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Open accessJournal ArticleDOI: 10.1038/S41467-021-21693-4

General molten-salt route to three-dimensional porous transition metal nitrides as sensitive and stable Raman substrates

02 Mar 2021-Nature Communications (Springer Science and Business Media LLC)-Vol. 12, Iss: 1, pp 1376-1376
Abstract: Transition metal nitrides have been widely studied due to their high electrical conductivity and excellent chemical stability. However, their preparation traditionally requires harsh conditions because of the ultrahigh activation energy barrier they need to cross in nucleation. Herein, we report three-dimensional porous VN, MoN, WN, and TiN with high surface area and porosity that are prepared by a general and mild molten-salt route. Trace water is found to be a key factor for the formation of these porous transition metal nitrides. The porous transition metal nitrides show hydrophobic surface and can adsorb a series of organic compounds with high capacity. Among them, the porous VN shows strong surface plasmon resonance, high conductivity, and a remarkable photothermal conversion efficiency. As a new type of corrosion- and radiation-resistant surface-enhanced Raman scattering substrate, the porous VN exhibits an ultrasensitive detection limit of 10−11 M for polychlorophenol. Fabrication of transition metal nitrides generally requires harsh conditions due to the high activation energy barrier for nucleation. Here, the authors report a mild molten-salt route for the synthesis of three-dimensional porous metal nitrides, VN, MoN, WN, and TiN.

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Topics: Tin (53%), Nucleation (52%), Activation energy (50%)

7 results found

Open accessJournal ArticleDOI: 10.1016/J.CONBUILDMAT.2021.124796
Anri Watanabe1, S. Tokuda2, S. Tokuda3, Y. Mizuta1  +4 moreInstitutions (4)
Abstract: This is a fundamental study of a non-destructive and contactless equipment to evaluate the chloride ion on concrete, with near infrared spectroscopy. Non-destructive measurements on Friedel’s salt, generated by ingress of chloride ion into concrete, have been studied; characteristic absorption unique to each substance was utilized to qualitative and quantitative analyses. However, there has been a difficulty in separating absorption peak of Friedel’ salt from that of other hydrates. This study investigates the method to extract the absorption peak of Friedel’s salt by Bayes’ theorem for quantitative evaluation, and its validity was confirmed using some conventional methods.

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Topics: Friedel's salt (62%), Chloride (51%)

3 Citations

Journal ArticleDOI: 10.1039/D1TB00289A
Abstract: Low molecular weight compounds play an important role in encoding the current physiological state of an individual Laser desorption/ionization mass spectrometry (LDI MS) offers high sensitivity with low cost for molecular detection, but it is not able to cover small molecules due to the drawbacks of the conventional matrix Advanced materials are better alternatives, showing little background interference and high LDI efficiency Herein, we first classify the current materials with a summary of compositions and structures Matrix preparation protocols are then reviewed, to enhance the selectivity and reproducibility of MS data better Finally, we highlight the biomedical applications of material-assisted LDI MS, at the tissue, bio-fluid, and cellular levels We foresee that the advanced materials will bring far-reaching implications in LDI MS towards real-case applications, especially in clinical settings

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2 Citations

Journal ArticleDOI: 10.1021/ACS.NANOLETT.1C02541
Damin Liu1, Xiaoyu Song, Wencai Yi2, Yahui Li  +4 moreInstitutions (2)
03 Sep 2021-Nano Letters
Abstract: The synthesis of metallic transition metal nitrides (TMNs) has traditionally been performed under harsh conditions, which makes it difficult to prepare TMNs with high surface area and porosity due to the grain sintering. Herein, we report a general and rapid (30 s) microwave synthesis method for preparing TMNs with high specific surface area (122.6-141.7 m2 g-1) and porosity (0.29-0.34 cm3 g-1). Novel single-crystal porous WN, Mo2N, and V2N are first prepared by this method, which exhibits strong surface plasmon resonance, photothermal conversion, and surface-enhanced Raman scattering effects. Different from the conventional low-temperature microwave absorbing media such as water and polymers, as new concept absorbing media, hydrated metal oxides and metallic metal oxides are found to have a remarkable high-temperature microwave heating effect and play key roles in the formation of TMNs. The current research results provide a new-concept microwave method for preparing high lattice energy compounds with high specific surface.

