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At least 91 records · Page 5

Use of a segmented cell for the combinatorial development of platinum group metal-free electrodes for polymer electrolyte fuel cells

The development of novel platinum group metal (PGM)-free catalysts is a difficult task, particularly when coupled with the integration into a cathode catalyst layer (CCL). The optimization of such PGM-free electrode structures is often non-linear and iterative, making it a demanding task due to the high number of parameters that affect performance. To accelerate both materials discovery and electrode development, this work demonstrates the application of a high-resolution segmented cell (SC) with 121 segments of 0.413 cm 2 size for combinatorial high-throughput PGM-free catalyst screening and CCL optimization. The approach utilizes three flow-field strips with active areas of 4.45 cm 2 each, distributed over 11 segments. Electrodes with identical catalyst material and fabrication method result in reproducible data with typically less than 10% variation between each segment and match in performance with differential single cell data. High throughput testing of combinatorial sample sets, with varied PGM-free electrocatalyst materials or electrode composition, demonstrated the ability to rapidly discern high performing outliers, and establish or confirm trends in electrode optimization. The results indicated significant performance benefits of electrodes with ionomer content of 45 wt% over lower values, and of water rich inks with 82% water content over those with 50%.

30 DIRECT ENERGY CONVERSION↗

Direct Comparison of the Activity and Selectivity of Rh 1 Cu and Ni 1 Cu Single-Atom Alloy Sites for Ethanol Decomposition

Ethanol is an important source of clean hydrogen, acetaldehyde, acetic acid, acetate esters, and light hydrocarbons. Controlling the divergent reaction pathways to these products requires understanding how different active sites influence the elementary steps involved. Herein, we present a combined surface science, theory, and nanoparticle catalysis study demonstrating how two single-atom dopants (Rh and Ni) in a Cu host can distinctively alter the selectivity of alcohol conversion. Specifically, our model studies reveal that ethanol reacts on Ni 1 Cu single-atom alloys to selectively produce acetaldehyde, whereas methane and CO are also formed on Rh 1 Cu single-atom alloys. Interestingly, these different reactivities are in contrast to the behavior of the pure metals as Ni(111) and Rh(111) surfaces favor methane/CO and surface carbon/CO, respectively. DFT calculations of reaction pathways and simulated product desorption based on microkinetic analyses explain these reactivity differences, demonstrating that C–C cleavage leading to methane formation has a lower barrier on Rh single-atom sites. To test the catalytic relevance of these fundamental results we synthesized and characterized supported Ni 1 Cu and Rh 1 Cu single-atom alloy nanoparticles with dopant:Cu ratios of 1:200. Flow reactor results revealed that both Ni and Rh increased ethanol conversion over Cu and that Ni 1 Cu catalysts were >99.9% selective to acetaldehyde, while Rh 1 Cu also produced 0.6%–2.6% of equimolar methane and CO between 433 and 493 K, demonstrating that C–C bond cleavage is enabled by isolated Rh sites. Furthermore, these catalytic results bridge the pressure and materials gaps, and together, this study provides insights into how different isolated dopant sites promote different catalytic pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design, fabrication and testing of a dual catalyst ammonia removal system for a urine VCD unit

A three-man capacity catalytic system for the recovery of water from urine was designed, constructed, and tested, it was designed to operate with feed streams containing high concentrations of urine vapor and only 5 to 7% of oxygen for the oxidation of ammonia and volatile organic vapor.It can operate either in a flow-through or a recycle mode and is capable of accepting the urine vapor produced by a vapor compression distillation evaporator. Testing consisted of short preliminary and optimization test, an endurance test of 74 hours continuous operation, and recycle tests using both air and oxygen. The system was designed for a urine processing rate of 0.86 liters/hr; however, it was tested at rates up to 1.2 liter/hr. Untreated urine evaporated by an electrically heated evaporator was used. The quality of the recovered water meets the U.S. Drinking Water Standards, with the exception of a low pH. Accumulation of solids in the urine sludge is reduced to approximately 65% of the anticipated value.

