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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 145 records · Page 8

Resolving Diverse Oxygen Transport Pathways Across Sr‐Doped Lanthanum Ferrite and Metal‐Perovskite Heterostructures

Abstract Perovskite structured transition metal oxides are important technological materials for catalysis and solid oxide fuel cell applications. Their functionality often depends on oxygen diffusivity and mobility through complex oxide heterostructures, which can be significantly impacted by structural and chemical modifications, such as doping. Further, when utilized within electrochemical cells, interfacial reactions with other components (e.g., Ni‐ and Cr‐based alloy electrodes and interconnects) can influence the perovskite's reactivity and ion transport, leading to complex dependencies that are difficult to control in real‐world environments. Here, this work uses isotopic tracers and atom probe tomography to directly visualize oxygen diffusion and transport pathways across perovskite and metal‐perovskite heterostructures, that is, (Ni‐Cr coated) Sr‐doped lanthanum ferrite (La 0.5 Sr 0.5 FeO 3 ; LSFO). Annealing in 18 O 2(g) results in elemental and isotopic redistributions through oxygen exchange (OE) in the LSFO while Ni‐Cr undergoes oxidation via multiple mechanisms and transport pathways. Complementary density functional theory calculations at experimental conditions provide rationale for OE reaction mechanisms and reveal a complex interplay of different thermodynamic and kinetic drivers. These results shed light on the fundamental coupling of defects and oxygen transport in an important class of catalytic materials.

36 MATERIALS SCIENCE↗

Divergent Stabilities of Tetravalent Cerium, Uranium, and Neptunium Imidophosphorane Complexes**

Abstract The study of the redox chemistry of mid‐actinides (U−Pu) has historically relied on cerium as a model, due to the accessibility of trivalent and tetravalent oxidation states for these ions. Recently, dramatic shifts of lanthanide 4+/3+ non‐aqueous redox couples have been established within a homoleptic imidophosphorane ligand framework. Herein we extend the chemistry of the imidophosphorane ligand (NPC=[N=P t Bu(pyrr) 2 ] − ; pyrr=pyrrolidinyl) to tetrahomoleptic NPC complexes of neptunium and cerium ( 1‐M , 2‐M , M=Np, Ce) and present comparative structural, electrochemical, and theoretical studies of these complexes. Large cathodic shifts in the M 4+/3+ (M=Ce, U, Np) couples underpin the stabilization of higher metal oxidation states owing to the strongly donating nature of the NPC ligands, providing access to the U 5+/4+ , U 6+/5+ , and to an unprecedented, well‐behaved Np 5+/4+ redox couple. The differences in the chemical redox properties of the U vs . Ce and Np complexes are rationalized based on their redox potentials, degree of structural rearrangement upon reduction/oxidation, relative molecular orbital energies, and orbital composition analyses employing density functional theory.

Otte, Kaitlyn S.↗

TiO 2 Nanoparticles Enabling Photocatalytic Desulfurization for C–C Coupling Reaction Using Visible Light

We uncover a surface-mediated mechanism for visible-light-driven photocatalytic desulfurization of thiols on titanium dioxide (TiO 2 ) nanoparticles under LED illumination (>420 nm). Combined diffuse reflectance, infrared, and cryogenic electron paramagnetic resonance spectroscopy verify the formation of a surface thiol–Ti charge-transfer complex that introduces visible-light absorption into an otherwise UV-active reaction system. Selective photoexcitation of this surface complex drives interfacial charge transfer, directly activating the adsorbed thiol and inducing C–S bond scission without the band gap excitation of TiO 2 . The resulting carbon-centered radical intermediates are intercepted by styrene to form C–C coupling products. These results uncover a distinct surface-mediated photocatalytic mechanism in which charge-transfer complex formation governs both light absorption and chemical activation, providing a mechanistic framework for extending visible-light reactivity to wide-bandgap metal oxide photocatalysts.

addition of carbon radical to vinyl groups↗

Divergent Stabilities of Tetravalent Cerium, Uranium, and Neptunium Imidophosphorane Complexes

