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In this study, we demonstrated a facile method to prepare a novel SnO2microporous rod with various microstructures by controlling NaOH molarities in precursor synthesis processes. Four different molarities of NaOH solution (0.005 M, 0.048 M, 0.12 M and 0.5 M) were used together with o-phthalic acid in Sn-MOF synthesis to determine the effect of ligand [o-C6H4CO222-] concentration on microstructure evolution. It was found that increasing NaOH molarity can effectively decrease the size of Sn-MOF rods. Then, the SnO2microporous rods were obtained by calcinating the as-prepared Sn-MOF as microstructures. Under an optimized experimental condition (NaOH molarity of 0.12 M), the SnO2rods shows a modest initial coulombic efficiency of 61.3% with a high reversible sodium storage capacity of 503 mAh g-1after 150 cycles at 50 mA g-1. Moreover, an impressive reversible sodium storage capacity of 206 mAh g-1can be obtained at long-term cycling performance (800 cycles at current density of 2 A g-1). Effects of morphologies to electrochemical performances have been further discussed in aspects of intrinsic resistance, pseudocapacitive contribution, surface area and porous structure and microstructural stability, and the enhanced electrochemical performance could be attributed to factors of enhanced pseudocapacitive charge contribution, optimized microstructures, and structural stability, which ensure the SnO2-0.12 M to have a good rate performance and cyclability. This nanoscale-engineering method adopted here could be a promising path to fabricate SnO2-based anodes with novel microstructures for sodium storage applications.
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Defect engineering (doping and vacancy) has emerged as a positive strategy to boost the intrinsic electrochemical reactivity and structural stability of MnO2 -based cathodes of rechargeable aqueous zinc ion batteries (RAZIBs). Currently, there is no report on the nonmetal element doped MnO2 cathode with concomitant oxygen vacancies, because of its low thermal stability with easy phase transformation from MnO2 to Mn3 O4 (≥300 °C). Herein, for the first time, novel N-doped MnO2- x (N-MnO2- x ) branch arrays with abundant oxygen vacancies fabricated by a facile low-temperature (200 °C) NH3 treatment technology are reported. Meanwhile, to further enhance the high-rate capability, highly conductive TiC/C nanorods are used as the core support for a N-MnO2- x branch, forming high-quality N-MnO2- x @TiC/C core/branch arrays. The introduced N dopants and oxygen vacancies in MnO2 are demonstrated by synchrotron radiation technology. By virtue of an integrated conductive framework, enhanced electron density, and increased surface capacitive contribution, the designed N-MnO2- x @TiC/C arrays are endowed with faster reaction kinetics, higher capacity (285 mAh g-1 at 0.2 A g-1 ) and better long-term cycles (85.7% retention after 1000 cycles at 1 A g-1 ) than other MnO2 -based counterparts (55.6%). The low-temperature defect engineering sheds light on construction of advanced cathodes for aqueous RAZIBs.
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Performance breakthrough of MoSe2 -based hydrogen evolution reaction (HER) electrocatalysts largely relies on sophisticated phase modulation and judicious innovation on conductive matrix/support. In this work the controllable synthesis of phosphate ion (PO43- ) intercalation induced-MoSe2 (P-MoSe2 ) nanosheets on N-doped mold spore carbon (N-MSC) forming P-MoSe2 /N-MSC composite electrocatalysts is realized. Impressively, a novel conductive N-MSC matrix is constructed by a facile mold fermentation method. Furthermore, the phase of MoSe2 can be modulated by a simple phosphorization strategy to realize the conversion from 2H-MoSe2 to 1T-MoSe2 to produce biphase-coexisted (1T-2H)-MoSe2 by PO43- intercalation (namely, P-MoSe2 ), confirmed by synchrotron radiation technology and spherical aberration-corrected TEM (SACTEM). Notably, higher conductivity, lower bandgap and adsorption energy of H+ are verified for the P-MoSe2 /N-MSC with the help of density functional theory (DFT) calculation. Benefiting from these unique advantages, the P-MoSe2 /N-MSC composites show superior HER performance with a low Tafel slope (≈51 mV dec-1 ) and overpotential (≈126 mV at 10 mA cm-1 ) and excellent electrochemical stability, better than 2H-MoSe2 /N-MSC and MoSe2 /carbon nanosphere (MoSe2 /CNS) counterparts. This work demonstrates a new kind of carbon material via biological cultivation, and simultaneously unravels the phase transformation mechanism of MoSe2 by PO43- intercalation.
