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1.
Small ; : e2400357, 2024 May 22.
Artículo en Inglés | MEDLINE | ID: mdl-38778724

RESUMEN

The Fenton reaction, induced by the H2O2 formed during the oxygen reduction reaction (ORR) process leads to significant dissolution of Fe, resulting in unsatisfactory stability of the iron-nitrogen-doped carbon catalysts (Fe-NC). In this study, a strategy is proposed to improve the ORR catalytic activity while eliminating the effect of H2O2 by introducing CeO2 nanoparticles. Transmission electron microscopy and subsequent characterizations reveal that CeO2 nanoparticles are uniformly distributed on the carbon substrate, with atomically dispersed Fe single-atom catalysts (SACs) adjacent to them. CeO2@Fe-NC achieves a half-wave potential of 0.89 V and a limiting current density of 6.2 mA cm-2, which significantly outperforms Fe-NC and commercial Pt/C. CeO2@Fe-NC also shows a half-wave potential loss of only 1% after 10 000 CV cycles, which is better than that of Fe-NC (7%). Further, H2O2 elimination experiments show that the introduction of CeO2 significantly accelerate the decomposition of H2O2. In situ Raman spectroscopy results suggest that CeO2@Fe-NC significantly facilitates the formation of ORR intermediates compared with Fe-NC. The Zn-air batteries utilizing CeO2@Fe-NC cathodes exhibit satisfactory peak power density and open-circuit voltage. Furthermore, theoretical calculations show that the introduction of CeO2 enhances the ORR activity of Fe-NC SAC. This study provides insights for optimizing SAC-based electrocatalysts with high activity and stability.

2.
Small ; : e2401100, 2024 May 09.
Artículo en Inglés | MEDLINE | ID: mdl-38721947

RESUMEN

The increasing need for energy storage devices with high energy density has led to significant interest in Li-metal batteries (LMBs). However, the use of commercial electrolytes in LMBs is problematic due to their flammability, inadequate performance at low temperatures, and tendency to promote the growth of lithium dendrites and other flaws. This study introduces a localized high-concentration electrolyte (LHCE) that addresses these issues by employing non-flammable electrolyte components and incorporating carefully designed additives to enhance flame retardancy and low-temperature performance. By incorporating additives to optimize the electrolyte, it is possible to attain inorganic-dominated solid electrolyte interphases on both the cathode and anode. This achievement results in a uniform deposition of lithium, as well as the suppression of electrolyte decomposition and cathode deterioration. Consequently, this LHCE achieve over 300 stable cycles for both LiNi0.9Mn0.05Co0.05O2||Li cells and LiCoO2||Li cells, as well as 50 cycles for LiNi0.8Mn0.1Co0.1O2 (NCM811||Li) pouch cells. Furthermore, NCM811||Li cells maintain 84% discharge capacity at -20 °C, in comparison to the capacity at room temperature. The utilization of this electrolyte presents novel perspectives for the safe implementation of LMBs.

3.
Small ; : e2400087, 2024 Feb 20.
Artículo en Inglés | MEDLINE | ID: mdl-38377283

RESUMEN

Increasing the charging cutoff voltage of LiCoO2 to 4.6 V is significant for enhancing battery density. However, the practical application of Li‖LiCoO2 batteries with a 4.6 V cutoff voltage faces significant impediments due to the detrimental changes under high voltage. This study presents a novel bifunctional electrolyte additive, 2-(trifluoromethyl)benzamide (2-TFMBA), which is employed to establish a stable and dense cathode-electrolyte interface (CEI). Characterization results reveal that an optimized CEI is achieved through the synergistic effects of the amide groups and trifluoromethyl groups within 2-TFMBA. The resulting CEI not only enhances the structural stability of LiCoO2 but also serves as a high-speed lithium-ion conduction channel, which expedites the insertion and extraction of lithium ions. The Li‖LiCoO2 batteries with 0.5 wt% 2-TFMBA achieves an 84.7% capacity retention rate after enduring 300 cycles at a current rate of 1 C, under a cut-off voltage of 4.6 V. This study provides valuable strategic insights into the stabilization of cathode materials in high-voltage batteries.

