RESUMEN
Modulating the chemical composition and structure has been considered as one of the most promising strategies for developing high-efficient water splitting catalysts. Here, a single-atom Ru doped Ni2P/Fe3P catalyst is synthesized by introducing the dispersed Ru atoms to adjust Ni2P/Fe3P heterostructure. Single atom Ru provides effective hydrogen evolution reaction (HER) active sites for boosting catalytic activities. The catalyst with only 0.2 wt.% content of Ru exhibits an overpotential of 19.3 mV at 10 mA cm-2, which is obviously lower than 146.1 mV of Ni2P/Fe3P. Notably, an alkaline overall water electrolyzer based on Ru-Ni2P/Fe3P catalysts achieves a cell voltage of 1.47 V and operates over 600 h at 10 mA cm-2, which is superior to that of benchmark RuO2//Pt/C (1.61 V). The theoretical calculations further confirm that Ru single atom doping can effectively optimize the hydrogen/water adsorption free energy of the active site and therefore improve the HER activity of heterostructure. This work provides a valuable reference to design high-activity and durability catalyst for water splitting through the double modulation of interface-effect and atomic doping.
RESUMEN
Electrochemical hydrogen evolution reaction (HER) from water splitting driven by renewable energy is considered a promising method for large-scale hydrogen production, and as an alternative to noble-metal electrocatalysts, molybdenum carbide (Mo2C) has exhibited effective HER performance. However, the strong bonding strength of intermediate adsorbed H (Hads) with Mo active site slows down the HER kinetics of Mo2C. Herein, using phase-transition strategy, hexagonal ß-Mo2C could be easily transferred to cubic δ-Mo2C through electron injection triggered by tungsten (W) doping, and heterointerface-rich Mo2C-based composites, including ß-Mo2C, δ-Mo2C, and MoO2, are presented. Experimental results and density functional theory calculations reveal that W doping mainly contributes to the phase-transition process, and the generated heterointerfaces are the dominant factor in inducing remarkable electron accumulation around Mo active sites, thus weakening the MoâH coupling. Wherein, the ß-Mo2C/MoO2 interface plays an important role in optimizing the electronic structure of Mo 3d orbital and hydrogen adsorption Gibbs free energy (ΔGH*), enabling these Mo2C-based composites to have excellent intrinsic catalytic activity like low overpotential (η10 = 99.8 mV), small Tafel slope (60.16 dec-1), and good stability in 1 m KOH. This work sheds light on phase-transition engineering and offers a convenient route to construct heterointerfaces for large-scale HER production.
RESUMEN
Electrolytic seawater is a green, sustainable, and promising approach for hydrogen production. Benefiting from the cost-effectiveness, crystal structures, and tailorable modification, transition metal phosphides become a highly attractive catalyst for the electrolysis of water. Considering the sufficient exposure and intrinsic catalytic activity of metal sites, here, carbon layer-coated NiFeP nanocrystals with a porous rugby structure are synthesized by Ar-H2 plasma. Activated PH radical in plasma is the key point to achieve phosphatization at a low temperature. The obtained porous rugby NiFeP catalyst exhibits excellent catalytic activity under alkaline conditions (300 mV in freshwater and 370 mV in seawater, 1000 mA cm-2), good corrosion resistance, and superior operational stability (>100 h). Theoretical calculations prove that Fe introduction and subsequent phosphorization weaken the adsorption of *O and *OH, thus improving the oxygen evolution reaction performance. Plasma phosphorization offers exciting opportunities for the in situ modification of other types of framework materials.
RESUMEN
Heterogeneous catalytic mediators have been proposed to play a vital role in enhancing the multiorder reaction and nucleation kinetics in multielectron sulfur electrochemistry. However, the predictive design of heterogeneous catalysts is still challenging, owing to the lack of in-depth understanding of interfacial electronic states and electron transfer on cascade reaction in Li-S batteries. Here, a heterogeneous catalytic mediator based on monodispersed titanium carbide sub-nanoclusters embedded in titanium dioxide nanobelts is reported. The tunable catalytic and anchoring effects of the resulting catalyst are achieved by the redistribution of localized electrons caused by the abundant built-in fields in heterointerfaces. Subsequently, the resulting sulfur cathodes deliver an areal capacity of 5.6 mAh cm-2 and excellent stability at 1 C under sulfur loading of 8.0 mg cm-2 . The catalytic mechanism especially on enhancing the multiorder reaction kinetic of polysulfides is further demonstrated via operando time-resolved Raman spectroscopy during the reduction process in conjunction with theoretical analysis.
RESUMEN
An electron-hole self-compensation effect is revealed and confirmed in nitrogen doped Magnéli phase Ti(n)O(2n-1) (n = 7, 8, and 9) by using hybrid density functional theory calculations. We found that the self-compensation effect between the free electrons in Magnéli phase Ti(n)O(2n-1) (n = 7, 8, and 9) and the holes induced by p-type nitrogen doping could not only prevent the recombination of photo-generated electron-hole pairs, but also lead to an effective bandgap reduction. This novel electron-hole self-compensation effect may provide a new approach for bandgap engineering of Magnéli phase metal suboxides.
