Surface-Reconstructed Ru-Doped Nickel/Iron Oxyhydroxide Arrays for Efficient Oxygen Evolution.

The generation of an active phase through dynamic surface reconstruction is a promising strategy for improving the activity of electrocatalysts. However, studies investigating the reconstruction process and its impact on the intrinsic properties of the catalysts are scarce. Herein, the surface reconstruction of NiFe2 O4 interfaced with NiMoO4 (Ru-NFO/NMO) facilitated by Ru doping is reported. The electrochemical and material characterizations demonstrate that Ru doping can regulate the electronic structure of NFO/NMO and induce the high-valence state of Ni3.6+ δ , facilitating the surface reconstruction to highly active Ru-doped NiFeOOH/NiOOH (SR-Ru-NFO/NMO). The optimized SR-Ru-NFO/NMO exhibits promising performance in the oxygen evolution reaction, displaying a low overpotential of 229 mV at 10 mA cm-2 and good stability at varying current densities for 80 h. Density functional theory calculations indicate that Ru doping can increase the electron density and optimize intermediate adsorption by shifting the d-band center downward. This work provides valuable insights into the tuning of electrocatalysts by surface reconstruction and offers a rational design strategy for the development of highly active oxygen evolution reaction electrocatalysts.

Rapid Synthesis of Oxygen-Enriched Porous Carbon through a Microwave Method and Its Application in Supercapacitors.

In this study, a strategy for the rapid and simple preparation of porous carbon (PC) using the microwave method was proposed. Oxygen-rich PC was synthesized by microwave irradiation in air, where potassium citrate and ZnCl2 served as the carbon source and microwave absorber, respectively. ZnCl2 achieves microwave absorption through dipole rotation, which uses ion conduction to convert heat energy in the reaction system. In addition, potassium salt etching improved the porosity of PCs. The PC prepared under optimal conditions had a large specific surface area (902 m2·g-1) and exhibited a significant specific capacitance (380 F·g-1) in the three-electrode system at 1 A·g-1. The energy and power densities of the assembled symmetrical supercapacitor device based on PC-375W-0.4 were 32.7 W·h·kg-1 and 0.65 kW·kg-1, respectively, at a current density of 1 A·g-1. Even after 5000 cycles at 5 A·g-1 current density, the excellent cycle life retained 94% of its initial capacitance.

Injectable biocompatible nanocomposites of Prussian blue nanoparticles and bacterial cellulose as a safe and effective photothermal cancer therapy.

Photothermal therapy (PTT) is a novel cancer treatment using a photoabsorber to cause hyperthermia to kill tumors by laser irradiation. Prussian blue nanoparticles (PB NPs) are considered as next-generation photothermal agents due to the facile synthesis and excellent absorption of near-infrared light. Although PB NPs demonstrate remarkable PTT capabilities, their clinical application is limited due to their systemic toxicity. Bacterial cellulose (BC) has been applied to various bio-applications based on its unique properties and biocompatibility. Herein, we design composites with PB NPs and BC as an injectable, highly biocompatible PTT agent (IBC-PB composites). Injectable bacterial cellulose (IBC) is produced through the trituration of BC, with PB NPs synthesized on the IBC surface to prepare IBC-PB composites. IBC-PB composites show in vitro and in vivo photothermal therapeutic effects similar to those of PB NPs but with significantly greater biocompatibility. Specifically, in vitro therapeutic index of IBC-PB composites is 26.5-fold higher than that of PB NPs. Furthermore, unlike PB NPs, IBC-PB composites exhibit no overt toxicity in mice as assessed by blood biochemical analysis and histological images. Hence, it is worth pursuing further research and development of IBC-PB composites as they hold promise as safe and efficacious PTT agents for clinical application.

Fabrication and Performance Evaluation of Gelatin/Sodium Alginate Hydrogel-Based Macrophage and MSC Cell-Encapsulated Paracrine System with Potential Application in Wound Healing.