The study of the redox chemistry of mid-actinides (U–Pu) has historically relied on cerium as a model, due to the accessibility of trivalent and tetravalent oxidation states for these ions. Recently, dramatic shifts of lanthanide 4+/3+ non-aqueous redox couples have been established within a homoleptic imidophosphorane ligand framework. Herein we extend the chemistry of the imidophosphorane ligand (NPC=[N=P t Bu(pyrr) 2 ] – ; pyrr=pyrrolidinyl) to tetrahomoleptic NPC complexes of neptunium and cerium (1-M, 2-M, M=Np, Ce) and present comparative structural, electrochemical, and theoretical studies of these complexes. Large cathodic shifts in the M 4+/3+ (M=Ce, U, Np) couples underpin the stabilization of higher metal oxidation states owing to the strongly donating nature of the NPC ligands, providing access to the U 5+/4+ , U 6+/5+ , and to an unprecedented, well-behaved Np 5+/4+ redox couple. Furthermore, the differences in the chemical redox properties of the U vs. Ce and Np complexes are rationalized based on their redox potentials, degree of structural rearrangement upon reduction/oxidation, relative molecular orbital energies, and orbital composition analyses employing density functional theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cyclic (Alkyl)- and (Aryl)-(amino)carbene Coinage Metal Complexes and Their Applications

Cyclic (alkyl)- and (aryl)-(amino)carbenes (CAACs and CAArCs) are stronger σ-donors and π-acceptors than imidazol-2-ylidenes and imidazolidin-2-ylidenes, the well-known N-heterocyclic carbenes (NHCs). Consequently, they form strong bonds with coinage metals and stabilize both low and high oxidation states. This Review shows that CAACs and CAArCs have allowed for the isolation of copper and gold complexes that were believed to be only transient intermediates. Here, this has not only allowed for a better understanding of the mechanism of known processes but has also led to the development of novel coinage metal-catalyzed reactions. In addition to their role in homogeneous catalysis, CAAC and CAArC coinage metal complexes have recently found applications in medicinal chemistry, as well as in materials science. When possible, the performance of CAAC and CAArC ligands are compared with those of classical NHCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Redox-Active Crown Ether Copolymer for Selective Lithium Recovery from Spent Lithium-Ion Batteries

The increasing demand for lithium, alongside concerns over resource scarcity and supply chain risks, has driven the need for alternative lithium sources, particularly from spent lithium-ion batteries (LIBs). Here, in this work, we introduce a redox-active crown ether copolymer designed for highly selective and electrochemically reversible lithium recovery from organic LIB leachates. A lithium-selective moiety, (12-crown-4)methyl methacrylate (12C4MA), is combined with a redox-active moiety, ferrocenylpropyl methacrylamide (FPMAm), into a redox copolymer electrosorbent to replace acid-based regeneration with electrostatic repulsion. The redox response enhances lithium ingress into the polymer, doubling lithium uptake (0.58 mol Li /mol CrE ) and enabling electrochemical regeneration upon the FPMAm oxidation. Our system exhibits exclusive lithium uptake, even in complex leachates containing competing metals (e.g., iron, nickel, and cobalt) and organic degradants. Techno-economic analysis highlights high energy efficiency and competitive lithium pricing to the market value (∼$12.7 per kg Li ). Overall, our work demonstrates a scalable, electrified adsorbent platform for sustainable and chemical-free critical metal recovery.

adsorption↗

Compositionally Complex Spinel Oxides as Conversion Anodes for Lithium-Ion Batteries

Four different compositionally complex multicomponent M 3 O 4 spinels containing 5–8 distinct metals were prepared by a rapid combustion synthesis method or solvothermal synthesis. High resolution synchrotron X-ray diffraction patterns show that the materials consist primarily of spinel phases with small amounts of rock salt impurities, and, in several samples, a minor amount of contracted spinel phase. Materials were investigated as conversion anodes in lithium half-cells and delivered significantly higher capacities than two-component MgFe 2 O 4 made by combustion synthesis. X-ray absorption near-edge structure (XANES) was used to estimate the oxidation states of the metals in the pristine, lithiated (discharged) and delithiated (charged) materials to better understand the redox processes in half cells that led to the improvement. Co, Ni, and Zn are reduced to low oxidation states during lithiation (cell discharge) but are only partially oxidized. The presence of a conductive metallic network that forms after lithiation is thought to account for the improved electrochemical characteristics. Interestingly, in most of the samples, iron is not fully reduced during initial lithiation unlike what happens with a set of related high entropy spinel ferrites studied previously. Finally, the improved electrochemical properties of these materials illustrates both the advantages of complexity and the difficulties in predicting their behavior.

