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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 37 records · Page 2

Diverse electron carriers drive syntrophic interactions in an enriched anaerobic acetate-oxidizing consortium

Abstract In many anoxic environments, syntrophic acetate oxidation (SAO) is a key pathway mediating the conversion of acetate into methane through obligate cross-feeding interactions between SAO bacteria (SAOB) and methanogenic archaea. The SAO pathway is particularly important in engineered environments such as anaerobic digestion (AD) systems operating at thermophilic temperatures and/or with high ammonia. Despite the widespread importance of SAOB to the stability of the AD process, little is known about their in situ physiologies due to typically low biomass yields and resistance to isolation. Here, we performed a long-term (300-day) continuous enrichment of a thermophilic (55 °C) SAO community from a municipal AD system using acetate as the sole carbon source. Over 80% of the enriched bioreactor metagenome belonged to a three-member consortium, including an acetate-oxidizing bacterium affiliated with DTU068 encoding for carbon dioxide, hydrogen, and formate production, along with two methanogenic archaea affiliated with Methanothermobacter_A. Stable isotope probing was coupled with metaproteogenomics to quantify carbon flux into each community member during acetate conversion and inform metabolic reconstruction and genome-scale modeling. This effort revealed that the two Methanothermobacter_A species differed in their preferred electron donors, with one possessing the ability to grow on formate and the other only consuming hydrogen. A thermodynamic analysis suggested that the presence of the formate-consuming methanogen broadened the environmental conditions where ATP production from SAO was favorable. Collectively, these results highlight how flexibility in electron partitioning during SAO likely governs community structure and fitness through thermodynamic-driven mutualism, shedding valuable insights into the metabolic underpinnings of this key functional group within methanogenic ecosystems.

59 BASIC BIOLOGICAL SCIENCES↗

Roles of interaction between components in CZZA/HZSM-5 catalyst for dimethyl ether synthesis via CO 2 hydrogenation

The roles of interaction between two catalyst components in CuO–ZnO–ZrO 2 –Al 2 O 3 (CZZA)/HZSM-5 bifunctional catalyst for dimethyl ether (DME) synthesis via carbon dioxide hydrogenation were investigated. It was found that CZZA catalyst showed excellent stability during methanol (MeOH) synthesis for 100 h, while there was a severe loss of catalytic activity in the bifunctional catalyst for DME synthesis. So, the effects of different degrees of intimacy of two catalyst components were studied for DME synthesis, including mixed and separated modes. For the mixed mode, the particle size of catalysts and the amount of reaction intermediates were proven to influence the catalyst deactivation. For the separated mode, the catalysts showed rapid deactivation within a short time. Various characterizations indicated that the remarkable deactivation of separated mode was mainly caused by the decrease of copper active centers (e.g., sintering and oxidation) and blockage of acid sites via increased coke deposition on HZSM-5.

42 ENGINEERING↗

Biohydrogen Generation from Un-Pretreated Spent Coffee Grounds with Clostridium Thermocellum

Coffee is among the world's most widely consumed beverages, generating 18 million wet tonnes of waste spent coffee grounds annually. Disposal of SCGs is complicated by their high moisture content, their recalcitrant chemical composition, and the presence of caffeine and other bioactive compounds. Dark fermentation is a promising technology for conversion of waste cellulosic biomass into renewable hydrogen, carbon dioxide, and volatile fatty acids. Typical SCGs have high moisture content, are pre-milled to fine particle sizes, and contain 8%-19% cellulose and up to 40% hemicellulose, making them an attractive feedstock for dark fermentation. In this study, we investigate biohydrogen production from unpretreated SCGs using Clostridium thermocellum strain KJC19-9, a cellulolytic bacterium engineered to co-utilize xylose, specifically examining the inhibitory effects of residual caffeine and high solids loadings on microbial growth and hydrogen production efficiency. While SCGs were initially resistant to both cell growth and biohydrogen production, a strategy to co-ferment with low concentrations of cellobiose dramatically enhanced process performance, reducing lag phase duration and enabling cellulosome production for efficient cellulose hydrolysis. This co-substrate approach generated up to 944 mL hydrogen per L reaction from 50 g/L of spent coffee grounds over 120 h (1.34 mol H2/mol carbohydrate), validating SCGs as a promising dark fermentation feedstock and underscoring the value of mixed substrate approaches in consolidated bioprocessing.