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Topics: Specific surface area (51%), Microwave (51%)

Journal ArticleDOI: 10.1002/ADMA.202103770
Jingru Zhang1, Yuankun Fang1, Wangen Zhao1, Ruijie Han1  +2 moreInstitutions (1)
23 Sep 2021-Advanced Materials
Abstract: Dynamic manipulation of crystallization is pivotal to the quality of polycrystalline films. A molten-salt-assisted crystallization (MSAC) strategy is presented to improve grain growth of the all-inorganic perovskite films. Compared with the traditional solvent annealing, MSAC enables more intensive mass transfer by means of convection and diffusion, which is beneficial to the interaction among the precursor colloids and to inducing in-plane growth of perovskite grains, resulting in the formation of high-quality perovskite films with suppressed pinhole and crack formation. Additionally, the introduction of molten salt alters the intermediate phases, and thus changes the crystallization pathways by reducing the energy barrier to produce films with desired optical and electrical properties. As a result, the MSAC strategy endows the devices with champion steady-state output efficiency of 19.83% and open-circuit voltage (Voc ) as high as 1.2 V, among the highest for this type of solar cell, thanks to its effectively reduced Voc deficit.

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Topics: Perovskite (structure) (56%), Crystallization (55%), Molten salt (52%) ... show more


44 results found

Open accessJournal ArticleDOI: 10.1038/NATREVMATS.2016.98
Abstract: The family of 2D transition metal carbides, carbonitrides and nitrides (collectively referred to as MXenes) has expanded rapidly since the discovery of Ti3C2 in 2011. The materials reported so far always have surface terminations, such as hydroxyl, oxygen or fluorine, which impart hydrophilicity to their surfaces. About 20 different MXenes have been synthesized, and the structures and properties of dozens more have been theoretically predicted. The availability of solid solutions, the control of surface terminations and a recent discovery of multi-transition-metal layered MXenes offer the potential for synthesis of many new structures. The versatile chemistry of MXenes allows the tuning of properties for applications including energy storage, electromagnetic interference shielding, reinforcement for composites, water purification, gas- and biosensors, lubrication, and photo-, electro- and chemical catalysis. Attractive electronic, optical, plasmonic and thermoelectric properties have also been shown. In this Review, we present the synthesis, structure and properties of MXenes, as well as their energy storage and related applications, and an outlook for future research. More than twenty 2D carbides, nitrides and carbonitrides of transition metals (MXenes) have been synthesized and studied, and dozens more predicted to exist. Highly electrically conductive MXenes show promise in electrical energy storage, electromagnetic interference shielding, electrocatalysis, plasmonics and other applications.

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Topics: MXenes (76%)

3,017 Citations

Journal ArticleDOI: 10.1038/NATURE08907
18 Mar 2010-Nature
Abstract: Surface-enhanced Raman scattering (SERS) is a powerful spectroscopy technique that can provide non-destructive and ultra-sensitive characterization down to single molecular level, comparable to single-molecule fluorescence spectroscopy. However, generally substrates based on metals such as Ag, Au and Cu, either with roughened surfaces or in the form of nanoparticles, are required to realise a substantial SERS effect, and this has severely limited the breadth of practical applications of SERS. A number of approaches have extended the technique to non-traditional substrates, most notably tip-enhanced Raman spectroscopy (TERS) where the probed substance (molecule or material surface) can be on a generic substrate and where a nanoscale gold tip above the substrate acts as the Raman signal amplifier. The drawback is that the total Raman scattering signal from the tip area is rather weak, thus limiting TERS studies to molecules with large Raman cross-sections. Here, we report an approach, which we name shell-isolated nanoparticle-enhanced Raman spectroscopy, in which the Raman signal amplification is provided by gold nanoparticles with an ultrathin silica or alumina shell. A monolayer of such nanoparticles is spread as 'smart dust' over the surface that is to be probed. The ultrathin coating keeps the nanoparticles from agglomerating, separates them from direct contact with the probed material and allows the nanoparticles to conform to different contours of substrates. High-quality Raman spectra were obtained on various molecules adsorbed at Pt and Au single-crystal surfaces and from Si surfaces with hydrogen monolayers. These measurements and our studies on yeast cells and citrus fruits with pesticide residues illustrate that our method significantly expands the flexibility of SERS for useful applications in the materials and life sciences, as well as for the inspection of food safety, drugs, explosives and environment pollutants.

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Topics: Raman spectroscopy (65%), Raman scattering (59%), Fluorescence spectroscopy (52%) ... show more

2,545 Citations

Journal ArticleDOI: 10.1021/J150668A038
Peter Hildebrandt1, M. Stockburger1Institutions (1)
Abstract: Resultats d'etudes par diffusion Raman augmentee en surface et par des mesures fluorescentes. Mise en evidence de l'existence de 2 types de sites d'adsorption

