Phonon properties and photo-thermal oxidation of micromechanically exfoliated antimonene nanosheets

Two-dimensional (2D) sheets of antimonene have attracted increasing attention due to their unique physical and chemical properties prompting potential for diverse applications. We present a facile method to prepare high-quality antimonene nanosheets (ANSs) by micromechanical exfoliation on SiO2/Si substrate. The temperature- and laser power-dependent Raman studies of exfoliated ANSs are reported and analyzed. It was found that both the out-of-plane A1g and the in-plane Eg modes red-shift linearly with increase in temperature, pointing towards anharmonic vibrations of the lattice. The thermal response of the ANSs on a SiO2/Si surface is also described using numerical simulation of the heat transfer to study their laser-induced oxidation mechanisms. These results offer a deeper understanding of the phonon properties and oxidation susceptibility of 2D antimonene paving the way for the development of antimonene-based technologies, such as electronic devices or photothermal cancer therapy

Two-dimensional antimony oxide

Two-dimensional (2D) antimony, so-called antimonene, can form antimonene oxide when exposed to air. We present different types of single- and few-layer antimony oxide structures, based on density functional theory (DFT) calculations. Depending on stoichiometry and bonding type, these novel 2D layers have different structural stability and electronic properties, ranging from topological insulators to semiconductors with direct and indirect band gaps between 2.0 and 4.9 eV. We discuss their vibrational properties and Raman spectra for experimental identification of the predicted structures

Antimonene: a tuneable post-graphene material for advanced applications in optoelectronics, catalysis, energy and biomedicine.

The post-graphene era is undoubtedly marked by two-dimensional (2D) materials such as quasi-van der Waals antimonene. This emerging material has a fascinating structure, exhibits a pronounced chemical reactivity (in contrast to graphene), possesses outstanding electronic properties and has been postulated for a plethora of applications. However, chemistry and physics of antimonene remain in their infancy, but fortunately recent discoveries have shed light on its unmatched allotropy and rich chemical reactivity offering a myriad of unprecedented possibilities in terms of fundamental studies and applications. Indeed, antimonene can be considered as one of the most appealing post-graphene 2D materials reported to date, since its structure, properties and applications can be chemically engineered from the ground up (both using top-down and bottom-up approaches), offering an unprecedented level of control in the realm of 2D materials. In this review, we provide an in-depth analysis of the recent advances in the synthesis, characterization and applications of antimonene. First, we start with a general introduction to antimonene, and then we focus on its general chemistry, physical properties, characterization and synthetic strategies. We then perform a comprehensive study on the allotropy, the phase transition mechanisms, the oxidation behaviour and chemical functionalization. From a technological point of view, we further discuss the applications recently reported for antimonene in the fields of optoelectronics, catalysis, energy storage, cancer therapy and sensing. Finally, important aspects such as new scalable methodologies or the promising perspectives in biomedicine are discussed, pinpointing antimonene as a cutting-edge material of broad interest for researchers working in chemistry, physics, materials science and biomedicine

Interface amorphization of two‐dimensional black phosphorus upon treatment with diazonium salts

Two-dimensional (2D) black phosphorus (BP) represents one of the most appealing 2D materials due to its electronic, optical, and chemical properties. Many strategies have been pursued to face its environmental instability, covalent functionalization being one of the most promising. However, the extremely low functionalization degrees and the limitations in proving the nature of the covalent functionalization still represent challenges in many of these sheet architectures reported to date. Here we shine light on the structural evolution of 2D-BP upon the addition of electrophilic diazonium salts. We demonstrated the absence of covalent functionalization in both the neutral and the reductive routes, observing in the latter case an unexpected interface conversion of BP to red phosphorus (RP), as characterized by Raman, 31P-MAS NMR, and X-ray photoelectron spectroscopies (XPS). Furthermore, thermogravimetric analysis coupled to gas chromatography and mass spectrometry (TG-GC-MS), as well as electron paramagnetic resonance (EPR) gave insights into the potential underlying radical mechanism, suggesting a Sandmeyer-like reaction

Unveiling the oxidation behavior of liquid-phase exfoliated antimony nanosheets

Antimonene, a monolayer of β-antimony, is increasingly attracting considerable attention, more than that of other monoelemental two-dimensional materials, due to its intriguing physical and chemical properties. Under ambient conditions, antimonene exhibits a high thermodynamic stability and good structural integrity. Some theoretical calculations predicted that antimonene would have a high oxidation tendency. However, it remains poorly investigated from the experimental point of view. In this work, we study the oxidation behavior of antimonene nanosheets (ANS) prepared by ultrasonication-assisted liquid-phase exfoliation. Using a set of forefront analytical techniques, a clear effect of sonication time on the surface chemistry of prepared ANS is found. A dynamic oxidation behavior has been observed, which upon annealing at moderate temperature (210 °C) resulted in a semiconducting behavior with a bandgap of approximately 1 eV measured by ultraviolet photoelectron spectroscopy. This study yields valuable information for future applications of antimonene and paves the way towards novel modification approaches in order to tailor its properties and complement its limitations