RESUMEN
Among various electrocatalysts, high-entropy alloys (HEAs) have gained significant attention for their unique properties and excellent catalytic activity in the hydrogen evolution reaction (HER). However, the precise synthesis of HEA catalysts in small sizes remains challenging, which limits further improvement in their catalytic performance. In this study, boron- and nitrogen-doped HEA porous carbon nanofibers (HE-BN/PCNF) with an in situ-grown dendritic structure were successfully prepared, inspired by the germination and growth of tree branches. Furthermore, the dendritic fibers constrained the growth of HEA particles, leading to the synthesis of quantum dot-sized (1.67 nm) HEA particles, which also provide a pathway for designing HEA quantum dots in the future. This work provides design ideas and guiding suggestions for the preparation of borated HEA fibers with different elemental combinations and for the application of dendritic nanofibers in various fields.
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We develop a facile, selective edge etching strategy to create edge sites in Pd metallene using acetic acid. The created edge sites remarkably increase the electrochemically active surface area but reduce the charge transfer resistance, resulting in significant enhancement of catalytic activity and stability toward formic acid oxidation.
RESUMEN
Noble metal-based metallenes are attracting intensive attention in energy catalysis, but it is still very challenging to precisely control the surface structures of metallenes for higher catalytic properties on account of their intrinsic thermodynamic instability. Herein, the synthesis of tensile-strained holey Pd metallene by oxidative etching is reported using hydrogen peroxide, which exhibits highly enhanced catalytic activity and stability in comparison with normal Pd metallene toward both oxygen reduction reaction and formic acid oxidation. The pre-prepared Pd metallene functions as a catalyst to decompose hydrogen peroxide, and the Pd atoms in amorphous regions of Pd metallene are preferentially removed by the introduced hydrogen peroxide during the etching process. The greatly enhanced ORR activity is mainly determined by the strong electrostatic repulsion between intermediate O* and the dopant O, which balances the adsorption strength of O* on Pd sites, ultimately endowing a weakened adsorption energy of O* on TH-Pd metallene. This work creates a facile and economical strategy to precisely shape metallene-based nanoarchitectures with broad applications for energy systems and sensing devices.
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A breakthrough in enhancing visible-light photocatalysis of wide-bandgap semiconductors such as prototypical titania (TiO2) via cocatalyst decoration is still challenged by insufficient heterojunctions and inevitable interfacial transport issues. Herein, we report a novel TiO2-based composite material composed of in situ generated polymorphic nanodomains including carbon nitride (C3N4) and (001)/(101)-faceted anatase nanocrystals. The introduction of ultrafine C3N4 results in the generation of many oxygen vacancies in the TiO2 lattice, and simultaneously induces the exposure and growth of anatase TiO2(001) facets with high surface energy. The photocatalytic performance of C3N4-induced TiO2 for degradation of 2,4-dichlorophenol under visible-light irradiation was tested, its apparent rate being up to 1.49 × 10-2 min-1, almost 3.8 times as high as that for the pure TiO2 nanofibers. More significantly, even under low operation temperature and after a long-term photocatalytic process, the composite still exhibits exceptional degradation efficiency and stability. The normalized degradation efficiency and effective lifespan of the composite photocatalyst are far superior to other reported modified photocatalysts.
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We use hybrid density functional calculations to find that the monolayer silicane (SiH) and the anatase TiO2(101) composite (i.e. the SiH/TiO2 heterojunction) is a promising TiO2-based photocatalyst under visible light. The band gap of the SiH/TiO2(101) heterojunction is 2.082â eV, which is an ideal material for the visible-light photoexcitation of electron-hole pairs. Furthermore, the SiH/TiO2(101) heterojunction has a favorable type-II band alignment and thus the photoexcited electron can be injected to the conduction band of anatase TiO2 from that of silicane. Finally, the proper interface charge distribution facilitates the carrier separation in the SiH/TiO2(101) interface region. The electron injection and carrier separation can prevent the recombination of electron-hole pairs. Our calculation results suggest that such electronic structure of SiH/TiO2(101) heterojunction has significant advantages over these of doped TiO2 systems for visible-light photocatalysis.
RESUMEN
Colored TiO2 has attracted enormous attention due to its visible light absorption and excellent photocatalytic activity. In this report, we develop a simple and facile solid-state chemical reduction approach for a large-scale production of colored TiO2 at mild temperature (300-350 °C). The obtained sample possesses a crystalline core/amorphous shell structure (TiO2@TiO2-x). The oxygen vacancy results in the formation of a disordered TiO2-x shell on the surface of TiO2 nanocrystals. XPS and theoretical calculation results indicate that valence band tail and vacancy band below the conduction band minimum appear for the TiO2-x, which implies that the TiO2@TiO2-x nanocrystal has a narrow band gap and therefore leads to a broad visible light absorption. Oxygen vacancy in a proper concentration promotes the charge separation of photogenerated carriers, which improves the photocatalytic activity of TiO2@TiO2-x nanocrystals. This facile and general method could be potentially used for large scale production of colored TiO2 with remarkable enhancement in the visible light absorption and solar-driven H2 production.