4.
Chemistry ; 30(17): e202303711, 2024 Mar 20.
Artículo en Inglés | MEDLINE | ID: mdl-38143240

RESUMEN

Carbon dioxide electroreduction reaction (CO2RR) can take full advantage of sustainable power to reduce the continuously increasing carbon emissions. Recycling CO2 to produce formic acid or formate is a technologically and economically viable route to accomplish CO2 cyclic utilization. Developing efficient and cost-effective electrocatalysts with high selectivity towards formate is prioritized for the industrialized applications of CO2RR electrolysis. From the previous explored CO2RR catalysts, Sn, Bi and In based materials have drawn increasing attentions due to the high selectivity towards formate. However, there are still confronted with several challenges for the practical applications of these materials. Therefore, a rational design of the catalysts for formate is urgently needed for the target of industrialized applications. Herein, we comprehensively summarized the recent development in the advanced electrocatalysts for the CO2RR to formate. Firstly, the reaction mechanism of CO2RR is introduced. Then the preparation and design strategies of the highly active electrocatalysts are presented. Especially the innovative design mechanism in engineering materials for promoting catalytic performance, and the efforts on mechanistic exploration using in situ (ex situ) characterization techniques are reviewed. Subsequently, some perspectives and expectations are proposed about current challenges and future potentials in CO2RR research.

5.
Chem Rev ; 122(23): 17155-17239, 2022 12 14.
Artículo en Inglés | MEDLINE | ID: mdl-36239919

RESUMEN

The ever-increasing demand for flexible and portable electronics has stimulated research and development in building advanced electrochemical energy devices which are lightweight, ultrathin, small in size, bendable, foldable, knittable, wearable, and/or stretchable. In such flexible and portable devices, semi-solid/solid electrolytes besides anodes and cathodes are the necessary components determining the energy/power performances. By serving as the ion transport channels, such semi-solid/solid electrolytes may be beneficial to resolving the issues of leakage, electrode corrosion, and metal electrode dendrite growth. In this paper, the fundamentals of semi-solid/solid electrolytes (e.g., chemical composition, ionic conductivity, electrochemical window, mechanical strength, thermal stability, and other attractive features), the electrode-electrolyte interfacial properties, and their relationships with the performance of various energy devices (e.g., supercapacitors, secondary ion batteries, metal-sulfur batteries, and metal-air batteries) are comprehensively reviewed in terms of materials synthesis and/or characterization, functional mechanisms, and device assembling for performance validation. The most recent advancements in improving the performance of electrochemical energy devices are summarized with focuses on analyzing the existing technical challenges (e.g., solid electrolyte interphase formation, metal electrode dendrite growth, polysulfide shuttle issue, electrolyte instability in half-open battery structure) and the strategies for overcoming these challenges through modification of semi-solid/solid electrolyte materials. Several possible directions for future research and development are proposed for going beyond existing technological bottlenecks and achieving desirable flexible and portable electrochemical energy devices to fulfill their practical applications. It is expected that this review may provide the readers with a comprehensive cross-technology understanding of the semi-solid/solid electrolytes for facilitating their current and future researches on the flexible and portable electrochemical energy devices.


Asunto(s)
Suministros de Energía Eléctrica , Electrólitos , Electrodos , Electrónica , Programas Informáticos
6.
Nanomedicine ; 58: 102743, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38484918

RESUMEN

Cancer-associated fibroblasts (CAFs) play a crucial role in creating an immunosuppressive environment and remodeling the extracellular matrix within tumors, leading to chemotherapy resistance and limited immune cell infiltration. To address these challenges, integrating CAFs deactivation into immunogenic chemotherapy may represent a promising approach to the reversal of immune-excluded tumor. We developed a tumor-targeted nanomedicine called the glutathione-responsive nanocomplex (GNC). The GNC co-loaded dasatinib, a CAF inhibitor, and paclitaxel, a chemotherapeutic agent, to deactivate CAFs and enhance the effects of immunogenic chemotherapy. Due to the modification with hyaluronic acid, the GNC preferentially accumulated in the tumor periphery and responsively released cargos, mitigating the tumor stroma as well as overcoming chemoresistance. Moreover, GNC treatment exhibited remarkable immunostimulatory efficacy, including CD8+ T cell expansion and PD-L1 downregulation, facilitating immune checkpoint blockade therapy. In summary, the integration of CAF deactivation and immunogenic chemotherapy using the GNC nanoplatform holds promise for rebuilding immune-excluded tumors.