08 HYDROGEN↗

System and method for removing water and hydrogen from anode exhaust

A fuel cell system includes an anode configured to output an anode exhaust stream comprising hydrogen, carbon dioxide, and water; and a membrane dryer configured to receive the anode exhaust stream, remove water from the anode exhaust stream, and output a membrane dryer outlet stream. The membrane dryer includes a first chamber configured to receive the anode exhaust stream; a second chamber configured to receive a purge gas; and a semi-permeable membrane separating the first chamber and the second chamber. The semi-permeable membrane is configured to allow water to diffuse therethrough, thereby removing water from the anode exhaust stream. The membrane dryer may further be configured to remove hydrogen from the anode exhaust stream.

Jolly, Stephen↗

Understanding and Predicting the Spatially Resolved Adsorption Properties of Nanoporous Materials

Using knowledge from statistical thermodynamics and crystallography, we develop an image–image translation model, called SorbIIT, that uses three-dimensional grids of adsorbate–adsorbent interaction energies as input to predict the spatially resolved loading surface of nanoporous materials over a broad range of temperatures and pressures. SorbIIT consists of a closed-form differential model for loading-surface prediction and a U-Net to generate spatial differential distributions from the energy grids. SorbIIT is trained using the energy grids and adsorbate distributions (obtained from high-throughput simulations) of 50 synthesized and 70 hypothetical zeolites and applied for predicting the adsorption of carbon dioxide, hydrogen sulfide, n-butane, 2-methylpropane, krypton, and xenon in other zeolites from 256 to 400 K. In conclusion, employing a quadratic isotherm model for the local differentiation, SorbIIT yields mean R 2 values of 0.998 for total adsorption and 0.6904 for local adsorption with a resolution of 0.2 Å, and a value of 0.721 for the structural similarity of the local loading distribution.

Sun, Yangzesheng↗

Electrolyzer Integrated Modular Nano-Array Monolithic Catalytic Reactors

The project objective is to design and develop a new class of electrolyzer-integrated, modular, nanostructure array (nano-array) monolithic catalytic reactors for high-flux, robust and selective methanol synthesis. The modular reactor features metal oxide nano-array grown on an additively-manufactured channeled honeycomb monolith made of ceramic or metals; this low-pressure carbon dioxide hydrogenation reactor is fueled with hydrogen from a low-temperature water electrolyzer having reduced platinum group metal (PGM) content. Through these nanostructured monolithic reactors, methanol synthesis is enabled with cost-effective hydrogenation reactions under low-temperature (<200°C) and low-pressure (<10 atm) conditions, thus significantly reducing the energy demand of the entire process.

08 HYDROGEN↗

Recent advances in polymeric facilitated transport membranes for carbon dioxide separation and hydrogen purification

Membrane and membrane process have been widely considered as one of the best candidates for mitigating CO 2 emissions from the combustion or utilization of fossil fuels. Various amine-containing polymers constitute an important class of membranes, where the highly selective CO 2 transport is achieved by the facilitated transport mechanism. In this review, the amine–CO 2 chemistry is discussed in conjunction with the mechanism of the reaction-mediated CO 2 transport. A wide variety of amine-containing polymers are discussed based on two synthesis motifs: (a) polyamines with amino groups covalently bound to the polymer backbone and (b) small molecule amines embedded in a polymer matrix. This review concludes with the remarks on the facilitated transport membranes for post-combustion carbon capture (CO 2 /N 2 ) and hydrogen purification (CO 2 /H 2 ).

