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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 91 records · Page 5

Catalytic Reduction of Carbon Monoxide to Liquid Fuels with Recyclable Hydride Donors

Solar light absorption and catalysis are physically separated processes in natural photosynthesis. Natural cofactors, such as nicotinamide adenine dinucleotides (NADH), transport electrons and hydrogen to regulate and activate enzymes at remote locations. The physical separation of light absorption from catalysis provides some inspiration for artificial photosynthesis. One rather extreme implementation is to use copper wires to transport carriers from photovoltaic cells to dark electrodes, where catalysis occurs. Indeed, with a futuristic electrical grid powered solely by photovoltaics, solar capture could be separated from catalysis by hundreds of miles. An alternative approach, that bares more similarity to natural photosynthesis, employs mobile NADH/NAD + -like species that shuttle between the light absorber and a proximate, yet unilluminated, location where catalysis occurs. Additionally, such a remote approach to solar photocatalysis was recently proposed for the reduction of carbon oxides, CO 2 and CO, to methanol by cascade catalysis. This developing artificial photosynthetic approach offers the promise of catalytic generation of methanol and oxygen gas with sunlight as the sole energy source and CO 2 and water as the only chemical feedstocks. This Viewpoint evaluates the strengths and weaknesses of this approach with an emphasis on CO reduction catalysis with photorecyclable hydride donors while looking forward to what might reasonably be achieved with continued research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal–Organic Framework

Conversion of methane (CH 4 ) to ethylene (C 2 H 4 ) and/or acetylene (C 2 H 2 ) enables routes to a wide range of products directly from natural gas. However, high reaction temperatures and pressures are often required to activate and convert CH 4 controllably, and separating C 2+ products from unreacted CH 4 can be challenging. Here, we report the direct conversion of CH 4 to C 2 H 4 and C 2 H 2 driven by non-thermal plasma under ambient (25 °C and 1 atm) and flow conditions over a metal–organic framework material, MFM-300(Fe). The selectivity for the formation of C 2 H 4 and C 2 H 2 reaches 96% with a high time yield of 334 μmol g cat –1 h –1 . At a conversion of 10%, the selectivity to C 2+ hydrocarbons and time yield exceed 98% and 2056 μmol g cat –1 h –1 , respectively, representing a new benchmark for conversion of CH 4 . In situ neutron powder diffraction, inelastic neutron scattering and solid-state nuclear magnetic resonance, electron paramagnetic resonance (EPR), and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modeling studies, reveal the crucial role of Fe–O(H)–Fe sites in activating CH 4 and stabilizing reaction intermediates via the formation of an Fe–O(CH 3 )–Fe adduct. In addition, a cascade fixed-bed system has been developed to achieve online separation of C 2 H 4 and C 2 H 2 from unreacted CH 4 for direct use. Integrating the processes of CH 4 activation, conversion, and product separation within one system opens a new avenue for natural gas utility, bridging the gap between fundamental studies and practical applications in this area.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reduction of CO to Methanol with Recyclable Organic Hydrides

We report the reaction steps for the selective conversion of a transition metal carbonyl complex to a hydroxymethyl complex that releases methanol upon irradiation with visible light have been successfully quantified in acetonitrile solution with dihydrobenzimidazole organic hydride reductants. Dihydrobenzimidazole reductants have been shown to be inactive toward H 2 generation in the presence of a wide range of proton sources and have been regenerated electrochemically or photochemically. Specifically, the reaction of cis-[Ru(bpy) 2 (CO) 2 ] 2+ (bpy = 2,2'-bipyridine) with one equivalent of a dihydrobenzimidazole quantitatively yields a formyl complex, cis-[Ru(bpy) 2 (CO)(CHO)] + , and the corresponding benzimidazolium on a seconds time scale. Kinetic experiments revealed a first-order dependence on the benzimidazole hydride concentration and an unusually large kinetic isotope effect, inconsistent with direct hydride transfer and more likely to occur by an electron transfer-proton-coupled electron transfer (EΤ-PCET) or related mechanism. Further reduction/protonation of cis-[Ru(bpy) 2 (CO)(CHO)] + with two equivalents of the organic hydride yields the hydroxymethyl complex cis-[Ru(bpy) 2 (CO)(CH 2 OH)] + . Visible light excitation of cis-[Ru(bpy) 2 (CO)(CH 2 OH)] + in the presence of excess organic hydride was shown to yield free methanol. Identification and quantification of methanol as the sole CO reduction product was confirmed by 1 H NMR spectroscopy and gas chromatography. The high selectivity and mild reaction conditions suggest a viable approach for methanol production from CO, and from CO 2 through cascade catalysis, with renewable organic hydrides that bear similarities to Nature's NADPH/NADP + .

