RESUMO
Quasi-one-dimensional materials are usually characterized by optical response spectroscopy methods, which show significant polarization dependence. Herein, we report a systematical investigation of polarized Raman scattering on the (110) crystal surface of the layered (TaSe4)2I compound. Taking into account group theory analysis of the crystal structure and the Raman tensor transformation technique, the vibrational mode of the Raman peaks can be differentiated by the angular dependence of the Raman peak intensity in parallel and vertical polarization Raman scattering tests. Moreover, density functional perturbation theory (DFPT) calculation confirmed the form of the Raman tensor of the (110) crystal surface, which was consistent with the result of the Raman tensor transformation technique, and the Raman spectrum and phonon dispersion curve calculations were also performed based on the Vienna ab initio simulation package (VASP). This new method provides useful insight for accurately identifying the lattice vibration behavior in new 2D layered structures.
RESUMO
It is highly desired yet challenging to steer the CO2 electroreduction reaction (CO2 ER) toward ethanol with high selectivity, for which the evolution of reaction intermediates on catalytically active sites holds the key. Herein, we report that K doping in Cu2 Se nanosheets array on Cu foam serves as a versatile way to tune the interaction between Cu sites and reaction intermediates in CO2 ER, enabling highly selective production of ethanol. As revealed by characterization and simulation, the electron transfer from K to Se can stabilize CuI species which facilitate the adsorption of linear *COL and bridge *COB intermediates to promote C-C coupling during CO2 ER. As a result, the optimized K11.2% -Cu2 Se nanosheets array can catalyze CO2 ER to ethanol as a single liquid product with high selectivity in a potential area from -0.6 to -1.2â V. Notably, it offers a Faradaic efficiency of 70.3 % for ethanol production at -0.8â V with as is stable for 130â h.
RESUMO
Reducing the lateral scale of two-dimensional (2D) materials to one-dimensional (1D) has attracted substantial research interest not only to achieve competitive electronic applications but also for the exploration of fundamental physical properties. Controllable synthesis of high-quality 1D nanoribbons (NRs) is thus highly desirable and essential for further study. Here, we report the implementation of supervised machine learning (ML) for the chemical vapor deposition (CVD) synthesis of high-quality quasi-1D few-layered WTe2 NRs. Feature importance analysis indicates that H2 gas flow rate has a profound influence on the formation of WTe2, and the source ratio governs the sample morphology. Notably, the growth mechanism of 1T' few-layered WTe2 NRs is further proposed, which provides new insights for the growth of intriguing 2D and 1D tellurides and may inspire the growth strategies for other 1D nanostructures. Our findings suggest the effectiveness and capability of ML in guiding the synthesis of 1D nanostructures, opening up new opportunities for intelligent materials development.
RESUMO
The relatively high recombination rate of charges remains the most critical limiting factor for solar-driven water splitting for hydrogen generation. Herein, a tandem 0D/2D/2D NbS2 quantum dot/Nb2 O5 nanosheet/g-C3 N4 flake (NSNOCN) system is designed. Owing to the unique spatial-arrangement and elaborate morphology of 0D NbS2 , 2D Nb2 O5 , and 2D g-C3 N4 in the newly designed NSNOCN, plenty of spatial charge-transfer cascades from g-C3 N4 to NbS2 via Nb2 O5 are formed to accelerate separation and transfer of charges significantly, thus contributing to a high photocatalytic H2 generation rate of 13.99 mmol h-1 g-1 (an apparent quantum efficiency of 10.8% at 420 nm), up to 107.6 and 43.7 times by contrast with that of g-C3 N4 and Nb2 O5 , respectively. This work can provide a new platform in the design of artificial photocatalytic systems with high charge-transfer efficiency.
RESUMO
Herein, a supermolecular-scale cage-confinement pyrolysis strategy is proposed to build two dielectric electromagnetic wave absorbents, in which MoO2 nanoparticles are sandwiched uniformly between porous carbon shells and reduced graphene oxide (RGO). Both sandwich structures are derived from hybrid hydrogels doped by two different crosslinkers (with/without oxygen bridge), which can precisely confine Mo source (e.g., PMo12 ). Without adding magnetic components, both absorbents exhibit excellent low frequency absorption performance in combination with electrically tunable ability and enhanced reflection loss value, which is superior over other relative 2D dielectric absorbers and satisfies the requirements of portable electronics. Notably, introducing oxygen bridges in the crosslinker generates a more stable confining configuration, which in turn renders its corresponding derivative exhibiting an extra multifrequency electromagnetic wave absorption trait. The intrinsic electromagnetic wave adjustment mechanism of the ternary hybrid absorbent is also explored. The result reveals that the elevated electromagnetic wave absorbing property is attributed to moderate attenuation constant and glorious impendence matching. The cage-confinement pyrolysis route to fabricate 2D MoO2 -based dielectric electromagnetic wave absorbents opens a new path for the design of electromagnetic wave absorbents used in multi/low frequency.
