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Electrochemical water splitting powered by renewable energy sources hold potential for clean hydrogen production. However, there is still persistent challenges such as low solar-to-hydrogen conversion efficiency and sluggish oxygen evolution reactions. Here, we address the poor kinetics by studying and strengthening the coupling between Ce and W, and concurrently establishing Ce-W bi-atomic clusters on P,N-doped carbon (WN/WC-CeO2-x@PNC) with a "treasure-bowl" style. The bifunctional active sites are established using a novel and effective self-sacrificial strategy involving in situ induced defect formation. In addition, by altering the coupling of the W(d)-N(p) and W(d)-Ce(f) orbitals in the WN/WC-CeO2-x supramolecular clusters, we are able to disrupt the linear relationship between the binding energies of reaction intermediates, a key to obtain high catalytic performance for transition metals. Through the confinement of the WN/WC-CeO2-x composite hetero-clusters within the sub-nanometre spaces of hollow nano-bowl-shaped carbon reactors, a stable and efficient hydrogen production via water electrolysis could be achieved. When assembled together with a solar GaAs triple junction solar cell, a solar-to-hydrogen conversion efficiency of 18.92% in alkaline media could be realized. We show that the key to establish noble metal free catalysts with high efficiency lies in the fine-tuning of the metal-metal interface, forming regions with near optimal adsorption energies for the reaction intermediates participating in water electrolysis.
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Understanding "efficiency roll-off" (i.e., the drop in emission efficiency with increasing current) is critical if efficient and bright emissive technologies are to be rationally designed. Emerging light-emitting electrochemical cells (LECs) can be cost- and energy-efficiently fabricated by ambient-air printing by virtue of the in situ formation of a p-n junction doping structure. However, this in situ doping transformation renders a meaningful efficiency analysis challenging. Herein, a method for separation and quantification of major LEC loss factors, notably the outcoupling efficiency and exciton quenching, is presented. Specifically, the position of the emissive p-n junction in common singlet-exciton emitting LECs is measured to shift markedly with increasing current, and the influence of this shift on the outcoupling efficiency is quantified. It is further verified that the LEC-characteristic high electrochemical-doping concentration renders singlet-polaron quenching (SPQ) significant already at low drive current density, but also that SPQ increases super-linearly with increasing current, because of increasing polaron density in the p-n junction region. This results in that SPQ dominates singlet-singlet quenching for relevant current densities, and significantly contributes to the efficiency roll-off. This method for deciphering the LEC efficiency roll-off can contribute to a rational realization of all-printed LEC devices that are efficient at highluminance.
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Foam-like NiMo coatings were produced from an inexpensive mixture of Ni, Al, and Mo powders via atmospheric plasma spraying. The coatings were deposited onto stainless-steel meshes forming a highly porous network mainly composed of nanostructured Ni and highly active Ni4Mo. High material loading (200 mg cm-2) with large surface area (1769 cm2 per cm2) was achieved without compromising the foam-like characteristics. The coatings exhibited excellent activity towards both hydrogen evolution (HER) and oxygen evolution (OER) reactions in alkaline media. The HER active coating required an overpotential of 42 mV to reach a current density of -50 mA cm-2 with minimum degradation after a 24 h chronoamperometry test at -10 mA cm-2. Theoretical simulations showed that several crystal surfaces of Ni4Mo exhibit near optimum hydrogen adsorption energies and improved water dissociation that benefit the HER activity. The OER active coating also consisting of nanostructured Ni and Ni4Mo required only 310 mV to achieve a current density of 50 mA cm-2. The OER activity was maintained even after 48 h of continuous operation. We envisage that the development of scalable production techniques for Ni4Mo alloys will greatly benefit its usage in commercial alkaline water electrolysers.
