhanced control over the reaction rate by tuning particle size. Our activity study with control experiments demonstrates that the activities of the catalysts are proved due to the unique metal support interaction offered by the Rh-X-MnO.

10 SYNTHETIC FUELS↗