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Metal-doped ruthenium oxides with low prices have gained widespread attention due to their editable compositions, distorted structures, and diverse morphologies for electrocatalysis. However, the mainstream challenge lies in breaking the so-called seesaw relationship between activity and stability during acidic oxygen evolution reaction (OER). Herein, strain wave-featured Mn-RuO2 nanowires (NWs) with asymmetric Ru-O-Mn bonds are first fabricated by thermally driven rapid solid phase conversion from RuMn alloy nanoparticles (NPs) at moderate temperature (450 °C). In 0.5 M H2SO4, the resultant NWs display a surprisingly ultralow overpotential of 168 mV at 10 mA cm-2 and run at a stable cell voltage (1.67 V) for 150 h at 50 mA cm-2 in PEMWE, far exceeding IrO2||Pt/C assemble. The simultaneous enhancement of both activity and stability stems from the presence of dense strain waves composed of alternating compressive and tensile ones in the distorted NWs, which collaboratively activate the Ru-O-Mn sites for faster OER. More importantly, the atomic strain waves trigger dynamic Ru-O-Mn regeneration via the refilling of oxygen vacancies by oxyanions adsorbed on adjacent Mn and Ru sites, achieving long-term stability. This work opens a door to designing non-precious metal-assisted ruthenium oxides with unique strains for practical application in commercial PEMWE.
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Rare earth microalloying nanocrystals have gotten widespread attention due to their unprecedented performances with customization-defected nanostructures, divided energy bands, and ensembled surface chemistry, regarded as a class of ideal electrocatalysts for oxygen evolution reaction (OER). Herein, a lanthanide microalloying strategy is proposed to fabricate strain wave-featured LaRuIr nanocrystals with oxide skin through a rapid crystal nucleation, using thermally assisted sodium borohydride reduction in aqueous solution at 60 °C. The atomic strain waves with alternating compressive and tensile strains, resulting from La-stabilized edge dislocations in form of Cottrell atmospheres. In 0.5 m H2SO4, the LaRuIr displays an overpotential of 184 mV at 10 mA cm-2, running at a steadily cell voltage for 60 h at 50 mA cm-2, eightfold enhancement of IrO2||Pt/C assemble in PEMWE. The coupled compressive and tensile profiles boost the OER kinetics via faster AEM and LOM pathways. Moreover, the tensile facilitates surface structure stabilization through dynamic refilling of lattice oxygen vacancies by the adsorbed oxyanions on La, Ru, and Ir sites, eventually achieving a long-term stability. This work contributes to developing advanced catalysts with unique strain to realize simultaneous improvement of activity and durability by breaking the so-called seesaw relationship between them during OER for water splitting.
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Atomic substructure engineering provides new opportunities for the designing newly and efficient catalysts with diverse atom ensembles, trimmed electron bands, and way-out coordination environments, creating unique contributing to concertedly catalyze water oxidation, which is of great significance for proton exchange membrane water electrolysis (PEMWE). Herein, nest-scheme RuIrLa nanocrystals with dense coherent interfaces as built-in substructures are firstly fabricated by using commercial ZnO particles as acid-removable templates, through a La-stabilized coherent epitaxial growth of nanoparticles (NPs). The obtained nests exhibit a low overpotential of 198 mV at 10 mA cm-2, and the RuIrLa||Pt/C module equipped in PEMWE operates stably at a cell voltage potential of 1.69 V at 100 mA cm-2 in 0.5 M H2SO4 for 55 h, which is far beyond the current IrO2||Pt/C. Within the nests, the position at the interface shows high tensile/compressive strain, significantly reducing the OER activation energy. More importantly, the La termination-stabilized coherent interfaces within the nests creates a unique self-healing process for the outstanding long-term stability. This work provides a promising substructure engineering to develop efficient catalysts with abundant substructures, such as coherent interfaces, dislocations, or grain boundaries, thereby realizing concerted improvement of activity and durability toward water oxidation.