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One-dimensional tellurium nanostructures can exhibit distinct electronic properties from those seen in bulk Te. The electronic properties of nanostructured Te are highly dependent on their morphology, and thus controlled synthesis processes are required. Here, highly crystalline tellurium nanowires were produced via physical vapour deposition. We used growth temperature, heating rate, flow of the carrier gas, and growth time to control the degree of supersaturation in the region where Te nanostructures are grown. The latter leads to a control in the nucleation and morphology of Te nanostructures. We observed that Te nanowires grow via the vapour-solid mechanism where a Te particle acts as a seed. Transmission electron microscopy (TEM) and electron diffraction studies revealed that Te nanowires have a trigonal crystal structure and grow along the (0001) direction. Their diameter can be tuned from 26 to 200 nm with lengths from 8.5 to 22 µm, where the highest aspect ratio of 327 was obtained for wires measuring 26 nm in diameter and 8.5 µm in length. We investigated the use of bismuth as an additive to reduce the formation of tellurium oxides, and we discuss the effect of other growth parameters.
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The position of the emission zone (EZ) in the active material of a light-emitting electrochemical cell (LEC) has a profound influence on its performance because of microcavity effects and doping- and electrode-induced quenching. Previous attempts of EZ control have focused on the two principal constituents in the active material-the organic semiconductor (OSC) and the mobile ions-but this study demonstrates that it is possible to effectively control the EZ position through the inclusion of an appropriate additive into the active material. More specifically, it is shown that a mere modification of the end group on an added neutral compound, which also functions as an ion transporter, results in a shifted EZ from close to the anode to the center of the active material, which translates into a 60% improvement of the power efficiency. This particular finding is rationalized by a lowering of the effective electron mobility of the OSC through specific additive: OSC interactions, but the more important generic conclusion is that it is possible to control the EZ position, and thereby the LEC performance, by the straightforward inclusion of an easily tuned additive in the active material.
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Nanoparticulate double-heterojunction photocatalysts comprising TiO2(Anatase)/WO3/TiO2(Rutile) were produced by a sol-gel method. The resulting photocatalysts exhibit clear synergistic effects when tested toward the degradation of methyl orange under both UV and visible light. Kinetic studies indicate that the degradation rate on the best double-heterojunction photocatalyst (10 wt % WO3-TiO2) depends mainly on the amount of dye concentration, contrary to pure oxides in which the degradation rate is limited by diffusion-controlled processes. The synergistic effects were confirmed through systematic and careful studies including holes and OH radical formation, X-ray diffraction, electron microscopy, elemental analysis, UV-vis diffuse reflectance spectroscopy, and surface area analysis. Our results indicate that the successful formation of a double heterojunction in the TiO2(Anatase)/WO3/TiO2(Rutile) system leads to enhanced photoactivity when compared to individual oxides and commercial TiO2 P25.
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The high catalytic activity of cobalt-doped MoS2 (Co-MoS2) observed in several chemical reactions such as hydrogen evolution and hydrodesulfurization, among others, is mainly attributed to the formation of the CoMoS phase, in which Co occupies the edge-sites of MoS2. Unfortunately, its production represents a challenge due to limited cobalt incorporation and considerable segregation into sulfides and sulfates. We, therefore, developed a fast and efficient solid-state microwave irradiation synthesis process suitable for producing thin Co-MoS2 flakes (â¼3-8 layers) attached on nitrogen-doped reduced graphene oxide. The CoMoS phase is predominant in samples with up to 15 at% of cobalt, and only a slight segregation into cobalt sulfides/sulfates is noticed at larger Co content. The Co-MoS2 flakes exhibit a large number of defects resulting in wavy sheets with significant variations in interlayer distance. The catalytic performance was investigated by evaluating the activity towards the hydrogen evolution reaction (HER), and a gradual improvement with increased amount of Co was observed, reaching a maximum at 15 at% with an overpotential of 197 mV at -10 mA cm-2, and a Tafel slope of 61 mV dec-1. The Co doping had little effect on the HER mechanism, but a reduced onset potential and charge transfer resistance contributed to the improved activity. Our results demonstrate the feasibility of using a rapid microwave irradiation process to produce highly doped Co-MoS2 with predominant CoMoS phase, excellent HER activity, and operational stability.