Exfoliation of Alpha-Germanium: A Covalent Diamond-Like Structure

2D materials have opened a new field in materials science with outstanding scientific and technological impact. A largely explored route for the preparation of 2D materials is the exfoliation of layered crystals with weak forces between their layers. However, its application to covalent crystals remains elusive. Herein, a further step is taken by introducing the exfoliation of germanium, a narrow-bandgap semiconductor presenting a 3D diamond-like structure with strong covalent bonds. Pure α-germanium is exfoliated following a simple one-step procedure assisted by wet ball-milling, allowing gram-scale fabrication of high-quality layers with large lateral dimensions and nanometer thicknesses. The generated flakes are thoroughly characterized by different techniques, giving evidence that the new 2D material exhibits bandgaps that depend on both the crystallographic direction and the number of layers. Besides potential technological applications, this work is also of interest for the search of 2D materials with new properties

Continuous‐Flow Synthesis of High‐Quality Few‐Layer Antimonene Hexagons

2D materials show outstanding properties that can bring many applications in different technological fields. However, their uses are still limited by production methods. In this context, antimonene is recently suggested as a new 2D material to fabricate different (opto)electronic devices, among other potential applications. This work focuses on optimizing the synthetic parameters to produce high-quality antimonene hexagons and their implementation in a large-scale manufacturing procedure. By means of a continuous-flow synthesis, few-layer antimonene hexagons with ultra-large lateral dimensions (up to several microns) and a few nanometers thick are isolated. The suitable chemical post-treatment of these nanolayers with chloroform gives rise to antimonene surfaces showing low oxidation that can be easily contacted with microelectrodes. Therefore, the reported procedure offers a way to solve two critical problems for using antimonene in many applications: large-scale preparation of high-quality antimonene and the ability to set electrical contacts useful for device fabrication.PNICTOCHEM 804110 (G.A.)PID2019-111742-GA-I00CIDEGENT/2018/00

Catalytic complete oxidation of acetylene and propene over clay versus cordierite honeycomb monoliths without and with chemical vapor deposited cobalt oxide

Assebban M, Tian Z-Y, El Kasmi A, Bahlawane N, Harti S, Chafik T. Catalytic complete oxidation of acetylene and propene over clay versus cordierite honeycomb monoliths without and with chemical vapor deposited cobalt oxide. Chemical Engineering Journal. 2015;262:1252-1259.The catalytic oxidation of acetylene (C2H2) and propene (C3H6), selected as model unsaturated hydrocarbons, was investigated over uncoated- and Co3O4-coated natural clay honeycomb monoliths and their performance was compared with commercial cordierite. Co3O4 was deposited using chemical vapor deposition (CVD) and chosen based on its recently demonstrated high activity. The catalytic behavior of the clay and cordierite-based monolithic samples has been investigated for the determination of the temperature-dependent conversion yield, specific reaction rate and related activation energy. The obtained results revealed a promising intrinsic catalytic performance of the uncoated clay monoliths. Furthermore, a synergetic interaction between the clay and the Co3O4 film has enabled an improved performance relative to the coated cordierite. The present paper reveals a promising potential application of the natural clay as catalyst and/or catalyst-support through the association of the advantages offered by the chemical composition and honeycomb monolithic structure of clay. (C) 2014 Elsevier B.V. All rights reserved

Non-Calorimetric Determination of the Adsorption Heat of Volatile Organic Compounds under Dynamic Conditions

Avoiding strong chemical bonding, as indicated by lower heat of adsorption value, is among the selection criteria for Volatile Organic Compounds adsorbents. In this work, we highlight a non-calorimetric approach to estimating the energy of adsorption and desorption based on measurement of involved amounts, under dynamic conditions, with gaseous Fourier Transform Infrared spectroscopy. The collected data were used for obtaining adsorption heat values through the application of three different methods, namely, isosteric, temperature programmed desorption (TPD), and temperature-programmed adsorption equilibrium (TPAE). The resulting values were compared and discussed with the scope of turning determination of the heat of adsorption with non-calorimetric methods into a relevant decision making tool for designing cost-effective and safe operating of adsorption facilities

Towards biofuel combustion with an easily extruded clay as a natural catalyst

Tian Z-Y, Chafik T, Assebban M, et al. Towards biofuel combustion with an easily extruded clay as a natural catalyst. APPLIED ENERGY. 2013;107:149-156