top-down synthesis
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The oxygen reduction reaction (ORR) is of great interest for future sustainable energy conversion and storage, especially concerning fuel cell applications. The preparation of active, affordable, and scalable electrocatalysts and their application in fuel cell engines of hydrogen cars is a prominent step toward the reduction of air pollution, especially in urban areas. Alloying nanostructured Pt with lanthanides is a promising approach to enhance its catalytic ORR activity, whereby the development of a simple synthetic route turned out to be a nontrivial endeavor. Herein, for the first time, we present a successful single-step, scalable top-down synthetic route for Pt-lanthanide alloy nanoparticles, as witnessed by the example of Pr-alloyed Pt nanoparticles. The catalyst was characterized by high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, and photoelectron spectroscopy, and its electrocatalytic oxygen reduction activity was investigated using a rotating disk electrode technique. Pt xPr/C showed ∼3.5 times higher [1.96 mA/cm2Pt, 0.9 V vs reversible hydrogen electrode (RHE)] specific activity and ∼1.7 times higher (0.7 A/mgPt, 0.9 V vs RHE) mass activity compared to commercial Pt/C catalysts. On the basis of previous findings and characterization of the Pt xPr/C catalyst, the activity improvement over commercial Pt/C originates from a lattice strain introduced by the alloying process.
- Klíčová slova
- cathodic corrosion, electrocatalysis, fuel cell, lanthanides, oxygen reduction, platinum alloys, top-down synthesis,
- Publikační typ
- časopisecké články MeSH
Nanostructured palladium (Pd) is a universal catalyst that is widely used in applications ranging from catalytic converters of combustion engine cars to hydrogenation catalysts in industrial processes. Standard protocols for synthesizing such nanoparticles (NPs) typically use bottom-up approaches. They utilize special and often expensive physical techniques or wet-chemical methods requiring organic surfactants. These surfactants should often be removed before catalytic applications. In this article, the synthesis of Pd NPs immobilized on carbon support by electrochemical erosion without using any surfactants or toxic materials is reported. The Pd NPs synthesis essentially relies on a Pd bulk pretreatment, which causes material embrittlement and allows the erosion process to evolve more efficiently, producing homogeneously distributed NPs on the support. Moreover, the synthesized catalyst is tested for hydrogen evolution reaction. The activity evaluations identify optimal synthesis parameters related to the erosion procedure. The electrocatalytic properties of the Pd NPs produced with sizes down to 6.4 ± 2.9 nm are compared with a commercially available Pd/C catalyst. The synthesized catalyst outperforms the commercial catalyst within all properties, like specific surface area, geometric activity, mass activity, specific activity, and durability.
- Klíčová slova
- electrochemical erosion, hydrogen embrittlement, hydrogen evolution reaction, nanoparticles, palladium,
- Publikační typ
- časopisecké články MeSH
The properties of zeolites, and thus their suitability for different applications, are intimately connected with their structures. Synthesizing specific architectures is therefore important, but has remained challenging. Here we report a top-down strategy that involves the disassembly of a parent zeolite, UTL, and its reassembly into two zeolites with targeted topologies, IPC-2 and IPC-4. The three zeolites are closely related as they adopt the same layered structure, and they differ only in how the layers are connected. Choosing different linkers gives rise to different pore sizes, enabling the synthesis of materials with predetermined pore architectures. The structures of the resulting zeolites were characterized by interpreting the X-ray powder-diffraction patterns through models using computational methods; IPC-2 exhibits orthogonal 12- and ten-ring channels, and IPC-4 is a more complex zeolite that comprises orthogonal ten- and eight-ring channels. We describe how this method enables the preparation of functional materials and discuss its potential for targeting other new zeolites.