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The tailored construction of non-noble metal bifunctional electrocatalysts for high-efficiency oxygen/hydrogen evolution reactions (OER/HER) is vital for the development of electrochemical energy conversion. Herein, we report a powerful combined wet chemical method to fabricate a novel binder-free NiFe layered double hydroxide@Ni3S2 (NiFe LDH@Ni3S2) heterostructure as an efficient bifunctional electrocatalyst for overall water splitting. The hydrothermal-synthesized NiFe LDH nanosheets are uniformly coated on the Ni3S2 nanosheet skeleton forming 3D porous heterostructure arrays. By virtue of its synergistic advantages, including its binder-free characteristics, increased catalysis sites and structural stability, the as-obtained NiFe LDH@Ni3S2/NF electrode exhibits low overpotentials of 184 and 271 mV at 20 mA cm-2 for HER and OER in 1 M KOH, respectively. Notably, a low operation potential of 1.74 V at a current density of 20 mA cm-2 is achieved for overall water splitting with a stable cycling life. In addition, the intimate composite structure and sensitive interface of NiFe LDH@Ni3S2 are responsible for the good electrocatalytic activity with a low Tafel slope, fast reaction kinetics and high stability. The versatile fabrication protocol and heterostructure interface engineering provide a new way to construct other bifunctional and cost-effective electrocatalysts for electrocatalysis.
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We design a facile approach to prepare a bimetallic transition-metal-sulphide-based 3D hierarchically-ordered porous electrode based on bimetallic metal-organic frameworks (Ni-Co-MOFs) by using confinement growth and in-situ sulphurisation techniques. In the novel resulting architectures, Ni-Co-S nanoparticles are confined in bowknot-like and flower-like carbon networks and are mechanically isolated but electronically well-connected, where the carbon networks with a honeycomb-like feature facilitate electron transfer with uninterrupted conductive channels from all sides. Moreover, these hierarchically-ordered porous structures together with internal voids can accommodate the volume expansion of the embedded Ni-Co-S nanoparticles. The pseudocapacitive behaviours displayed in the NCS@CBs and NCS@CFs occupied a significant portion in the redox processes. Because of these merits, both the as-built bowknot and flower networks show excellent electrochemical properties for lithium storage with superior rate capability and robust cycling stability (994 mAh g-1 for NCS@CBs and 888 mAh g-1 for NCS@CFs after 200 cycles). This unique 3D hierarchically-ordered structural design is believed to hold great potential applications in propagable preparation of carbon networks teamed up with sulphide nanocrystals for high energy storage.
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Wound infection caused by multiantibiotic-resistant bacteria has become a serious problem, and more effective antibacterial agents are required. Herein, we report the preparation of wound dressings using the biocompatible chitosan (CS) as a reducing and stabilizing agent in the synthesis of 2-mercapto-1-methylimidazole (MMT)-capped gold nanocomposites (CS-Au@MMT), with efficient antibacterial effects. The synergistic effects of AuNPs, MMT, and CS led to the disruption of bacterial membranes. After blending with gelatin, crosslinking with tannin acid, and freeze-drying, CS-gelatin (CS-Au@MMT/gelatin) dressing was prepared. It had good mechanical properties as well as efficient water absorption and retention capacities. It exhibited outstanding biocompatibility both in vitro and in a cell-based wound infection model. Moreover, the in vivo rabbit wound healing model revealed that the CS-Au@MMT/gelatin dressing possesses significant antibacterial potential against methicillin-resistant Staphylococcus aureus-associated wound infection. Therefore, the CS-Au@MMT/gelatin dressing described in this study may have huge potential in biomedical applications.