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The oxygen evolution reaction is a crucial step in water electrolysis to develop clean and renewable energy. Although noble metal-based catalysts have demonstrated high activity for the oxygen evolution reaction, their application is limited by their high cost and low availability. Here we report the use of a molecule-to-cluster strategy for preparing ultrasmall trimetallic clusters by using the polyoxometalate molecule as a precursor. Ultrafine (0.8 nm) transition-metal clusters with controllable chemical composition are obtained. The transition-metal clusters enable highly efficient oxygen evolution through water electrolysis in alkaline media, manifested by an overpotential of 192 mV at 10 mA cm-2, a low Tafel slope of 36 mV dec-1, and long-term stability for 30 h of electrolysis. We note, however, that besides the excellent performance as an oxygen evolution catalyst, our molecule-to-cluster strategy provides a means to achieve well-defined transition-metal clusters in the subnanometer regime, which potentially can have an impact on several other applications.
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The oxygen reduction reaction (ORR), the rate-limiting reaction in proton exchange membrane fuel cells, can efficiently be facilitated by properly manufactured platinum catalysts alloyed with late 3d transition metals. Herein we synthesize a platinum : cobalt nanoparticulate catalyst with a 3 : 1 atomic ratio by reduction of a dry metalorganic precursor blend within a commercial household microwave oven. The formed nanoparticles are simultaneously anchored to a carbon black support that enables large Pt surface area. Two separate microwave treatment steps were employed, where step one constitutes a fast oxidative treatment for revealing active surface area while a reductive secondary annealing treatment promotes a Pt rich surface. The resulting Pt3Co/C catalyst (â¼3.4 nm) demonstrates an enhanced ORR activity directly attributed to incorporated Co with a specific and mass activity of 704 µA cmPt -2 and 352 A gPt -1 corresponding to an increase by 279% and 66% respectively compared to a commercial Pt/C (â¼1.8 nm) catalyst measured under identical conditions. The method's simplicity, scalability and novelty is expected to further assist in Pt-Co development and bring the catalyst one step closer toward commercialization and utility in fuel cells.
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To exploit the full potential of hematite (α-Fe2O3) as an efficient photoanode for water oxidation, the redox processes occurring at the Fe2O3/electrolyte interface need to be studied in greater detail. Ex situ doping is an excellent technique to introduce dopants onto the photoanode surface and to modify the photoanode/electrolyte interface. In this context, we selected antimony (Sb5+) as the ex situ dopant because it is an effective electron donor and reduces recombination effects and concurrently utilize the possibility to tuning the surface charge and wettability. In the presence of Sb5+ states in Sb-doped Fe2O3 photoanodes, as confirmed by X-ray photoelectron spectroscopy, we observed a 10-fold increase in carrier concentration (1.1 × 1020 vs 1.3 × 1019 cm-3) and decreased photoanode/electrolyte charge transfer resistance (â¼990 vs â¼3700 Ω). Furthermore, a broad range of surface characterization techniques such as Fourier-transform infrared spectroscopy, ζ-potential, and contact angle measurements reveal that changes in the surface hydroxyl groups following the ex situ doping also have an effect on the water splitting capability. Theoretical calculations suggest that Sb5+ can activate multiple Fe3+ ions simultaneously, in addition to increasing the surface charge and enhancing the electron/hole transport properties. To a greater extent, the Sb5+- surface-doped determines the interfacial properties of electrochemical charge transfer, leading to an efficient water oxidation mechanism.
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We present a theoretical study on the formation of graphene nanoribbons-via polymerization of coronene molecules-inside the inner cavity of boron nitride nanotubes. We examine the electronic property of the hybrid system, and we show that the boron nitride nanotube does not significantly alter the electronic properties of the encapsulated graphene nanoribbon. Motivated by previous experimental works, we examine graphene nanoribbons with two different widths and investigate probable scenarios for defect formation and/or twisting of the resulting graphene nanoribbons and their effect on the electronic properties of the hybrid system.