Budinikas, P.↗

Airborne Measurements of Nitric Oxide, Nitrogen Dioxide, Ozone, and Total Reactive Nitrogen During the NASA Global Tropospheric Experiment

Fabrication of the University of Michigan Multichannel Chemiluminescence Instrument (UMMCI) was completed in early 1996 and the instrument participated in test flights on the NASA P3B at Wallops Island prior to integration and deployment for the PEM- Tropics A Mission. The UMMCI consists of 4 channels for simultaneous measurements of ozone and NO with the option for measurements of NO2 and NOy (total reactive nitrogen) when converters are placed upstream of the NO channels. Each NO channel consists of a zeroing volume and reaction vessel, while the ozone channel consists of an ozone catalyst (or scrubber) trap that is not in line with the reaction vessel. The detectors in all for channels are Hamamatsu photomultiplier tubes, which are followed by pulse amplifier discriminators on the NO channels and an electrometer on the ozone channel. Schematics of the Detector Module and NOx/03 Probe Insert and Diagrams of the Control and Data System, the Power and Ground System, the Gas Flow System, and the Calibration System Flow are attached. Intercomparisons were conducted with G. Gregory, NASA/Langley, during the test flights (following prior calibration of the ozone generator/calibrators at the Wallops Long-Path Absorption facility). Initial test results appeared to be reasonable, and instrument characterization studies proceeded for the ozone channel and the 3 NO channels until deployment for integration for the PEM-Tropics Mission. Ozone data was obtained for Flights #4, and 6-2 1, and finalized data was submitted to the PEM-Tropics Data Archive and to the Science Team during the April 1997 Data Workshop. Although it initially appeared that the instrument sensitivity varied, subsequent tests showed that this was the fault of a leak in the ozone calibrator. In fact; the instrument sensitivity has not been observed to vary in a large number of tests over the years since the PEM-Tropics mission. We have, therefore, a very high degree of confidence in the O3 data that we submitted. NO data was obtained for all flights except the mission out of Christmas Island and the subsequent return to Hawaii, during which time the NO channels were contaminated with back-flushing pure NO from the O3 channel. The NO channels were found to suffer from a varying artifact (7 - 22 pptv) which made the instrument's results unreliable for the marine boundary layer portions of the missions (where conditions were extremely clean with NO typically < 2 pptv and O3 only 8 ppbv). Nonetheless, the NO values were an upper limit and were quite useful in identifying pollution layers and outflow from the Latin American Continent. NO data was submitted to the archive for all flights during which data was obtained. Ozone data from the P3B was among the results presented in several peer-reviewed publications. Notably, the ozone data supported the first published finding of evidence for the occurrence of aerosol nucleation in the marine boundary layer. As well, the ozone data was utilized in a treatment of the wavenumber spectra of winds, temperature and trace gases and to demonstrate the occurrence of layering as observed by the P3B during PEM-Tropics A . O3 and NO data were used in an assessment of the impact of southern hemispheric biomass burning, and in the role of NOx and O3 in HOx photochemistry during the PEM Tropics A mission. These data, along with other species measured during PEM-Tropics A, have also been employed in the generation of climatologies for tropospheric ozone and its precursors by the PI's research group.

Carroll, Mary Anne↗

A channel flow cell with double disk electrodes for oxygen electroreduction study at elevated temperatures and pressures: Theory

We report a new double-disk-electrode channel flow cell has been designed, constructed and tested. A theoretical treatment and implicit finite difference numerical simulations are presented, which permit the computation of the hydrodynamic behavior of this cell under steady state conditions, i.e., the diffusion limited current at the working electrode and the collection efficiency of the detector. The simulated results are consistent with those measured experimentally, indicating that our simulations appropriately describe the hydrodynamic behavior of this cell. The oxygen reduction reaction (ORR) on a carbon-supported nanoparticle Pt catalyst at both room temperature and 110 °C were preliminarily studied with this cell.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diesel Oxidation Catalyst Performance with Biodiesel Formulations