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In this Letter, we demonstrate 8°-tilted fiber Bragg grating (TFBG) inscription in single-mode step-index TOPAS/ZEONEX polymer optical fibers (POFs) using a 520â nm femtosecond laser and the line-by-line (LbL) writing technique. As a result of the tilt angle and the fiber refractive index, a large spectral range of cladding mode resonances covering 147â nm is obtained. The evolution of the transmitted spectrum is analyzed as a function of the surrounding refractive index (SRI) in a large range from 1.30 to 1.50. The cutoff cladding mode shows a refractive index sensitivity of 507â nm/RIU (refractive index unit). For single-resonance tracking near the cutoff mode, the sensitivity is at least 6â nm/RIU, depending on the exact wavelength position of the cladding modes. The main originality of our work is that it produces, for the first time, to the best of our knowledge, a TFBG in POF that operates in the refractive index range of aqueous solutions. The sensing capability for a large range of refractive index values is also relevant for (bio)chemical sensing in different media.
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We experimentally report high reflectivity on the poly(methyl methacrylate) (PMMA)-based polymer optical fiber Bragg gratings by means of a 266 nm pulsed laser and phase mask technique. In the first recipe, fiber Bragg gratings (FBGs) were manufactured with a single pulse up to 3.7 mJ. After post-annealing, a stable refractive index change up to 4.2×10-4 was obtained. In the second recipe, FBGs were inscribed by 22 pulses with a lower pulse energy of 1.4 mJ, showing a stable refractive index change of 6.2×10-4. Both behaviors may mainly be attributed to the movement of initiating radicals arising from benzyl dimethyl ketal (BDK) under UV irradiation. The high refractive index change in step-index fibers paves the way to tilted FBG manufacturing with large tilt angles potentially for biomedical applications.
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Inspired by the spongy bone structures, three-dimensional (3D) sponge-like carbons with meso-microporous structures are synthesized through one-step electro-reduction of CO2 in molten carbonate Li2 CO3 -Na2 CO3 -K2 CO3 at 580 °C. SPC4-0.5 (spongy porous carbon obtained by electrolysis of CO2 at 4â A for 0.5â h) is synthesized with the current efficiency of 96.9 %. SPC4-0.5 possesses large electrolyte ion accessible surface area, excellent wettability and electronical conductivity, ensuring the fast and effective mass and charge transfer, which make it an advcanced supercapacitor electrode material. SPC4-0.5 exhibits a specific capacitance as high as 373.7â F g-1 at 0.5â A g-1 , excellent cycling stability (retaining 95.9 % of the initial capacitance after 10000 cycles at 10â A g-1 ), as well as high energy density. The applications of SPC4-0.5 in quasi-solid-state symmetric supercapacitor and all-solid-state flexible devices for energy storage and wearable piezoelectric sensor are investigated. Both devices show considerable capacitive performances. This work not only presents a controllable and facile synthetic route for the porous carbons but also provides a promising way for effective carbon reduction and green energy production.
Assuntos
Dióxido de Carbono , Carbono , Capacitância Elétrica , Eletrodos , PorosidadeRESUMO
Soil moisture measurement is very important for soil system monitoring. Compared to the traditional thermo-gravimetric technique, which is time-consuming and can be only performed in labs, the optic-fiber technique has unique advantages, such as small size, remote application in fields, fast response time and immunity to electromagnetic fields. In this paper, the soil moisture is measured by using a polymer optical fiber Bragg grating (POFBG) probe with a packaged dimension of 40 mm × 15 mm × 8 mm. Due to the intrinsic water-absorbing property of poly (methyl methacrylate) (PMMA), optical fiber Bragg gratings based on PMMA have been widely investigated for humidity measurement. Taking advantage of this, a sensor based on the POFBG is investigated to verify the soil condition. The POFBG is protectively integrated inside a stainless-steel package. A window is opened with a thin polypropylene mat as a filter, which allows the air to go through but prevents the soil from going inside to pollute the POFBG. The sensor probe is embedded in soils with different gravimetric soil moisture contents (SMCs) ranging from 0% to 40% and, then, insulated by polyethylene films to minimize the impact from the external environment, showing an average temperature cross sensitivity of -0.080 nm/°C. For a constant temperature, an exponential relationship between the Bragg wavelength and the SMC is obtained. For the SMCs between 8% and 24%, linear relationships are presented showing a temperature-corresponded sensitivity between 0.011 nm/% and 0.018 nm/%. The maximal sensitivity is calculated to be 0.018 nm/% at 20 °C, which is 28 times as high as that in the previous work. For the SMC over 24%, the sensor becomes insensitive because of humidity saturation in the cavity of the sensor probe. Though temperature cross sensitivity is problematic for SMC measurement, the influence could be eliminated by integrating another humidity-insensitive temperature sensor, such as a silica FBG temperature sensor.
