Due to their high conductivity and low cost, carbon materials have attracted great attention in the field of energy storage, especially as anode material for sodium ion batteries. Current research focuses on introducing external defects through heteroatom engineering to improve the sodium storage performance of carbon materials. However, there is still a lack of systematic investigation of the effects of intrinsic defects prevalent in carbon materials on sodium storage performance. Herein, template‐assisted method was used to design carbon materials with different degrees of intrinsic defects and explore their sodium storage properties. The experimental results show that the intrinsic defects in the carbon materials facilitates the adsorption behavior of Na+ during the surface induction capacitance process. Among them, the best carbon anode material exhibits high reversible capacity (221 mAh g−1 at 1 A g−1) and excellent rate performance. In addition, the density functional theory calculations also show that the existence of intrinsic defects can optimize the distribution of electron density, thereby increasing the Na‐adsorption capacity. This work makes an important contribution to understanding the role of intrinsic defects in the sodium storage performance of carbon materials.
Heteroatom doping plays a significant role in optimizing the catalytic performance of electrocatalysts. However, research on heteroatom doped electrocatalysts with abundant defects and well-defined morphology remain a great challenge. Herein, a class of defect-engineered nitrogen-doped Co 3 O 4 nanoparticles/nitrogen-doped carbon framework (N-Co 3 O 4 @NC) strongly coupled porous nanocubes, made using a zeolitic imidazolate framework-67 via a controllable N-doping strategy, is demonstrated for achieving remarkable oxygen evolution reaction (OER) catalysis. X-ray photoelectron spectroscopy, X-ray absorption fine structure, and electron spin resonance results clearly reveal the formation of a considerable amount of nitrogen dopants and oxygen vacancies in N-Co 3 O 4 @NC. The defect engineering of N-Co 3 O 4 @NC makes it exhibit an overpotential of only 266 mV to reach 10 mA cm −2 , a low Tafel slope of 54.9 mV dec −1 and superior catalytic stability for OER, which is comparable to that of commercial RuO 2 . Density functional theory calculations indicate N-doping could promote catalytic activity via improving electronic conductivity, accelerating reaction kinetics, and optimizing the adsorption energy for intermediates of OER. Interestingly, N-Co 3 O 4 @ NC also shows a superior oxygen reduction reaction activity, making it a bifunctional electrocatalyst for zinc-air batteries. The zinc-air battery with the N-Co 3 O 4 @NC cathode demonstrates superior efficiency and durability, showing the feasibility of N-Co 3 O 4 /NC in electrochemical energy devices.
The polar surface of (001) wurtzite-structured MnO possesses substantial electrostatic instabilities that facilitate a wurtzite to graphene-like sheet transformation during the lithiation/delithiation process when used in battery technologies. This transformation results in cycle instability and loss of cell efficiency. In this work, we synthesized MnO hexagonal sheets (HSs) possessing abundant oxygen vacancy defects (MnO-Vo HSs) by pyrolyzing and reducing MnCO3 HSs under an atmosphere of Ar/H2. The oxygen vacancies (Vos) were generated in the reduction process and have been characterized using a range of techniques: X-ray absorption fine structure, electron-spin resonance, X-ray absorption near edge structure, Artemis modeling, and R space Feff modeling. The data arising from these analyses inform us that the introduction of one Vo defect within each O atom layer can reduce the charge density by 3.2 × 10–19 C, balancing the internal nonzero dipole moment and rendering the wurtzite structure more stable, so inhibiting the change to a graphene-like structure. Density function theory calculations demonstrate that the incorporation of Vos sites significantly improves the charge accumulation around Li atoms and increases Li+ adsorption energies (−2.720 eV). When used as an anode material for lithium ion batteries, the MnO-Vo HSs exhibit high specific capacity (1228.3 mAh g–1 at 0.1 A g–1) and excellent cell cycling stabilities (∼88.1% capacity retention after 1000 continuous charge/discharge cycles at 1.0 A g–1).
Carbonaceous materials are promising anodes for potassium‐ion batteries (PIBs). However, it is hard for large K ions (1.38 Å) to achieve long‐distance diffusion in pristine carbonaceous materials. In this work, the following are synthesized: S/N codoped carbon nanofiber aerogels (S/N‐CNFAs) with optimized electronic structure by S/N codoping, enhanced interlayer spacing by S doping, and a 3D interconnected porous structure of aerogel, through a pyrolysis sustainable seaweed (Fe‐alginate) aerogel strategy. Specifically, the S/N‐CNFAs electrode delivers high reversible capacities of 356 and 112 mA h g−1 at 100 and 5000 mA g−1, respectively. The capacity reaches 168 mA h g−1 at 2000 mA g−1 after 1000 cycles. A full cell with a S/N‐CNFAs anode and potassium prussian blue cathode displays a specific capacity of 198 mA h g−1 at 200 mA g−1. Density functional theory calculations indicate that S/N codoping is beneficial to synergistically improve K ions storage of S/N‐CNFAs by enhancing the adsorption of K ions and reducing the diffusion barrier of K ions. This work offers a facile heteroatom doping paradigm for designing new carbonaceous anodes for high‐performance PIBs.
Objective Although the connection of oxidative stress and inflammation has been long recognized in diabetes, the underlying mechanisms are not fully elucidated. This study defined the role of 26S proteasomes in promoting vascular inflammatory response in early diabetes. Methods and Results The 26S proteasome functionality, markers of autophagy, and unfolded protein response (UPR) were assessed in: (a) cultured 26S proteasome reporter cells and endothelial cells challenged with high glucose, (b) transgenic reporter (UbG76V-GFP) and wild type (C57BL/6J) mice rendered diabetic, and (c) genetically diabetic (Akita and OVE26) mice. In glucose-challenged cells, and also in aortic, renal, and retinal tissues from diabetic mice, enhanced 26S proteasome functionality was observed, evidenced by augmentation of proteasome (chymotrypsin-like) activities and reduction in 26S proteasome reporter proteins, accompanied by increased nitrotyrosine-containing proteins. Also, while IκBα proteins were decreased, an increase was found in NF-κB nucleus translocation, which enhanced the NF-κB-mediated pro-inflammatory response, without affecting markers of autophagy or UPR. Importantly, the alterations were abolished by MG132 administration, siRNA knockdown of PA700 (proteasome activator protein complex), or superoxide scavenging in vivo. Conclusions Early hyperglycemia enhances 26S proteasome functionality, not autophagy or UPR, through peroxynitrite/superoxide-mediated PA700-dependent proteasomal activation, which elevates NF-κB-mediated endothelial inflammatory response in early diabetes.
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