RESUMEN
Electroreduction of CO2 to value-added low-carbon chemicals is a promising way for carbon neutrality and CO2 utilization. It was found that the diiron complex [(µ-bdt)Fe2(CO)6] (bdt = benzene-1,2-dithiolate) has high catalytic activity for electrocatalytic CO2 reduction. To further study the effect of the S-to-S bridge on the catalytic performances of diiron complexes for electrochemical CO2 reduction, four diiron complexes 1-4 with different rigid and conjugated S-to-S bridges were either selected or designed. The electrocatalytic studies showed that under optimal conditions, 2 with a 2,3-naphthalenedithiolato bridge exhibited the lowest catalytic onset potential (Eonset = -1.75 V vs Fc+/0), while 4 with a diphenyl-1,2-vinylidene bridge displayed the highest catalytic activity (TOFmax = 295 s-1), which is 1.5 times that of [(µ-bdt)Fe2(CO)6]. The controlled potential electrolysis experiments of 4 in 0.1 M MeOH/MeCN at -2.35 V vs Fc+/0 gave a total faradaic yield close to 100%, with selectivities of 77%, 9%, and 14% for HCOOH, CO, and H2, respectively. The mechanism for CO2 reduction was studied using density functional theory, IR spectroelectrochemistry, and electrochemical methods. The results indicate that modifying the structure of the S-to-S bridge is an effective strategy to improve the catalytic performance of diiron complexes for electrocatalytic CO2 reduction.
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High areal capacity and stable Coulombic efficiency (CE) in lithium metal anodes (LMAs) play pivotal roles in developing high-energy-density rechargeable batteries. However, few reported LMAs delivering high and stable CE (>50 cycles) under ultrahigh areal capacity (>10 mA h cm-2). We demonstrated that the simultaneous homogenization of electric field and Li ion flux by using self-supported and surface-oxidized 3D hollow porous copper fibers (3D-HPCFs) can greatly increase both the areal capacity and reversibility of Li deposition. Li can be easily confined inside the hollow porous fibers and within the interspaces among fibers without uncontrollable Li dendrites. The 3D-HPCF-based anode can be deeply cycled at high capacity of 15 mA h cm-2 with average CE of 98.87% for 53 cycles, enabling a practical cell to realize high capacity retentions at a surplus Li of 10%. This work provides a novel Li deposition-regulation technology in LMAs targeting for next generation high-energy-density batteries.
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The CO2 reduction reaction (CO2 RR) driven by renewable electricity represents a promising strategy toward alleviating the energy shortage and environmental crisis facing humankind. Cu species, as one type of versatile electrocatalyst for the CO2 RR, attract tremendous research interest. However, for C2 products, ethanol formation is commonly less favored over Cu electrocatalysts. Herein, AuCu alloy nanoparticle embedded Cu submicrocone arrays (AuCu/Cu-SCA) are constructed as an active, selective, and robust electrocatalyst for the CO2 RR. Enhanced selectivity for EtOH is gained, whose Faradaic efficiency (FE) reaches 29 ± 4%, while ethylene formation is relatively inhibited (16 ± 4%) in KHCO3 aqueous solution. The ratio between partial current densities of EtOH and C2 H4 (jEtOH /jC2H4 ) can be tuned in the range from 0.15 ± 0.27 to 1.81 ± 0.55 by varying the Au content of the electrocatalysts. The combined experimental and theoretical calculation results identify the importance of Au in modifying binding energies of key intermediates, such as CH2 CHO*, CH3 CHO*, and CH3 CH2 O*, which consequently modify the activity and selectivity (jEtOH /jC2H4 ) for the CO2 RR. Moreover, AuCu/Cu-SCA also shows high durability with both the current density and FEEtOH being largely maintained for 24 h electrocatalysis.
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The shuttle effect of lithium-sulfur (Li-S) batteries and the poor conductivity of sulfur (S) and lithium polysulfide severely limit their practical applications. Currently, compounding carbon materials with S is one of the effective ways to solve this problem. Therefore, green, low-cost chestnut inner shell biochar (CISC) with graded porous structure was used as the S carrier in this experiment, and carbon nanotubes (CNTs) coating was employed as the S protective layer to improve the electrical conductivity and inhibit the shuttle effect. The results showed that the CISC prepared in this experiment had a relatively high specific surface area (1135.11â m2 g-1 ), and the S loading rate was as high as 65.72 %. The graded porous structure and high specific surface area of CISC can increase the loading rate of S and thus increase the battery capacity. Meanwhile, the naturally contained O and N elements can improve the chemisorption of S. The initial discharge capacity of the CISC@S/CNTs battery at 0.1â C is 967.3â mAh g-1 , and the capacity retention rate is 74.3 % after 500 cycles. The unique composite structure improves the battery's electrical conductivity, reduces the dissolution of polysulfides, and enhances the battery cycle stability.
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Extensive research has been performed using two-dimensional (2D) carbon materials as catalyst supports to achieve high-performance hydrogen storage composites through the hydrogen spillover phenomenon. However, the kinetics and mechanism effects of different support materials still need to be investigated. This study employed high-energy ball milling to fabricate Co1-xS/C60 and C1-xS/rGO composites with stable structures and abundant hydrogen storage sites. We explored the mechanism of hydrogen adsorption behavior through electrode kinetic studies and density functional theory calculations, revealing the intrinsic relationship between material composition, structure, and hydrogen diffusion kinetics. The 2D flakes of C60 and rGO support and connect C1-xS nanoparticles, providing electron transport pathways for the composites. Theoretically, the spherical C60 support with less steric hindrance showed a more vital ability to increase the hydrogen adsorption capacity, while kinetically, thin film rGO offers fast channels for hydrogen diffusion. These findings contribute to our understanding of hydrogen spillover and present opportunities to investigate the synergistic effects in 2D carbon-based composites.