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1,282 Citations

Journal ArticleDOI: 10.1002/ANIE.201200699
Wei-Fu Chen1, Kotaro Sasaki1, Chao Ma1, Anatoly I. Frenkel2  +4 moreInstitutions (3)
18 Jun 2012-Angewandte Chemie
Abstract: Hydrogen production through splitting of water has attracted great scientific interest because of its relevance to renewable energy storage and its potential for providing energy without the emission of carbon dioxide. Electrocatalytic systems for H2 generation typically incorporate noble metals such as Pt in the catalysts because of their low overpotential and fast kinetics for driving the hydrogen evolution reaction (HER). However, the high costs and limited world-wide supply of these noble metals make their application in viable commercial processes unattractive. Several non-noble metal materials, such as transition-metal chalcogenides, carbides, and complexes as well as metal alloys have been widely investigated recently, and characterized as catalysts and supports for application in the evolution of hydrogen. Nitrides of early transition-metals have been shown to have excellent catalytic activities in a variety of reactions. One of the primary interests in the applications of nitrides in these reactions was to use them in conjunction with low-cost alternative metals to replace group VIII noble metals. For example, the function of molybdenum nitride as a catalyst for hydrocarbon hydrogenolysis resembles that of platinum. The catalytic and electronic properties of transition-metal nitrides are governed by their bulk and surface structure and stoichiometry. While there is some information concerning the effect of the bulk composition on the catalytic properties of this material, there is currently little known about the effects of the surface nanostructure. Nickel and nickel–molybdenum are known electrocatalysts for hydrogen production in alkaline electrolytes, and in the bulk form they exhibited exchange current densities between 10 6 and 10 4 Acm , compared to 10 3 Acm 2 for Pt. Jaksic et al. postulated a hypo-hyper-d-electronic interactive effect between Ni and Mo that yields the synergism for the HER. Owing to their poor corrosion stability, few studies in acidic media have been reported.With the objective of exploiting the decrease in the overpotential by carrying out the HER in acidic media, we have developed a low-cost, stable, and active molybdenum-nitride-based electrocatalyst for the HER. Guided by the “volcano plot” in which the activity for the evolution of hydrogen as a function of the M H bond strength exhibits an ascending branch followed by a descending branch, peaking at Pt, we designed a material on the molecular scale combining nickel, which binds H weakly, with molybdenum, which binds H strongly. Here we report the first synthesis of NiMo nitride nanosheets on a carbon support (NiMoNx/C), and demonstrate the high HER electrocatalytic activity of the resulting NiMoNx/C catalyst with low overpotential and small Tafel slope. The NiMoNx/C catalyst was synthesized by reduction of a carbon-supported ammonium molybdate [(NH4)6Mo7O24·4H2O] and nickel nitrate (Ni(NO3)2·4H2O) mixture in a tubular oven in H2 at 400 8C, and subsequent reaction with NH3 at 700 8C. During this process, the (NH4)6Mo7O24 and Ni(NO3)2 precursors were reduced to NiMo metal particles by H2, and then they were mildly transformed to NiMoNx nanosheets by reaction with ammonia. The atomic ratio of Ni/Mo was 1/4.7 determined by energy dispersive X-ray spectroscopy (EDX) on the NiMoNx/ C sample. The transmission electron microscopy (TEM) images, as shown in Figure 1a, display NiMo particles that are mainly spherical. The high-resolution TEM image, as shown in the inset of Figure 1a, corroborated the presence of an amorphous 3 to 5 nm Ni/Mo oxide layer (see Figure S4 in the Supporting Information for resolved image), whereas NiMoNx is characterized by thin, flat, and flaky stacks composed of nanosheets with high radial-axial ratios (Figure 1b and Figure S5 in the Supporting Information for a magnified image). Figure 1c shows that some of the nanosheets lay flat on the graphite carbon (as indicated by the black arrows), and some have folded edges that show different layers of NiMoNx sheets (white arrows). The thickness of the sheets ranged from 4 to 15 nm. The average stacking number of sheets measured from Figure 1b is about [*] Dr. W.-F. Chen, Dr. K. Sasaki, Dr. J. T. Muckerman, Dr. R. R. Adzic Chemistry Department, Brookhaven National Laboratory Upton, NY 11973 (USA) E-mail:

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Topics: Overpotential (56%), Electrocatalyst (55%), Catalysis (55%) ... show more

1,011 Citations

Journal ArticleDOI: 10.1002/ADFM.201202502
Mohammad Khazaei1, Masao Arai1, Taizo Sasaki1, Chan Yeup Chung2  +4 moreInstitutions (2)
Abstract: Layered MAX phases are exfoliated into 2D single layers and multilayers, so-called MXenes. Using fi rst-principles calculations, the formation and electronic properties of various MXene systems, M 2 C (M = Sc, Ti, V, Cr, Zr, Nb, Ta) and M 2 N (M = Ti, Cr, Zr) with surfaces chemically functionalized by F, OH, and O groups, are examined. Upon appropriate surface functionalization, Sc 2 C, Ti 2 C, Zr 2 C, and Hf 2 C MXenes are expected to become semiconductors. It is also derived theoretically that functionalized Cr 2 C and Cr 2 N MXenes are magnetic. Thermoelectric calculations based on the Boltzmann theory imply that semiconducting MXenes attain very large Seebeck coeffi cients at low temperatures.

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Topics: MXenes (70%), MAX phases (59%), Thermoelectric effect (50%)

880 Citations

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