Biodiesel (i.e., mono-alkyl esters of long chain fatty acids derived from vegetable oils and animal fats) is a renewable diesel fuel providing life-cycle greenhouse gas emission reductions relative to petroleum-derived diesel. With the expectation that there would be widespread use of biodiesel as a substitute for ultra-low sulfur diesel (ULSD), there have been many studies looking into the effects of biodiesel on engine and aftertreatment, particularly its compatibility to the current aftertreatment technologies. The objective of this study was to generate experimental data to measure the effectiveness of a current technology diesel oxidation catalysts (DOC) to oxidize soy-based biodiesel at various blend levels with ULSD. Biodiesel blends from 0 to 100% were evaluated on an engine using a conventional DOC. In the steady-state performance test where fuel dosing rate was increased at fixed DOC inlet temperature, B20 performed similarly to ULSD at the lowest flow rate or exhaust temperature over 340 degrees C for medium and high flows. B50 blends performed nearly as well under most conditions. Higher blends exhibited reduced thermal efficiency and DOC outlet temperature with increasing dosing rate under most conditions and required exhaust temperatures over 400 degrees C to achieve or nearly achieve performance similar to ULSD. In the steady-state light of test where fuel dosing rate is fixed but exhaust temperature is increased incrementally, B20 generally performed similarly to ULSD at the highest inlet temperature, with only minor deficiencies at lower temperatures. Higher blends exhibited lower thermal efficiency and did not achieve as high DOC outlet temperatures. In the transient light-off test light-off temperature for ULSD was typically less than 225 degrees C, while for B100 it ranged from 290 degrees C to 330 degrees C. Based on the data set, it can be concluded that biodiesel fuels have a higher light-off temperature primarily because of their higher boiling points, with a minor secondary impact of their lower energy content.

ADVANCED PROPULSION SYSTEMS,BIOMASS FUELS↗

Packing Optimization of an Intentionally Stratified Sorbent Bed Containing Dissimilar Media Types

The Fire Cartridge is a packed bed air filter with two different and separate layers of media designed to provide respiratory protection from combustion products after a fire event on the International Space Station (ISS). The first layer of media is a carbon monoxide catalyst made from gold nanoparticles dispersed on iron oxide. The second layer of media is universal carbon, commonly used in commercial respirator filters. Each layer must be optimally packed to effectively remove contaminants from the air. Optimal packing is achieved by vibratory agitations. However, if post-packing movement of the media within the cartridge occurs, mixing of the bed layers, air voids, and channeling could cause preferential air flow and allow contaminants to pass. Several iterations of prototype fire cartridges were developed to reduce post-packing movement of the media within each layer (settling), and to prevent mixing of the two media types. Both types of movement of the media contribute to decreased fire cartridge performance. Each iteration of the fire cartridge design was tested to demonstrate mechanical loads required to cause detrimental movement within the bed, and resulting level of functionality of the media beds after movement was detected. In order to optimally pack each layer, vertical, horizontal, and orbital agitations were tested and a final packed bulk density was calculated for each method. Packed bulk density must be calculated for each lot of catalyst to accommodate variations in particle size, shape, and density. In addition, a physical divider sheet between each type of media was added within the fire cartridge design to further inhibit intermixing of the bed layers.

Kidd, Jessica↗

Development of an advanced Sabatier CO2 reduction subsystem

A preprototype Sabatier CO2 reduction subsystem was successfully designed, fabricated and tested. The lightweight, quick starting (less than 5 minutes) reactor utlizes a highly active and physically durable methanation catalyst composed of ruthenium on alumina. The use of this improved catalyst permits a simple, passively controlled reactor design with an average lean component H2/CO2 conversion efficiency of over 99% over a range of H2/CO2 molar ratios of 1.8 to 5 while operating with process flows equivalent to a crew size of up to five persons. The subsystem requires no heater operation after start-up even during simulated 55 minute lightside/39 minute darkside orbital operation.