Asunto(s)
Fibroblastos Asociados al Cáncer , Paclitaxel , Fibroblastos Asociados al Cáncer/efectos de los fármacos , Fibroblastos Asociados al Cáncer/inmunología , Fibroblastos Asociados al Cáncer/patología , Fibroblastos Asociados al Cáncer/metabolismo , Animales , Humanos , Ratones , Paclitaxel/farmacología , Paclitaxel/uso terapéutico , Dasatinib/farmacología , Dasatinib/uso terapéutico , Neoplasias/inmunología , Neoplasias/tratamiento farmacológico , Neoplasias/terapia , Neoplasias/patología , Línea Celular Tumoral , Nanopartículas/química , Microambiente Tumoral/efectos de los fármacos , Microambiente Tumoral/inmunología , Antineoplásicos/farmacología , Antineoplásicos/uso terapéutico , Femenino , Glutatión/metabolismo
7.
Angew Chem Int Ed Engl ; 63(10): e202318149, 2024 Mar 04.
Artículo en Inglés | MEDLINE | ID: mdl-38169516

RESUMEN

Aqueous Zn-based batteries have emerged as compelling candidates for grid-scale energy storage, owing to their intrinsic safety, remarkable theoretical energy density and cost-effectiveness. Nonetheless, the dendrite formation, side reactions, and corrosion on anode have overshadowed their practical applications. Herein, we present an in situ grown carbon network reinforcing Zn matrix anode prepared by powder metallurgy. This carbon network provides an uninterrupted internal electron transport pathway and optimize the surface electric field distribution, thereby enabling highly reversible Zn deposition. Consequently, symmetrical cells demonstrate impressive stability, running for over 880 h with a low voltage hysteresis (≈32 mV). Furthermore, this Zn matrix composite anode exhibits enhanced performance in both the aqueous Zn-ion and the Zn-air batteries. Notably, Zn//MnO2 cells display superior rate capabilities, while Zn-air batteries deliver high power density and impressive Zn utilization rate (84.9 %). This work provides a new idea of powder metallurgy method for modified Zn anodes, showcasing potential for large-scale production.

8.
Angew Chem Int Ed Engl ; 63(1): e202316116, 2024 Jan 02.
Artículo en Inglés | MEDLINE | ID: mdl-37983741

RESUMEN

The water-soluble salt-template technique holds great promise for fabricating 3D porous materials. However, an equipment-free and pore-size controllable synthetic approach employing salt-template precursors at room temperature has remained unexplored. Herein, we introduce a green room-temperature antisolvent precipitation strategy for creating salt-template self-assembly precursors to universally produce 3D porous materials with controllable pore size. Through a combination of theoretical simulations and advanced characterization techniques, we unveil the antisolvent precipitation mechanism and provide guidelines for selecting raw materials and controlling the size of precipitated salt. Following the calcination and washing steps, we achieve large-scale and universal production of 3D porous materials and the recycling of the salt templates and antisolvents. The optimized nitrogen-doped 3D porous carbon (N-3DPC) materials demonstrate distinctive structural benefits, facilitating a high capacity for potassium-ion storage along with exceptional reversibility. This is further supported by in situ electrochemical impedance spectra, in situ Raman spectroscopy, and theoretical calculations. The anode shows a high rate capacity of 181 mAh g-1 at 4 A g-1 in the full cell. This study addresses the knowledge gap concerning the room-temperature synthesis of salt-template self-assembly precursors for the large-scale production of porous materials, thereby expanding their potential applications for electrochemical energy conversion and storage.

