Topics in Current Chemistry最新文献

Sustainable and?high performance energy devices such as solar cells, fuel cells, metal–air batteries, as well as alternative energy conversion and storage systems have been considered as promising technologies to meet the ever-growing demands for clean energy. Hydrogen evolution reaction (HER) is a crucial process for cost-effective hydrogen production; however, functional electrocatalysts are potentially desirable to expedite reaction kinetics and supply high energy density. Thus, the development of inexpensive and catalytically active electrocatalysts is one of the most significant and challenging issues in the field of electrochemical energy storage and conversion. Realizing that advanced nanomaterials could engender many advantageous chemical and physical properties over a wide scale, tremendous efforts have been devoted to the preparation of earth-abundant transition metals as electrocatalysts for HER in both acidic and alkaline environments because of their?low processing costs, reasonable catalytic activities, and chemical stability. Among all transition metal-based catalysts, nickel compounds are the most widely investigated, and have exhibited pioneering performances in various electrochemical reactions. Heterostructured nickel phosphide (Ni_xP_y) based compounds were introduced as promising candidates of a new category, which often display chemical and electronic characteristics that are distinct from those of non-precious metals counterparts, hence providing an opportunity to construct new catalysts with an?improved activity and stability. As a result, the library of Ni_xP_y catalysts has been enriched very rapidly, with the possibility of fine-tuning their surface adsorption properties through synergistic coupling with nearby elements or dopants as the basis of future practical implementation. The current review distils recent advancements in Ni_xP_y compounds/hybrids and their application for HER, with a robust emphasis on breakthroughs in composition refinement. Future perspectives for modulating the HER activity of Ni_xP_y compounds/hybrids, and the challenges that need to be overcome before their practical use in sustainable hydrogen production are also discussed.

The article provides an overview of the most relevant characterization results of heterogeneous photo-catalytic materials available in the literature. First, we present a summary of the ex situ utilization of physico-chemical characterization techniques. In the majority of current works, pre and post-reaction samples are subjected to ex situ analysis using a multitechnique approach which attempts to render information about the morphological, structural, and electronic properties of relevance to interpret photoactivity. Details of the effects on physico-chemical observables of the nanostructure and the complex chemical nature (considering mono and multiphase materials with presence of several chemical elements) of typical photo-catalysts will be analyzed. Modern studies however emphasize the use of in situ tools in order to establish activity–structure links. To this end, the first point to pay attention to is to consider carefully the interaction between light and matter at the reaction cell where the characterization is carried out. Operando and spectro-kinetic methodologies will be reviewed as they would render valuable and trusting results and thus will pave the way for the future developments in photocatalysis.

Elemental sulfur is an abundant and inexpensive chemical feedstock, yet it is underused as a starting material in chemical synthesis. Recently, a process coined inverse vulcanization was introduced in which elemental sulfur is converted into polymers by ring-opening polymerization, followed by cross-linking with an unsaturated organic molecule such as a polyene. The resulting materials have high sulfur content (typically 50–90% sulfur by mass) and display a range of interesting properties such as dynamic S–S bonds, redox activity, high refractive indices, mid-wave IR transparency, and heavy metal affinity. These properties have led to a swell of applications of these polymers in repairable materials, energy generation and storage, optical devices, and environmental remediation. This article will discuss the synthesis of polymers by inverse vulcanization and review case studies on their diverse applications. An outlook is also presented to discuss future opportunities and challenges for further advancement of polymers made by inverse vulcanization.

Over the past few years, significant progress has been made in the design of organic semi-conducting conjugated polymers that readily transport holes or electrons and can result in light emission. The conjugated backbone consist mainly of electron-donating (donor) and electron-withdrawing (acceptor) units as alternating groups in a conjugated oligomer or polymer that can be regulated by physical properties such as π conjugation length, monomer alteration, inter/intramolecular interactions and energy levels. Certainly, it is notable today that the highest occupied molecular orbital level of the producing material is localized predominantly on the electron-donating moiety and lowest unoccupied molecular orbital level on the electron-accepting moiety. Conjugated oligomers or polymers are used in many detecting fields due to their exceptional ability to sense toxic chemicals, metal ions and biomolecules. The conjugated polymers have unique delocalized π-electronic “molecular wires” that can expand the fluorescence intensity considerably. The fluorescence intensity of polymers can be quenched by particular quenching molecules. In this review, the fluorescence intensity, detecting of multiple metal ions, solubility, photochemical stability and optoelectronic properties of these conjugated polymers, and how they can be regulated by different functional groups, are discussed in detail.