14 SOLAR ENERGY↗

Photoproduction of Cascade Baryons Using the GlueX Detector at Jefferson Laboratory

Multi-strange baryons have played an important role in understanding the strong interaction. Despite their importance to advancing quantum chromodynamics (QCD), little is known about such hyperons due to the lack of a strange probe. Almost all knowledge of Cascade baryons today stems from kaon-nucleon interactions in bubble chamber experiments performed in the 1960s and 1970s. The 1980s saw advancement in electronics and computational resources allowing for higher statistic experiments such as the MultiParticle Spectrometer (MPS) at Brookhaven National Laboratory. From these previous experiments, the octet and decuplet ground states, Xi(1320) and Xi(1530) respectively, were well established with known properties and four excited states were well established. This research uses the GlueX experiment at Jefferson Laboratory to extend photoproduction cross section measurements for Xi(1320)- to higher beam energies to further understand the production mechanism, as well as to search for the first excited Cascade resonance observation in photoproduction through the decay Xi-* -> K-Lambda. The GlueX Spectrometer is a nearly hermetic detector used to study exclusive photoproduction reactions with photon beam energies up to 12 GeV. The first phase of GlueX running has recently been completed. Preliminary results for the total cross section and differential cross sections in terms of momentum transfer -t are shown within. Additionally, the first observation of an excited Cascade baryon, in particular Xi(1820)-, is shown.

Ernst, Ashley↗

Converting polyisoprene rubbers into bio-jet fuels via a cascade hydropyrolysis and vapor-phase hydrogenation process

Producing alternative drop-in bio-jet fuels from biomass provides a promising approach to achieve carbon neutrality. Here, to upcycle biomass-based polyisoprene rubbers into jet-fuel range C 10 cycloalkane, we proposed a cascade hydropyrolysis and vapor-phase hydrogenation process in a flow-through two-stage pressurized fixed-bed reactor. The hydropyrolysis temperature in the first stage is of vital importance for the formation of primary limonene intermediate in the non-catalytic degradation of polyisoprene rubbers, and a reaction temperature of 460 °C maximized limonene yield to 588.6 mg/g for natural rubber and 546.2 mg/g for Eucommia rubber. Over a Pt/C catalyst loaded in the second stage, the limonene intermediate produced from the first-stage reactor can be completely hydrogenated, giving a 642.7 mg/g yield of jet-fuel range C 10 cycloalkane with 83.6% selectivity. The depolymerization mechanism of polyisoprene rubbers was thoroughly studied, and a competitive reaction between limonene hydrogenation and limonene dehydrogenation was observed. This is the first report on producing C 10 cycloalkane from natural rubbers via a cascade hydropyrolysis and hydrogenation process, providing a promising strategy to upcycle polyisoprene rubbers into bio-jet fuels.

30 DIRECT ENERGY CONVERSION↗

From Atom to Engine: Understanding Fundamental Effects of Structure on Combustion Using Tandem Experiment and Computation