A gelatin/sodium alginate-based hydrogel microsphere has been fabricated after reaction condition optimization. Macrophages (RAW246.7) and adipose mesenchymal stem cells (ADSC) have been subsequently encapsulated in the microsphere in order to construct a 3D paracrine system for wound healing treatment. The synthesized microsphere displayed neglectable cytotoxicity toward both encapsulated cells until 10 days of incubation, indicating promising biocompatibility of the microsphere. A qRT-PCR and ELISA experiment revealed positive regulation of cytokines (Arg-1, IL-6, IL-8, IL-10, bFGF, HGF, VEGF, TLR-1, and CXCL13) expression regarding macrophage phenotype transformation and anti-inflammatory performance both inside the microsphere and in the microenvironment of established in vitro inflammatory model. Additionally, positive tendency of cytokine expression benefit wound healing was more pronounced in a fabricated 3D paracrine system than that of a 2D paracrine system. Furthermore, the 3D paracrine system exhibited more efficiently in the wound healing rate compared to the 2D paracrine system in an in vitro model. These results suggested the current paracrine system could be potentially used as a robust wound healing dressing.

Nitrogen and Sulfur Codoped Porous Carbon Directly Derived from Potassium Citrate and Thiourea for High-Performance Supercapacitors.

By introducing a heteroatom into carbon material, an effective improvement in capacitance can be realized owing to surface oxidation and reduction reactions of pseudocapacitors. Herein, a simple one-pot carbonization activation method was proposed to convert potassium citrate into three-dimensional interconnected porous carbon (PC). Then, an effective double heteroatom doping method by thiourea was used to prepare nitrogen-sulfur-doped PC (N,S-PC). This porous structure facilitates the storage of a large number of ions and reduces their diffusion path. The synthesized N,S-PC nanomaterial has a capacitance of 674 F/g at 1 A/g in a 1 M H2SO4 electrolyte, can retain 94.41% of the initial capacitance after 10 000 cycles at 5 A/g, and has a long cycle life. More importantly, a symmetric supercapacitor assembled with this material can exhibit an energy density of up to 32.6 (W·h)/kg at a high-power density of 750 W/kg. This is due to the high performance of N,S-PC in supercapacitor electrode materials.

Supramolecular Design Strategy of a Water-Soluble Diphenylguanidine-Cyclodextrin Polymer Inclusion Complex.

Diphenylguanidine (DPG) is a widely used secondary accelerator for the vulcanization of natural rubber (NR) latex. However, its low water solubility and high toxicity limit its use in high-end NR products. In this study, a water-soluble inclusion complex of DPG and a ß-cyclodextrin polymer (ß-CDP), termed DPG-ß-CDP, was prepared through supramolecular interactions and characterized using Fourier-transform infrared spectroscopy, 1H NMR, scanning electron microscopy, and UV-vis spectroscopy techniques. In comparison with that of DPG, the water solubility of DPG-ß-CDP was greatly enhanced because of the water-soluble host molecule. The molar ratio of DPG to the CD unit in ß-CDP was determined to be 1:1. At 25 °C, the binding constant of DPG-ß-CDP was found to be 9.2 × 105 L/mol by UV-vis spectroscopy. The proposed method for forming inclusion complexes with high potential for use as water-soluble vulcanization accelerators is promising.

Recent Development of Flexible and Stretchable Supercapacitors Using Transition Metal Compounds as Electrode Materials.

Flexible and stretchable supercapacitors (FS-SCs) are promising energy storage devices for wearable electronics due to their versatile flexibility/stretchability, long cycle life, high power density, and safety. Transition metal compounds (TMCs) can deliver a high capacitance and energy density when applied as pseudocapacitive or battery-like electrode materials owing to their large theoretical capacitance and faradaic charge-storage mechanism. The recent development of TMCs (metal oxides/hydroxides, phosphides, sulfides, nitrides, and selenides) as electrode materials for FS-SCs are discussed here. First, fundamental energy-storage mechanisms of distinct TMCs, various flexible and stretchable substrates, and electrolytes for FS-SCs are presented. Then, the electrochemical performance and features of TMC-based electrodes for FS-SCs are categorically analyzed. The gravimetric, areal, and volumetric energy density of SC using TMC electrodes are summarized in Ragone plots. More importantly, several recent design strategies for achieving high-performance TMC-based electrodes are highlighted, including material composition, current collector design, nanostructure design, doping/intercalation, defect engineering, phase control, valence tuning, and surface coating. Integrated systems that combine wearable electronics with FS-SCs are introduced. Finally, a summary and outlook on TMCs as electrodes for FS-SCs are provided.