42 ENGINEERING↗

Light Water Reactor Sustainability Program: Technical and Economic Considerations for Uprate of Existing Nuclear Reactors with Cogeneration

The United States nuclear reactor fleet consists of 63 pressurized water reactors and 31 boiling water reactors and is a pivotal component in the nation's energy infrastructure, supplying approximately 97 GW e of clean power. With the country's commitment to decarbonization by 2050, these reactors are not only instrumental in decarbonizing the electricity grid but also play a critical role in decarbonizing industrial processes, producing clean fuels, and scaling up CO 2 removal. This report delves into the potential for power uprates in the existing fleet to contribute to these decarbonization efforts, focusing on the expansion of capacity for applications such as hydrogen production and carbon capture and sequestration. Building on previous research, the report explores regional market demands for hydrogen, oxygen, and carbon dioxide, financial implications of oxygen and CO 2 sales from high-temperature steam electrolysis systems, and the potential for direct air capture systems paired with uprated nuclear plants.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

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↗

Effect of operating parameters on H 2 /CO 2 conversion to methanol over Cu-Zn oxide supported on ZrO 2 polymorph catalysts: Characterization and kinetics

Kinetic aspects of the operating parameters for the catalytic conversion of H 2 /CO 2 to methanol over two novel catalysts were evaluated to understand the effect of the polymorphic ZrO 2 phase composed of Cu 0/+ -ZnO sites at the atomic level and its impact on the reaction mechanism. The catalysts were characterized by in situ and ex-situ XRD, N 2 adsorption/desorption isotherms, FRX, TPR, TPD-N 2 O, in situ XANES, TPD-CO 2 , and in situ DRIFTS techniques. The influence of different reaction variables such as the GHSV, temperature, pressure, and H 2 /CO 2 ratio were studied using a fixed bed continuous plug flow reactor. The Cu-ZnO catalyst supported on the tetragonal zirconia polymorph exhibited the highest methanol yield due to the lower activation energy when compared to the catalyst with a greater amount of the monoclinic phase. In addition, the catalysts were reused for 8 cycles of 6 hours to evaluate their stability, which can translate into lower costs for large-scale methanol production. As a result, the estimation of the kinetic parameters over Cu-Zn oxide supported on ZrO 2 polymorphs was significant for understanding the reaction mechanism, as well as to provide a pathway for scaling-up of the process.

36 MATERIALS SCIENCE↗

Design of Efficient Molecular Electrocatalysts for Water and Carbon Dioxide Reduction Using Predictive Models of Thermodynamic Properties