25 ENERGY STORAGE↗

Reductive Dynamic and Static Excited State Quenching of a Homoleptic Ruthenium Complex Bearing Aldehyde Groups

A new homoleptic Ru polypyridyl complex bearing two aldehyde groups on each bipyridine ligand, [Ru(dab) 3 ](PF 6 ) 2 , where dab is 4,4′-dicarbaldehyde-2,2′-bipyridine, was synthesized, characterized, and utilized for iodide photo-oxidation studies. In acetonitrile (CH 3 CN) solution, the complex displayed an intense metal-to-ligand charge transfer (MLCT) absorbance maximum at 475 nm (ε = 22,000 M –1 cm –1 ) and an infrared (IR) band at 1712 cm –1 assigned to the pendent aldehyde groups. Visible light excitation in air-saturated solution resulted in room temperature photoluminescence (PL) with a maximum at 675 nm, a quantum yield, ϕ PL = 0.048, and an excited state lifetime, τ ο = 440 ns, from which radiative and nonradiative relaxation rate constants were extracted, k r = 9.1 × 10 4 s –1 and knr = 1.8 × 10 6 s –1 . Pulsed visible light excitation yielded transient UV–vis and IR absorption spectra consistent with an MLCT excited state; relaxation occurred with the maintenance of two isosbestic points in the visible region, and a lifetime that agreed with that measured by time-resolved PL. Cyclic voltammetry studies in a CH 3 CN solution with 0.1 M TBAPF 6 electrolyte revealed a quasi-reversible oxidation, E°(Ru III/II ) = +1.25 V vs. Fc +/0 , and three sequential one-electron reductions at −1.10, −1.25, and −1.54 V vs. Fc +/0 . Here, an excited state reduction potential of E°(Ru *2+/+ ) = +0.89 V vs. Fc +/0 was estimated with the Rehm–Weller expression. Titration of tetrabutylammonium iodide, TBAI, into a CD 3 CN solution of [Ru(dab) 3 ](PF 6 ) 2 resulted in significant shifts in the aldehyde H atom and 3,3′-biypridyl resonances that were analyzed with a 1:1 equilibrium model, from which K eq = 460 M –1 was extracted, increasing to 5800 M –1 when the solvent was changed to acetone-d 6 . Iodide titrations resulted in a significant quenching of the [Ru(dab) 3 ] *2+ lifetime and quantum yield in both CH 3 CN and acetone solvents. In CH 3 CN, the quenching was mainly dynamic and well described by the Stern–Volmer model, from which a quenching rate constant, k q , of 4.5 × 10 10 M –1 s –1 and an equilibrium constant, K eq , of 8.3 × 10 3 M –1 were obtained. In acetone, the static quenching pathway by iodide was greatly enhanced, with a K eq of 1.2 × 10 4 M –1 and a higher k q of 9.2 × 10 10 M –1 s –1 .

Aldehydes↗

Multiplet lines in seeded stimulated Mn 𝐾⁢𝛼 1 x-ray emission

We report the successful resolution of the multiplet structure of 𝐾⁢𝛼 1 x-ray emission in manganese (Mn) complexes through seeded stimulated x-ray emission spectroscopy (seeded S-XES). Using a femtosecond pump pulse above the Mn 𝐾 edge to generate simultaneous 1⁢𝑠 core holes, and a second-color tunable seed pulse to initiate the stimulated emission process, we were able to enhance individual lines within the 𝐾⁢𝛼 1 emission. This approach allows to resolve the fine multiplet features that are obscured by lifetime broadening in conventional (spontaneous) Mn 𝐾⁢𝛼 XES. The work builds on our previous observation that S-XES from Mn(II) and Mn(VII) complexes pumped at high intensities can exhibit stimulated emission without sacrificing the chemical sensitivity to oxidation states. Furthermore, this technique opens the door to controlled high-resolution electronic structure spectroscopy in transition-metal complexes beyond the core-hole lifetime, with potential applications in catalysis, inorganic chemistry, and materials science.