- MeSH
- magnetická rezonanční spektroskopie MeSH
- molekulární modely MeSH
- prášková difrakce MeSH
- zeolity chemie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- zeolity MeSH
Arsenene, as an exotic representative of two-dimensional (2D) materials, has received great interest, yet the interest is mainly based on theoretical study. The reason for this is a restricted ability to operate the material from its synthesis to implementation. Beginning with the production, electrochemical exfoliation has been found as an extremely effective method for the preparation of 2D materials from bulk materials. Here, for the first time, we demonstrate the electrochemical exfoliation of bulk black arsenic in the anhydrous electrolyte medium. Spectro- and microscopic analyses evidence micrometer lateral size few-layer arsenene in a netlike porous shape formed of 2D flakes. We demonstrate that the surfactant-free exfoliation successfully resulted in a stable dispersion for which only washing with the corresponding solvent was sufficient. This electrochemistry route for the black arsenic exfoliation toward few-layer arsenene will broaden the materials' scope applications in new-generation devices.
- Publikační typ
- časopisecké články MeSH
Two-dimensional germanene has been recently explored for applications in sensing, catalysis, and energy storage. The potential of this van der Waals material lies in its optoelectronic and chemical properties. However, pure free-standing germanene cannot be found in nature, and the synthesis methods are hindering the potentially fascinating properties of germanene. Herein, we report a single-step synthesis of few-layer germanene by electrochemical exfoliation in a nonaqueous environment. As a result of simultaneous decalcification and intercalation of the electrolyte's active ions, we achieved low-level hydrogenation of germanene that occurs at the edges of the material. The obtained edge-hydrogenated germanene flakes have a lateral size of several micrometers and possess a cubic structure. We have pioneered the potential application of edge-hydrogenated germanene for vapor sensing and demonstrated its specific sensitivity to methanol and ethanol. Furthermore, we have shown a selective behavior of the germanene-based sensor that appears to increase the electrical resistance in the vapors where methanol prevails. We anticipate that these results can provide an approach for emerging layered materials with the potential utility in advanced gas sensing.
- Klíčová slova
- edge-hydrogenated germanene, electrochemical exfoliation, semiconductor, top-down synthesis, vapor sensing,
- Publikační typ
- časopisecké články MeSH
Carbon and graphene quantum dots are prepared using top-down and bottom-up methods. Sustainable synthesis of quantum dots has several advantages such as the use of low-cost and non-toxic raw materials, simple operations, expeditious reactions, renewable resources and straightforward post-processing steps. These nanomaterials are promising for clinical and biomedical sciences, especially in bioimaging, diagnosis, bioanalytical assays and biosensors. Here we review green methods for the fabrication of quantum dots, and biomedical and biotechnological applications.
- Klíčová slova
- Bioimaging, Biomedical applications, Biotechnological applications, Cancer, Carbon dots, Diagnosis, Graphene quantum dots, Quantum dots, Sustainable synthesis,
- Publikační typ
- časopisecké články MeSH
- přehledy MeSH
A two-dimensional (2D) silicene-germanene alloy, siligene (SixGey), a single-phase material, has attracted increased attention due to its two-elemental low-buckled composition and unique physics and chemistry. This 2D material has the potential to address the challenges caused by low electrical conductivity and the environmental instability of corresponding monolayers. Yet, the siligene structure was studied in theory, demonstrating the material's great electrochemical potential for energy storage applications. The synthesis of free-standing siligene remains challenging and therefore hinders the research and its application. Herein we demonstrate nonaqueous electrochemical exfoliation of a few-layer siligene from a Ca1.0Si1.0Ge1.0 Zintl phase precursor. The procedure was conducted in an oxygen-free environment applying a -3.8 V potential. The obtained siligene exhibits a high quality, high uniformity, and excellent crystallinity; the individual flake is within the micrometer lateral size. The 2D SixGey was further explored as an anode material for lithium-ion storage. Two types of anode have been fabricated and integrated into lithium-ion battery cells, namely, (1) siligene-graphene oxide sponges and (2) siligene-multiwalled carbon nanotubes. The as-fabricated batteries both with/without siligene exhibit similar behavior; however there is an increase in the electrochemical characteristics of SiGe-integrated batteries by 10%. The corresponding batteries exhibit a 1145.0 mAh·g-1 specific capacity at 0.1 A·g-1. The SiGe-integrated batteries demonstrate a very low polarization, confirmed by their good stability after 50 working cycles and a decrease in the solid electrolyte interphase level that occurs after the first discharge/charge cycle. We anticipate the growing potential of emerging two-component 2D materials and their great promise for energy storage and beyond.