Objectives: 1) To design and synthesize water soluble transition metal complexes that function as electrocatalysts for the reduction of water to hydrogen or carbon dioxide to formate 2) To experimentally measure thermochemical properties, such as hydride donor ability, and use these quantities to optimize catalyst performance in solutions of varying pH 3) To incorporate results from detailed mechanistic and kinetic studies to direct improvements in catalyst design 4) To use thermochemical data from objective 2 to generate predictive models for the properties of new complexes to apply to the development of catalysts for other reductive reactions, with an emphasis on carbon dioxide reduction to methanol Description: Wide-spread implementation of renewable but intermittent energy sources, such as solar, requires the development of efficient methods for energy storage. The high energy density of chemical bonds makes chemical fuels an ideal solution for energy storage. Hydrogen and reduced carbon compounds have been proposed as ideal candidates for chemical fuels. However, the generation of chemical fuels from electricity requires competent electrocatalysts. The proposed research focuses on developing electrocatalysts for the reduction of water to hydrogen, and carbon dioxide to formate. Both products can be used directly as an energy carrier in fuel cells, or as a reductant for more saturated chemical fuels. Hydrogen is the most common fuel used in current commercial fuel cells. Additionally, there is interest in formic acid as a liquid carrier for hydrogen because of its increased storage density and ease of dehydrogenation. Formate is also an intermediate in the sequential reduction of CO 2 to methanol, another potential chemical fuel with high energy storage density. Despite the utility of formate as a chemical fuel or precursor, there are very few examples of electrocatalysts for its production from CO 2 , and even fewer demonstrate high product selectivity. In heterogeneous catalysis, the Sabatier principle is used to generate volcano curves that describe optimal thermochemical properties for key intermediates that result in peak catalytic activity. In most cases, such as hydrogen production and oxidation, the most favorable metals (Pt, Re, Rh, and Ir) are rare and expensive. Molecular inorganic complexes provide an opportunity to use electronic and steric ligand effects to tune the critical thermodynamic parameters of abundant metals to values comparable to key surface intermediates on precious metals. This principle will be applied to the design of aqueous homogeneous catalysts for the reduction of H 2 O and CO 2 optimized to function at specific pH ranges. The critical intermediate in both of these reactions is a metal hydride. The strength of this bond, or hydricity (ΔGH - ) dictates the overall thermodynamics of the reduction of H + to H 2 and the sequential reduction of C1 substrates, such as CO 2 , CO, and H 2 CO (the latter to CH 3 OH). ΔGH - will be systematically measured for a series of first row metal complexes to form predictive models for metal and ligand electronic effects. Benefits and Outcomes: This approach addresses thermodynamic requirements essential for energy-efficient catalyst design and transition state barrier considerations for faster catalysis. The advancements made from this research will include the discovery of efficient, stable, and fast catalysts for hydrogen and formate generation from electricity. The ability to store energy efficiently is critical to the widespread use of renewable energy schemes. This provides a viable solution to produce high energy density fuels for stationary and mobile energy applications. The fundamental research conducted is also directly applicable to the design of catalysts for the generation of further reduced products such as methanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Status Report 2: Advanced Nuclear Reactors Utilized for Synthetic Fuel Creation

Synthetic fuels (synfuels) are hydrocarbon fuels that source energy from electricity. Synfuels have the potential to significantly reduce greenhouse gas emissions throughout the transportation sector. To achieve this substantial reduction in greenhouse gas emissions, the electricity must be sourced from zero- or near-zero-carbon fuel sources such as solar, wind, hydroelectricity, and nuclear power. Synfuels are produced from a combination of carbon and hydrogen sources. Hydrogen can be sourced from water electrolysis with near-zero-carbon electricity and heat (e.g., nuclear), while carbon dioxide can be sourced from ethanol and ammonia plants. In the hydrocarbon fuel synthesis process, hydrogen and carbon dioxide can be reacted to produce carbon monoxide and water, via the so-called reverse watergas shift reaction. Carbon monoxide can then react with additional hydrogen to form hydrocarbons, with carbon chains ranging from C1–C30 in the reaction known as the Fischer-Tropsch (F-T) synthesis reaction. The synthesized hydrocarbon molecules can then be hydro-processed with additional hydrogen and distilled into different carbon chain lengths so as to be compatible with existing conventional gasoline, jet, and diesel fuels. Carbon-free synfuel production comes with a “green premium” over the manufacture of identical products via conventional fossil fuels. Reports from Argonne National Laboratory (ANL) reveal that hydrogen costs dominate the cost of carbon-free synfuel production. This suggests that for the cost of green synfuel to approach that of conventional petroleum fuel, the cost of hydrogen must be approximately $\$1$/kg. Of the primary low-carbon energy sources, only nuclear carries the potential to produce hydrogen at below $\$2$/kg. (Still a bit above the lofty $\$1$/kg goal, but perhaps manageable). To further identify the potential for creating low-cost synfuels capable of competing with legacy technologies, the Department of Energy Office of Nuclear Energy has funded a multi-program, multi-lab effort among ANL, Idaho National Laboratory (INL), the Integrated Energy Systems (IES) program, and the Light Water Reactor Sustainability (LWRS) program. This collaboration effort will determine the possibility of using current and next generation nuclear reactors to create low-cost carbon-free synfuels for sale in the U.S. energy and commodities market.

