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Manipulating catalytic active sites and reaction kinetics in alkaline media is crucial for rationally designing mighty water-splitting electrocatalysts with high efficiency. Herein, the coupling between oxygen vacancies and interface engineering is highlighted to fabricate a novel amorphous/crystalline CrOx -Ni3 N heterostructure grown on Ni foam for accelerating the alkaline hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Density functional theory (DFT) calculations reveal that the electron transfer from amorphous CrOx to Ni3 N at the interfaces, and the optimized Gibbs free energies of H2 O dissociation (ΔGH-OH ) and H adsorption (ΔGH ) in the amorphous/crystalline CrOx -Ni3 N heterostructure are conducive to the superior and stable HER activity. Experimental data confirm that numerous oxygen vacancies and amorphous/crystalline interfaces in the CrOx -Ni3 N catalysts are favorable for abundant accessible active sites and enhanced intrinsic activity, resulting in excellent catalytic performances for HER and OER. Additionally, the in situ reconstruction of CrOx -Ni3 N into highly active Ni3 N/Ni(OH)2 is responsible for the optimized OER performance in a long-term stability test. Eventually, an alkaline electrolyzer using CrOx -Ni3 N as both cathode and anode has a low cell voltage of 1.53 V at 10 mA cm-2 , together with extraordinary durability for 500 h, revealing its potential in industrial applications.
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Metal-organic frameworks (MOFs) are a novel class of crystalline materials which find widespread applications in the field of microporous conductors, catalysis, separation, biomedical engineering, and electrochemical sensing. With a specific emphasis on the MOF composites for electrochemical sensor applications, this review summarizes the recent construction strategies on the development of conductive MOF composites (post-synthetic modification of MOFs, in situ synthesis of functional materials@MOFs composites, and incorporating electroactive ligands). The developed composites are revealed to have excellent electrochemical sensing activity better than their pristine forms. Notably, the applicable functionalized MOFs to electrochemical sensing/biosensing of various target species are discussed. Finally, we highlight the perspectives and challenges in the field of electrochemical sensors and biosensors for potential directions of future development.
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Técnicas Biossensoriais , Estruturas Metalorgânicas , Catálise , Condutividade Elétrica , Estruturas Metalorgânicas/químicaRESUMO
Solid-state lithium metal batteries built with composite polymer electrolytes using cubic garnets as active fillers are particularly attractive owing to their high energy density, easy manufacturing and inherent safety. However, the uncontrollable formation of intractable contaminant on garnet surface usually aggravates poor interfacial contact with polymer matrix and deteriorates Li+ pathways. Here we report a rational designed intermolecular interaction in composite electrolytes that utilizing contaminants as reaction initiator to generate Li+ conducting ether oligomers, which further emerge as molecular cross-linkers between inorganic fillers and polymer matrix, creating dense and homogeneous interfacial Li+ immigration channels in the composite electrolytes. The delicate design results in a remarkable ionic conductivity of 1.43×10-3 â S cm-1 and an unprecedented 1000â cycles with 90 % capacity retention at room temperature is achieved for the assembled solid-state batteries.
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Microencapsulated phase change materials (MicroPCMs)-incorporated in epoxy composites have drawn increasing interest due to their promising application potential in the fields of thermal energy storage and temperature regulation. However, the study on the effect of MicroPCMs on their microstructure, thermal and viscoelastic properties is quite limited. Herein, a new type of smart epoxy composite incorporated with polyurea (PU)-shelled MicroPCMs was fabricated via solution casting method. Field emission-scanning electron microscope (FE-SEM) images revealed that the MicroPCMs were uniformly distributed in the epoxy matrix. The thermal stabilities, conductivities, phase change properties, and dynamic mechanical behaviors of the composite were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), thermal constant analyzer and infrared thermography. The results suggested that the heat storage ability of the composites was improved by increasing the MicroPCMs content. The thermal stability of MicroPCMs was found to be enhanced after incorporation into the matrix, and the MicroPCMs-incorporated epoxy composites showed a good thermal cycling reliability. Moreover, the incorporation of MicroPCMs reduced the composites' storage modulus but increased the glass transition temperature (Tg) as a result of their restriction to the chain motion of epoxy resin. Besides, a less marked heating effect for the composite was explored through infrared thermography analysis, demonstrating the good prospect for temperature regulation application.