9.
Angew Chem Int Ed Engl ; 63(9): e202316640, 2024 Feb 26.
Artículo en Inglés | MEDLINE | ID: mdl-38146810

RESUMEN

The catalyst-reconstruction makes it challenging to clarify the practical active sites and unveil the actual reaction mechanism during the CO2 electroreduction reaction (CO2 RR). However, currently the impact of the electrolyte microenvironment in which the electrolyte is in contact with the catalyst is overlooked and might induce a chemical evolution, thus confusing the reconstruction process and mechanism. In this work, the carbonate adsorption properties of metal oxides were investigated, and the mechanism of how the electrolyte carbonate affect the chemical evolution of catalysts were discussed. Notably, Bi2 O3 with weak carbonate adsorption underwent a chemical reconstruction to form the Bi2 O2 CO3 /Bi2 O3 heterostructure. Furthermore, in situ and ex situ characterizations unveiled the formation mechanism of the heterostructure. The in situ formed Bi2 O2 CO3 /Bi2 O3 heterostructure with strong electron interaction served as the highly active structure for CO2 RR, achieving a formate Faradaic efficiency of 98.1 % at -0.8 Vvs RHE . Theoretical calculations demonstrate that the significantly tuned p-orbit electrons of the Bi sites in Bi2 O2 CO3 /Bi2 O3 optimized the adsorption of the intermediate and lowered the energy barrier for the formation of *OCHO. This work elucidates the mechanism of electrolyte microenvironment for affecting catalyst reconstruction, which contributes to the understanding of reconstruction process and clarification of the actual catalytic structure.

10.
Angew Chem Int Ed Engl ; 63(27): e202401238, 2024 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-38651232

RESUMEN

Emerging high entropy compounds (HECs) have attracted huge attention in electrochemical energy-related applications. The features of ultrafine size and carbon incorporation show great potential to boost the ion-storage kinetics of HECs. However, they are rarely reported because high-temperature calcination tends to result in larger crystallites, phase separation, and carbon reduction. Herein, using the NaCl self-assembly template method, by introducing a high-pressure field in the calcination process, the atom diffusion and phase separation are inhibited for the general formation of HECs, and the HEC aggregation is inhibited for obtaining ultrafine size. The general preparation of ultrafine-sized (<10 nm) HECs (nitrides, oxides, sulfides, and phosphates) anchored on porous carbon composites is realized. They are demonstrated by combining advanced characterization technologies with theoretical computations. Ultrafine-sized high entropy sulfides-MnFeCoCuSnMo/porous carbon (HES-MnFeCoCuSnMo/PC) as representative anodes exhibit excellent sodium-ion storage kinetics and capacities (a high rating capacity of 278 mAh g-1 at 10 A g-1 for full cell and a high cycling capacity of 281 mAh g-1 at 20 A g-1 after 6000 cycles for half cell) due to the combining advantages of high entropy effect, ultrafine size, and PC incorporation. Our work provides a new opportunity for designing and fabricating ultrafine-sized HECs.

11.
J Am Chem Soc ; 145(3): 1924-1935, 2023 Jan 25.
Artículo en Inglés | MEDLINE | ID: mdl-36571792

RESUMEN

High-entropy compounds with extraordinary properties due to the synergistic effect of multiple components have exhibited great potential and attracted extensive attention in various fields, including physics, mechanical property analysis, and energy storage. Achieving universal stability and synthesis of high-entropy compounds with a wide range of components and structures continues to be difficult due to the high complexity of multicomponent mixing. Here, we propose a design strategy with high generality for realizing the stability and synthesis of high-entropy compounds that one metal site like the framework in the compound structures with bimetallic sites stabilizes another site to accommodate different elements. Several typical metal compounds with bimetallic sites, including perovskite hydroxides, layered double hydroxide, spinel sulfide, perovskite fluoride, and spinel oxides, have been synthesized into high-entropy compounds. High-entropy perovskite hydroxides (HEPHs) as representative compounds have been synthesized with a highly wide range of components even a septenary component and exhibit great oxygen evolution activity. Our work provides a design platform to develop more high-entropy compound systems with promising development potential for electrocatalysts.

