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Li, Hong

Publications and source records attributed to Li, Hong.

At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Rational design of stable sulfur vacancies in molybdenum disulfide for hydrogen evolution

Sulfur (S) vacancies in MoS 2 have been found to act as a new active center, which shows an unprecedented intrinsic HER activity under elastic strain. However, such S-vacancies are unstable and the activities are very sensitive to the vacancy concentration. A strategy to stabilize these abundant active sites is thus highly desirable. Herein, we rationally design a catalyst system to stabilize S-vacancies in the basal plane of $2H-$MoS 2 supported on defective vertical graphene network (VGN). The energetically favorable line-shaped S-vacancies in MoS 2 shows a consistently high HER activity that is insensitive to S-vacancy concentration. Moreover, the defective graphene support effectively stabilizes these S-vacancies. The optimized catalyst exhibits a superior HER activity with overpotential of 128 mV at 10 mA cm -2 and Tafel slope of 50 mV dec -1 . Most importantly, the catalyst shows greatly increased stability over 500 h; benchmarking the most stable nonprecious HER catalyst in acidic media to date.

2D heterostructure↗
DOE OSTI2019

Correlated Migration Invokes Higher Na + ‐Ion Conductivity in NaSICON‐Type Solid Electrolytes

Abstract Na super ion conductor (NaSICON), Na 1+ n Zr 2 Si n P 3– n O 12 is considered one of the most promising solid electrolytes; however, the underlying mechanism governing ion transport is still not fully understood. Here, the existence of a previously unreported Na5 site in monoclinic Na 3 Zr 2 Si 2 PO 12 is unveiled. It is revealed that Na + ‐ions tend to migrate in a correlated mechanism, as suggested by a much lower energy barrier compared to the single‐ion migration barrier. Furthermore, computational work uncovers the origin of the improved conductivity in the NaSICON structure, that is, the enhanced correlated migration induced by increasing the Na + ‐ion concentration. Systematic impedance studies on doped NaSICON materials bolster this finding. Significant improvements in both the bulk and total ion conductivity (e.g., σ bulk = 4.0 mS cm −1 , σ total = 2.4 mS cm −1 at 25 °C) are achieved by increasing the Na content from 3.0 to 3.30–3.55 mol formula unit −1 . These improvements stem from the enhanced correlated migration invoked by the increased Coulombic repulsions when more Na + ‐ions populate the structure rather than solely from the increased mobile ion carrier concentration. The studies also verify a strategy to enhance ion conductivity, namely, pushing the cations into high energy sites to therefore lower the energy barrier for cation migration.

Zhang, Zhizhen↗
DOE OSTI2019

Pathway Complexity in the Stacking of Imine-Linked Macrocycles Related to Two-Dimensional Covalent Organic Frameworks

Interlayer interactions play an important role in the formation of two-dimensional covalent organic frameworks (2D COFs), yet the effects of monomer structure on COF formation, crystallinity, and susceptibility to exfoliation are not well understood. Here we probe these effects by studying the stacking behavior of imine-linked macrocycles that represent discrete models of 2D COFs. Specifically, macrocycles based on terephthaldehyde (PDA) or 2,5-dimethoxyterephthaldehyde (DMPDA) stack upon cooling molecularly dissolved solutions. Both macrocycles assemble cooperatively with similar Delta H-e values of -97 kJ/mol and -101 kJ/mol, respectively, although the DMPDA macrocycle assembly process showed a more straightforward temperature dependence. Density functional theory calculations of the stacking of PDA macrocycles suggested two stable configurations that were close in energy. Circular dichroism spectroscopy performed on macrocycles bearing chiral side chains revealed a helix reversion process for the PDA macrocycles that was not observed for the DMPDA macrocycles. Given the structural similarity of these monomers, these findings demonstrate that the stacking processes associated with nanotubes derived from these macrocycles, as well as for the corresponding COFs, are complex and susceptible to kinetic traps, casting doubt on the relevance of thermodynamic arguments for improving materials quality. Rather, a deeper understanding of the mechanism of supramolecular polymerization and its interplay with polymerization and error correction during COF synthesis is needed for improved control of the crystallinity and morphology of these emerging materials.