Assuntos
Antibacterianos/administração & dosagem , Bandagens , Nanopartículas Metálicas/administração & dosagem , Infecção dos Ferimentos/tratamento farmacológico , Animais , Antibacterianos/química , Materiais Biocompatíveis , Linhagem Celular , Quitosana/química , Farmacorresistência Bacteriana Múltipla/efeitos dos fármacos , Escherichia coli/efeitos dos fármacos , Gelatina/química , Ouro/química , Ouro/farmacologia , Humanos , Nanopartículas Metálicas/química , Staphylococcus aureus Resistente à Meticilina/efeitos dos fármacos , Testes de Sensibilidade Microbiana , Microscopia Eletrônica de Varredura , Coelhos , Infecção dos Ferimentos/microbiologiaRESUMO
Construction of electrodes with fast reaction kinetics is of great importance for achieving advanced supercapacitors. Herein we report a facile combined synthetic strategy with atomic layer deposition (ALD) and electrodeposition to rationally fabricate nanotube/nanoflake core/shell arrays. ALD-TiO2 nanotubes are used as the skeleton core for assembly of electrodeposited MnO2-C nanoflake shells forming a core/shell structure. Highly porous architecture and good electrical conductivity are combined in this unique core/shell structure, resulting in fast ion/electron transfer. In tests of electrochemical performance, the TiO2/MnO2-C core/shell arrays are characterized as cathode for asymmetric supecapacitors and exhibit high specific capacitance (880 F g-1 at 2.5 A g-1), excellent rate properties (735 F g-1 at 30 A g-1) and good long-term cycling stability (94.3% capacitance retention after 20 000 cycles). The proposed electrode construction strategy is favorable for fabrication of other advanced supercapacitor electrodes.
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High-performance electrochemical energy storage (EES) devices require the ability to modify and assemble electrode materials with superior reactivity and structural stability. The fabrication of different oxide/metal core-branch nanoarrays with adjustable components and morphologies (e.g., nanowire and nanoflake) is reported on different conductive substrates. Hollow metal branches (or shells) wrapped around oxide cores are realized by electrodeposition using ZnO nanorods as a sacrificial template. In battery electrode application, the thin hollow metal branches can provide a mechanical protection of the oxide core and a highly conductive path for charges. As a demonstration, arrays of Co3O4/Ni core-branch nanowires are evaluated as the anode for lithium ion batteries. The thin metal branches evidently improve the electrochemical performance with higher specific capacity, rate capability, and capacity retention than the unmodified Co3O4 counterparts.
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High-quality metal oxide/conducting polymer (CP) heterostructured nanoarrays are fabricated by controllable electrochemical polymerization of CP shells on preformed metal oxides nanostructures for both electrochromic and electrochemical energy storage applications. Coaxial and branched CP shells can be obtained on different backbones (nanowire, nanorod, and nanoflake) simply by controlling the electrodeposition time. "Solvophobic" and "electrostatic" interactions are proposed to account for the preferential growth of CP along metal oxides to form core/shell heterostructures. The coaxial TiO2/polyaniline core/shell nanorod arrays exhibit remarkable electrochromic performance with rich color changes, fast optical modulation, and superior cycling stability. In addition, the Co3O4/polyaniline core/shell nanowire arrays are evaluated as an anode material of Li ion battery and exhibit enhanced electrochemical property with higher and more stable capacity than the bare Co3O4 nanowires electrode. These unique organic-inorganic heterostructures with synergy pave the way for developing new functional materials with enhanced properties or new applications.
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Floral scent (FS) plays a crucial role in the ecological functions and industrial applications of plants. However, the physiological and metabolic mechanisms underlying FS formation remain inadequately explored. Our investigation focused on elucidating the differential formation mechanisms of 2-phenylethanol (2-PE) and benzyl alcohol (BA) by examining seven related enzyme concentrations and the content of soluble sugar, soluble proteins, carbon (C) and nitrogen (N), as well as the C/N ratio. The findings revealed that the peak content of 2-PE in M. 'Praire Rose' and BA in M. 'Lollipop' occurred during the end flowering stage (S4) and flowering stage (S3) periods, respectively. The enzyme concentration change trends of phenylpyruvate decarboxylase (PDL), phenylacetaldehyde reductase (PAR), soluble protein, C, N, and C/N ratio changes during the S3-S4 period in M. 'Praire Rose' and M. 'Lollipop' were entirely opposite. Correlation and PCA analysis demonstrated that the content of CYP79D73 (a P450) and N, and the C/N ratio were key factors in 2-PE production in M. 'Praire Rose'. The production of BA in M. 'Lollipop' was more influenced by the content of phenylacetaldehyde synthase (PAAS), CYP79D73, and soluble sugar. As CYP79D73 exits oppositely in correlation to 2-PE (M. 'Praire Rose') and BA (M. 'Lollipop'), it is hypothesized that CYP79D73 was postulated as the primary factor contributing to the observed differences of 2-PE (M. 'Praire Rose') and BA (M. 'Lollipop') formation. These results carry significant implications for crabapple aromatic flower breeding and the essential oil industry etc.