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Cápsulas/síntese química , Resinas Epóxi/química , Transição de Fase , Alcanos/química , Emulsões/química , Temperatura Alta , Cinética , Teste de Materiais/métodos , Fenômenos Mecânicos , Tamanho da Partícula , Reprodutibilidade dos Testes , Propriedades de Superfície , Temperatura , TermodinâmicaRESUMO
Constructing efficient thermal management system to settle the thermal runaway of energy storage devices via employing phase change microcapsules (MEPCMs) is of great significance. However, it is still a challenge that the conventional MEPCMs go against the electrochemical performance and hardly be homogenously fixed in the electrodes. In order to conquer these long-standing critical issues, we designed a novel electrochemically active double-shell phase change microcapsule by introducing polypyrrole on the surface of dense amine resin shell of the conventional inert MEPCM. The active MEPCMs@PPy are uniformly immobilized on the surface of the electrode material using reduced graphene oxide to ensure the stable and efficient operation of the flexible supercapacitor. The assembled all-solid-state supercapacitor containing MEPCMs@PPy (SCs@MEPCMs@PPy) lagged 103 s to 55 °C than the SCs@00 without the added phase change material. At a high temperature of 55 °C and a scan rate of 50 mV s-1, SCs@MEPCMs@PPy exhibits an areal specific capacitance of 110.6 mA cm-2, which is higher than that of the original SCs@MEPCMs. A capacitance retention of 79.8 % and coulombic efficiency of 98.4 % can be reached after 3000 cycles. This study opens a new avenue for developing applicable microencapsulated phase change materials in temperature-regulated electrode systems for supercapacitors and alkaline-ion batteries.
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Although solid composite electrolytes show tremendous potential for the practical solid-state lithium metal batteries, searching for a straightforward tactic to promote the ion conduction at electrolyte/electrode interface, especially settling lithium dendrites formation caused by the concentration gradient polarization, are still long-standing problems. Here, the authors report a corrugated 3D nanowires-bulk ceramic-nanowires (NCN) skeleton reinforced composite electrolyte with regulated interfacial Li-ion transport behavior. The special and integrated NCN skeleton endows the electrolyte with fast Li-ion transfer and solves the Li+ concentration polarization at electrode/electrolyte interface, thereby eliminating the energy barrier originated from the redistribution of charge carriers and offering homogeneous interfacial Li-ion flux on lithium anode. As a "double insurance", the bulk ceramic sheet in 3D framework enables the electrolyte to block the mobility of anions. The rational designed NCN composite electrolyte exhibits excellent ionic conductivity and the assembled all-solid-state battery possesses 90.2% capacity retention after 500 cycles. The proposed strategy affords a special insight in designing high-performance solid composite electrolytes.
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Multichannel regulable circularly polarized luminescence (CPL) is fascinating because of its fundamental and application interest. There are few reports on helical sense (P-/M-helix) modulation and chiral signal amplification of polyacetylenes with the assistance of achiral polymers and further applications in precisely and conveniently regulating CPL handedness and magnitude. Herein, a helical poly(phenylacetylene)-based CPL-active system was constructed, in which CPL inversion occurred by adding achiral PMMA into a helical poly(phenylacetylene)-CHCl3 solution. Significantly, there is almost 10 times magnification of luminescence dissymmetry factor values (|glum|) during this process. The above phenomena could be ascribed to the PMMA-assisted polyene backbone elongation and the formation of a more ordered helical structure for the poly(phenylacetylene)s. More interestingly, the CPL signal can be facilely inverted and switched by simply changing the thickness of the PPhAD/PMMA layer. The temperature-driven dynamic CPL handedness inversion and magnitude modulation can also be achieved. Based on the multiple regulations for CPL, logic operations were developed, and the practical application is further facilitated by designing various CPL patterns. This study establishes effective and convenient strategies to switch the handedness, magnitude, and wavelength of CPL, which may generate a breakthrough in the manufacturing of CPL-active smart materials and devices with promising application potential.
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Metallic vanadium dichalcogenides with high conductivity and large layer spacing are fantastically potential to be cathode candidates for aqueous zinc ion batteries. However, simply reliance on the reversible Zn2+ intercalation/deintercalation process in the layer structure of vanadium dichalcogenides makes it suffer from low specific capacity and limited cycling number. Here we report a facile in-situ electrochemical oxidation strategy to boost the zinc ion storage capacity of interlayer-expanded vanadium disulfide (VS2·NH3) hollow spheres with satisfying cyclic stability. The hydrated vanadium oxide (V2O5·nH2O) generated from oxidized VS2·NH3, are endowed with reduced nanosheet size and subordinated porous structure, which provides abundant accessible sites and accelerates the zinc ion diffusion process. As a result, the VS2·NH3 derived cathode after the electrochemical oxidation process delivers a high reversible capacity of 392â¯mAâ¯hâ¯g-1 at 0.1 A g-1 and long cyclic stability (110% capacity retention at 3 A g-1 after 2000 cycles). The efficient oxidation process of VS2·NH3 cathode and the storage mechanism in the subsequent cycles are schematically investigated. This work not only reveals the zinc ion storage mechanism of the oxidized VS2·NH3 but also sheds light on advanced design for high-performance Zn ion cathode materials.
