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At least 1,513 records · Page 84

Direct regeneration of degraded LiFePO4 cathodes via a separator-enabled prelithiation strategy

A persistent challenge in lithium-ion batteries is the loss of active lithium due to the solid electrolyte interphase (SEI) formation and associated side reactions. While prelithiation employing lithium replenishment separator (LRS) has been proven effective in compensating for lithium loss, previous studies have largely been accompanied by gas evolution or solid residue formation during the prelithiation process. To surmount this challenge, we present a LRS based on 4-fluoro-1,2-dihydroxybenzene lithium salt (LiDF), capable of mitigating lithium loss while producing decomposition products that integrate directly into the electrolyte as functional additives which can assist with the stability of the SEI, free from gas or solid formation, thus establishing a sustainable and environmentally benign strategy for lithium compensation. Incorporation of the LRS enables the pristine LiFePO4||graphite (Gr) full cell to achieve 10.8% higher capacity than the cell with a polypropylene separator (PPS) after 200 cycles at 0.5C. Remarkably, the degraded LiFePO4 (D-LFP)||Gr full cell with the LRS exhibits a 135.8% capacity improvement over the PPS-based cell after 500 cycles. These findings establish the LRS as a powerful approach for both boosting high-performance lithium-ion batteries and recovering the capacity of degraded batteries.

Tao, Fujun↗

A Novel Zero-Discharge Supercritical Water-Based Wave Energy Desalination System

This paper presents a sustainable and innovative wave-energy-based water desalination system combined with an emerging supercritical water process for a zero-liquid-discharge technology. There is growing demand for producing clean water. Within desalination technologies, reverse osmosis, one of the most popular methods, uses a semipermeable membrane that separates fresh water from pressurized seawater. However, this technology produces brine, which is harmful to the environment. Supercritical water desalination is employed here as a means of using the brine to extract more fresh water and eliminate this environmentally toxic output. Wave energy is integrated with reverse osmosis to provide direct seawater pressurization for the first stage in the process. This wave energy converter converts the motion of waves into pressurized water through a power takeoff unit.

reverse osmosis↗

Impact of trivalent f-element complexation and chemical environment on the radiation-induced chemical reactivity of TODGA and HOPO ligands

Understanding the impact of ionizing radiation on ligands employed and proposed for the separation, recovery, and transport of actinide ions is of vital importance for the innovation of nuclear fuel cycle technologies. In the presence of ionizing radiation fields, complexing ligands are subject to radiolytic processes, that lead to their destruction and the formation of potentially detrimental degradation products. Consequently, mastery of the radiation-induced behavior of these ligands is essential for predicting and optimizing their effectiveness, longevity, and minimizing the negative impacts of radiolysis. Furthermore, this knowledge is critical for the design of more radiation resistant molecules to be incorporated into advanced separation technologies. That said, the radiation chemistry of most actinide complexants have only been studied in the absence of their targeted metal ion complexes, which can lead to inaccurate conclusions on their radiolytic robustness and impacts on performance. With this in mind, we present our findings on the impact of f-element complexation and chemical environment on the radiation-induced chemical reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) and the model octadentate hydroxypyridinone ligand 3,4,3-LI(1,2-HOPO) (abbreviated as HOPO), both promising candidates for actinide separations

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Carbon Capture from ArcelorMittal Hot Briquetted Iron Plant Using Air Liquide Cryocap™ FG Technology – FEED Study