The ability to tie structural features to a fuel candidate’s ignition properties provides a path for rational design of advantaged fuels that facilitate higher-efficiency, lower-emitting combustion in engines. The time evolution of a fuel’s radical population directly correlates with global combustion parameters, and because the generated radicals depend on the initial structure and reaction pathways of the fuel molecule, it follows that the molecular structure of a fuel has a direct impact on this cascade, and therefore salient ignition-tied fuel properties. This work aims to understand the impact of structural features in the context of global combustion properties for direct application to emerging engine technologies. Specifically, we highlight the ability to identify potential fuel blendstocks for specific engine strategies by examining and elucidating the radical cascade tied to ignition. A representative subset of alcohols possessing a variety of structural features (e.g. branching, chain length) was selected for study using a robust combination of experimental and computational methods. The approach begins with identifying short-lived radicals and likely abstraction sites upon pyrolysis in a microreactor coupled with photoionization mass spectrometry for direct detection of product species. In tandem, electronic structure calculations were performed to calculate the relevant potential energy surfaces for fuel pyrolysis as well as the subsequent O2 addition-isomerization reactions, which govern ignition behavior. Furthermore, the theoretical energetic and ro-vibrational data are used to calculate rate constants for direct ignition modeling to explore how structural effects impact NTC behavior. The microreactor data combined with electronic structure theory calculations provide a well-informed picture of the reactions relevant to ignition for each fuel in this study, as well as the most likely radicals generated under engine conditions. This thorough fundamental picture of fuel decomposition and ignition chemistry is used to correlate the observed ignition behavior to molecular structural effects.

advanced biofuels↗

Polyethylene upcycling to fuels: Narrowing the carbon number distribution in n-alkanes by tandem hydropyrolysis/hydrocracking

The extensive use of plastics in modern life has resulted in a global waste crisis to the environment. Polyethylene (PE) is one of the most popular and hardest plastics to recycle because of its strong C(sp 3 )-C(sp 3 ) bonds. In this study, a tandem conversion process, i.e., hydropyrolysis and subsequent vapor-phase hydrocracking of primary intermediates (C n>5 alkenes and long-chain alkanes), was conducted via a two-step pressurized flow-through fixed-bed reactor over a CoAl 2 O 4 spinel-derived catalyst. The product distribution could be flexibly tuned by regulating operating parameters in the cascade fixed-bed reactor and Co/Al molar ratio in CoAl 2 O 4 spinel catalysts. Under optimal reaction conditions (0.2 MPa H 2 , 550 °C for hydropyrolysis in the 1st reactor, 300–325 °C for hydrocracking in the 2nd reactor, 20 s -1 of gas hourly space velocity), the maximum single-pass yields of gasoline (C 5 -C 12 ) and jet-fuel (C 8 -C 16 ) range n-alkanes reached 86.0 wt% and 68.1 wt%, respectively. The CoAl 2 O 4 spinel catalysts also gained high activity in degrading realistic post-consumer plastics such as linear low-, low-, and high-density PE, and a ~ 73.1 wt% gasoline yield and a ~ 54.7 wt% C 8 -C 16 yield were retained even after 3 cycles in-situ regeneration of deactivated CoAl 2 O 4 catalysts. This work provides an efficient and tunable approach to upcycle PE wastes into liquid fuels with an ideal carbon length.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Implementation of INCL Nuclear Model in GENIE Generator

The Li ge Intranuclear Cascade (INCL) model is a nuclear-physics model that simulates hadron (baryon, anti-baryon and meson) reactions on nuclei, for incident energies ranging from a few tens of MeV to 10-20 GeV. The INCL model has been well validated by hadron scattering data. In my work, I implement an interface in GENIE to use the INCL nuclear model in the simulations of both the initial state of the target nucleus and the Final State Interaction in neutrino-nucleus interaction. It has a consistent treatment of nuclear models in both neutrino interaction and hadron rescattering. A full event record including neutrino vertex and each vertex of hadron rescattering has been accomplished. Several processes, e.g. cluster production, Delta transportation and de-excitation will also be included as benefits of the implementation of the INCL model in GENIE. I will show some initial simulation results showcasing the new GENIE features and discuss plans for making them available for use in experimental analyses.