Despite its attractive features as a power source for direct alcohol fuel cells, utilization of ethanol is still hampered by both fundamental and technical challenges. The rationale behind the slow and incomplete ethanol oxidation reaction (EOR) with low selectivity towards CO₂ on most Pt-based catalysts is still far from being understood, and a number of practical problems need to be addressed before an efficient and low-cost catalyst is designed. Some recent achievements towards solving these problems are presented. Pt film electrodes and Pt monolayer (Pt_ML) electrodes on various single crystal substrates showed that EOR follows the partial oxidation pathway without C–C bond cleavage, with acetic acid and acetaldehyde as the final products. The role of the substrate lattice on the catalytic properties of Pt_ML was proven by the choice of appropriate M(111) structure (M = Pd, Ir, Rh, Ru and Au) showing enhanced kinetics when Pt_ML is under tensile strain on Au(111) electrode. Nanostructured electrocatalysts containing Pt–Rh solid solution on SnO₂ and Pt monolayer on non-noble metals are shown, optimized, and characterized by in situ methods. Electrochemical, in situ Fourier transform infrared (FTIR) and X-ray absorption spectroscopy (XAS) techniques highlighted the effect of Rh in facilitating C–C bond splitting in the ternary PtRh/SnO₂ catalyst. In situ FTIR proved quantitatively the enhancement in the total oxidation pathway to CO₂, and in situ XAS confirmed that Pt and Rh form a solid solution that remains in metallic form through a wide range of potentials due to the presence of SnO₂. Combination of these findings with density functional theory calculations revealed the EOR reaction pathway and the role of each constituent of the ternary PtRh/SnO₂ catalyst. The optimal Pt:Rh:Sn atomic ratio was found by the two in situ techniques. Attempts to replace Rh with cost-effective alternatives for commercially viable catalysts has shown that Ir can also split the C–C bond in ethanol, but the performance of optimized Pt–Rh–SnO₂ is still higher than that of the Pt–Ir–SnO₂ catalyst.

Malaria represents a significant health issue, and novel effective drugs are needed to address parasite resistance that has emerged to the current drug arsenal. The most popular antimalarial drugs are focused on the 7-chloro-4-aminoquinoline [e.g., chloroquine (CQ), amodiaquine (AQ), isoquine (IQ), and tebuquine (TBQ)], artemisinin, and atovaquone systems. Recently, endochin has been used as a platform to design a variety of novel potent and safe antimalarial agents named endochin-like quinolones (ELQs). Also, antimalarial quinolones have been constructed from other quinolones drugs such as ICI-56780 and floxacrine. Trifluoromethyl substitution has provided a significant increase in the antimalarial response of many of the designed ELQs against Plasmodium-resistant strains and for in?vivo models. In particular, attachment of a substituted trifluoromethoxy (or trifluoromethyl in some cases) biaryl side chain at 2-, 3-, 4-, or 6-position of the quinolone core has shown to be crucially important to generate selective and potent novel ELQs. Furthermore, 6-chloro and 7-methoxy moieties on the quinolone core have been identified as essential pharmacophores when the trifluoromethoxy biaryl side chain is placed at 2- or 3-position of the quinolone core. Methyl or ethyl ester attached at 3-position is essential when the trifluoromethoxy aryl side chain is attached at 6- or 7-position of the quinolone core. Some promising ELQs are currently under clinical trials, representing an excellent platform for the design of new potent, selective, effective, and safe antimalarial drugs against emergent resistance malarial models.

Since the original idea was explored by James in 1976, the use of chiral sulfoxides as ligands with transition metals in asymmetric catalysis has undergone a long period of development. There have been many studies into their properties, design and application in various kinds of asymmetric transformations. In this article, we document the literatures on chiral sulfoxide ligands in asymmetric catalytic reactions.