Chemical Physics & Physical Chemistry↗

Strongly correlated and topological states in [111] grown transition metal oxide thin films and heterostructures

We highlight recent advances in the theory, materials fabrication, and experimental characterization of strongly correlated and topological states in [111] oriented transition metal oxide thin films and heterostructures, which are notoriously difficult to realize compared to their [001] oriented counterparts. We focus on two classes of complex oxides, with the chemical formulas ABO 3 and A 2 B 2 O 7 , where the B sites are occupied by an open-shell transition metal ion with a local moment and the A sites are typically a rare earth element. The [111] oriented quasi-two-dimensional lattices derived from these parent compound lattices can exhibit peculiar geometries and symmetries, namely, a buckled honeycomb lattice, as well as kagome and triangular lattices. These lattice motifs form the basis for emergent strongly correlated and topological states expressed in exotic magnetism, various forms of orbital ordering, topological insulators, topological semimetals, quantum anomalous Hall insulators, and quantum spin liquids. For transition metal ions with high atomic number, spin–orbit coupling plays a significant role and may give rise to additional topological features in the electronic band structure and in the spectrum of magnetic excitations. We conclude this perspective by articulating open challenges and opportunities in this actively developing field.

36 MATERIALS SCIENCE↗

Effects of oxygen on the adsorption/oxidation of aqueous Sb(III) by Fe-loaded biochar: An X-ray absorption spectroscopy study

Fe-loaded biochar (FeBC) has been considered for Sb(III) adsorption, but the effects of oxygen (O 2 ) on the adsorption need further investigation. Liquid-/solid-phase analyses were conducted to investigate the role of O 2 in the Sb(III) adsorption by FeBC. The adsorption was best described by the pseudo-second-order (PSO) model for kinetic results and by the Langmuir model for thermodynamic results. More than 96.8 % of Sb(III) was adsorbed by FeBC, and available O 2 increased the liquid-phase Sb(III) oxidation efficiency by 2.1–7.5 times. The peak changes at ~1640 and 3450 cm -1 in FTIR spectra indicated the occurrence of inner-sphere complexation between Sb(III)/Sb(V) and hydroxyl (–OH)/carboxyl (–COOH) groups in FeBC under aerobic and anaerobic conditions. Fe/Sb X-ray absorption spectroscopy (XAS) analysis results showed aqueous Sb(III) complexed to the edge-sharing Fe(III)-O-Fe(III) in FeBC. Regardless of whether O 2 was available or not, solid-phase edge-sharing Fe(III)-O-Sb(V) complexes (~3.05 Å), which had lower toxicity and migration ability than aqueous Sb(III), formed through a ligand-to-metal charge-transfer (LMCT) process. More than 91 % of adsorbed Sb(III) was oxidized to edge-sharing Fe(III)-O-Sb(V) complexes in 3 h. Additionally, the Sb(V) from liquid-phase oxidation could also directly complex to the Fe(III)-O-Fe(III) and form edge-sharing Fe(III)-O-Sb(V) complexes. Here these results provide evidence to inform further FeBC application for the Sb-contaminated water treatment.

54 ENVIRONMENTAL SCIENCES↗

Uranium-Mediated Peroxide Activation and a Precursor toward an Elusive Uranium cis -Dioxo Fleeting Intermediate