RESUMO
In this study, we report an oxygen-doped MoS2 quantum dot (O-MoS2 QD) hybrid electrocatalyst for the hydrogen evolution reaction (HER). The O-MoS2 QDs were prepared with a one-pot microwave method by hydrazine-mediated oxygen-doping. The synthetic method is straightforward, time-saving, and can be applied in large scale preparation. Ultra-small O-MoS2 QDs with the average size of 5.83 nm and 1-4 layers can be uniformly distributed on the surface of reduced graphene oxide (RGO). Benefited from the unique structure and the doping effect of oxygen in the MoS2 QDs and the great number of active sites, the O-MoS2 QD hybrid displayed outstanding electrocatalytic performance toward HER. A low overpotential of 76 mV at 10 mA/cm2 and a Tafel slope of 58 mV/dec were obtained in an acidic solution toward HER. Additionally, the resultant O-MoS2 QD hybrid also exhibited excellent stability and durability toward HER, displaying negligible current density loss after 1000 cycles of cyclic voltammetry. The design and synthesis of the electrocatalyst in this work open up a prospective route to prepare active and stable electrocatalysts toward substituting precious metals for hydrogen generation.
RESUMO
This experiment aims to evaluate the effect of bile acids (BAs) in alleviating fatty liver disease induced by a high-fat diet (HFD) in broilers, and the modulation of the gut microbiota involved in this process. A total of 192 one-day-old Arbor Acres (AA) commercial male broilers were randomly divided into 4 groups and treated with the following diet: a basal-fat diet (BFD), a basal-fat diet plus bile acids (BFD + BAs), an HFD, and a high-fat diet plus bile acids (HFD + BAs). Bile acids were supplemented at the early growth stage (3-7 d), middle stage (17-21 d), and late stage (31-35 d). Results showed that BAs treatment had a significant effect on body weight on 14 d and 35 d, and increased the breast muscle weight and its index, but decreased the liver weight and abdominal fat weight on 35 d (P < 0.05). The supplementation of BAs significantly improved the serum lipid profile and decreased the level of triglycerides (TG), total cholesterol (TCHO), and nonesterified fatty acids (NEFA) on 35 d (P < 0.05). Dietary BAs supplementation significantly alleviated the hepatic TG deposition induced by HFD (P < 0.05), which was accompanied by upregulation of peroxisome proliferator-activated receptor gamma (PPARγ) and lipoprotein lipase (LPL) gene expression (P < 0.05). Moreover, the expression levels of hepatic gene adipose triglyceride lipase (ATGL), peroxisome proliferator-activated receptor α (PPARα), and apolipoprotein B (APOB) were greatly increased by BAs treatment. The analysis of 16S rRNA sequencing showed that the microbial diversity of the cecal digesta was increased by BAs in broilers with elevated abundances of Firmicutes, Lactobacillus, Anaerostipes, Sellimonas, and CHKCI002 and decreased abundances of Barnesiella and Akkermansia genus (P < 0.05). Hepatic TG content was positively correlated with the abundance of Oscillospiraceae, but it was negatively correlated with the abundance of Lactobacillus in cecal digesta (P < 0.05). These results indicate that dietary BAs can improve growth performance and alleviate fatty liver disease induced by an HFD via modulating gut microbiota in broilers.
Assuntos
Microbioma Gastrointestinal , Hepatopatia Gordurosa não Alcoólica , Masculino , Animais , Dieta Hiperlipídica/efeitos adversos , Dieta Hiperlipídica/veterinária , Galinhas/fisiologia , Ácidos e Sais Biliares/metabolismo , RNA Ribossômico 16S , Fígado/metabolismo , Hepatopatia Gordurosa não Alcoólica/veterinária , Suplementos Nutricionais/análise , Triglicerídeos/metabolismoRESUMO
The importance of catalysts today as workhorses in most modern industrial fields cannot be downplayed. As a result, rational design and engineering of targeted catalysts have emerged as key objectives and are dependent on in-depth understanding of complex catalytic dynamics. Synchrotron radiation (SR) light sources with rich advanced experimental methods are being recognized as a comprehensive characterization platform, which can draw a full picture on such multiparameter-involved catalysis under actual working conditions. Herein, the recent progress of catalytic dynamics process studied by the means of various SR techniques is summarized. In particular, SR-based spectroscopic, scattering, and imaging investigations on true catalysts are first introduced with the potential of in situ and operando characterizations. Apparently, the limitations from single SR technique naturally prompt a simple combination of SR techniques to better understand the whole catalysis process. Moreover, the discrepancies among various online testing facilities and batches of samples, along with random/systematic errors introduced by traditional intermittent/asynchronous measurement make it imperative to develop more prolific systems, complementary of multiple SR techniques for deep probing of dynamic catalytic processes. It is believed that the booming new light sources can further enrich the current multiple SR techniques, and thus may realize the true visualization on future catalytic dynamic processes.