Confinement Growth of Layered WS2 in Hollow Beaded Carbon Nanofibers with Synergistic Anchoring Effect to Reinforce Li+ /Na+ Storage Performance.

Novel nitrogen doped (N-doped) hollow beaded structural composite carbon nanofibers are successfully applied for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). Tungsten disulfide (WS2 ) nanosheets are confined, through synergistic anchoring, on the surface and inside of hollow beaded carbon nanofibers (HB CNFs) via a hydrothermal reaction method to construct the hierarchical structure HB WS2 @CNFs. Benefiting from this unique advantage, HB WS2 @CNFs exhibits remarkable lithium-storage performance in terms of high rate capability (≈351 mAh g-1 at 2 A g-1 ) and stable long-term cycle (≈446 mAh g-1 at 1 A g-1 after 100 cycles). Moreover, as an anode material for SIBs, HB WS2 @CNFs obtains excellent long cycle life and rate performance. During the charging/discharging process, the evolution of morphology and composition of the composite are analyzed by a set of ex situ methods. This synergistic anchoring effect between WS2 nanosheets and HB CNFs is capable of effectively restraining volume expansion from the metal ions intercalation/deintercalation process and improving the cycling stability and rate performance in LIBs and SIBs.

Synthesis of Copper Oxide/Graphite Composite for High-Performance Rechargeable Battery Anode.

A novel copper oxide/graphite composite (GCuO) anode with high capacity and long cycle stability is proposed. A simple, one-step synthesis method is used to prepare the GCuO, through heat treatment of the Cu ion complex and pristine graphite. The gases generated during thermal decomposition of the Cu ion complex (H2 and CO2 ) induce interlayer expansion of the graphite planes, which assists effective ion intercalation. Copper oxide is formed simultaneously as a high-capacity anode material through thermal reduction of the Cu ion complex. Material analyses reveal the formation of Cu oxide nanoparticles and the expansion of the gaps between the graphite layers from 0.34 to 0.40 nm, which is enough to alleviate layer stress for reversible ion intercalation for Li or Na batteries. The GCuO cell exhibits excellent Li-ion battery half-cell performance, with a capacity of 532 mAh g-1 at 0.2 C (C-rate) and capacity retention of 83 % after 250 cycles. Moreover, the LiFePO4 /GCuO full cell is fabricated to verify the high performance of GCuO in practical applications. This cell has a capacity of 70 mAh g-1 and a coulombic efficiency of 99 %. The GCuO composite is therefore a promising candidate for use as an anode material in advanced Li- or Na-ion batteries.

Novel Synthesis, Coating, and Networking of Curved Copper Nanowires for Flexible Transparent Conductive Electrodes.

In this work, a whole manufacturing process of the curved copper nanowires (CCNs) based flexible transparent conductive electrode (FTCE) is reported with all solution processes, including synthesis, coating, and networking. The CCNs with high purity and good quality are designed and synthesized by a binary polyol coreduction method. In this reaction, volume ratio and reaction time are the significant factors for the successful synthesis. These nanowires have an average 50 nm in width and 25-40 µm range in length with curved structure and high softness. Furthermore, a meniscus-dragging deposition (MDD) method is used to uniformly coat the well-dispersed CCNs on the glass or polyethylene terephthalate substrate with a simple process. The optoelectrical property of the CCNs thin films is precisely controlled by applying the MDD method. The FTCE is fabricated by networking of CCNs using solvent-dipped annealing method with vacuum-free, transfer-free, and low-temperature conditions. To remove the natural oxide layer, the CCNs thin films are reduced by glycerol or NaBH4 solution at low temperature. As a highly robust FTCE, the CCNs thin film exhibits excellent optoelectrical performance (T = 86.62%, R(s) = 99.14 Ω â—»(-1)), flexibility, and durability (R/R(0) < 1.05 at 2000 bending, 5 mm of bending radius).