The process of steel production is energy and carbon intensive with global average energy consumption of 5.5 MWh/tonne of steel and CO2 emission intensity of 1.83 tonne CO2/tonne of steel. The steel making process has inherent CO2 emissions from mineral conversion and is considered major contributors to the global carbon emissions. The steel industry is responsible for 8% of global carbon emissions. The main objective of this research project is to execute and complete a front-end engineering and design (FEED) study for a commercial-scale, carbon capture project that separates 95% of the total CO2 emissions at the ArcelorMittal’s Hot Briquetted Iron (HBI) plant in Portland, TX (Figure 1). The HBI is an ore-based metallic that is used as high-grade feedstock for high-quality steel via an Electric Arc Furnace (EAF) route. The HBI plant produces 2.0 million metric tonnes of high-quality HBI and emits approximately 1 million tonnes CO2/yr. The capture system is a Pressure Swing Adsorption (PSA) system assisted Cryocap™ FG technology (Figure 2). The captured CO2 will be pipeline grade and will be geologically stored in a facility within 10 miles of the CO2 source. The Host Site location in Corpus Christi, TX, is near hydrocarbon processing facilities and near Environmental Justice (EJ) and Qualified Opportunity Zone (QOZ) communities. Due to the location of the Host Site, the retrofit project offers the ability to demonstrate how a workforce focused on the fossil energy sector can be redirected to the clean- energy sector. The Air Liquide Cryocap™ capture technology is a proven technology and has been extensively examined for large industrial applications. It has been shown to be applicable to a variety of industrial applications including the steel industry. Cryocap™ FG (specific setup for Flue Gas application) consists of a Pressure Swing Adsorption (PSA) unit coupled with a Cryogenic System. The PSA pre-concentrates the CO2 from the flue gas, while the cryogenic unit enables the CO2 purity to be increased to the desired level. The scope of this study incorporates completing FEED study of the CO2 capture system which includes point-source CO2 capture and balance-of-plant; Business Case Analysis (BCA) outlining the current and projected volumes of the steel plant’s point sources of CO2 and the potential utilization of tax credits, including its projected revenue and duration; Life Cycle Analysis (LCA); Environmental Justice Analysis; Economic Revitalization and Job Creation Outcomes Analysis; and Workforce Readiness Plan. The plant design work was divided into two components: Inside Battery Limits (ISBL) and Outside Battery Limits (OSBL). The ISBL focuses on the capture system, while the OSBL focuses on the utility feeds and ducting from the plant to the capture system. Various design and engineering deliverables will be developed to define commodity quantities, equipment specifications, and labour effort required to execute the project. These FEED study deliverables will be prepared with the intent to develop an overall project capital cost estimate consistent with an AACE Class 3 estimate. The modular approach for the Cryocap™ FG that is being designed for this study integrates compression, PSA, and cryogenic “bricks” to achieve the desired CO2 capture rates. This carbon capture system integrates easily with the existing plant, thus reducing project costs and risks. It is also capable of managing impurities such as nitrogen oxides (NOx), sulfur oxides (SOx), mercury, hydrocarbons, and particulate matter. The capture system has a smaller footprint than amine-based systems. The two-step process uses PSA to preconcentrate the CO2 in the feedstream and then uses the cryogenic portion to purify and compress the resulting high purity CO2 product. This combination of purification and compression (i.e., process intensification) significantly reduces the CAPEX associated with use of a separate compressor commonly utilized for amine solvent-based systems. Successful completion of the FEED study will provide DOE with a detailed understanding of the costs for scaling up this proven capture technology for commercial applications at industrial facilities.

42 ENGINEERING↗

Use of Novel Diglycolamide Extractants in Liquid-liquid Separations of Light Rare Earths

Creation of a novel extractant that can improve rare earth separations both economically and environmentally will be pivotal for industry progression. Diglycolamide (DGA) extractants provide chemistries that support this goal by serving as an extractant with high affinity for lanthanides and improved separation factors for light rare earths as compared to current extractants like PC88A. Initial organic phase loading capacity and phase dispersion tests performed with various modified DGAs generated results that were unfavorable for industrial processing, but further modification of the DGA alkyl chain substituents have resulted in new structures with promising results. Dispersion time measurements taken in small scale batch contacts of the extractant with a simulated leach liquor containing La, Ce, Nd, and Pr support implementation in both mixer-settlers and centrifugal contactors for larger scale separations. Furthermore, this confirmation allowed for preliminary flowsheet design using extraction equilibria at various organic to aqueous flow ratios (O/A) for extraction, scrubbing, and stripping stages. These values along with expected product/effluent compositions for each section aid in the testing for specific distribution ratios and final flowsheet design. Implementation of the DGA extractant into solvent extraction equipment will provide essential information for the next steps of this project and how this extractant may be optimized for future applications.