The activation of chalcogen–chalcogen bonds using organometallic uranium complexes has been well documented for S–S, Se–Se, and Te–Te bonds. In stark contrast, reports concerning the ability of a uranium complex to activate the O–O bond of an organic peroxide are exceedingly rare. Herein, we describe the peroxide O–O bond cleavage of 9,10-diphenylanthracene-9,10-endoperoxide in nonaqueous media, mediated by a uranium(III) precursor [(( Me,Ad ArO) 3 N)U III (dme)] to generate a stable uranium(V) bis-alkoxide complex, namely, [(( Me,Ad ArO) 3 N)U V (DPAP)]. This reaction proceeds via an isolable, alkoxide-bridged diuranium(IV/IV) species, implying that the oxidative addition occurs in two sequential, single-electron oxidations of the metal center, including rebound of a terminal oxygen radical. Furthermore, this uranium(V) bis-alkoxide can then be reduced with KC 8 to form a uranium(IV) complex, which upon exposure to UV light, in solution, releases 9,10-diphenylanthracene to generate a cyclic uranyl trimer through formal two-electron photooxidation. Analysis of the mechanism of this photochemical oxidation via density functional theory (DFT) calculations indicates that the formation of this uranyl trimer occurs through a fleeting uranium cis-dioxo intermediate. At room temperature, this cis-configured dioxo species rapidly isomerizes to a more stable trans configuration through the release of one of the alkoxide ligands from the complex, which then goes on to form the isolated uranyl trimer complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Entrapped Molecule‐Like Europium‐Oxide Clusters in Zinc Oxide with Nearly Unaffected Host Structure

Abstract Nanocrystalline ZnO sponges doped with 5 mol% EuO 1.5 are obtained by heating metal–salt complex based precursor pastes at 200–900 °C for 3 min. X‐ray diffraction, transmission electron microscopy, and extended X‐ray absorption fine structure (EXAFS) show that phase separation into ZnO:Eu and c ‐Eu 2 O 3 takes place upon heating at 700 °C or higher. The unit cell of the clean oxide made at 600 °C shows only ≈0.4% volume increase versus undoped ZnO, and EXAFS shows a ZnO local structure that is little affected by the Eu‐doping and an average Eu 3+ ion coordination number of ≈5.2. Comparisons of 23 density functional theory‐generated structures having differently sized Eu‐oxide clusters embedded in ZnO identify three structures with four or eight Eu atoms as the most energetically favorable. These clusters exhibit the smallest volume increase compared to undoped ZnO and Eu coordination numbers of 5.2–5.5, all in excellent agreement with experimental data. ZnO defect states are crucial for efficient Eu 3+ excitation, while c ‐Eu 2 O 3 phase separation results in loss of the characteristic Eu 3+ photoluminescence. The formation of molecule‐like Eu‐oxide clusters, entrapped in ZnO, proposed here, may help in understanding the nature of the unexpected high doping levels of lanthanide ions in ZnO that occur virtually without significant change in ZnO unit cell dimensions.

36 MATERIALS SCIENCE↗

Surface Hydration and Hydroxyl Configurations of Gibbsite and Boehmite Nanoplates

Discontinuation of the bulk structure at the interface between metal oxide particles and water leads to altered bonding characteristics and unique facet-dependent molecular environments. Surface hydration and consequent hydroxylation adds further complexity to the interface, details that for metal (oxy)hydroxides are especially difficult to isolate from the background signal of bulk structural hydroxyls. Here we probe for the first time the hydroxylation and hydration structures on basal surfaces of gibbsite (?-Al(OH)3) and boehmite (?-AlOOH) nanoplates at ambient conditions, using the interface-sensitive technique vibrational sum frequency generation spectroscopy (VSFG). Hydroxyl stretching modes at the interfaces with adsorbed water layers compared directly to Raman and infrared bulk modes show that while gibbsite surface frequencies were sharp and nearly identical to those in the bulk, boehmite surface hydroxyls displayed a very different broad spectrum of states. Ab initio molecular dynamics simulations of both basal surfaces with and without hydration waters reveal that gibbsite surface hydroxyls interact only weakly with overlying hydration waters remaining essentially unperturbed, whereasthose on boehmite can interact more strongly facilitated by higher configurational degrees of freedom at the interface. The findings clearly unveil substantial differences in the hydrated interfacial dynamics of these two otherwise similar materials, with implications for their interfacial chemistry and wettability.