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Lack of vascularization is directly associated with refractory wound healing in diabetes mellitus (DM). Enrichment of endothelial precursor cells (EPCs) is a promising but challenging approach for the treatment of diabetic wounds. Herein, we investigate the action of nicotinamide riboside (NR) on EPC function for improved healing of diabetic wounds. Db/db mice that were treated with NR-supplemented food (400 mg/kg/d) for 12 weeks exhibited higher wound healing rates and angiogenesis than untreated db/db mice. In agreement with this phenotype, NR supplementation significantly increased the number of blood EPCs and bone marrow (BM)-derived EPCs of db/db mice, as well as the tube formation and adhesion functions of BM-EPCs. Furthermore, NR-supplemented BM-EPCs showed higher expression of sirtuin 1 (Sirt1), phosphorylated adenosine monophosphate-activated protein kinase (p-AMPK), and lower expression of acetylated peroxisome proliferator-activated receptor γ coactivator (PGC-1α) than BM-EPCs isolated from untreated db/db mice. Knockdown of Sirt1 in BM-EPCs significantly abolished the tube formation and adhesion function of NR as well as the expression of p-AMPK and deacetylated PGC-1a. Inhibition of AMPK abolished the NR-regulated EPC function but had no effect on Sirt1 expression, demonstrating that NR enhances EPC function through the Sirt1-AMPK pathway. Overall, this study demonstrates that the oral uptake of NR enhances the EPC function to promote diabetic wound healing, indicating that NR supplementation might be a promising strategy to prevent the progression of diabetic complications.
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Excessive apoptosis and inflammatory responses of nucleus pulposus (NP) cells induced by oxidative stress contribute to intervertebral disc degeneration (IVDD). Though some microRNAs are associated with IVDD, the specific microRNA that can mediate apoptotic and inflammatory responses of NP cells induced by oxidative stress synchronously still needs further identification. Here, we find that microRNA-623 (miR-623) is downregulated in IVDD and its expression is regulated by hypoxia-inducible factor-1α (HIF-1α) under oxidative stress conditions. Mechanistically, HIF-1α is observed to promote miR-623 expression by directly binding to its promoter region (-1,994/-1,987 bp). Functionally, miR-623 is found to work as an intermediator in alleviating apoptosis and inflammatory responses of NP cells induced by oxidative stress via regulating thioredoxin-interacting protein (TXNIP) expression by directly targeting its 3'-untranslated region (3'-UTR). Thus, on elucidating the expression and functional mechanisms of miR-623, our study suggests that miR-623 can be a valuable therapeutic target for treating oxidative stress-induced IVDD.
Asunto(s)
Apoptosis , Proteínas Portadoras/metabolismo , Citocinas/metabolismo , Subunidad alfa del Factor 1 Inducible por Hipoxia/metabolismo , MicroARNs/metabolismo , Estrés Oxidativo , Regiones no Traducidas 3' , Adolescente , Adulto , Anciano , Antagomirs/metabolismo , Proteínas Portadoras/química , Proteínas Portadoras/genética , Supervivencia Celular , Células Cultivadas , Femenino , Humanos , Subunidad alfa del Factor 1 Inducible por Hipoxia/genética , Degeneración del Disco Intervertebral/metabolismo , Degeneración del Disco Intervertebral/patología , Masculino , MicroARNs/antagonistas & inhibidores , MicroARNs/genética , Persona de Mediana Edad , Núcleo Pulposo/citología , Núcleo Pulposo/metabolismo , Regiones Promotoras GenéticasRESUMEN
In order to research the corrosion behavior of bioglass-ceramic coated magnesium alloys under applied forces, mesoporous 45S5 bioactive glass-ceramic (45S5 MBGC) coatings were successfully prepared on AZ31 substrates using a sol-gel dip-coating technique followed by a heat treatment at the temperature of 400°C. In this work, corrosion behavior of the coated samples under applied forces was characterized by electrochemical tests and immersion tests in simulated body fluid. Results showed that the glass-ceramic coatings lost the protective effects to the magnesium substrate in a short time when the applied compressive stress was greater than 25MPa, and no crystallized apatite was formed on the surface due to the high Mg(2+) releasing and the peeling off of the coatings. Whereas, under low applied forces, apatite deposition and crystallization on the coating surface repaired cracks to some extent, thus improving the corrosion resistance of the coated magnesium during the long-term immersion period.
Asunto(s)
Aleaciones/química , Cerámica/química , Fuerza Compresiva , Magnesio/química , Ensayo de Materiales , Corrosión , Electroquímica , Minerales/química , Porosidad , Estrés Mecánico , TemperaturaRESUMEN
In this study, bioglass-ceramic coatings were prepared on magnesium alloy substrates through sol-gel dip-coating route followed by heat treatment at the temperature range of 350-500°C. Structure evolution, bond strength and corrosion resistance of samples were studied. It was shown that increasing heat treatment temperature resulted in denser coating structure as well as increased interfacial residual stress. A failure mode transition from cohesive to adhesive combined with a maximum on the measured bond strength together suggested that heat treatment enhanced the cohesion strength of coating on the one hand, while deteriorated the adhesion strength of coating/substrate on the other, thus leading to the highest bond strength of 27.0MPa for the sample heat-treated at 450°C. This sample also exhibited the best corrosion resistance. Electrochemical tests revealed that relative dense coating matrix and good interfacial adhesion can effectively retard the penetration of simulated body fluid through the coating, thus providing excellent protection for the underlying magnesium alloy.