42 ENGINEERING↗

A New Workflow of X-ray CT Image Processing and Data Analysis of Structural Features in Rock Using Open-Source Software

X-ray computed tomography (CT) images of rock specimens often contain artifacts which must be corrected before scientific analyses are performed. Here, we present a new workflow of automated image processing to utilize poor-quality X-ray CT scan images. The workflow runs on the open-source image analysis software and efficiently separates desired features from low-contrast scanned images. The new workflow is a two-step technique using contrast enhancement and automated feature segmentation to generate noise-free binary images. The results of binary images using the proposed workflow and using a conventional thresholding technique are analyzed to show the quality of the proposed method. The paper also presents a workflow of estimating the structural geometries of features in two and three dimensions. The results of the structural feature analyses and computational time were compared between the open-source (ImageJ) and commercial image analysis software (Bruker Computed Tomography Analyzer). The commercial software was more computationally efficient, but the task-specific macros in open-source software enabled the user-desired automation in image processing and data extraction of desired structural features of comparable quality.

47 OTHER INSTRUMENTATION↗

Oxides and Nitrides with Asymmetric Pore Structure from Block Copolymer Co–Assembly and Non–Solvent Induced Phase Separation

Materials combining an asymmetric pore structure with mesopores everywhere enable high surface area accessibility and fast transport, making them attractive for e.g., energy conversion and storage applications. Block copolymer (BCP)/inorganic precursor co-assembly combined with non-solvent induced phase separation (NIPS) provides a route to materials in which a mesoporous top surface layer merges into an asymmetric support with graded porosity along the film normal and mesopores throughout. Here, the co-assembly and non-solvent-induced phase separation (CNIPS) of poly(isoprene)-b-poly(styrene)-b-poly(4-vinylpyridine) (ISV) triblock terpolymer and titanium dioxide (TiO 2 ) sol-gel nanoparticlesare reported. Heat-treatment in air results in free-standing asymmetric porous TiO 2 . Further thermal processing in ammonia results in free-standing asymmetric porous titanium nitride (TiN). processing changes alter structural membrane characteristics is demonstrated. Changing the CNIPS evaporation time results in various membrane cross-sections ( finger-like to sponge-like). Further, oxide and nitride material composition, crystallinity, and porosity are tuned by varying thermal processing conditions. Finally, thermal processing condition effects are probed on phase-pure asymmetric nitride membrane behavior using cyclic voltammetry to elucidate their influence, e.g., on specific capacitance. Results provide further insights into improving asymmetric and porous materials for applications including energy conversion and storage, separation, and catalysis and motivate a further expansion of CNIPS to other (in)organic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Molecular Conformation on Intermolecular Interactions and Photovoltaic Performances of Giant Molecule Acceptors

The molecular conformation of giant molecule acceptors (GMAs) plays a significant role in regulating the intermolecular interactions and their photovoltaic performances in organic solar cells (OSCs). For the linear GMA GT‐l, the stronger homo‐molecular interaction causes its aggregation being weakly affected by the donor, thus forming an ordered molecular stacking and proper phase separation in its blend film. The star‐shaped GMA GT‐s‐based blend film shows a dominant hetero‐molecular interaction that suppresses the aggregation of the donor and acceptor, resulting in smaller phase separation and more uniform vertical phase distribution. While for another star‐shaped GMA GTs, the weakest hetero‐molecular interaction causes its blend film to form larger phase separation. Therefore, the GT‐l based OSC with PM6 as donor shows the highest charge mobilities, the fastest charge transfer (CT) process, reduced energy loss and less charge recombination, contributing to a higher power conversion efficiency (PCE) of 19.03%. Comparatively, the PCEs of the OSCs based on GTs and GT‐s are 18.05% and 17.58% respectively. Notably, all the three GMAs based OSCs show excellent thermal stability and long‐term storage stability. This study provides a facile strategy by tuning the linking unit and its connecting mode for designing highly efficient and stable organic photovoltaic materials.