RESUMO
Photocatalytic degradation of pollutants is considered a promising approach for wastewater treatment, but is hampered by low efficiency and limited understanding of degradation pathways. A novel oxygen-doped porous g-C3N4/oxygen vacancies-rich BiOCl (OCN/OVBOC) heterostructure was prepared for photocatalytic degradation of bisphenol A (BPA). The synergistic defect and doping engineering favor the formation of strong bonded interface for S-scheme mechanism. Among them, 0.3 OCN/OVBOC showed the most excellent degradation rate, which was 8 times and 4 times higher than that of pure g-C3N4 and BiOCl, respectively. This excellent performance is mainly attributed to the significantly enhanced charge separation via strong bonded interface and redox capability of the S-scheme heterojunction structure, by tuning the coordination excitation and electron localization of the catalyst via O doping and vacancies. This work provides important insights into the role of synergistic defect and doping engineering in facilitating the formation of strong bonded S-scheme heterojunction and ultimately sheds new light on the design of efficient photocatalysts.
Assuntos
Elétrons , Poluentes Ambientais , Oxigênio , PorosidadeRESUMO
CO2 electrocatalytic reduction (CO2 ER) to multicarbon (C2+ ) products is heavily pursued because of their commercial values, and the efficiency and selectivity have both attracted tremendous attention. A flow-cell is a device configuration that can greatly enhance the conversion efficiency but requires catalysts to possess high electrical conductivity and gas permeability; meanwhile, the catalysts should enable the reaction pathway to specific products. Herein, it is reported that V-doped Cu2 Se nanotubes with a hierarchical structure can be perfectly compatible with flow-cells and fulfil such a task, achieving CO2 electroreduction to ethanol with high efficiency and selectivity. As revealed by the experimental characterization and theoretical calculation, the substitutional vanadium doping alters the local charge distribution of Cu2 Se and diversifies the active sites. The unique active sites promote the formation of bridge *COB and its further hydrogenation to *COH, and, as such, the subsequent coupling of *COH and *COL eventually generates ethanol. As a result, the optimal Cu1.22 V0.19 Se nanotubes can electrocatalyze CO2 to ethanol with a Faradaic efficiency of 68.3% and a partial current density of -207.9 mA cm-2 for the single liquid product of ethanol at -0.8 V in a flow-cell. This work provides insights into the materials design for steering the reaction pathway toward C2+ products, and opens an avenue for flow-cell CO2 ER toward a single C2+ liquid fuel.
RESUMO
Metal nanostructures with high atom utilization, abundant active sites, and special electron structures should be beneficial to the electrochemical monitoring of hydroquinone (HQ), a highly toxic environmental pollutant. However, traditional nanostructures, especially non-noble metals generally suffer from severe aggregation, or consist of a mixture of nanoparticles and nanoclusters, resulting in low detection sensitivity. Herein, we precisely control the size of Mo-based nanostructures spanning four scales (viz. Mo2C nanoparticles, Mo2C nanodots, Mo nanoclusters and Mo single atoms) anchored on N, P, O co-doped carbon support. The detection sensitivity of four samples toward the HQ follows the orders of Mo single atomsï¼Mo2C nanodotsï¼Mo nanoclustersï¼Mo2C nanoparticles. The catalytic ability of four catalysts is investigated, also showing the same order. The supported Mo single atoms show superior electro-sensing performance for HQ with wide linear range (0.02-200 µM) and low detection limit (0.005 µM), surpassing most previously reported catalysts. Moreover, the coexistence of dihydroxybenzene isomers of catechol (CC) and resorcinol (RC) does not interfere with the detection of HQ on the Mo single-atom sensor. This work opens up a polyoxometalate-based confinement pyrolysis approach to constructing ultrafine metal-based nanostructures spanning multiple-scales for efficient electrochemical applications.