Liu, Liang [Fermilab]↗

Implementation of INCL nuclear model in GENIE Generator

The Liège Intranuclear Cascade (INCL) model is a nuclear-physics model that simulates hadron (baryon, anti-baryon and meson) reactions on nuclei, for incident energies ranging from a few tens of MeV to 10-20 GeV. The INCL model has been well validated by hadron scattering data. In my work, I implement an interface in GENIE to use the INCL nuclear model in the simulations of both the initial state of the target nucleus and the Final State Interaction in neutrino-nucleus interaction. It has a consistent treatment of nuclear models in both neutrino interaction and hadron rescattering. A full event record including neutrino vertex and each vertex of hadron rescattering has been accomplished. Several processes, e.g. cluster production, Delta transportation and de-excitation will also be included as benefits of the implementation of the INCL model in GENIE. I will show some initial simulation results showcasing the new GENIE features and discuss plans for making them available for use in experimental analyses.

Liu, Liang [Fermilab] (ORCID:000000026753925X)↗

Coupling Pulse Radiolysis with Nanosecond Time-Resolved Step-Scan Fourier Transform Infrared Spectroscopy: Broadband Mid-Infrared Detection of Radiolytically Generated Transients

We describe the first implementation of broadband, nanosecond time-resolved step-scan Fourier transform infrared (S 2 -FT-IR) spectroscopy at a pulse radiolysis facility. This new technique allows the rapid acquisition of nano- to microsecond time-resolved infrared (TRIR) spectra of transient species generated by pulse radiolysis of liquid samples at a pulsed electron accelerator. Wide regions of the mid-infrared can be probed in a single experiment, which often takes < 20–30 min to complete. It is therefore a powerful method for rapidly locating the IR absorptions of short-lived, radiation-induced species in solution, and for directly monitoring their subsequent reactions. Time-resolved step-scan FT-IR detection for pulse radiolysis thus complements our existing narrowband quantum cascade laser-based pulse radiolysis-TRIR detection system, which is more suitable for acquiring single-shot kinetics and narrowband TRIR spectra on small-volume samples and in strongly absorbing solvents, such as water. We have demonstrated the application of time-resolved step-scan FT-IR spectroscopy to pulse radiolysis by probing the metal carbonyl and organic carbonyl vibrations of the one-electron-reduced forms of two Re-based CO 2 reduction catalysts in acetonitrile solution. Transient IR absorption bands with amplitudes on the order of 1 × 10 −3 are easily detected on the sub-microsecond timescale using electron pulses as short as 250 ns.

(S2-FT-IR)↗

Search for Weak Side Branches in the Electromagnetic Decay Paths of the 6526-keV 10 + Isomer in 54 Fe

High-spin nuclear isomers in $N≈Z$ nuclei between doubly magic 40 Ca and 56 Ni provide an excellent testing ground for the nuclear shell model and questions related to isospin symmetry breaking in the vicinity of the proton drip line. The purpose of the present study is to investigate the possibility of weak electromagnetic decay branches along the decay paths of the 6526-keV 10 + isomer in 54 Fe. The isomer was strongly populated by means of the fusion-evaporation reaction 24 Mg( 36 Ar,$α$2$p$) 54$m$ Fe. The Gammasphere array was used to detect $γ$-ray cascades emitted from the isomeric state. By means of $γγγ$ coincidences, weak non-yrast decay branches can be discriminated, with the isomer’s half-life confirmed at $T$ 1/2 = 363 (4) ns. The yrast ${6}_{1}^{+}$ → ${2}_{1}^{+}$ $E4$ cross-over transition was interrogated. The observations are compared with shell-model calculations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Iron(III) Nitrate/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Distinguishing between Serial versus Integrated Redox Cooperativity

Aerobic alcohol oxidations catalyzed by transition metal salts and aminoxyls are prominent examples of cooperative catalysis. Cu/aminoxyl catalysts have been studied previously and feature “integrated cooperativity”, in which Cu II and the aminoxyl participate together to mediate alcohol oxidation. Here we investigate a complementary Fe/aminoxyl catalyst system and provide evidence for “serial cooperativity”, involving a redox cascade wherein the alcohol is oxidized by an in situ-generated oxoammonium species, which is directly detected in the catalytic reaction mixture by cyclic step chronoamperometry. The mechanistic difference between the Cu- and Fe-based catalysts arises from the use iron(III) nitrate, which initiates a NO x -based redox cycle for oxidation of aminoxyl/hydroxylamine to oxoammonium. Here, the different mechanisms for the Cu- and Fe-based catalyst systems are manifested in different alcohol oxidation chemoselectivity and functional group compatibility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ene Reductase Enabled Intramolecular β–C–H Functionalization of Substituted Cyclohexanones for Efficient Synthesis of Bridged Bicyclic Nitrogen Scaffolds