Chemistry↗

Increased Static Charge–Induced Threshold Voltage Shifts and Memristor Activity in Pentacene OFETs Comprising Polystyrene–Based Gate Dielectrics Containing Electroactive Small Molecule Crystallites

Top-contact bottom-gate pentacene OFETs are fabricated with single layer dielectrics comprised of either polystyrene (PS), poly(4-methylstyrene) (P4MS), or poly(4-tert-butylstyrene) (P4TBS). The polystyrenes are blended with varying concentrations of two different small molecules, dibenzotetrathiafulvalene (DBTTF) and 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TES-ADT), to form small, separated crystallites contained throughout the polymer dielectric layer. The OFET characteristics of these devices are investigated and their threshold voltage shifts are measured after –70 V static charging for 5 min. Two-terminal measurements are conducted using multiple different gate biases in the range of –50 to +50 V to investigate memristor behavior in the devices. OFETs containing DBTTF exhibited ΔVth increases as large as 330% relative to control OFETs containing no DBTTF, while OFETs containing at least 7.5 wt.% DBTTF exhibited memristor activity, with currents ranging from 20 nA to 44 µA depending on the applied bias. Furthermore, this work demonstrates that including small, separated crystallites in polymer dielectrics enhances their charge storage ability and can be promising for creating nonbinary memory devices for data processing. Additionally, the observed memristor activity indicates the OFETs in this work can be used in development of neuromorphic systems that aim to mimic the synaptic behavior of the human nervous system.

25 ENERGY STORAGE↗

Binary Blend All‐Polymer Solar Cells with a Record Efficiency of 17.41% Enabled by Programmed Fluorination Both on Donor and Acceptor Blocks

Abstract Despite remarkable breakthrough made by virtue of “polymerized small‐molecule acceptor (PSMA)” strategy recently, the limited selection pool of high‐performance polymer acceptors and long‐standing challenge in morphology control impede their further developments. Herein, three PSMAs of PYDT‐2F, PYDT‐3F, and PYDT‐4F are developed by introducing different fluorine atoms on the end groups and/or bithiophene spacers to fine‐tune their optoelectronic properties for high‐performance PSMAs. The PSMAs exhibit narrow bandgap and energy levels that match well with PM6 donor. The fluorination promotes the crystallization of the polymer chain for enhanced electron mobility, which is further improved by following n ‐doping with benzyl viologen additive. Moreover, the miscibility is also improved by introducing more fluorine atoms, which promotes the intermixing with PM6 donor. Among them, PYDT‐3F exhibits well‐balanced high crystallinity and miscibility with PM6 donor; thus, the layer‐by‐layer processed PM6/PYDT‐3F film obtains an optimal nanofibril morphology with submicron length and ≈23 nm width of fibrils, facilitating the charge separation and transport. The resulting PM6/PYDT‐3F devices realizes a record high power conversion efficiency (PCE) of 17.41% and fill factor of 77.01%, higher than the PM6/PYDT‐2F (PCE = 16.25%) and PM6/PYDT‐4F (PCE = 16.77%) devices.

Zhou, Dehong↗

Parallel projection—An improved return mapping algorithm for finite element modeling of shape memory alloys

Here, we present a novel finite element analysis of inelastic structures containing Shape Memory Alloys (SMAs). Phenomenological constitutive models for SMAs lead to material nonlinearities, that require substantial computational effort to resolve. Finite element analysis methods, which rely on Gauss quadrature integration schemes, must solve two sets of coupled differential equations: one at the global level and the other at the local, i.e. Gauss point level. In contrast to the conventional return mapping algorithm, which solves these two sets of coupled differential equations separately using a nested Newton procedure, we propose a scheme to solve the local and global differential equations simultaneously. In the process we also derive closed-form expressions used to update the internal/constitutive state variables, and unify the popular closest-point and cutting plane methods with our formulas. Numerical testing indicates that our method allows for larger thermomechanical loading steps and provides increased computational efficiency, over the standard return mapping algorithm.