Kleiner, G. N.↗

A recirculation system for concentrating CO 2 electrolyzer products

Electrochemical carbon dioxide reduction represents a promising path to utilize CO 2 as a feedstock for generating valuable products such as fuels and chemicals. Faradaic efficiencies near 100% have been achieved for certain CO 2 reduction products such as CO, but the electrolyzer outlet streams usually contain large fractions of unreacted CO 2 , dropping the product concentrations below 1% in many cases. The system disclosed here recycles the unreacted CO 2 together with the products and flows them back into the CO 2 reduction reactor, enabling much higher CO 2 conversion rates without dropping the gas flow rate. However, simple recirculation is shown to accumulate significant amounts of hydrogen, impeding effective CO 2 reduction. In this looped system, an electrochemical H 2 pump is placed in series with the CO 2 reactor, which effectively removes all the H 2 from the recycled gas stream, increasing the concentrations of carbon-containing products. Here, the system was initially tested with a CO-generating catalyst and CO concentrations above 70% were achieved in the recycled gas stream, compared to a maximum CO concentration of 8% in single-pass configuration. Results with a CO 2 reactor targeting ethylene as the main product show that ethylene concentrations of at least 10% can be achieved, which is roughly 20 times higher compared to a single-pass system.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Impact of Hydrogen on Methane and Pollutant Emissions over Three-Way Catalysts with Natural Gas–Hydrogen Blends

Blending natural gas (NG) with hydrogen (H₂) can improve combustion and engine performance while potentially facilitating the catalytic conversion of methane and other pollutants, resulting in cleaner tailpipe emissions. This study evaluates the impact of H2 on the conversion of methane, CO, and NOx emissions on a commercial three-way catalyst (TWC) in a flow reactor using synthetic gas mixtures that simulate stoichiometric engine exhausts with NG or NG+H₂ combustion. The work examines whether, and how, the additional amount of H₂ in the exhaust stream affects the conversion efficiency of methane and other pollutants. Experiments were conducted with both degreened and aged catalysts under controlled conditions, systematically varying temperature, the air-to-fuel equivalence ratio (λ), and λ modulation. Test conditions covered λ values from 0.996 to 1.000 to represent nominally stoichiometric engine operation with different λ modulation amplitudes, as well as a range of temperatures to inform control strategies for effective CH₄, CO, and NOₓ reduction. Overall, the results show that hydrogen addition significantly improves the conversion efficiency of CH₄ and NOₓ, particularly at temperatures below 500 °C. More significantly, this study highlights that exhaust gas composition, operating temperature, λ management, and the oxygen storage capacity of the TWC all play major roles in affecting the tailpipe emissions from NG and NG+H₂ combustion.

Prikhodko, Vitaly [ORNL] (ORCID:0000000244685836)↗

Catalytic hydrogenation of HMF to BHMF over copper catalysts

2,5-Bis(hydroxymethyl)furan (BHMF) is a bio-derived building block for polyester production, obtained via the hydrogenation of 5-hydroxymethylfurfural (HMF). First-principles thermodynamic equilibrium calculations indicate that this reaction is not thermodynamically limited under relevant conditions (e.g., 100 °C and high H 2 partial pressure). In this work, crude HMF was employed as the feedstock for BHMF synthesis. Initially, acidic impurities and humins were removed from unrefined HMF through filtration using a packed bed of γ-alumina. A comprehensive study of the filtration process is presented, including filtration kinetics, breakthrough curve analysis, and mathematical modeling. The purified HMF was subsequently hydrogenated over a 10 wt% CuZrO 2 catalyst, using ethanol as the reaction solvent. Batch reactions were first performed for collection of kinetic data to guide the transition to continuous flow operation. Kinetic data was collected in a fixed bed reactor at varying contact time, time on stream, temperature, and HMF concentration. This data was used to develop a kinetic model for HMF hydrogenation. Maximum BHMF production rates were achieved at 130 °C, accompanied by minor formation of byproducts from BHMF ring-opening reactions. The BHMF selectivity was 100 % at 100 °C although with lower reaction rates. Furthermore, catalyst stability tests revealed a loss of up to 50 % in catalytic activity within the first 24 h, likely due to the adsorption of HMF-derived oligomers that are not easily removed by filtration.