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Engineering the electronic properties of transition metal phosphides has shown great effectiveness in improving their intrinsic catalytic activity for the hydrogen evolution reaction (HER) in water splitting applications. Herein, we report for the first time, the creation of Fe vacancies as an approach to modulate the electronic structure of iron phosphide (FeP). The Fe vacancies were produced by chemical leaching of Mg that was introduced into FeP as "sacrificial dopant". The obtained Fevacancy-rich FeP nanoparticulate films, which were deposited on Ti foil, show excellent HER activity compared to pristine FeP and Mg-doped FeP, achieving a current density of 10â mA cm-2 at overpotentials of 108â mV in 1 m KOH and 65â mV in 0.5 m H2 SO4 , with a near-100 % Faradaic efficiency. Our theoretical and experimental analyses reveal that the improved HER activity originates from the presence of Fe vacancies, which lead to a synergistic modulation of the structural and electronic properties that result in a near-optimal hydrogen adsorption free energy and enhanced proton trapping. The success in catalytic improvement through the introduction of cationic vacancy defects has not only demonstrated the potential of Fe-vacancy-rich FeP as highly efficient, earth abundant HER catalyst, but also opens up an exciting pathway for activating other promising catalysts for electrochemical water splitting.
Asunto(s)
Técnicas Electroquímicas/métodos , Hidrógeno/química , Hierro/química , Agua/química , Catálisis , Cationes/química , Magnesio/química , TitanioRESUMEN
Various advanced catalysts based on sulfur-doped Fe/N/C materials have recently been designed for the oxygen reduction reaction (ORR); however, the enhanced activity is still controversial and usually attributed to differences in the surface area, improved conductivity, or uncertain synergistic effects. Herein, a sulfur-doped Fe/N/C catalyst (denoted as Fe/SNC) was obtained by a template-sacrificing method. The incorporated sulfur gives a thiophene-like structure (C-S-C), reduces the electron localization around the Fe centers, improves the interaction with oxygenated species, and therefore facilitates the complete 4â e- ORR in acidic solution. Owing to these synergistic effects, the Fe/SNC catalyst exhibits much better ORR activity than the sulfur-free variant (Fe/NC) in 0.5 m H2 SO4 .
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We demonstrate an inflatable nanoballoon actuator based on geometrical transitions between the inflated (cylindrical) and collapsed (flattened) forms of a carbon nanotube. In situ transmission electron microscopy experiments employing a nanoelectromechanical manipulator show that a collapsed carbon nanotube can be reinflated by electrically charging the nanotube, thus realizing an electrostatically driven nanoballoon actuator. We find that the tube actuator can be reliably cycled with only modest control voltages (few volts) with no apparent wear or fatigue. A complementary theoretical analysis identifies critical parameters for nanotube nanoballoon actuation.
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For ex-situ co-doping methods, sintering at high temperatures enables rapid diffusion of Sn(4+) and Be(2+) dopants into hematite (α-Fe2O3) lattices, without altering the nanorod morphology or damaging their crystallinity. Sn/Be co-doping results in a remarkable enhancement in photocurrent (1.7 mA/cm(2)) compared to pristine α-Fe2O3 (0.7 mA/cm(2)), and Sn(4+) mono-doped α-Fe2O3 photoanodes (1.0 mA/cm(2)). From first-principles calculations, we found that Sn(4+) doping induced a shallow donor level below the conduction band minimum, which does not contribute to increase electrical conductivity and photocurrent because of its localized nature. Additionally, Sn(4+)-doping induce local micro-strain and a decreased Fe-O bond ordering. When Be(2+) was co-doped with Sn(4+)-doped α-Fe2O3 photoanodes, the conduction band recovered its original state, without localized impurities peaks, also a reduction in micro-strain and increased Fe-O bond ordering is observed. Also the sequence in which the ex-situ co-doping is carried out is very crucial, as Be/Sn co-doping sequence induces many under-coordinated O atoms resulting in a higher micro-strain and lower charge separation efficiency resulting undesired electron recombination. Here, we perform a detailed systematic characterization using XRD, FESEM, XPS and comprehensive electrochemical and photoelectrochemical studies, along with sophisticated synchrotron diffraction studies and extended X-ray absorption fine structure.