Sassi, Michel JPC↗

Elucidation of Design Criteria for V‐based Redox Mediators: Structure‐Function Relationships that Dictate Rates of Heterogeneous Electron Transfer

Redox mediators are attractive solutions for addressing the stringent kinetic stipulations required for efficient energy conversion processes. In this work, we compare the electrochemical properties of four vanadium complexes, namely [V(acac) 3 ], [V 6 O 7 (OMe) 12 ], [ n Bu 4 N] 3 [V 6 O 13 (TRIS NO2 ) 2 ], and [ n Bu 4 N] 5 [V 18 O 46 (NO 3 )] in non-aqueous solutions on glassy carbon electrodes. The goal of this study is to investigate the electron transfer kinetics and diffusivity of these compounds under identical experimental conditions to develop an understanding of structure-function relationships that dictate the physicochemical properties of vanadium oxide assemblies. Complex selection was dictated by two criteria – (1) nuclearity of the transition metal complexes (2) distribution of electron density in the native electronic configuration. In conclusion, our analyses establish that electronic communication between metal centers significantly impacts charge transfer kinetics of these vanadium-based compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermochemical reduction modeling in a high-temperature moving-bed reactor for energy storage: 1D model

The design of robust and efficient high-temperature thermochemical reactors and determination of operating conditions are critical steps toward enabling high-efficiency long-duration solar energy storage. This work presents a computational model for the thermal reduction of a metal oxide material (Mg-Mn-O) up to 1450 °C and the coupled complex transport phenomena in a novel tubular thermal reactor design that features the capability for a high extent-of-reduction (high energy storage density) and inherent heat recuperation. A one-dimensional model coupling counter-current gas–solid flow, two-phase heat transfer, thermochemical redox reactions, and species transport in a moving-bed reactor is developed. Simplified versions of the model are validated with published results in the literature for packed beds with both inert and reactive particles; the fully coupled model is also validated with experimental measurements of a moving-bed reactor in terms of local temperatures and oxygen release at the exit. Detailed comparisons on the effects of different boundary conditions in the reaction zone (prescribed wall temperature vs. heat flux conditions) and formulations based on a simple uniform flow assumption vs. plug flow using Ergun equation for gas flow are investigated. The results are compared with experimental measurements, and for all cases, the energy flow components in the reactor system and the thermal to chemical conversion efficiency and overall system efficiency are computed. Finally, the predicted high thermal-to-chemical efficiency ~95% and system efficiency ~30% agree with experimental measurements.

25 ENERGY STORAGE↗

Conclusions from 3 years of continuous capture plant operation without exchange of the AMP/PZ-based solvent at Niederaussem – insights into solvent degradation management

A many times heard mantra of solvent degradation management in amine-based post combustion capture is “keep the solvent clean” to minimize solvent consumption. It is assumed that the amine losses would decrease by the removal of metals, degradation products, and reactive trace components which are captured from the flue gas, like NO 2 (as potentially driving components of the amine degradation besides dissolved O 2 ). However, this theoretical hypothesis – based on results from laboratory experiments typically generated with fresh amines – disregards the complexity of the solvent matrix, interaction of potential metal catalysts with degradation products and oxidizing agents, and specific chemical requirements which must be fulfilled before a degradation mechanism can proceed. Degradation of the solvent CESAR1 (aqueous solution of 3.0 molar 2-amino-2-methylpropan-1-ol (AMP) and 1.5 molar piperazine (PZ)) is investigated in a unique long-time test campaign (testing time up to now 40 months; 24/7 operation) without replacement of the solvent inventory at the capture pilot plant at the lignite-fired power plant in Niederaussem. Three solvent management strategies with different effect mechanisms are investigated and evaluated: (a) removal of only anionic compounds and trace elements (within 75 days solvent inventory treated two times) and anionic as well as cationic compounds and trace elements (114 days, inventory treated four times) from the solvent by ion exchange, (b) adsorptive removal of trace elements from the solvent by active carbon in 35% of the operating time, and (c) removal of >80% NO 2 by flue gas pretreatment with thiosulfate/sulfite solution (dosing for 2,000 h). The results of the testing program clearly show that “solvent cleanliness” is not a well-defined parameter and that results from laboratory tests, tests without fully representative industrial flue gasses, and short-term testing of monoethanolamine cannot be generalized for other solvents and industrial application. Furthermore, these results showcase that specific degradation management considering solvent, capture plant and flue gas quality is reasonable. Overshooting efforts for solvent management are contra-productive and produce unnecessary waste streams, efficiency losses and costs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