10 SYNTHETIC FUELS↗

Visualizing Size-Dependent Dynamics of CeO 2-δ {100}-Supported CoO x Nanoparticles Under CO 2 Hydrogenation Conditions

Carbon dioxide is a major greenhouse gas. In order to optimize processes focused on its chemical valorization, one needs detailed information about the effects of CO 2 and/or CO 2 /H 2 mixtures on the structure and morphology of metal/oxide catalysts. Here, in this study, the evolution of a catalyst with cobalt supported on CeO 2 -cube nanostructures under CO 2 hydrogenation conditions was investigated by using a set of in situ characterization techniques (X-ray absorption fine structure, X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, and environmental transmission electron microscopy (TEM)). The {100} facets of the ceria support displayed an unexpectedly high stability due to strong interactions with the aggregates of cobalt oxide. A significant influence of interfacial bonding between CoO x and CeO 2-δ {100} is evident through a clear preference in the orientation of CoO x nanoparticles (NPs) with respect to the substrate. For initially reduced Co/CeO 2 -cube nanostructures, a kinetically controlled oxidation of cobalt upon the introduction of CO 2 was observed during the early stages of CO 2 hydrogenation. Environmental TEM revealed the size-dependent morphological behavior of cobalt oxide NPs due to strong interactions with the CeO 2 {100} surface. When the environment was switched from H 2 to a mixture of H 2 and CO 2 at 250 °C, small CoO x NPs (in the largest dimension < 2.5 nm) rapidly transformed from a pyramidal three-dimensional (3D) form to a planar, monatomic layer attached to the concurrently oxidized CeO 2-δ {100} surface. This maximizes the number of sites available for the binding of CO 2 or reaction intermediates. The shape transformation reflected the oxophilic character of cobalt and strong metal–support interactions. The removal of CO 2 from the gas phase led to a reduction of the cobalt oxide NPs by hydrogen and a reversible two-dimensional → 3D transformation. In contrast, no significant morphological changes, apart from further oxidation, were observed for big CoO x NPs (in the largest dimension > 3 nm). These trends are not seen for nanoparticles of noble metals. The observed morphological and structural changes in the small CoO x NPs affected the stability of reaction intermediates and modified the selectivity of the CoO x /CeO 2 catalyst system for methane production.

36 MATERIALS SCIENCE↗

Critical Review of Platinum Group Metal-Free Materials for Water Electrolysis: Transition from the Laboratory to the Market : Earth-abundant borides and phosphides as catalysts for sustainable hydrogen production

To combat the global problem of carbon dioxide emissions, hydrogen is the desired energy vector for the transition to environmentally benign fuel cell power. Water electrolysis (WE) is the major technology for sustainable hydrogen production. Despite the use of renewable solar and wind power as sources of electricity, one of the main barriers for the widespread implementation of WE is the scarcity and high cost of platinum group metals (pgms) that are used to catalyse the cathodic hydrogen evolution reaction (HER) and the anodic oxygen evolution reaction (OER). Hence, the critical pgm-based catalysts must be replaced with more sustainable alternatives for WE technologies to become commercially viable. This critical review describes the state-of-the-art pgm-free materials used in the WE application, with a major focus on phosphides and borides. Several emerging classes of HER and OER catalysts are reviewed and detailed structure-property correlations are comprehensively summarised. The influence of the crystallographic and electronic structures, morphology and bulk and surface chemistry of the catalysts on the activity towards OER and HER is discussed.