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We report efficient electrolysis of both water-splitting half reactions in the same medium by a bifunctional 3D electrode comprising Co3O4 nanospheres nucleated on the surface of nitrogen-doped carbon nanotubes (NCNTs) that in turn are grown on conductive carbon paper (CP). The resulting electrode exhibits high stability and large electrochemical activity for both oxygen and hydrogen evolution reactions (OER and HER). We obtain a current density of 10 mA/cm(2) in 0.1 M KOH solution at overpotentials of only 0.47 and 0.38 V for OER and HER, respectively. Additionally, the experimental observations are understood and supported by analyzing the Co3O4:NCNT and NCNT:CP interfaces by ab initio calculations. Both the experimental and the theoretical studies indicate that firm and well-established interfaces along the electrode play a crucial role on the stability and electrochemical activity for both OER and HER.
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One-dimensional (1D) zigzag [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) nanoribbons are produced by folding two-dimensional ultrathin PCBM nanosheets in a simple solvent process. The unique 1D PCBM nanostructures exhibit uniform width of 3.8 ± 0.3 nm, equivalent to four PCBM molecules, and lengths of 20-400 nm. These nanoribbons show well-defined crystalline structure, comprising PCBM molecules in a hexagonal arrangement without trapped solvent molecules. First-principle calculations and detailed experimental characterization provide an insight into the structure and formation mechanism of the 1D PCBM nanoribbons. Given their dimensions and physical properties, we foresee that these nanostructures should be ideal as acceptor material in organic solar cells.
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We show specific heat data for Na4C60 and Li4C60 in the range 0.4-350 K for samples characterized by Raman spectroscopy and X-ray diffraction. At high temperatures, the two different polymer structures have very similar specific heats both in absolute values and in general trend. The specific heat data are compared with data for undoped polymeric and pristine C60. At high temperatures, a difference in specific heat between the intercalated and undoped C60 polymers of 100 J K(-1) mol(-1) is observed, in agreement with the Dulong-Petit law. At low temperatures, the specific heat data for Li4C60 and Na4C60 are modified by the stiffening of vibrational and librational molecular motion induced by the polymer bonds. The covalent twin bonds in Li4C60 affect these motions to a somewhat higher degree than the single intermolecular bonds in Na4C60. Below 1 K, the specific heats of both materials become linear in temperature, as expected from the effective dimensionality of the structure. The contribution to the total specific heat from the inserted metal ions can be well described by Einstein functions with TE = 386 K for Li4C60 and TE = 120 K for Na4C60, but for both materials we also observe a Schottky-type contribution corresponding to a first approximation to a two-level system with ΔE = 9.3 meV for Li4C60 and 3.1 meV for Na4C60, probably associated with jumps between closely spaced energy levels inside "octahedral-type" ionic sites. Static magnetic fields up to 9 T had very small effects on the specific heat below 10 K.
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We examine a variant of so-called carbon nanotube peapods by packing C60 molecules inside the open edge ducts of collapsed carbon nanotubes. C60 insertion is accomplished through a facile single-step solution-based process. Theoretical modeling is used to evaluate favorable low-energy structural configurations. Overfilling of the collapsed tubes allows infiltration of C60 over the full cross-section of the tubes and consequent partial or complete reinflation, yielding few-wall, large diameter cylindrical nanotubes packed with crystalline C60 solid cores.
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The sluggish kinetics of the oxygen reduction reaction at the cathode side of proton exchange membrane fuel cells is one major technical challenge for realizing sustainable solutions for the transportation sector. Finding efficient yet cheap electrocatalysts to speed up this reaction therefore motivates researchers all over the world. Here we demonstrate an efficient synthesis of palladium-tungsten bimetallic nanoparticles supported on ordered mesoporous carbon. Despite a very low percentage of noble metal (palladium:tungsten=1:8), the hybrid catalyst material exhibits a performance equal to commercial 60% platinum/Vulcan for the oxygen reduction process. The high catalytic efficiency is explained by the formation of small palladium islands embedded at the surface of the palladium-tungsten bimetallic nanoparticles, generating catalytic hotspots. The palladium islands are ~1 nm in diameter, and contain 10-20 palladium atoms that are segregated at the surface. Our results may provide insight into the formation, stabilization and performance of bimetallic nanoparticles for catalytic reactions.