Assuntos
Hidroquinonas , Nanoestruturas , Ânions , Carbono/química , Eletrodos , Polieletrólitos , PiróliseRESUMO
Light utilization largely governs the performance of CO2 photoconversion, whereas most of the materials that are implemented in such an application are restricted in a narrow spectral absorption range. Plasmonic metamaterials with a designable regular pattern and facile tunability are excellent candidates for maximizing light absorption to generate substantial hot electrons and thermal energy. Herein, a concept of coupling a Au-based stacked plasmonic metamaterial with single Cu atoms in alloy, as light absorber and catalytic sites, respectively, is reported for gas-phase light-driven catalytic CO2 hydrogenation. The metamaterial structure works in a broad spectral range (370-1040 nm) to generate high surface temperature for photothermal catalysis, and also induces strong localized electric field in favor of transfer of hot electrons and reduced energy barrier in CO2 hydrogenation. This work unravels the significant role of a strong localized electric field in photothermal catalysis and demonstrates a scalable fabrication approach to light-driven catalysts based on plasmonic metamaterials.
RESUMO
Cocatalyst design is a key approach to acquire high solar-energy conversion efficiency for photocatalytic hydrogen evolution. Here a new in situ vapor-phase (ISVP) growth method is developed to construct the cocatalyst of 2D PtS nanorectangles (a length of â¼7 nm, a width of â¼5 nm) on the surface of g-C3N4 nanosheets. The 2D PtS nanorectangles/g-C3N4 nanosheets (PtS/CN) show an unusual metal sulfide-support interaction (MSSI), which is evidenced by atomic resolution HAADF-STEM, synchrotron-based GIXRD, XPS and DFT calculations. The effect of MSSI contributes to the optimization of geometrical structure and energy-band structure, acceleration of charge transfer, and reduction of hydrogen adsorption free energy of PtS/CN, thus yielding excellent stability and an ultrahigh photocatalytic H2 evolution rate of 1072.6 µmol h-1 (an apparent quantum efficiency of 45.7% at 420 nm), up to 13.3 and 1532.3 times by contrast with that of Pt nanoparticles/g-C3N4 nanosheets and g-C3N4 nanosheets, respectively. This work will provide a new platform for designing high-efficiency photocatalysts for sunlight-driven hydrogen generation.
RESUMO
Developing efficient electrocatalysts for alkaline water electrolysis is central to substantial progress of alkaline hydrogen production. Herein, a Ni5 P4 electrocatalyst incorporating single-atom Ru (Ni5 P4 -Ru) is synthesized through the filling of Ru3+ species into the metal vacancies of nickel hydroxides and subsequent phosphorization treatment. Electron paramagnetic resonance spectroscopy, X-ray-based measurements, and electron microscopy observations confirm the strong interaction between the nickel-vacancy defect and Ru cation, resulting in more than 3.83 wt% single-atom Ru incorporation in the obtained Ni5 P4 -Ru. The Ni5 P4 -Ru as an alkaline hydrogen evolution reaction catalyst achieves low onset potential of 17 mV and an overpotential of 54 mV at a current density of 10 mA cm-2 together with a small Tafel slope of 52.0 mV decade-1 and long-term stability. Further spectroscopy analyses combined with density functional theory calculations reveal that the doped Ru sites can cause localized structure polarization, which brings the low energy barrier for water dissociation on Ru site and the optimized hydrogen adsorption free energy on the interstitial site, well rationalizing the experimental reactivity.
RESUMO
Herein, size-controllable molybdenum carbide nanoparticles (Mo2C NPs) encapsulated by N, P-codoped carbon shells which simultaneously wrapping on the surface of carbon nanotube (Mo2C@NPC/CNT) is synthesized through a molecular-scale cage-confinement pyrolysis route. Such confinement achieves a good coating and protection of Mo2C and the effective control over the size of Mo2C NPs ranging from 2.5 to 10 nm facilitates a rational investigation into their electrochemical sensor behavior at nanometer scales. The optimized structure consisting of Mo2C nanoparticles with size of ~5 nm showed an outstanding electrochemical response toward dopamine (DA) and acetaminophen (AC) with detection limits (S/N = 3) of 0.008 µM for AC and 0.01 µM for DA.
Assuntos
Técnicas Biossensoriais , Nanopartículas , Técnicas Eletroquímicas , Eletrodos , Molibdênio , PiróliseRESUMO
A carbon microtube aerogel (CMA) with hydrophobicity, strong adsorption capacity, and superb recyclability was obtained by a feasible approach with economical raw material, such as kapok fiber. The CMA possesses a great adsorption capacity of 78-348 times its weight. Attributed to its outstanding thermal stability and excellent mechanical properties, the CMA can be used for many cycles of distillation, squeezing, and combustion without degradation, which suggests a potential practical application in oil-water separation. In addition, the adsorption capacity still retained 98% by distillation, 97% by squeezing, and 90% by combustion after 10 cycles. Therefore, the obtained CMA has a broad prospect as an economical, efficient, and environmentally friendly adsorbent.