Synthesis of Cu3Sn alloy nanocrystals through sequential reduction induced by gradual increase of the reaction temperature.

Cu3Sn alloy nanocrystals are synthesized by sequential reduction of Cu and Sn precursors through a gradual increase of the reaction temperature. By transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), UV/Vis spectroscopy, and X-ray diffraction (XRD) analyses, the alloy formation mechanism of Cu3Sn nanocrystals has been studied. The incremental increase of the reaction temperature sequentially induces the reduction of Sn, the diffusion of Sn into the preformed Cu nanocrystals, resulting in the intermediate phase of Cu-Sn alloy nanocrystals, and then the formation of Cu3Sn alloy nanocrystals. We anticipate that the synthesis of Cu3Sn alloy nanocrystals encourages studies toward the synthesis of various alloy nanomaterials.

Facile synthesis of oxidation-resistant copper nanowires toward solution-processable, flexible, foldable, and free-standing electrodes.

Oxidation-resistant copper nanowires (Cu NWs) are synthesized by a polyol reduction method. These Cu NWs show excellent oxidation resistance, good dispersibility, and have a low sintering temperature. A Cu NW-based flexible, foldable, and free-standing electrode is fabricated by filtration and a sintering process. The electrode also exhibits high electrical conductivity even bending, folding, and free-standing.

Facile synthesis of one-dimensional iron-oxide/carbon hybrid nanostructures as electrocatalysts for oxygen reduction reaction in alkaline media.

One-dimensional iron-oxide/carbon hybrid nano tubular structures were synthesized via anodic aluminium oxide (AAO) template method. Highly unform iron oxide nanoparticles and carbon structures were formed simultaneously on the wall surface of the AAO template from an iron-oleate precursor by solventless thermal decomposition method. The 1D iron-oxide/carbon nanostructures were obtained after removing the AAO template. The typical size of the iron oxide nanoparticles was - 6 nm, and the nanoparticles had a crystalline structure of maghemite (γ-Fe2O3), which was determined from the HRTEM and X-ray diffraction (XRD). This nanocrystalline spinel structure could provide more active sites for oxygen reduction reaction (ORR) catalysis due to the higher specific surface area and numerous defects. As an ORR catalyst, the hybrid nanotubes showed higher limiting mass activity (8.8 A/g) and a more positive onset potential (-0.241 V, vs. Hg/HgCl) than iron oxide nanoparticles in alkaline media. This electrocatalytic activity of the nanocomposites is mainly attributed to the synergetic effects of the iron oxide nanoparticles and carbon matrix in the one-dimensional nanostructure.

Tailoring Versatile Cathodes and Induced Anodes for Zn-Se Batteries: Anisotropic Orientation of Tin-Based Materials within Bowl-In-Ball Carbon.

The advancement of Zn-Se batteries has been hindered by significant challenges, such as the sluggish kinetics of Se cathodes, limited Se loading, and uncontrollable formation of Zn dendrites. In this study, a bidirectional optimization strategy is devised for both cathode and anode to bolster the performance of Zn-Se batteries. A novel bowl-in-ball structured carbon (BIBCs) material is synthesized to serve as a nanoreactor, in which tin-based materials are grown and derived in situ to construct cathodes and anodes. Within the cathode, the multifunctional host material (SnSe@BIBCs) exhibits large adsorption capacity for selenium, and demonstrates supreme catalytic properties and spatially confined characteristics toward the selenium reduction reaction (SeRR). On the anode, Sn@BIBCs displays triple-induced properties, including the zincophilic of the internal metallic Sn, the homogenized spatial electric field from the 3D spatial structure, and the curvature effect of the bowl-shaped carbon. Collectively, these factors induce preferential nucleation of Zn, ensuring its uniform deposition. As a result, the integrated Zn-Se battery system achieves a remarkable specific capacity of up to 603 mAh g-1 and an impressive energy density of 581 W kg-1, highlighting its tremendous potential for practical applications.