Assuntos
Polimetil Metacrilato , Água , Umidade , Solo , TemperaturaRESUMO
Wire and arc additive manufacturing based on cold metal transfer (WAAM-CMT), as a kind of clean and advanced technology, has been widely researched recently. It was analyzed in detail for the microstructure and mechanical properties of WAAM-CMT printed TiB2/AlSi7Mg0.6 samples fore-and-aft heat treatment in this study. Compared with the grain size of casted AlSi7Mg0.6 samples (252 µm), the grain size of WAAM-CMT printed AlSi7Mg0.6 samples (53.4 µm) was refined, showing that WAAM-CMT process could result in significant grain refinement. Besides, the grain size of WAAM-CMT printed TiB2/AlSi7Mg0.6 samples was about 35 µm, revealing that the addition of TiB2 particles played a role in grain refinement. Nevertheless, the grain size distribution was not uniform, showing a mixture of fine grain and coarse grain, and the mechanical properties were anisotropic of the as-printed samples. This study shows that T6 heat treatment is an efficient way to improve the nonuniform microstructure and eliminate the anisotropy in mechanical properties.
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The corrosion of 316SS in contact with lead complicates the realization of high coolant temperature. To explore the corrosion behavior at high temperature, the corrosion test of 316SS was performed in liquid lead at a high temperature of 650 °C under Ar with oxygen levels of 10-2 wt% and 10-5 wt% by the static corrosion method. The mass changes after corrosion were determined; then, the corrosion depth and the oxide product formed were further characterized. A multi-oxide layer was formed on the 316SS alloy surface, and the thickness reached 17.5 µm over a period of 100 h at the oxygen level of â¼10-2 wt%. Fe oxide was the main product in the outer layer; the dense Fe-Cr oxide was formed in the inner layer and lead was isolated from the metal substrate. When the oxygen content was 10-5 wt%, corrosion by dissolution at a rather high rate was dominant, and the corrosion depth was as high as 50 µm for 100 h. It is speculated that the oxide layer is also formed at the initial stage but gets dissociated when there is no oxygen supply to sustain the oxide layer with prolonged exposure time. The oxygen content in the cover gas greatly influences the corrosion behavior of 316SS, thus directly affecting the application of 316SS immersed in liquid lead at high temperature.
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We experimentally report fiber Bragg gratings (FBGs) in a single mode step-index polymer optical fiber (POF) with a core made of TOPAS and cladding made of ZEONEX using 520 nm femtosecond pulses and a point-by-point (PbP) inscription method. With different pulse energies between 9.7 nJ and 11.2 nJ, 12 FBGs are distributed along the cores of two pieces of POFs with negative averaged effective index change up to ~6 × 10−4 in the TOPAS. For POF 1 with FBGs 16, the highest reflectivity 45.1% is obtained with a pulse energy of 10.6 nJ. After inscription, good grating stability is reported. Thanks to the post-annealing at 125 °C for 24 h, after cooling the grating reflectivity increases by ~10%. For POF 2 with FBGs 712, similar FBG data are obtained showing good reproducibility. Then, the FBGs are annealed at 125 °C for 78 h, and the average reflectivity of the FBGs during the annealing process increases by ~50% compared to that before the annealing, which could be potentially applied to humidity insensitive high temperature measurement.
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The authors wish to make a change to the published paper [...].