Chemistry↗

Carbon Dioxide Utilization for Plasma Nanosynthesis of Carbon

This DOE Phase I SBIR project has developed a glow discharge-based plasma process to convert carbon dioxide to sold carbon and water. By adding natural gas, the additional enthalpy can be used to reform the output carbon dioxide to value added carbon and EPA-compliance-grade water, thus creating a process that has no gaseous products at all, such as: CO 2 + CH 4 → 2C + 2H 2 O, which is simply the exothermic reverse of the syngas reaction. During the Phase I work, several milestones were accomplished successfully. a. First, a synthesis reactor was designed, assembled, and successfully operated using the combined simultaneous operation of glow discharge and microwaves. DC discharge and microwaves can also be operated individually, allowing multiple configurations to be used This is one of the first reactors of its kind, and perhaps the first ever. b. Second, the research team successfully produced carbon nanomaterials using carbon dioxide as the source of carbon via CO 2 + 2H 2 → C + 2H 2 O. This is certainly one of the first processes to use plasma to convert carbon dioxide to nanocarbon, and perhaps the first ever demonstration. c. Third, it was also shown that carbon monoxide and carbon dioxide can be used with methane to reduce the synthesis temperature of ASI graphene decorated carbon nanotubes (GDCNT). Hitherto GDCNT were only fabricated above 1200 °C. GDCNT was synthesized at 780 °C. CO 2 + C → 2CO; 2 CO + CH 4 → 3 C + 2H 2 O, and also, CH 4 + CO 2 → 2 C + 2H 2 O. d. Fourth, closed cycle synthesis of nanomaterial was demonstrated with over 80% conversion of carbon dioxide to carbon and water was achieved, on the basis of pressure drop during glow discharge. e. Fifth, plasma operation was achieved via glow discharge and microwaves at 500 Torr, demonstrating a path forward to atmospheric pressure operation f. Sixth, using carbon monoxide and carbon dioxide in an electrothermal furnace, we produced 350 grams per hour of high-quality nanotubes in a single furnace, compared to 200 grams per hour for the commercial process. Controlling the enthalpy prevents self-extinguishing hot gas pyrolysis. Thus, carbon dioxide enhances the properties and reduces the production cost. This is a near term advance that can go into trial production in the near term. g. Seventh, economic analysis suggests an economic plan forward, producing carbon nanotubes for less than $50 per pound. The use of hydrogen and carbon dioxide as the feedstocks is acceptable from a cost basis, and in fact hydrogen is less expensive than carbon monoxide. Niche applications are available in the near term, though quantities relevant to sequestration remain a far-term goal. h. Eighth, though it was not the research team’s intention to create a new process for producing carbon monoxide, it was realized that almost by accident we demonstrated plasma reforming of carbon dioxide via a plasma version of the reverse Boudouard reaction. Accordingly, we have contacted a major gas manufacturer (Matheson Gas) to determine whether there is interest in creating an industrial version of the process. i. Ninth, a long-range strategy is identified in which a progressively more carbon-conscious world will seek to create solid carbon as a means of sequestering carbon dioxide, impeding its return to the atmosphere. In the long term the price must drop by orders of magnitude with larger production, and assuming success, solid carbon could be the preferred form for sequestration rather than underground storage. If carbon can be made as cheaply as dirt, or nearly so, then it can serve a useful purpose as structural material for housing, soil amendments in agriculture and fillers to modify low areas.

03 NATURAL GAS↗

Oxygen Evolution Reaction in Alkaline Environment: Material Challenges and Solutions

Abstract The oxygen evolution reaction (OER) generally exists in electrochemistry‐enabled applications that are coupled with cathodic reactions like hydrogen evolution, carbon dioxide reduction, ammonia synthesis, and electrocatalytic hydrogenation. The OER heavily impacts the overall energy efficiency of these devices because the sluggish OER kinetics result in a huge overpotential, thus, a large amount of efficient catalysts are needed. The benchmark iridium and ruthenium (Ir/Ru)‐based materials (mostly used in acid media) are, however, significantly limited by their scarcity. Non‐precious metal‐based catalysts (NPMCs) have emerged as the most promising alternatives; however, they tend to degrade quickly under the harsh operating conditions of typical OER devices. Another challenge is the unsatisfying performance of OER catalysts when integrated in real‐world devices. Herein, the OER active sites for three mainstream types of NPMCs including non‐precious transition metal oxides/(oxy)hydroxides, metal‐free carbon materials, and hybrid non‐precious metal and carbon composites are reviewed. In addition, possible degradation mechanisms for active sites and mitigation strategies are discussed in detail. This review also provides insights into the gaps between R&D of NPMCs for the OER and their applications in practical devices.

Xie, Xiaohong↗