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All-solid-state lithium metal batteries are highly attractive because of their high energy density and inherent safety. However, it is still a great challenge to design the solid electrolytes with high ionic conductivity at room temperature and good electrode/electrolyte interfacial compatibility simultaneously in a facile and scalable way. In this work, for the first time, the combination of salt affluent Poly(ethylene oxide) with Li6.75La3Zr1.75Ta0.25O12 nanofibers was designed and intensively evaluated. The synergistic effect of each component in the electrolyte enhances the ionic conductivity to 2.13 × 10-4 S cm-1 at 25 °C and exhibits a high transference number of 0.57. The composite electrolyte possesses superior interfacial stability against Li metal for over 680 h in Li symmetric cells even at a relatively high current density of 2 mA cm-2. The all-solid-state batteries employing the solid electrolytes exhibit excellent cycling stability at room temperature and superior safety performance. This work proposes a brand-new strategy to design and fabricate solid electrolytes in a versatile way for room-temperature all-solid-state batteries.
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This paper reports on a chip cooling solution using polydimethylsiloxane (PDMS) based microfluidic devices filled with n-Octadecane. A thick SU-8 layer of 150 µm is used as the master mold for patterning PDMS fabrication. With the SU-8 mold, patterns with straight lines at microscale have been fabricated with standard micro-electro-mechanical system (MEMS) technology. Thermal polymer bonding technique is used to bond the PDMS pattern directly to a flat polydimethylsiloxane (PDMS) film which results in the sealed microchannels. n-Octadecane as a phase-change material has been successfully filled in the microchannels using a dispensing machine. Infrared thermal image shows a sharp contrast of the temperature distribution between the chip with n-Octadecane and the empty chip during the same heating process. This result indicates an efficient cooling performance of the microchannel device with phase-change material. A thermal stimulation test demonstrates that a 16 °C-lower temperature difference can be achieved. This microchannel device, benefited from the flexibility of PDMS substrate, shows specific advantages in meeting the need for the heat dissipation of flexible electronics such as flexible displays, electronic skins, and wearable electronics. Latent heat of the phase-change material can keep the temperature of devices relatively lower over a period of time, which shows potential application values on discontinuously active flexible electronic devices.
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Monodisperse silver nanoparticles (Ag NPs) were facilely loaded on the inner and outer surface of hierarchical wrinkled mesoporous silica (WMSs) via an in situ chemical reduction, and the antibacterial capacity of the obtained nanocomposite was investigated in detail. Typical sulfydryl-functionalized wrinkled mesoporous silica nanoparticle with radical pore channels was firstly prepared through sol-gel technique with cetyltrimethylammonium bromide (CTAB) as the templating surfactant. After sulfonation of the as-prepared WMSs, Ag(+) ions were then densely locked up on the inner and outer surface of WMSs via electrostatic interactions. Well distributed Ag NPs (ca. 3-5nm) on WMSs without any agglomeration were finally obtained via a simple in situ reduction reaction with sodium borohydride. Minimal inhibitory concentration (MIC) and minimal bactericidal concentration (MBC) test indicated that the obtained products can achieve durable and much better antibacterial performance both against Gram-negative bacterium Escherichia coli (E. coli) and Gram-positive bacterium Staphylococcus aureus (S. aureus) comparing to pure colloidal silver nanoparticles, which rendered them as favorable candidate for the development of effective antibacterial agents.
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Antibacterianos/química , Nanopartículas Metálicas/química , Dióxido de Silício/química , Prata/química , Antibacterianos/farmacologia , Cetrimônio , Compostos de Cetrimônio/química , Escherichia coli/efeitos dos fármacos , Nanopartículas Metálicas/toxicidade , Nanopartículas Metálicas/ultraestrutura , Testes de Sensibilidade Microbiana , Microscopia Eletrônica de Varredura , Oxirredução , Porosidade , Staphylococcus aureus/efeitos dos fármacosRESUMO
The application of thermal energy storage with phase change materials (PCMs) for energy efficiency of buildings grew rapidly in the last few years. In this research, octadecane paraffin was served as a PCM, and a structural concrete with the function of indoor temperature control was developed by using a macro-encapsulated PCM hollow steel ball (HSB). The macro-encapsulated PCM-HSB was prepared by incorporation of octadecane into HSBs through vacuum impregnation. Test results showed that the maximum percentage of octadecane carried by HSBs was 80.3% by mass. The macro-encapsulated PCM-HSB has a latent heat storage capacity as high as 200.5 J/g. The compressive strength of concrete with macro-encapsulated PCM-HSB at 28 days ranged from 22 to 40 MPa. The indoor thermal performance test revealed that concrete with macro-encapsulated octadecane-HSB was capable of reducing the peak indoor air temperature and the fluctuation of indoor temperature. It can be very effective in transferring the heating and cooling loads away from the peak demand times.