12.
Biochem Biophys Res Commun ; 668: 62-69, 2023 08 06.
Artículo en Inglés | MEDLINE | ID: mdl-37244036

RESUMEN

This study aims to examine the impacts of Scutellaria strigillosa Hemsl. (SSH) on the proliferation, apoptosis of human hepatoma cell HepG2 and screen the bioactive components. We found that SSH extract inhibited HepG2 proliferation, arrested cell division prior to S phase. Additionally, SSH extract exposure induced apoptosis, and increased the proportions of late apoptotic cells. Specifically, we focus on the inhibitory effect of SSH extract on aspartate ß-hydroxylase, a key therapeutic target of hepatocellular carcinoma closely related with the proliferation and apoptosis of HepG2. We found SSH extract with notable inhibitory activity against aspartate ß-hydroxylase, elucidated the main bioactive constituents by HPLC-Q-TOF/MS and Molecular docking analysis. In conclusion, these results provided the antiproliferative and proapoptotic effects of SSH on HepG2 cell, elucidated the main bioactive constituents based on aspartate ß-hydroxylase inhibition. These data revealed the potential value of SSH and its bioactive components for the prevention and treatment of liver cancer for the first time.


Asunto(s)
Carcinoma Hepatocelular , Neoplasias Hepáticas , Scutellaria , Humanos , Células Hep G2 , Ácido Aspártico , Scutellaria/química , Simulación del Acoplamiento Molecular , Carcinoma Hepatocelular/patología , Neoplasias Hepáticas/patología , Proliferación Celular , Apoptosis , Oxigenasas de Función Mixta , Extractos Vegetales/farmacología , Extractos Vegetales/uso terapéutico
13.
Small ; : e2307725, 2023 Dec 06.
Artículo en Inglés | MEDLINE | ID: mdl-38057130

RESUMEN

The Ru-based catalyst for hydrogen oxidation reaction (HOR) with remarkable activity and reliability at high potential range remains a formidable challenge. Herein, the RuNi/C nanoparticles are customized, in which NiRu alloy is tightly wrapped with a carbon layer, delivering 2.2-fold and 8.3-fold enhancement in kinetic current density than that of commercial Pt/C and Ru/C, respectively. Notably, the current density maintains 2.93 mA cm-2 disk at 0.6 V vs RHE, which effectively improves the stability of Ru-based catalysts at high voltage. The NiRu alloy triggers electron redistribution between two metal elements and regulates the surface adsorption performance, coupled with a tightly wrapped outer carbon layer which is in situ formed with alloy as a good conductor of electronic and protection from the electrolyte. This work not only provides a novel electrocatalyst for efficient HOR with its potential for industrial application but also opens up a new avenue for designing highly active catalytic systems.

14.
Opt Express ; 31(17): 27462-27481, 2023 Aug 14.
Artículo en Inglés | MEDLINE | ID: mdl-37710821

RESUMEN

An embedded spherical dot taper structure (EDT) based on the MZI principle is proposed in this paper, which is mainly fabricated by using two special arc discharges in the preparation process. The proposed structure involves two specialized arc discharge techniques. First, an oversaturated discharge fusion process creates a micro-arc spherical area on the fiber end face to form the first link type. Second, an unsaturated discharge-pulling taper fusion joint creates a local micro-extrusion operation on this micro-arc fiber end face to form the second link. The thermal stress from instantaneous discharge causes a reverse spherical expansion zone to form in the end face structure, similar to the micromachining of long-period fiber gratings that use local CO2 laser etching to create modulated zones. The study involves a mathematical and theoretical analysis of how geometric parameters in the spherical modulation zone impact the structure's characteristic spectrum. The research demonstrates the potential for this structure to function as a light-intensity modulated strain sensor device through both theoretical and experimental means. As per the experimental findings, the optimized structure displays a high level of strain sensing sensitivity at 0.03 dB/µÎµ and temperature sensing sensitivity of 73 pm/°C (20°C-75°C) and 169 pm/°C (75°C-120°C). Additionally, it possesses excellent cross-sensitivity at only ∼0.0015 µÎµ/°C. Therefore, this sensor presents a favorable option for strain and temperature synchronization sensing and monitoring components, and exhibits notable application prospects in precision engineering, which encompasses mechanical manufacturing, the power and electrical industry, healthcare domain, and certain specialized areas of small-scale precision engineering.

