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I-III-VI2 semiconductor nanocrystals have been applied to a host of energy conversion devices with great success. Large scale implementation of device concepts based on these materials has, however, been somewhat stymied by the strong role of defects in determining the optoelectronic characteristics of these materials. Here we present a perspective view of the role of electronic structure and defects on the physical properties, particularly the spectroscopy, of this family of materials. Applications of these materials are further discussed in this context.
We present a divergent strategy for the fluorination of phenylacetic acid derivatives that is induced by a charge-transfer complex between Selectfluor and 4-(dimethylamino)pyridine. A comprehensive investigation of the conditions revealed a critical role of the solvent on the reaction outcome. In the presence of water, decarboxylative fluorination through a single-electron oxidation is dominant. Non-aqueous conditions result in the clean formation of alpha-fluoro-alpha-arylcarboxylic acids.
Laser-induced breakdown spectroscopy (LIBS) analysers are becoming increasingly common for material classification purposes. However, to achieve good classification accuracy, mostly noncompact units are used based on their stability and reproducibility. In addition, computational algorithms that require significant hardware resources are commonly applied. For performing measurement campaigns in hard-to-access environments, such as mining sites, there is a need for compact, portable, or even handheld devices capable of reaching high measurement accuracy. The optics and hardware of small (i.e., handheld) devices are limited by space and power consumption and require a compromise of the achievable spectral quality. As long as the size of such a device is a major constraint, the software is the primary field for improvement. In this study, we propose a novel combination of handheld LIBS with non-negative tensor factorisation to investigate its classification capabilities of copper minerals. The proposed approach is based on the extraction of source spectra for each mineral (with the use of tensor methods) and their labelling based on the percentage contribution within the dataset. These latent spectra are then used in a regression model for validation purposes. The application of such an approach leads to an increase in the classification score by approximately 5% compared to that obtained using commonly used classifiers such as support vector machines, linear discriminant analysis, and the k-nearest neighbours algorithm.
This study aims to explore the photoinitiated cationic ring-opening polymerization of levoglucosenyl methyl ether (LGME), a chemical obtained from the most abundant biomass - cellulose. Direct and sensitized photopolymerizations of LGME using photoinitiators acting at the near UV or visible range in conjunction with diphenyliodonium hexafluoroantimonate (DPI) yielded unsaturated polyacetals with varying molar masses and distributions.
Despite intensive research on porous carbon materials as hosts for sulfur in lithium-sulfur battery cathodes, it remains a problem to restrain the soluble lithium polysulfide intermediates for a long-term cycling stability without the use of metallic or metal-containing species. Here, we report the synthesis of nitrogen-doped carbon materials with hierarchical pore architecture and a core-shell-type particle design including an ordered mesoporous carbon core and a polar microporous carbon shell. The initial discharge capacity with a sulfur loading up to 72 wt% reaches over 900 mA h g(sulf)(ur)(-1) at a rate of C/2. Cycling performance measured at C/2 indicates similar to 90% capacity retention over 250 cycles. In comparison to other carbon hosts, this architecture not only provides sufficient space for a high sulfur loading induced by the high-pore-volume particle core, but also enables a dual effect of physical and chemical confinement of the polysulfides to stabilize the cycle life by adsorbing the soluble intermediates in the polar microporous shell. This work elucidates a design principle for carbonaceous hosts that is capable to provide simultaneous physical-chemical confinement. This is necessary to overcome the shuttle effect towards stable lithium-sulfur battery cathodes, in the absence of additional membranes or inactive metal-based anchoring materials.
On-demand motion of highly swollen polymer systems can be triggered by changes in pH, ion concentrations, or by heat. Here, shape-programmable, architectured hydrogels are introduced, which respond to ultrasonic-cavitation-based mechanical forces (CMF) by directed macroscopic movements. The concept is the implementation and sequential coupling of multiple functions (swellability in water, sensitivity to ultrasound, shape programmability, and shape-memory) in a semi-interpenetrating polymer network (s-IPN). The semi-IPN-based hydrogels are designed to function through rhodium coordination (Rh-s-IPNH). These coordination bonds act as temporary crosslinks. The porous hydrogels with coordination bonds (degree of swelling from 300 +/- 10 to 680 +/- 60) exhibit tensile strength sigma(max) up to 250 +/- 60 kPa. Shape fixity ratios up to 90% and shape recovery ratios up to 94% are reached. Potential applications are switches or mechanosensors.