- Klíčová slova
- electrochemical exfoliation, germanene, lithium-ion battery, lithium-ion storage, low-hydrogenated siligene, silicene, top-down synthesis,
- Publikační typ
- časopisecké články MeSH
Carbon quantum dots (CQDs), a new family of photoluminescent 0D NPs, have recently received a lot of attention. They have enormous future potential due to their unique properties, which include low toxicity, high conductivity, and biocompatibility and accordingly can be used as a feasible replacement for conventional materials deployed in various optoelectronic, biomedical, and energy applications. The most recent trends and advancements in the synthesizing and setup of photoluminescent CQDs using environmentally friendly methods are thoroughly discussed in this review. The eco-friendly synthetic processes are emphasized, with a focus on biomass-derived precursors. Modification possibilities for creating newer physicochemical properties among different CQDs are also presented, along with a brief conceptual overview. The extensive amount of writings on them found in the literature explains their exceptional competence in a variety of fields, making these nanomaterials promising alternatives for real-world applications. Furthermore, the benefits, drawbacks, and opportunities for CQDs are discussed, with an emphasis on their future prospects in this emerging research field.
- Klíčová slova
- bottom-up approach, carbon quantum dots (CQDs), green synthesis, photoluminescent, top-down approach,
- Publikační typ
- časopisecké články MeSH
- přehledy MeSH
In the last few decades, there has been a trend involving the use of nanoscale fillers in a variety of applications. Significant improvements have been achieved in the areas of their preparation and further applications (e.g., in industry, agriculture, and medicine). One of these promising materials is magnesium oxide (MgO), the unique properties of which make it a suitable candidate for use in a wide range of applications. Generally, MgO is a white, hygroscopic solid mineral, and its lattice consists of Mg2+ ions and O2- ions. Nanostructured MgO can be prepared through different chemical (bottom-up approach) or physical (top-down approach) routes. The required resultant properties (e.g., bandgap, crystallite size, and shape) can be achieved depending on the reaction conditions, basic starting materials, or their concentrations. In addition to its unique material properties, MgO is also potentially of interest due to its nontoxicity and environmental friendliness, which allow it to be widely used in medicine and biotechnological applications.
- Klíčová slova
- bottom-up, crystallite size, dielectric properties, electrotechnical applications, magnesium oxide, nanomaterials, structural properties, synthesis,
- MeSH
- adsorpce MeSH
- chemické modely MeSH
- nanočástice chemie MeSH
- oxid hořečnatý chemie MeSH
- Publikační typ
- časopisecké články MeSH
- přehledy MeSH
- Názvy látek
- oxid hořečnatý MeSH
Since the debut of silicene in the experimental stage more than a decade ago, the family of two-dimensional elementary layers beyond graphene, called Xenes or transgraphenes, has rapidly expanded to include elements from groups II to VI of the periodic table. This expansion has opened pathways for the engineering of elementary monolayers that are inherently different from their bulk counterparts in terms of fundamental physical properties. Common guidelines for synthesizing Xenes can be categorized into well-defined methodological approaches. On the one hand, bottom-up methods, such as physical epitaxial methods, enable the growth of monolayers, multilayers, and heterostructured Xenes. On the other hand, top-down chemical methods, including topotactic deintercalation and liquid-phase exfoliation, are gaining prominence due to the possibility of massive production. This review provides an extensive view of the currently available synthesis routes for Xenes, highlighting the full range of Xenes reported to date, along with the most relevant identification techniques.
- Publikační typ
- časopisecké články MeSH
- přehledy MeSH