15.
Biomacromolecules ; 24(11): 5230-5244, 2023 11 13.
Artículo en Inglés | MEDLINE | ID: mdl-37733485

RESUMEN

As an acute ophthalmic infection, bacterial keratitis (BK) can lead to severe visual morbidity, such as corneal perforation, intraocular infection, and permanent corneal opacity, if rapid and effective treatments are not available. In addition to eradicating pathogenic bacteria, protecting corneal tissue from oxidative damage and promoting wound healing by relieving inflammation are equally critical for the efficient treatment of BK. Besides, it is very necessary to improve the bioavailability of drugs by enhancing the ocular surface adhesion and corneal permeability. In this investigation, therefore, a synergistic antibiotic-antioxidant treatment of BK was achieved based on multifunctional block copolymer vesicles, within which ciprofloxacin (CIP) was simultaneously encapsulated during the self-assembly. Due to the phenylboronic acid residues in the corona layer, these vesicles exhibited enhanced muco-adhesion, deep corneal epithelial penetration, and bacteria-targeting, which facilitated the drug delivery to corneal bacterial infection sites. Additionally, the abundant thioether moieties in the hydrophobic membrane enabled the vesicles to both have ROS-scavenging capacity and accelerated CIP release at the inflammatory corneal tissue. In vivo experiments on a mice model demonstrated that the multifunctional polymer vesicles achieved efficient treatment of BK, owing to the enhanced corneal adhesion and penetration, bacteria targeting, ROS-triggered CIP release, and the combined antioxidant-antibiotic therapy. This synergistic strategy holds great potential in the treatment of BK and other diseases associated with bacterial infections.


Asunto(s)
Infecciones Bacterianas del Ojo , Queratitis , Animales , Ratones , Antioxidantes/farmacología , Polímeros/química , Especies Reactivas de Oxígeno , Queratitis/tratamiento farmacológico , Queratitis/microbiología , Antibacterianos/farmacología , Antibacterianos/uso terapéutico , Ciprofloxacina , Infecciones Bacterianas del Ojo/tratamiento farmacológico , Infecciones Bacterianas del Ojo/microbiología
16.
Nano Lett ; 22(16): 6492-6500, 2022 Aug 24.
Artículo en Inglés | MEDLINE | ID: mdl-35950973

RESUMEN

High-entropy oxide (HEO) including multiple principal elements possesses great potential for various fields such as basic physics, mechanical properties, energy storage, and catalysis. However, the synthesis method of high-entropy compounds through the traditional heating approach is not conducive to the rapid properties screening, and the current elemental combinations of HEO are also highly limited. Herein, we report a rapid synthesis method for HEO through the Joule-heating of nickel foil with dozens of seconds. High-entropy rocksalt oxides (HERSO) with the new elemental combination, high-entropy spinel oxides (HESO), and high-entropy perovskite oxide (HEPO) have been synthesized through the Joule-heating. The synthesized HERSO with new elemental combinations proves to be a great promotion of OER activity due to the synergy of multiple components and the continuous electronic structure experimentally and theoretically. The demonstrated synthesis approach and the new component combination of HERSO provide a broad platform for the development of high-entropy materials and catalysts.

17.
Angew Chem Int Ed Engl ; 62(39): e202308686, 2023 Sep 25.
Artículo en Inglés | MEDLINE | ID: mdl-37503553

RESUMEN

Rational design of Pt single-atom catalysts provides a promising strategy to significantly improve the electrocatalytic activity for hydrogen evolution reaction. In this work, we presented a novel and efficient strategy for utilizing the low electron-density region of substrate to effectively trap and confine high electron-density metal atoms. The Pt single-atom catalyst supported by nickel selenide with rich vacancies was prepared via a hydrothermal-impregnation stepwise approach. Through experimental testation and DFT theoretical calculation, we confirm that Pt single atoms are well distributed at cationic vacancies of nickel selenide with loading amount of 3.2 wt. %. Moreover, the atomic Pt combined with the high electronegative Se to form Pt-Se bond as a "bridge" between single atoms and substrate for fast electron translation. This novel catalyst shows an extremely low overpotential of 45 mV at 10 mA cm-2 and an excellent stability over 120 h. Furthermore, the nickel selenide supported Pt SACs exhibits long-term stability for practical application, which maintains a high current density of 390 mA cm-2 over 80 h with a retention of 99 %. This work points a promising direction for designing single atoms catalysts with high catalytic activity and stability for advanced green energy conversion technologies.