Enhancing Lithium-Ion Diffusion Kinetics in a 3D Lithium Metal Host through Surface Modification with Hierarchical Multimetal Oxides.

Lithium metal is a promising anode candidate to achieve high-energy-density lithium metal batteries (LMBs) due to its ultrahigh theoretical capacity (3860 mA h g-1) and low electrochemical potential (-3.04 V vs S.H.E). Unfortunately, the commercialization of lithium metal anodes is hindered by the growth of Li dendrites and the infinite Li volume changes during the cycling process. Herein, we introduce a 3D hierarchical multimetal oxide nanowire framework as a current collector for Li metal anodes. The hierarchical metal oxide layers of CoO and CuxO provide abundant Li nucleation sites and thus offer uniform Li plating and regulate Li nucleation during the charge/discharge process. As a result, half cells present a prolonging Coulombic efficiency of 97% at 1 mA cm-2 with a capacity of 1 mA h cm-2 for over 300 cycles. A stable cyclability of symmetric cells is demonstrated under 1 mA cm-2 with a capacity of 1 mA h cm-2 for 1500 h. Full cells paired with an LFP cathode show a stable capacity of 131.5 mA h g-1 with a capacity retention of 92% for 200 cycles. These results will shed insights into the design of 3D Cu current collectors for high-performance composite Li metal anodes.

Preparation of cyclodextrin polymer-functionalized polyaniline/MXene composites for high-performance supercapacitor.

Controlled aggregation is of great significance in designing nanodevices with high electrochemical performance. In this study, an in situ aggregation strategy with cyclodextrin polymer (CDP) was employed to prepare polyaniline (PANI)/MXene (MX) composites. MXene served as a two-dimensional structure template. Due to supramolecular interactions, CDP could be controllably modified with PANI layers, effectively preventing the self-polymerization of PANI. As a result, this integration facilitated a more uniform growth of PANI on MXene and further improved the capacitance performance of CDP-MX/PA. In a three-electrode system, the specific capacitance of MX/PA at 1 A g-1 was 460.8 F g-1, which increased to 523.8 F g-1 after CDP-induced growth. CDP-MX/PA exhibited a high energy density of 27.7 W h kg-1 at a power density of 700 W kg-1. This suggests that the synthetic strategy employed in this study holds promise in providing robust support for the preparation of high-performance energy-storage device.

A densely packed air-stable free-standing film with FeP nanoparticles@C@P-doped reduced graphene oxide for sodium-ion batteries.

Developing a facile strategy which enhances the structural stability and air/moisture stability of transition metal phosphides for practical applications is important but challenging. Herein, we designed a densely packed free-standing film consisting of carbon-coated FeP nanoparticles anchored on P-doped graphene (FeP@C@PG film) through solventless thermal decomposition and the roll-press method. Phytic acid serves a multifunctional role as both a phosphorus source to prepare ultrafine FeP nanoparticles and a protective layer to improve air stability along with hydrophobic graphene and maximize the utilization of phosphide. This structure can enhance electron/ion transport kinetics, allowing for full utilization of active materials, and buffer large volume expansions while preventing pulverization/aggregation during cycling. Noticeably, the densely packed structure can greatly enhance oxidation resistance by effectively blocking the penetration of air/moisture. Therefore, the FeP@C@PG film delivers a stable reversible capacity of 536.6 mA h g-1 after 1000 cycles at 1 A g-1 with good capacity retention, an excellent rate capability of 440.7 mA h g-1 at 5 A g-1, and excellent oxidation stability at 80 °C in air. Furthermore, a pouch-type full-cell exhibits excellent rate/cycling performance and bendability. This study provides a new direction for the rational design and practical applications of advanced P-based materials used in alkali metal-ion batteries.

In vitro magnetic hyperthermia properties of angle-shaped superparamagnetic iron oxide nanoparticles synthesized by a bromide-assisted polyol method.