Herein we report that ene reductases (EREDs) can facilitate an unprecedented intramolecular β-C–H functionalization reaction for the synthesis of bridged bicyclic nitrogen heterocycles containing the 6-azabicyclo[3.2.1]octane scaffold. To streamline the synthesis of these privileged motifs, we developed a gram-scale one-pot chemoenzymatic cascade by combining iridium photocatalysis with EREDs, using readily available N-phenylglycines and cyclohexenones that can be obtained from biomass. Further derivatization using enzymatic or chemical methods can convert 6-azabicyclo[3.2.1]octan-3-one into 6-azabicyclo[3.2.1]octan-3α-ols, which can be potentially utilized for the synthesis of azaprophen and its analogues for drug discovery. Furthermore, mechanistic studies revealed the reaction requires oxygen, presumably to produce oxidized flavin, which can selectively dehydrogenate the 3-substituted cyclohexanone derivatives to form the α,β-unsaturated ketone, which subsequently undergoes spontaneous intramolecular aza-Michael addition under basic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ene Reductase Enabled Intramolecular β–C–H Functionalization of Substituted Cyclohexanones for Efficient Synthesis of Bridged Bicyclic Nitrogen Scaffolds

Herein we report that ene reductases (EREDs) can facilitate an unprecedented intramolecular β-C–H functionalization reaction for the synthesis of bridged bicyclic nitrogen heterocycles containing the 6-azabicyclo[3.2.1]octane scaffold. To streamline the synthesis of these privileged motifs, we developed a gram-scale one-pot chemoenzymatic cascade by combining iridium photocatalysis with EREDs, using readily available N-phenylglycines and cyclohexenones that can be obtained from biomass. Further derivatization using enzymatic or chemical methods can convert 6-azabicyclo[3.2.1]octan-3-one into 6-azabicyclo[3.2.1]octan-3α-ols, which can be potentially utilized for the synthesis of azaprophen and its analogues for drug discovery. Here, mechanistic studies revealed the reaction requires oxygen, presumably to produce oxidized flavin, which can selectively dehydrogenate the 3-substituted cyclohexanone derivatives to form the α,β-unsaturated ketone, which subsequently undergoes spontaneous intramolecular aza-Michael addition under basic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cascade CO 2 electroreduction enables efficient carbonate-free production of ethylene

CO 2 electroreduction provides a route to convert waste emissions into chemicals such as ethylene (C 2 H 4 ). However, the direct transformation of CO 2 -to-C 2 H 4 suffers from CO 2 loss to carbonate, consuming up to 72% of energy input. A cascade approach—coupling a solid-oxide CO 2 -to-CO electrochemical cell (SOEC) with a CO-to-C 2 H 4 membrane electrode assembly (MEA)—would eliminate CO 2 loss to carbonate. However, this approach requires a CO-to-C 2 H 4 MEA with energy efficiency well beyond demonstrations to date. Focusing on the MEA, in this study we find that an N-tolyl substituted tetrahydro-bipyridine film improves the stabilization of key reaction intermediates, while an SSC ionomer enhances CO transport to the Cu surface, enabling a C 2 H 4 faradaic efficiency of 65% at 150 mA cm –2 for 110 h. Demonstrating a cascade SOEC-MEA approach, we achieve CO 2 -to-C 2 H 4 with a ~48% reduction in energy intensity compared with the direct route. We further reduce the energy intensity by coupling CO electroreduction (CORR) with glucose electrooxidation.