We present a microcontact printing (mu CP) routine suitable to introduce defined (sub-) microscale patterns on surface substrates exhibiting a high capillary activity and receptive to a silane-based chemistry. This is achieved by transferring functional trivalent alkoxysilanes, such as (3-aminopropyl)-triethoxysilane (APTES) as a low-molecular weight ink via reversible covalent attachment to polymer brushes grafted from elastomeric polydimethylsiloxane (PDMS) stamps. The brushes consist of poly{N-[tris(hydroxymethyl)-methyl]acrylamide} (PTrisAAm) synthesized by reversible addition-fragmentation chain-transfer (RAFT)-polymerization and used for immobilization of the alkoxysilane-based ink by substituting the alkoxy moieties with polymer-bound hydroxyl groups. Upon physical contact of the silane-carrying polymers with surfaces, the conjugated silane transfers to the substrate, thus completely suppressing ink-flow and, in turn, maximizing printing accuracy even for otherwise not addressable substrate topographies. We provide a concisely conducted investigation on polymer brush formation using atomic force microscopy (AFM) and ellipsometry as well as ink immobilization utilizing two-dimensional proton nuclear Overhauser enhancement spectroscopy (H-1-H-1-NOESY-NMR). We analyze the mu CP process by printing onto Si-wafers and show how even distinctively rough surfaces can be addressed, which otherwise represent particularly challenging substrates.
CH2 + O-2
(2022)
The singlet and triplet potential surfaces for the title reaction were investigated using the CBS-QB3 level of theory. The wave functions for some species exhibited multireference character and required the CASPT2/6-31+G(d,p) and CASPT2/aug-cc-pVTZ levels of theory to obtain accurate relative energies. A Natural Bond Orbital Analysis showed that triplet (CH2OO)-C-3 (the simplest Criegee intermediate) and (CH2O2)-C-3 (dioxirane) have mostly polar biradical character, while singlet (CH2OO)-C-1 has some zwitterionic character and a planar structure. Canonical variational transition state theory (CVTST) and master equation simulations were used to analyze the reaction system. CVTST predicts that the rate constant for reaction of (CH2)-C-1 + O-3(2) is more than ten times as fast as the reaction of (CH2)-C-3 ((XB1)-B-3) + O-3(2) and the ratio remains almost independent of temperature from 900 K to 3000 K. The master equation simulations predict that at low pressures the (CH2O)-C-1 + O-3 product set is dominant at all temperatures and the primary yield of OH radicals is negligible below 600 K, due to competition with other primary reactions in this complex system.
exo-Methylene-beta-lactams were synthesized in two steps from commercially available 3-bromo-2-(bromomethyl)-propionic acid and reacted with arene diazonium salts in a Heck-type arylation in the presence of catalytic amounts of Pd(OAc)(2) under ligand-free conditions. The products, arylidene-beta-lactams, were obtained in high yields as single isomers. The beta-hydride elimination step of the Pd-catalyzed coupling reaction proceeds with high exo-regioselectivity and E-stereoselectivity. With aryl iodides, triflates, or bromides, the coupling products were isolated only in low yields, due to extensive decomposition of the starting material at elevated temperatures. This underlines that arene diazonium salts can be superior arylating reagents in Heck-type reactions and yield coupling products in synthetically useful yields and selectivities when conventional conditions fail.
Metal sulfide nanoparticle synthesis with ionic liquids state of the art and future perspectives
(2021)
Metal sulfides are among the most promising materials for a wide variety of technologically relevant applications ranging from energy to environment and beyond. Incidentally, ionic liquids (ILs) have been among the top research subjects for the same applications and also for inorganic materials synthesis. As a result, the exploitation of the peculiar properties of ILs for metal sulfide synthesis could provide attractive new avenues for the generation of new, highly specific metal sulfides for numerous applications. This article therefore describes current developments in metal sulfide nano-particle synthesis as exemplified by a number of highlight examples. Moreover, the article demonstrates how ILs have been used in metal sulfide synthesis and discusses the benefits of using ILs over more traditional approaches. Finally, the article demonstrates some technological challenges and how ILs could be used to further advance the production and specific property engineering of metal sulfide nanomaterials, again based on a number of selected examples.