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Dictyophora rubrovolvata volva, an agricultural by-product, is often directly discarded resulting in environmental pollution and waste of the proteins' resources. In this study, D. rubrovolvata volva proteins (DRVPs) were recovered using the ultrasound-assisted extraction (UAE) method. Based on one-way tests, orthogonal tests were conducted to identify the effects of the material-liquid ratio, pH, extraction time, and ultrasonic power on the extraction rate of DRVPs. Moreover, the impact of UAE on the physicochemical properties, structure characteristics, intermolecular forces, and functional attributes of DRVPs were also examined. The maximum protein extraction rate was achieved at 43.34% under the best extraction conditions of UAE (1:20 g/mL, pH 11, 25 min, and 550 W). UAE significantly altered proteins' morphology and molecular size compared to the conventional alkaline method. Furthermore, while UAE did not affect the primary structure, it dramatically changed the secondary and tertiary structure of DRVPs. Approximately 13.42% of the compact secondary structures (α-helices and ß-sheets) underwent a transition to looser structures (ß-turns and random coils), resulting in the exposure of hydrophobic groups previously concealed within the molecule's core. In addition, the driving forces maintaining and stabilizing the sonicated protein aggregates mainly involved hydrophobic forces, disulfide bonding, and hydrogen bonding interactions. Under specific pH and temperature conditions, the water holding capacity, oil holding capacity, foaming capacity and stability, emulsion activity, and stability of UAE increased significantly from 2.01 g/g to 2.52 g/g, 3.90 g/g to 5.53 g/g, 92.56% to 111.90%, 58.97% to 89.36%, 13.85% to 15.37%, and 100.22% to 136.53%, respectively, compared to conventional alkali extraction. The findings contributed to a new approach for the high-value utilization of agricultural waste from D. rubrovolvata.
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The sustainable development of infrastructure construction projects heavily depends on favorable cooperation of all parties and ethical code of conduct, while Un-ethical pro-organizational behavior (UPB) may undermine the mutual efforts and cause serious consequences. UPB has aroused wide interest of researchers, but what may trigger construction employees to engage in UPB at team-level has not been elucidated completely. With information asymmetry and huge uncertainty, the behaviors of employees in temporary project teams are marked by environmental and personal characters. The study discusses the influences of collective moral judgement focus on self (CMJS) and Machiavellianism on UPB. Through a moderated mediation analysis conducted on a set of survey data from Chinese construction projects, the empirical results of the two-level hierarchical linear model indicate that CMJS positively impacts UPB directly, and meanwhile Machiavellianism acts as a partial mediator in the relationship between CMJS and UPB. The findings also reveal that performance-avoidance goal orientation (PAGO) and motivation to learn (MTL) moderate and strengthen the relationship between Machiavellianism and UPB. The study offers practical suggestions for both project managers and policymakers of construction projects.
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Sustained drug release has attracted increasing interest in targeted drug therapy. However, existing methods of drug therapy suffer drug action time, large fluctuations in the effective concentration of the drug, and the risk of side effects. Here, a biodegradable composite of polybutylene adipate co-terephthalate/polyvinylpyrrolidone (PBAT/PVP) consisting of electrospun hollow microspheres as sustained-released drug carriers is presented. The as-prepared PBAT/PVP composites show faster degradation rate and drug (Erlotinib) release than that of PBAT. Furthermore, PBAT/PVP composites loaded with Erlotinib provide sustained release effect, thus achieving a better efficacy than that after the direct injection of erlotinib due to the fact that the composites allow a high drug concentration in the tumor for a longer period. Hence, this work provides a potential effective solution for clinical drug therapy and tissue engineering using drug microspheres with a sustained release.