Crude HMF filtration↗

Experimental evaluation of catalytic combustion with heat removal at near stoichiometric conditions

Two concentric tube configurations were tested. Tests were conducted at an inlet pressure of 150,000 Pa, inlet fuel air mixture temperatures from 780 to 960 K, combustion air flow rates from 0.78 to 1.5 g/s, equivalence ratios up to 0.90, and a range of cooling air flow rates. Propane and propylene fuels were used. Both configurations used air flowing through the center tube for cooling and combustion in the annulus on the catalytic surface. One configuration had the catalyst applied to the outside surface of the inner tube. Conversion of the fuel was very low for this configuration. The other configuration had the catalyst applied to the inside surface of the outer tube. Conversion of the fuel was considerably better in this configuration.

Bulzan, D. L.↗

NASA Tech Briefs, May 2013

Topics include: Test Waveform Applications for JPL STRS Operating Environment; Pneumatic Proboscis Heat-Flow Probe; Method to Measure Total Noise Temperature of a Wireless Receiver During Operation; Cursor Control Device Test Battery; Functional Near-Infrared Spectroscopy Signals Measure Neuronal Activity in the Cortex; ESD Test Apparatus for Soldering Irons; FPGA-Based X-Ray Detection and Measurement for an X-Ray Polarimeter; Sequential Probability Ratio Test for Spacecraft Collision Avoidance Maneuver Decisions; Silicon/Carbon Nanotube Photocathode for Splitting Water; Advanced Materials and Fabrication Techniques for the Orion Attitude Control Motor; Flight Hardware Packaging Design for Stringent EMC Radiated Emission Requirements; RF Reference Switch for Spaceflight Radiometer Calibration; An Offload NIC for NASA, NLR, and Grid Computing; Multi-Scale CNT-Based Reinforcing Polymer Matrix Composites for Lightweight Structures; Ceramic Adhesive and Methods for On-Orbit Repair of Re-Entry Vehicles; Self-Healing Nanocomposites for Reusable Composite Cryotanks; Pt-Ni and Pt-Co Catalyst Synthesis Route for Fuel Cell Applications; Aerogel-Based Multilayer Insulation with Micrometeoroid Protection; Manufacturing of Nanocomposite Carbon Fibers and Composite Cylinders; Optimized Radiator Geometries for Hot Lunar Thermal Environments; A Mission Concept: Re-Entry Hopper-Aero-Space-Craft System on-Mars (REARM-Mars); New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications; Reliability of CCGA 1152 and CCGA 1272 Interconnect Packages for Extreme Thermal Environments; Using a Blender to Assess the Microbial Density of Encapsulated Organisms; Mixed Integer Programming and Heuristic Scheduling for Space Communication; Video Altimeter and Obstruction Detector for an Aircraft; Control Software for Piezo Stepping Actuators; Galactic Cosmic Ray Event-Based Risk Model (GERM) Code; Sasquatch Footprint Tool; and Multi-User Space Link Extension (SLE) System.

Source record↗

Development and Testing of a Methane/Oxygen Catalytic Microtube Ignition System for Rocket Propulsion

This study sought to develop a catalytic ignition advanced torch system with a unique catalyst microtube design that could serve as a low energy alternative or redundant system for the ignition of methane and oxygen rockets. Development and testing of iterations of hardware was carried out to create a system that could operate at altitude and produce a torch. A unique design was created that initiated ignition via the catalyst and then propagated into external staged ignition. This system was able to meet the goals of operating across a range of atmospheric and altitude conditions with power inputs on the order of 20 to 30 watts with chamber pressures and mass flow rates typical of comparable ignition systems for a 100 lbf engine.

