However, the shuttle effect triggered by the dissolution of long-chain polysulfides (Li 2 S x , 4 ≤ x ≤ 8) results in severe active sulfur loss and fast capacity decay, which severely hinders the commercial application of these batteries. [4,6] Fundamentally, these problems are a result of the slow and complex sulfur reduction reaction (SRR), i.e., the sluggish kinetic transformation of soluble lithium polysulfides (LiPSs) to insoluble Li 2 S 2 /Li 2 S (discharge products). [7,8] Therefore, exploring effective strategies to accelerate the conversion of LiPSs from the liquid to the solid state is essential to boost the practical energy density and lifespan of lithium-sulfur batteries. [9,10] Considerable efforts have been devoted to addressing the aforementioned problems, typically by using sulfides, nitrides, phosphides as host materials to trap the LiPSs in the sulfur cathode. [11][12][13][14] However, these physical or electrostatic confinement/trapping methods fail to entirely avoid the dissolution and accumulation of LiPSs in the electrolyte. [8] A catalytic approach has therefore been proposed as a more proactive solution to cure the shuttle effect by accelerating the conversion of the liquid-phase long-chain LiPSs into final solid-phase discharge products. [15,16] Like the oxygen Seeking an electrochemical catalyst to accelerate the liquid-to-solid conversion of soluble lithium polysulfides to insoluble products is crucial to inhibit the shuttle effect in lithium-sulfur (Li-S) batteries and thus increase their practical energy density. Mn-based mullite (SmMn 2 O 5 ) is used as a model catalyst for the sulfur redox reaction to show how the design rules involving lattice matching and 3d-orbital selection improve catalyst performance. Theoretical simulation shows that the positions of Mn and O active sites on the (001) surface are a good match with those of Li and S atoms in polysulfides, resulting in their tight anchoring to each other. Fundamentally, dz 2 and dx 2 −y 2 around the Fermi level are found to be crucial for strongly coupling with the p-orbitals of the polysulfides and thus decreasing the redox overpotential. Following the theoretical calculation, SmMn 2 O 5 catalyst is synthesized and used as an interlayer in a Li-S battery. The resulted battery has a high cycling stability over 1500 cycles at 0.5 C and more promisingly a high areal capacity of 7.5 mAh cm −2 is achieved with a sulfur loading of ≈5.6 mg cm −2 under the condition of a low electrolyte/sulfur (E/S) value ≈4.6 µL mg −1 .
A super-low-temperature ozone decomposition is realized without energy consumption on a ternary oxide catalyst mullite YMn2O5 for the first time. The YMn2O5 oxide catalyzed ozone decomposition from a low temperature of −40 °C with 29% conversion (reaction rate: 1534.2 μmol g–1 h–1) and quickly reached 100% (5459.5 μmol g–1 h–1) when warmed up to −5 °C. The superior low-temperature performance over YMn2O5 could surpass that of the reported ozone decomposition catalysts. The structure and element valence characterizations confirmed that YMn2O5 remained the same after 100 h of room-temperature reaction, indicating excellent durability of the catalyst. O2-TPD (O2-temperature-programmed desorption) showed that the active sites are the Mn3+ sites bonded with singly coordinated oxygen on the surface. Combined with in situ Raman measurements and density functional theory calculations, we found that the ozone decomposition reaction on YMn2O5 showed a barrier of only 0.29 eV, following the Eley–Rideal (E–R) mechanism with a rate-limiting step of intermediate O2 2– desorption. The low barrier minimizes the accumulation of intermediate products and realizes the fast O3 decomposition even at super-low temperatures. Fundamentally, the moderate Mn–O bonding strength in the low-symmetry ternary oxides is crucial to produce singly coordinated active species on the surface responsible for the efficient ozone degradation at low temperatures.
Developing fast‐charging Zn–air batteries is crucial for widening their application but remains challenging owing to the limitation of sluggish oxygen evolution reaction (OER) kinetics and insufficient active sites of electrocatalysts. To solve this issue, a reconstructed amorphous FeCoNiSx electrocatalyst with high density of efficient active sites, yielding low OER overpotentials of 202, 255, and 323 mV at 10, 100, and 500 mA cm−2, respectively, is developed for fast‐charging Zn–air batteries with low charging voltages at 100–400 mA cm−2. Furthermore, the fabricated 3241.8 mAh (20 mA cm−2, 25 °C) quasi‐solid Zn–air battery shows long lifetime of 500 h at −10 and 25 °C as well as 150 h at 40 °C under charging 100 mA cm−2. The detailed characterizations combine with density functional theory calculations indicate that the defect‐rich crystalline/amorphous ternary metal (oxy)hydroxide forms by the reconstruction of amorphous multi‐metallic sulfide, where the electron coupling effect among multi‐active sites and migration of intermediate O* from Ni site to the Fe site breaks the scaling relationship to lead to a low theoretical OER overpotential of 170 mV, accounting for the outstanding fast‐charging property. This work not only provides insights into designing advanced OER catalysts by the self‐reconstruction of the pre‐catalyst but also pioneers a pathway for practical fast‐charging Zn–air batteries.
MicroRNAs are critical regulators of the development and progression of laryngeal squamous cell carcinoma (LSCC). However, the role of microRNA-154 (miR-154) in the development and progression of LSCC has not been clarified. We found that down-regulated miR-154 expression in LSCC tissues was associated with poorer prognosis in LSCC patients. MiR-154 over-expression inhibited the proliferation, clonogenicity, and migration of LSCC cells and induced cell cycle arrest, which were reversed by miR-154 inhibition. MiR-154 targeted GALNT7 expression by reducing GALNT7-regulated luciferase activity in LSCC cells while up-regulating GALNT7 mRNA transcription in LSCC tissues and cells. GALNT7 silencing significantly attenuated the proliferation, clonogenicity, and migration of LSCC cells and induced cell cycle arrest. Finally, intravenous treatment with lentivirus for miR-154, but not scrambled control miRNA, significantly restrained the growth of implanted LSCC Hep-2 tumors and decreased the tumor mass by reducing GALNT7 expression in mice. Therefore, miR-154 may serve as a novel prognostic marker and therapeutic target for LSCC.
The cooperation among different surface coordination environments is beneficial to reach a moderate interaction with the oxygen intermediates and therefore achieve an optimal electrochemical oxygen reduction reaction (ORR) activity. A facilely effective strategy is essential to regulate the electronic structure and then the ratio of Mn3+ to Mn4+ in the intrinsically strong Mn–O bonding SmMn2O5. In this work, a two-step photochemical reduction method was adopted to load the Pd nanoparticles on the SmMn2O5 nanorods to form an atomic interface contact. The optimized catalyst 7.5 wt % Pd@SmMn2O5 shows an excellent activity with the half-wave potential 0.83 V (vs RHE) and the charge-transfer resistance ∼38 Ω smaller than that of commercial platinum. The electrons transferring from Pd to p-type SmMn2O5 at the interface contribute to the moderate d-band center and Mn valence and then the neither too strong nor too weak interaction with oxygen intermediates. The accumulated electrons on the conduction band of mullite occupy the anti-bonding states of oxygen in mullite and then activate more oxygen, which favors the labile oxygen participant adsorbate evolving mechanism (LAM) for the ORR process. The assembled Zn–air battery exhibits a high peak power density of ∼236 mW/cm2 and a large open-circuit potential of ∼1.43 V. This work provides insights into the activity optimization of the intrinsically stable catalysts from the aspect of the metal–semiconductor interface.
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