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Single-crystalline Ni(2)P nanotubes (NTs) were facilely synthesized by using a Ni nanowire template. The mechanism for the formation of the tubular structures was related to the nanoscale Kirkendall effect. These NTs exhibited a core/shell structure with an amorphous carbon layer that was grown in situ by employing oleylamine as a capping agent. Galvanostatic charge/discharge measurements indicated that these Ni(2)P/C NTs exhibited superior high-rate capability and good cycling stability. There was still about 310â mA h g(-1) retained after 100â cycles at a rate of 5â C. Importantly, the tubular nanostructures and the single-crystalline nature of the Ni(2)P NTs were also preserved after prolonged cycling at a relatively high rate. These improvements were attributed to the stable nanotubular structure of Ni(2)P and the carbon shell, which enhanced the conductivity of Ni(2)P, suppressed the aggregation of active particles, and increased the electrode stability during cycling.
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Carbon materials play a critical role in the advancement of electrochemical energy storage and conversion. Currently, it is still a great challenge to fabricate versatile carbon-based composites with controlled morphology, adjustable dimension, and tunable composition by a one-step synthesis process. In this work, a powerful one-step maltose-based puffing carbonization technology is reported to construct multiscale carbon-based composites on large scale. A quantity of composite examples (e.g., carbon/metal oxides, carbon/metal nitrides, carbon/metal carbides, carbon/metal sulfides, carbon/metals, metal/semiconductors, carbon/carbons) are prepared and demonstrated with required properties. These well-designed composites show advantages of large porosity, hierarchical porous structure, high conductivity, tunable components, and proportion. The formation mechanism of versatile carbon composites is attributed to the puffing-carbonization of maltose plus in situ carbothermal reaction between maltose and precursors. As a representative example, Li2 S is in situ implanted into a hierarchical porous cross-linked puffed carbon (CPC) matrix to verify its application in lithium-sulfur batteries. The designed S-doped CPC/Li2 S cathode shows superior electrochemical performance with higher rate capacity (621 mAh g-1 at 2 C), smaller polarization and enhanced long-term cycles as compared to other counterparts. The research provides a general way for the construction of multifunctional component-adjustable carbon composites for advanced energy storage and conversion.
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Exploring advanced battery materials with fast charging/discharging capability is of great significance to the development of modern electric transportation. Herein we report a powerful synergistic engineering of carbon and deficiency to construct high-quality three/two-dimensional cross-linked Ti2Nb10O29-x@C composites at primary grain level with conformal and thickness-adjustable boundary carbon. Such exquisite boundary architecture is demonstrated to be capable of regulating the mechanical stress and concentration of oxygen deficiency for desired performance. Consequently, significantly improved electronic conductivity and enlarged lithium ion diffusion path, shortened activation process and better structural stability are realized in the designed Ti2Nb10O29-x@C composites. The optimized Ti2Nb10O29-x@C composite electrode shows fast charging/discharging capability with a high capacity of 197 mA h g-1 at 20 C (â¼3 min) and excellent long-term durability with 98.7% electron and Li capacity retention over 500 cycles. Most importantly, the greatest applicability of our approach has been demonstrated by various other metal oxides, with tunable morphology, structure and composition.
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Rational design of hybrid carbon host with high electrical conductivity and strong adsorption toward soluble lithium polysulfides is the main challenge for achieving high-performance lithium-sulfur batteries (LSBs). Herein, novel binder-free Ni@N-doped carbon nanospheres (N-CNSs) films as sulfur host are firstly synthesized via a facile combined hydrothermal-atomic layer deposition method. The cross-linked multilayer N-CNSs films can effectively enhance the electrical conductivity of electrode and provide physical blocking "dams" toward the soluble long-chain polysulfides. Moreover, the doped N heteroatoms and superficial NiO layer on Ni layer can work synergistically to suppress the shuttle of lithium polysulfides by effective chemical interaction/adsorption. In virtue of the unique composite architecture and reinforced dual physical and chemical adsorption to the soluble polysulfides, the obtained Ni@N-CNSs/S electrode is demonstrated with enhanced rate performance (816 mAh g-1 at 2 C) and excellent long cycling life (87% after 200 cycles at 0.1 C), much better than N-CNSs/S electrode and other carbon/S counterparts. Our proposed design strategy offers a promising prospect for construction of advanced sulfur cathodes for applications in LSBs and other energy storage systems.