RESUMO
Two-dimensional (2D) magnets with intrinsic ferromagnetic/antiferromagnetic (FM/AFM) ordering are highly desirable for future spintronic devices. However, the direct growth of their crystals is in its infancy. Here we report a chemical vapor deposition approach to controllably grow layered tetragonal and non-layered hexagonal FeTe nanoplates with their thicknesses down to 3.6 and 2.8 nm, respectively. Moreover, transport measurements reveal these obtained FeTe nanoflakes show a thickness-dependent magnetic transition. Antiferromagnetic tetragonal FeTe with the Néel temperature (TN) gradually decreases from 70 to 45 K as the thickness declines from 32 to 5 nm. And ferromagnetic hexagonal FeTe is accompanied by a drop of the Curie temperature (TC) from 220 K (30 nm) to 170 K (4 nm). Theoretical calculations indicate that the ferromagnetic order in hexagonal FeTe is originated from its concomitant lattice distortion and Stoner instability. This study highlights its potential applications in future spintronic devices.
RESUMO
Molybdenum disulfide (MoS2) has attracted much attention as a promising alternative to Pt-based catalysts for highly efficient hydrogen generation. However, it suffers sluggish kinetics for driving the hydrogen evolution reaction (HER) process because of inert basal planes, especially in alkaline solution. Here, we show a combination of heteroatom doping and phase transformation strategies to engineer the in-plane structure of MoS2, that trigger their catalytic activities. Systematic characterizations are performed with advanced aberration-corrected microscopy and X-ray techniques, indicating that an as-designed MoS2 catalyst has a distorted zigzag-chain superlattice in metallic phase, while its in-plane structure was engineered via the incorporation of cobalt and oxygen species. The optimal Co, O dual-doped metallic phase molybdenum disulfide (1T-MoS2) electrocatalyst shows a significantly enhanced HER activity with a low overpotential of 113 mV at 10 mA cm-2 and corresponding small Tafel slope of 50 mV dec-1, accompanied by the robust stability in alkaline media. The calculated turnover frequency is higher than 6.65 H2 s-1 at an overpotential of 200 mV. More in-depth insights from the first-principle calculations illustrate that the water dissociation as a rate-determining step was largely accelerated by the in-plane Co-O-Mo species and fast electron transfer of the catalyst. Benefiting from ingenious design and fine identifications, this work provides a fundamental understanding of the relationships among heteroatom doping, phase transformation, and performance for MoS2-based catalysts.
RESUMO
Surface defects in semiconductors have a significant role to tune the photocatalytic reactions. However, the dominant studied defect type is oxygen vacancy, and metal cation vacancies are seldom explored. Herein, bismuth vacancies are engineered into BiOBr through ultrathin structure control and employed to tune photocatalytic CO2 reduction. VBi-BiOBr ultrathin nanosheets deliver a high selective CO generation rate of 20.1 µmol g-1 h-1 in pure water, without any cocatalyst, photosensitizer, and sacrificing reagent, roughly 3.8 times higher than that of BiOBr nanosheets. The increased CO2 reduction activity is ascribed to the tuned electronic structure, optimized CO2 adsorption, activation, and CO desorption process over VBi-BiOBr ultrathin nanosheets. This work offers new opportunities for designing surface metal vacancies to optimize the CO2 photoreduction performances.
RESUMO
It is still a great challenge to improve deformability and fatigue-resistance of stretchable conductors when maintaining their high-level conductivity for practical use. Herein, a high-performance stretchable conductor with hierarchically ternary network and self-healing capability is demonstrated through in situ polymerizing N-isopropylacrylamide (NIPAM) on well-defined sulfur-containing molecule-modified Ag nanowire (AgNW) aerogel framework. Owing to hierarchical architecture from nanoscale to microscale and further to macroscale and strong interactions of polymer chains and AgNWs, the composite exhibits good conductivity of 93 S cm-1, excellent electromechanical stability up to superhigh tensile strain of 800% and strong fatigue-resistant ability through well accommodating the applied deformations and sharing external force in the network. Furthermore, the composite delivers a fast and strong healing capability induced by reversible Ag-S bonds, which enables the healed conductor to hold an impressive electromechanical property. These prominent demonstrations confirm this material as top performer for use as flexible, stretchable electronic devices.