Currently, research on superparamagnetic iron oxide nanoparticles (SPIONs) for magnetic hyperthermia applications is steadily increasing. In this work, SPIONs were synthesized by the bromide-assisted polyol method and angle-shaped SPIONs were successfully generated with the optimized concentration of bromide. The influence of bromide concentration on the shape of the generated SPIONs as well as the heating characteristics under an alternating magnetic field (AMF) was thoroughly investigated. At a concentration of 20 mg mL-1 of the angle-shaped SPIONs, the highest temperature curve up to 23 °C was observed under AMF with 140 Oe and 100 kHz for 10 min. With the biotoxicity assay, no significant cytotoxicity was observed in the normal fibroblast of HFB-141103 as well as tumor cells of U87MG and FSall treated with the angle-shaped SPIONs at a concentration below 100 µg mL-1. However, significantly decreased cellular viability was observed in tumor cells of U87MG and FSall treated with 100 µg mL-1 of the angle-shaped SPIONs under AMF with 140 Oe and 100 kHz. Based on these results, it is thought that the angle-shaped SPIONs synthesized by the bromide-assisted polyol method will provide highly efficient magnetic hyperthermia therapy for cancers under biologically safe AMF with 140 Oe and 100 kHz.

Wrapping silicon microparticles by using well-dispersed single-walled carbon nanotubes for the preparation of high-performance lithium-ion battery anode.

Silicon microparticles (SiMPs) show considerable promise as an anode material in high-performance lithium-ion batteries (LIBs) because of their low-cost starting material and high capacity. The failure issues associated with the intrinsically low conductivity and significant volume expansion of Si have largely been resolved by designing silicon/carbon composites using carbon nanotubes (CNTs). The CNTs are important in terms of stress dissipation and the conductive network in Si/CNT composites. Here, we synthesized a SiMP/2D CNT sheet wrapping composite (SiMP/CNT wrapping) via a facile freeze-drying method with the use of highly dispersed single-walled CNTs. In this work, the well-dispersed CNTs are easily mixed with Si, resulting in effective CNT wrapping on the SiMP surface. During freeze-drying, the CNTs are self-assembled into a segregated 2D CNT sheet morphology via van der Waals interactions. The resulting CNT wrapping shows a unique wide range of conductive networks and mesh-like CNT sheets with void spaces. The SiMP/CNT wrapping 9 : 1 electrode exhibits good rate and cycle performance. The first charge/discharge capacity of SiMP/CNT wrapping 9 : 1 is 3160.7 mA h g-1/3469.1 mA h g-1 at 0.1 A g-1 with superior initial coulombic efficiency of 91.11%. After cycling, the SiMP/CNT wrapping electrode shows good structural integrity with preserved electrical conductivity. The superior electrochemical performance of the SiMP/CNT wrapping composite can be explained by an extensive conductive CNT network on the SiMPs and facile lithium-ion diffusion via mesh-like CNT wrapping.

Ultrafast Synthesis of Graphene-Embedded Cyclodextrin-Metal-Organic Framework for Supramolecular Selective Absorbency and Supercapacitor Performance.

Limited by preparation time and ligand solubility, synthetic protocols for cyclodextrin-based metal-organic framework (CD-MOF), as well as subsequent derived materials with improved stability and properties, still remains a challenge. Herein, an ultrafast, environmentally friendly, and cost-effective microwave method is proposed, which is induced by graphene oxide (GO) to design CD-MOF/GOs. This applicable technique can control the crystal size of CD-MOFs from macro- to nanocrystals. CD-MOF/GOs are investigated as a new type of supramolecular adsorbent. It can selectively adsorb the dye molecule methylene green (MG) owing to the synergistic effect between the hydrophobic nanocavity of CDs, and the abundant O-containing functional groups of GO in the composites. Following high temperature calcination, the resulting N, S co-doped porous carbons derived from CD-MOF/GOs exhibit a high capacitance of 501 F g-1 at 0.5 A g-1 , as well as stable cycling stability with 90.1% capacity retention after 5000 cycles. The porous carbon exhibits good electrochemical performance due to its porous surface containing numerous electrochemically active sites after dye adsorption and carbonization. The design strategy by supramolecular incorporating a variety of active molecules into CD-MOFs optimizes the properties of their derived materials, furthering development toward the fabrication of zeitgeisty and high-performance energy storage devices.