Deans, Matthew↗

Development and Testing of a Methane/Oxygen Catalytic Microtube Ignition System for Rocket Propulsion

This study sought to develop a catalytic ignition advanced torch system with a unique catalyst microtube design that could serve as a low energy alternative or redundant system for the ignition of methane and oxygen rockets. Development and testing of iterations of hardware was carried out to create a system that could operate at altitude and produce a torch. A unique design was created that initiated ignition via the catalyst and then propagated into external staged ignition. This system was able to meet the goals of operating across a range of atmospheric and altitude conditions with power inputs on the order of 20 to 30 watts with chamber pressures and mass flow rates typical of comparable ignition systems for a 100 Ibf engine.

Deans, Matthew C.↗

Monolith catalysts for closed-cycle carbon dioxide lasers

The objective was to explore ways of making a monolithic form of catalyst for CO2 lasers. The approach chosen was to pelletize the catalyst material, Au/MnO2 powder, and epoxy the pellets to stainless steel sheets as structural supports. The CO oxidation reaction over Au/MnO2 powder was found to be first overall, and the reaction rate constant at room temperature was 4.4 +/- 0.3 cc/(g x sec). The activation energy was 5.7 kcal/mol. The BET surface area of the pellets was found to vary from 125 to 140 sq m/g between different batches of catalyst. Pellets epoxied to stainless steel strips showed no sign of fracture or dusting when subjected to thermal tests. Pellets can be dropped onto hard surfaces with chipping of edges but no breakage of the pellets. Mechanical strength tests performed on the pellets showed that the crush strength is roughly one-fourth of the pelletizing force. The apparent activity and activation energy over the pellets were found to be less than over the powdered form of the catalyst. The lower apparent activity and activation energy of the pellets are due to the fact that the internal surface area of a pellet is not exposed to the reactant concentration present in the flowing gas as a result of intrapellet diffusion resistance. Effectiveness factors varied from 0.44, for pellets having thickness of 2 mm and attached with epoxy to a stainless steel strip. The epoxy and the stainless steel strip were found to simply block off one of the circular faces of the pellets. The epoxy did not penetrate the pellets and block the active sites. The values of the effective diffusivities were estimated to be between 2.3 x 10(exp -3) and 4.9 x 10(exp -3) sq cm/s. With measurements performed on one powder sample and one pellet configuration, reasonable accurate predictions can be made of conversions that would be obtained with other pellet thickness and configurations.

Herz, Richard K.↗

Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

Valdez, Thomas I.↗

Facet‐Selective Deposition of Ultrathin Al 2 O 3 on Copper Nanocrystals for Highly Stable CO 2 Electroreduction to Ethylene

Abstract Catalysts based on Cu nanocrystals (NCs) for electrochemical CO 2 ‐to‐C 2+ conversion with high activity have been a subject of considerable interest, but poor stability and low selectivity for a single C 2+ product remain obstacles for realizing sustainable carbon‐neutral cycles. Here, we used the facet‐selective atomic layer deposition (FS‐ALD) technique to selectively cover the (111) surface of Cu NCs with ultrathin Al 2 O 3 to increase the exposed facet ratio of (100)/(111), resulting in a faradaic efficiency ratio of C 2 H 4 /CH 4 for overcoated Cu NCs 22 times higher than that for pure Cu NCs. Peak performance of the overcoated catalyst (Cu NCs/Al 2 O 3 ‐10C) reaches a C 2 H 4 faradaic efficiency of 60.4 % at a current density of 300 mA cm −2 in 5 M KOH electrolyte, when using a gas diffusion electrode flow cell. Moreover, the Al 2 O 3 overcoating effectively suppresses the dynamic mobility and the aggregation of Cu NCs, which explains the negligible activity loss and selectivity degradations of Cu NCs/Al 2 O 3 ‐10C shown in stability tests.

Li, Hui↗