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The ability to develop novel nanomaterials, and to precisely manufacture their functional structures at the nano- and microscales would benefit many emerging device applications. Herein, as a first example, we describe the exploration of feasibility for the morphological replacement of an iron-based MOF bearing trimeric FeIII-O clusters, MIL-88A preform, with a polyhedral architecture of around 0.4 × 1.2 µm by a lithium ferrite (LiFe3O5) phase via solid-liquid pseudomorphic transformation reactions in biologically and environmentally favourable aqueous lithium hydroxide (LiOH). The reaction proceeds at 170 °C, and the overall reaction can be described as Fe3O(H2O)2(FMA)3(OH)·nH2O (MIL-88A) + 7OH- + Li+ â LiFe3O5 + 3FMA2- + (n + 6) H2O (FMA = fumarate). It was proposed that through the coordination substitution of a MOF ligand by OH-, follow-up dehydration and dehydroxylation, and final H+/Li+ ionic exchange, the monolithiated iron oxides formed thermodynamically at comparatively low temperatures, which transcribe the global nanostructure morphologies of the polyhedral MOF preforms with the hexagonal symmetry, but were composed of interconnected LiFe3O5 particles (about 16 nm) that crystallize in a typical magnetite-type cubic (Fd3[combining macron]m) structure. Given the characteristic texture and structure of the Li-Fe oxide replica, cubic LiFe3O5 was preferentially employed as a new type of electrode material in rechargeable lithium cells. Notably, from the electrochemical evaluation, this metal oxide system exhibits decent anodic performances by undergoing a nine-electron conversion reaction, showing a substantially high specific capacity with an average potential of 0.8 V versus lithium metal, a long service life (700 cycles), and exceptional high-rate capability (up to 2.0 A g-1). The synthetic paradigms demonstrated that the MIL-88A to LiFe3O5 conversion may be transferable to other advanced inorganic-based electrodes from the parent metal compound such as LiFeO2, LiMn2O4 or LiCoO2 toward sustainable energy fields.
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Hierarchical NiCo2O4@NiCo2O4 core/shell nanoflake arrays on nickel foam for high-performance supercapacitors are fabricated by a two-step solution-based method which involves in hydrothermal process and chemical bath deposition. Compared with the bare NiCo2O4 nanoflake arrays, the core/shell electrode displays better pseudocapacitive behaviors in 2 M KOH, which exhibits high areal specific capacitances of 1.55 F cm(-2) at 2 mA cm(-2) and 1.16 F cm(-2) at 40 mA cm(-2) before activation as well as excellent cycling stability. The specific capacitance can achieve a maximum of 2.20 F cm(-2) at a current density of 5 mA cm(-2), which can still retain 2.17 F cm(-2) (98.6% retention) after 4000 cycles. The enhanced pseudocapacitive performances are mainly attributed to its unique core/shell structure, which provides fast ion and electron transfer, a large number of active sites, and good strain accommodation.
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A Fe2O3@NiO core/shell nanorod array on carbon cloth was prepared with the aid of hydrothermal synthesis combined with subsequent chemical bath deposition. The resultant array structure is composed of Fe2O3 nanorods as the core and interconnected ultrathin NiO nanoflakes as the shell. As an anode material for lithium-ion batteries, the heterostructured array electrode delivers a high discharge capacity of 1047.2 mA h g(-1) after 50 cycles at 200 mA g(-1), and 783.3 mA h g(-1) at a high current density of 2000 mA g(-1). The excellent electrochemical performance is attributed to the unique 3D core/shell nanorod array architecture and a rational combination of two electrochemical active materials. Our growth approach offers a simple and effective technique for the design and synthesis of a transition metal oxide hierarchical array that is promising for high-performance electrochemical energy storage.