10 SYNTHETIC FUELS↗

Tandem Electrocatalytic CO 2 Reduction with Efficient Intermediate Conversion over Pyramid-Textured Cu–Ag Catalysts

If combined with renewably generated electricity, electrochemical CO 2 reduction (E-CO 2 R) could be used as a sustainable source of chemicals and fuels. Tandem catalysis approaches are attractive for providing the product selectivity, which would be required for commercial applications. Here, we demonstrate a two-step tandem electrocatalytic E-CO 2 R with efficient conversion of the intermediate species. The catalyst scaffold is Si(100), which is etched to form a textured surface consisting of micron-sized pyramid structures with the {111} facets. Two metals are used in the electrocatalytic cascade: Ag is employed to perform a two-electron reduction of CO 2 to the intermediate CO, and Cu performs conversion to more reduced products. Using high-angle physical vapor deposition, we form separated, micron-scale areas of the two electrocatalysts on opposite sides of the pyramids, with their relative surface coverages being tunable with the deposition angle. Compared to the textured scaffolds with blanket Ag and Cu used as controls, bimetallic pyramid tandem catalysts have higher current densities and much lower faradic efficiencies (FE) for CO. These effects are due to efficient conversion of the CO formed on Ag to more reduced products on Cu. Methane is the main product to be enhanced by the cascade pathway: a bimetallic catalyst with approximately equal coverages of Ag and Cu produces methane with a FE of 62% at -1.1 V RHE , corresponding to a partial current density of 12.7 mA cm -2 . We estimate an intermediate conversion yield for the CO intermediate of 80-90%, which is close to the mass-transport limited value predicted by reaction-diffusion simulations.

36 MATERIALS SCIENCE↗

Energizing Robust Sulfur/Lithium Electrochemistry via Nanoscale-Asymmetric-Size Synergism

Sluggish redox kinetics and dendrite growth perplex the fulfillment of efficient electrochemistry in lithium–sulfur (Li–S) batteries. The complicated sulfur phase transformation and sulfur/lithium diversity kinetics necessitate an all-inclusive approach in catalyst design. Herein, a compatible mediator with nanoscale-asymmetric-size configuration by integrating Co single atoms and defective CoTe 2–x (Co SA -CoTe 2–x @NHCF) is elaborately developed for regulating sulfur/lithium electrochemistry synchronously. Substantial electrochemistry and theoretical analyses reveal that CoTe 2–x exhibits higher catalytic activity in long-chain polysulfide transformation and Li 2 S decomposition, while monodispersed Co sites are more effective in boosting sulfur reduction kinetics to regulate Li 2 S deposition. Such cascade catalysis endows Co SA -CoTe 2–x @NHCF with the all-around service of “trapping-conversion-recuperation” for sulfur species during the whole redox reaction. Furthermore, it is demonstrated by in situ transmission electron microscopy that initially formed electronic-conductive Co and ionic-conductive Li 2 Te provide sufficient lithiophilic sites to regulate homogeneous Li plating and stripping with markedly suppressed dendrite growth. Consequently, by coupling the Co SA -CoTe 2–x @NHCF interlayer and Li@Co SA -CoTe 2–x @NHCF anode, the constructed Li–S full batteries deliver superior cycling stability and rate performance, and the flexible pouch cell exhibits stable cycling performance at 0.3 C. In conclusion, the gained insights into the synergistic effect of asymmetric-size structures pave the way for the integrated catalyst design in advanced Li–S systems.

36 MATERIALS SCIENCE↗

Electrode strain dynamics in layered intercalation battery cathodes

Rechargeable batteries using electrodes based on intercalation chemistry exhibit notable cyclability, yet their performance still suffers from chemomechanical degradation. In this study, by combining a suite of operando microscopy methods, we explored electrode strain evolution and observed intricate particle cluster rearrangement under electrochemical stimuli. We show that early-stage strain accumulation in intercalation cathodes occurs during the period of interparticle charge transfer and redox reactions stemming from asynchronous coupling and decoupling between chemical (de)intercalation and physical grain motion. This interplay drives heterogeneous redox activity, localized charge equilibration, and multiscale strain cascades that propagate through an asynchronous network of chemical-mechanical interactions. Together, these findings reveal how collective particle dynamics and hierarchical strain transmission dictate electrode deformation and degradation in intercalation cathodes.

25 ENERGY STORAGE↗