42 ENGINEERING↗

Catalyzed oxidation of IG-110 nuclear graphite by simulated fission products Ag and Pd nanoparticles

To evaluate the stability of nuclear materials in high temperature gas reactors under air ingress conditions, catalytic oxidation of IG-110 graphite by two simulated fission products, metallic Pd and Ag, was studied in oxidative atmosphere and at temperatures up to 1000°C using an integrated furnace, mass spectroscopy and infrared spectroscopy system. Transmission electron microscopy and X-ray diffraction studies show that Pd and Ag nanoparticles were successfully introduced onto powdery IG-110 graphite through an impregnation and subsequent heat-treatment process. The combined mass spectroscopy and infrared spectroscopy methods allow simultaneous analysis of two gaseous products, CO and CO 2 , and separate measurements of activation energy for their formation reactions. It was found that the introduction of Pd or Ag to IG-110 graphite substantially catalyzed the oxidation of graphite, characteristic of decreased onset temperatures for the oxidation of graphite. Moreover, the catalytic effects by Pd and Ag are considerably different based on measured concentration ratios of CO 2 to CO as a function of oxidation temperatures. Ag makes the graphite oxidation commence at approximately 400°C with CO 2 being the dominant product. In contrast, Pd significantly increases the concentration ratio of CO 2 to CO at temperatures higher than approximately 690°C, although it decreases the onset temperature for the oxidation reaction to around 525°C. To understand the catalytic difference, the mechanism of the graphite oxidation was discussed based on the changes of surface oxygen species on Ag and Pd.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Flexible cryogenic air separation unit—An application for low-carbon fossil-fuel plants

In this study, the rapid integration of intermittent renewable sources into the electricity grid is driving the need for a flexible cryogenic air separation unit (ASU) coupled with a low-carbon fossil-fuel plant. However, the state-of-the-art ASU process is highly integrated and nonlinear, which can significantly restrict its ramping rate. In this work, we study the fundamental dynamics of a state-of-the-art double-column ASU, focusing on the dynamic characteristics of the highly integrated and nonlinear heat and mass transfers, and we propose basic control methods for achieving high process ramping rates. We found that the vapor–liquid countercurrent flows in the low-pressure column are critical to the cryogenic rectification of air, which governs the ramp rate of the ASU. This countercurrent flow structure is created through a complex heat integration process in the ASU. Here, this process is simplified as a countercurrent heat transfer to reduce the complexity of studying the ASU dynamics. To preserve this flow structure, the heat integration is maintained so that its heat duty follows the ASU load, using several basic controllers on the critical stream flowrates. A flow-driven dynamic ASU model is built in Aspen Plus Dynamics to capture the basic ramping dynamics. This model revealed a fundamental mismatch in the dynamics in the ASU column that causes a significant loss of O 2 product purity when ramping down the ASU and slightly increases the purity when ramping up. Based on these findings, we propose a basic control method for rapidly ramping down/up the ASU while maintaining O 2 product purity. Simulation results show the ASU basic dynamic process successfully ramps at a rate up to 10 %/min (40–100 % load) while maintaining the O 2 product purity at 95.2–95.6 mol%.

42 ENGINEERING↗

Understanding the Adsorption of Rare-Earth Elements in Oligo-Grafted Mesoporous Carbon

Rare-earth elements (REEs) are 17 elements of the periodic table primarily consisting of lanthanides. In modern society, the usage of REEs is ubiquitous in almost all modern gadgets and therefore efficient recovery and separation of REEs are of high importance. Selective adsorption and chelation of REEs in solid sorbents is a unique and sustainable process for their recovery. In this work, single-stranded oligos with 100 units of thymine were grafted onto carboxylated mesoporous carbon to synthesize a sorbent with phosphorus and oxygen functionalities. Additionally, the sorbent was characterized by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and scanning electron microscopy-energy-dispersive X-ray spectroscopy. Three different REEs with varying atomic radii and densities, Lu, Dy, and La, were adsorbed onto the carbon from aqueous solutions. It was observed that the adsorbed amounts increased with the increase in the atomic radius or decrease in the atomic density. Calculation of the distribution coefficients for all the equilibrium adsorption amounts suggested that adsorption is more effective in the lower concentration region. The L 3 -edge X-ray absorption near-edge structure confirmed a 3+ oxidation state of REEs in the adsorbed phase. Extended X-ray absorption fine structure (EXAFS) confirmed the binding of REEs with oxygen functionalities in the adsorbed phase. The radial distribution functions calculated from the EXAFS data suggest a longer RE–O distance for La compared to those for Lu and Dy. The coordination numbers and Debye–Waller factors have typical values of about 8–9 atoms and 0.01–0.02 Å 2 , respectively.