Wang, Shiwei↗
DOE OSTI2019

Trace doping of multiple elements enables stable battery cycling of LiCoO 2 at 4.6 V

LiCoO 2 is a dominant cathode material for lithium-ion (Li-ion) batteries due to its high volumetric energy density, which could potentially be further improved by charging to high voltages. However, practical adoption of high-voltage charging is hindered by LiCoO 2 ’s structural instability at the deeply delithiated state and the associated safety concerns. Here, we achieve stable cycling of LiCoO 2 at 4.6 V (versus Li/Li+) through trace Ti–Mg–Al co-doping. Using state-of-the-art synchrotron X-ray imaging and spectroscopic techniques, we report the incorporation of Mg and Al into the LiCoO 2 lattice, which inhibits the undesired phase transition at voltages above 4.5 V. We also show that, even in trace amounts, Ti segregates significantly at grain boundaries and on the surface, modifying the microstructure of the particles while stabilizing the surface oxygen at high voltages. These dopants contribute through different mechanisms and synergistically promote the cycle stability of LiCoO 2 at 4.6 V.

25 ENERGY STORAGE↗
DOE OSTI2019

Equilibrium, Kinetic and Thermodynamic Studies on Methylene Blue Adsorption by Konjac Glucomannan/Activated Carbon Aerogel

Activated carbon (AC) is a common adsorbent used for the purification of aqueous solutions, yet its poor aqueous dispersion may negatively affects its practicability significantly. In the present study, the fabrication of an AC aerogel immobilized with konjac glucomannan (KGM/AC) for environmental protection was reported, and the parameters (e.g. AC content in aerogel, solution pH, adsorption duration, adsorption temperature and adsorbent dosage) were analyzed systematically using methylene blue (MB) as a model adsorbate. Further, to explore the adsorption equilibrium isotherm at equilibrium, the adsorption data were respectively fitted to Langmuir and Freundlich models, while kinetics study was conducted to explain the adsorption mechanism and predict the adsorption efficiency. Besides, the effect of temperature on the adsorption behavior was assessed using Van’t Hoff equation. According to the experimental and calculative results, the adsorption data at equilibrium could be well geared into the Langmuir model, and the adsorption kinetics behavior was better consistent with the pseudo-second-order expression as well as the intra-particle diffusion model. The Brunauer, Emmett and Teller surface area of KGM/AC aerogel was 352.44 m{sup 2}/g. KGM/AC aerogel exhibited the maximal capacity of adsorption of 416.67 mg/g at 323 K, and its adsorption behavior toward MB was endothermic and spontaneous in nature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Exploring reaction dynamics in lithium–sulfur batteries by time-resolved operando sulfur K-edge X-ray absorption spectroscopy

A time-resolved operando X-ray absorption spectroscopy experiment was successfully designed to explore the sulfur reaction dynamics in lithium–sulfur (Li–S) batteries. It presents direct real-time experimental evidence for the distinct sulfur dynamics at different discharge rates, deepening the understanding of reaction mechanisms in Li–S batteries.

25 ENERGY STORAGE↗
DOE OSTI2019

Stabilizing the Oxygen Lattice and Reversible Oxygen Redox Chemistry through Structural Dimensionality in Lithium-Rich Cathode Oxides

Lattice-oxygen redox (l-OR) has become an essential companion to the traditional transition-metal (TM) redox charge compensation to achieve high capacity in Li-rich cathode oxides. However, the understanding of l-OR chemistry remains elusive, and a critical question is the structural effect on the stability of l-OR reactions. As such, the coupling between l-OR and structure dimensionality is studied herein. We reveal that the evolution of the oxygen-lattice structure upon l-OR in Li-rich TM oxides which have a three-dimensional (3D)-disordered cation framework is relatively stable, which is in direct contrast to the clearly distorted oxygen-lattice framework in Li-rich oxides which have a two-dimensional (2D)/3D-ordered cation structure. Our results highlight the role of structure dimensionality in stabilizing the oxygen lattice in reversible l-OR, which broadens the horizon for designing high-energy-density Li-rich cathode oxides with stable l-OR chemistry.