18.
Angew Chem Int Ed Engl ; 62(24): e202302689, 2023 Jun 12.
Artículo en Inglés | MEDLINE | ID: mdl-36967232

RESUMEN

The sluggish kinetics and mutual interference of oxygen evolution and reduction reactions in the air electrode resulted in large charge/discharge overpotential and low energy efficiency of Zn-air batteries. In this work, we designed a breathing air-electrode configuration in the battery using P-type Ca3 Co4 O9 and N-type CaMnO3 as charge and discharge thermoelectrocatalysts, respectively. The Seebeck voltages generated from thermoelectric effect of Ca3 Co4 O9 and CaMnO3 synergistically compensated the charge and discharge overpotentials. The carrier migration and accumulation on the cold surface of Ca3 Co4 O9 and CaMnO3 optimized the electronic structure of metallic sites and thus enhanced their intrinsic catalytic activity. The oxygen evolution and reduction overpotentials were enhanced by 101 and 90 mV, respectively, at temperature gradient of 200 °C. The breathing Zn-air battery displayed a remarkable energy efficiency of 68.1 %. This work provides an efficient avenue towards utilizing waste heat for improving the energy efficiency of Zn-air battery.

19.
Small ; 18(43): e2106904, 2022 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-35187802

RESUMEN

Development of efficient non-noble metal catalysts for water splitting is of great significance but challenging due to the sluggish kinetics of the hydrogen evolution reaction (HER) in alkaline medium. Herein, a bimetallic multi-level layered catalytic electrode composed of Ni3 S2 nanosheets with secondary Co-NiOOH layer of 3D porous and free-standing cathode in alkaline medium is reported. This integrated synergistic catalytic electrode exhibits excellent HER electrocatalytic performance. The resultant Ni0.67 Co0.33 /Ni3 S2 @NF electrode displays the highest HER activity with only overpotentials of 87 and 203 mV to afford current densities of 10 and 100 mA·cm-2 , respectively, and its Tafel slope is 80 mV·dec-1 . The chronopotentiometry operated at high current density of 50 mA·cm-2 shows negligible deterioration, indicating better stability of Ni0.67 Co0.33 /Ni3 S2 @NF electrode than Pt/C (20 wt.%). Such a desirable catalytic performance is attributed to the modification of physical and electronic structure that exposes abundant active sites and improves the intrinsic catalytic activity toward HER, which is also confirmed by electrochemically active surface area and X-ray photoelectron spectroscopy analysis. This work provides a strong support for the rational design of high-performance bimetallic electrodes for industrial water splitting.

20.
Angew Chem Int Ed Engl ; 61(3): e202114441, 2022 Jan 17.
Artículo en Inglés | MEDLINE | ID: mdl-34806271

RESUMEN

Owing to their unique electronic structure and maximum atom utilization efficiency, single-atom catalysts have received widespread attention and exhibited efficient activity. Herein, we report the preparation of non-metal Se single atoms embedded in nitrogen-doped carbon (NC) via a high-temperature reduction strategy for electrocatalytic oxygen reduction reaction (ORR). Selenium dioxide is reduced to selenium by NC at high temperature and partially anchored to form C-Se-C bond. Impressively, the obtained single-atom catalyst exhibits outstanding ORR activity and stability that even surpasses state-of-the-art noble metal catalysts and many previously reported nanocatalysts. Experimental and theoretical calculations reveal that the Se single atoms can serve as the ORR active sites and contribute to lowering the reaction barrier. Our discoveries demonstrate the promising prospects for utilizing metal-free single-atom-based materials for efficient electrocatalysis.

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