36 MATERIALS SCIENCE↗

Cross-Linker Selection Controls Glass Transition Elevation or Reduction in Dynamic Covalently Bonded Polymer Networks

Introducing cross-links is a powerful approach to improve polymeric material performance relevant to controlling viscoelasticity, thermal and creep resistance, degradability, and efficient membrane separations. The chemically specific glass transition temperature T g is of fundamental importance in determining the time scales of key dynamical processes and physical state of the material in such applications. Here, we study experimentally how the introduction of relatively large cross-linking molecules in slowly exchanging dynamic bond-forming polymers (vitrimers) impacts vitrification for diverse polymer chemistries and a wide range of cross-link fractions. We find T g can increase, decrease, or even remain essentially unchanged, in qualitative contrast to the generic elevation of T g in traditional permanent polymer networks. We formulate an effective terpolymer network model to understand this rich behavior, which emerges as a consequence of a competition between pure cross-linking and generalized plasticization effects. The latter is associated with the tunable cross-linker size and intrinsic dynamic mobility that can offset slowing down due to traditional permanent cross-linking constraints. Here, a new strategy for functional polymer network design is suggested based on adjusting the relative importance of the two competing physical effects, which potentially can significantly enhance energy savings in applications while retaining other intrinsic properties germane to advanced materials performance.

Copolymers↗

Bayesian Inference for Integrating Yarrowia lipolytica Multiomics Datasets with Metabolic Modeling

Optimizing the metabolism of microbial cell factories for yields and titers is a critical step for economically viable production of bioproducts and biofuels. In this process, tuning the expression of individual enzymes to obtain the desired pathway flux is a challenging step, in which data from separate multiomics techniques must be integrated with existing biological knowledge to determine where changes should be made. Following a design-build-test-learn strategy, building on recent advances in Bayesian metabolic control analysis, we identify in this work key enzymes in the oleaginous yeast Yarrowia lipolytica that correlate with the production of itaconate by integrating a metabolic model with multiomics measurements. To this extent, we quantify the uncertainty for a variety of key parameters, known as flux control coefficients (FCCs), needed to improve the bioproduction of target metabolites and statistically obtain key correlations between the measured enzymes and boundary flux. Based on the top five significant FCCs and five correlated enzymes, our results show phosphoglycerate mutase, acetyl-CoA synthetase (ACSm), carbonic anhydrase (HCO3E), pyrophosphatase (PPAm), and homoserine dehydrogenase (HSDxi) enzymes in rate-limiting reactions that can lead to increased itaconic acid production.

59 BASIC BIOLOGICAL SCIENCES↗

Anodized Aluminum Oxide Membrane Ionic Memristors

Memory effect in ion transport (IT) at the solid–solution interface is uniquely attractive in that the conductance depends on or “memorizes” the previous states. Hysteretic and rectified transport properties offer exciting potential to developing advanced iontronics and neuromorphic functions, improving the efficiency of energy conversion and electrochemical processes, and overcoming the selectivity-throughput bottleneck in the enrichment of low abundant species for environment- and energy-friendly separations, among others. Herein, memory effects are discovered in the rectified electrokinetic IT through anodized aluminum oxide (AAO) membranes containing densely packed highly ordered nanochannels (10 10 per cm 2 ). Characteristic memristor responses of pinched current–potential loops are resolved in voltammetric experiments and successfully reproduced through finite element simulation. Excitatory and inhibitory conductance states are shown to arise from the enrichment and depletion of mobile charge carriers. Structurewise, the transport symmetry is broken by the barrier oxide layer (BOL) on the one end of the cylindrical nanochannels across the AAO membranes. Charge selectivity is attributed to the gradient(s) of the space charge density across the BOL characterized by depth profiling via X-ray photoelectron spectroscopy analysis. The space charge gradient(s) overcomes the fundamental limitation of widely exploited surface charge effects to enable intense rectification and hysteresis prevailing at very high ionic concentrations up to 1–2 M. A new strategy is developed for controlling the preferential IT direction and selectivity via counterion intercalation and extraction/exchange. Mechanistic understanding is further confirmed through parameter variations such as potential scan rate and ionic strength, which also demonstrates convenient controls of the related functions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