25 ENERGY STORAGE↗
DOE OSTI2019

Enhancing Electrocatalytic Water Splitting by Strain Engineering

Electrochemical water splitting driven by sustainable energy such as solar, wind, and tide is attracting ever-increasing attention for sustainable production of clean hydrogen fuel from water. Leveraging these advances requires efficient and earth-abundant electrocatalysts to accelerate the kinetically sluggish hydrogen and oxygen evolution reactions (HER and OER). A large number of advanced water-splitting electrocatalysts have been developed through recent understanding of the electrochemical nature and engineering approaches. Specifically, strain engineering offers a novel route to promote the electrocatalytic HER/OER performances for efficient water splitting. Herein, the recent theoretical and experimental progress on applying strain to enhance heterogeneous electrocatalysts for both HER and OER are reviewed and future opportunities are discussed. A brief introduction of the fundamentals of water-splitting reactions, and the rationalization for utilizing mechanical strain to tune an electrocatalyst is given, followed by a discussion of the recent advances on strain-promoted HER and OER, with special emphasis given to combined theoretical and experimental approaches for determining the optimal straining effect for water electrolysis, along with experimental approaches for creating and characterizing strain in nanocatalysts, particularly emerging 2D nanomaterials. Finally, a vision for a future sustainable hydrogen fuel community based on strain-promoted water electrolysis is proposed.

42 ENGINEERING↗
DOE OSTI2019

Electrochemically activated spinel manganese oxide for rechargeable aqueous aluminum battery

Aluminum is a naturally abundant, trivalent charge carrier with high theoretical specific capacity and volumetric energy density, rendering aluminum-ion batteries a technology of choice for future large-scale energy storage. Nonetheless, the frequent collapse of the host structure of the cathode materials and sluggish kinetics of aluminum ion diffusion have thus far hampered the realization of practical battery devices. Here, we synthesize Al x MnO 2 •nH 2 O by an in-situ electrochemical transformation reaction to be used as a cathode material for an aluminum-ion battery with a configuration of Al/Al(OTF) 3- H 2 O/Al x MnO 2 •nH 2 O. This cell is not only based on aqueous electrolyte chemistry but also delivers a high specific capacity of 467 mAh g -1 and a record high energy density of 481 Wh kg -1 . The high safety of aqueous electrolyte, facile cell assembly and the low cost of materials suggest that this aqueous aluminum-ion battery holds promise for large-scale energy applications.

25 ENERGY STORAGE↗
DOE OSTI2018

SmpB down-regulates proton-motive force for the persister tolerance to aminoglycosides in Aeromonas veronii

Highlights: • The smpB deletion exhibited a higher susceptibility to aminoglycosides in A. veronii. • The expression level of SmpB was enhanced by gentamicin challenge. • The effect of SmpB on persistence formation was eliminated by PMF inhibition. • The smpB deletion downregulated proton-motive force-related metabolic genes. Bacterial persisters comprise a small fraction of phenotypically heterogeneous variants with transient capability for survival when exposed to high concentrations of antibiotic. In aquatic pathogenic bacteria Aeromonas veronii, Small Protein B (SmpB), the core factor of trans-translation system, was identified as a new persistence-related gene. The SmpB deletion exhibited a higher susceptibility and lower persister cell formation under aminoglycosides antibiotics pressure compared with wild type. The transcriptional and translational activities of smpB gene were significantly enhanced by the gentamicin challenge in exponential phase, but not changed in stationary phase. The transcriptomic analysis revealed that the smpB deletion stimulated the production of proton-motive force (PMF). The cell survival induced by carbonyl cyanide m-chlorophenyl hydrazone (CCCP) further verified that SmpB variation affected the quantities of PMF. Taken together, these results uncovered a novel mechanism of persister formation mediated by SmpB under aminoglycosides treatments.

60 APPLIED LIFE SCIENCES↗