Two-dimensional (2D) layered nanomaterials have attracted increasing attention in gas sensing due to their graphene-like properties. Although the gas sensing performances of 2D layered semiconductor transition metal dichalcogenides (TMDs), including MoS2, WS2, MoSe2 and WSe2, have been extensively studied, it has remained a grand challenge to develop a high-performance gas sensing material that can meet practical applications. Tantalum disulfide (TaS2), as a metallic TMD with low resistance and high current signal, has great promise in high-performance gas sensing. In stark contrast with Mo and W, Ta has a stronger positive charge, which contributes to a higher surface energy to capture gas molecules. Herein, through calculating the adsorption energy, charge transfer, electronic structure, and work function of the adsorption system with first-principles calculations, we first systematically studied the performance of noble metal atom substitution doping on a TaS2 monolayer for toxic nitrogen-containing gas (NH3, NO and NO2) sensing. We found that the TaS2 monolayer exhibits excellent NO sensing performance with an adsorption energy of 0.49 eV and a charge transfer of 0.17 e. However, it has a considerable adsorption energy (-0.22 and -0.39 eV) to NH3 and NO2 molecules, but a low charge transfer (-0.03 and 0.04 e) between the gas molecules and the TaS2 monolayer. To further enhance the gas-sensing performance of the TaS2 monolayer, noble metal atoms (Ag, Au, Pd and Pt) were substitutionally doped into the lattice of the TaS2 monolayer. The results showed that the values of adsorption energy and charge transfer can be significantly improved, and the electronic structure and work function of the doping system has also greatly changed, which makes it much easier to detect the changes in electrical signal due to gas adsorption. Our work indicates that the intrinsic as well as the noble metal doped TaS2 monolayers are promising candidates for high-performance gas sensors.The stabilization mechanism of the Zn-terminated (Zn-) ZnO(0001) surface in electrolyte solutions has been investigated by using atomic-resolution liquid-environment atomic force microscopy (AFM) and an electrochemical method. The electrochemically measured pH dependence of the flat band potential of the Zn-ZnO(0001) surface indicated the adsorption of OH groups onto the (0001) surface in the wide pH range of 1-13. Atomic-scale AFM images of the Zn-ZnO(0001) surface showed a well-ordered hydroxide superstructure in an alkaline solution but a disordered structure in an acidic solution, which is probably attributed to the rapid diffusion of the adsorbed OH groups. Furthermore, the density of the O-terminated step edge on the Zn-ZnO(0001) surface in an acidic solution was higher than that in an alkaline solution. From these findings, we concluded that the excess positive charges of the Zn-ZnO(0001) surface are compensated by the adsorbed OH groups and the O-terminated step edges. In acidic solutions, a higher density of the O-terminated step edge is required for charge compensation. In addition, it was found that potential-dependent reversible surface reconstruction occurs in the local transition area with disordered step orientation by electrochemical AFM. We concluded that the reconstruction compensates the excess surface charges of the local transition area which are induced and varied by potential-dependent local surface states.Protic ionic liquids (PILs) have currently been indicated as promising alternative electrolytes in electrical storage devices, such as lithium-ion batteries and supercapacitors. However, compared with the well-studied aprotic ionic liquids (AILs), the knowledge of the interface between PILs and electrode material surfaces is very rare to date. In this work, the adsorption behaviors of three groups of PILs, i.e. pyrrolidinium-based, imidazolium-based, and ammonium-based, on graphite was systematically investigated using first-principles calculations. The corresponding AILs were also taken into account for comparison. The adsorption mechanism of these ILs on the surface is controlled by the interplay of strong electrostatic interactions between adsorbed ions, weak vdW forces between ILs and substrate, and many aromatic interactions including π-π stacking and C-H/N-Hπ contacts. PILs do show quite different preferential interfacial interactions and structures on the graphite surface with respect to AILs, arising mainly from the anion-substrate interactions. Particularly, proton transfer takes place in the PILs consisting of the imidazolium/ammonium cation and the nitrate anion in the gas phase, but it tends to be attenuated or even disappears on graphite caused by interfacial interactions.The speciation of framework-interacting CuII sites in Cu-chabazite zeolite catalysts active in the selective catalytic reduction of NOx with NH3 is studied, to investigate the influence of the Al content on the copper structure and their reactivity towards a NO/O2 mixture. To this aim, three samples with similar Cu densities and different Si/Al ratios (5, 15 and 29) were studied using in situ X-ray absorption spectroscopy (XAS), FTIR and diffuse reflectance UV-Vis during pretreatment in O2 followed by the reaction. XAS and UV-Vis data clearly show the main presence of Z2CuII sites (with Z representing a framework negative charge) at a low Si/Al ratio, as predicted. EXAFS wavelet transform analysis showed a non-negligible fraction of proximal Z2CuII monomers, possibly stabilized into two 6-membered rings within the same cage. These sites are not able to form Cu-nitrates by interaction with NO/O2. By contrast, framework-anchored Z[CuII(NO3)] complexes with a chelating bidentate structure are formed in samples with a higher Si/Al ratio, by reaction of NO/O2 with Z[CuII(OH)] sites or structurally similar mono- or multi-copper Zx[CuIIxOy] sites. Linear combination fit (LCF) analysis of the XAS data showed good agreement between the fraction of Z[CuII(OH)]/Zx[CuIIxOy] sites formed during activation in O2 and that of Z[CuII(NO3)] complexes formed by reaction with NO/O2, further confirming the chemical inertia of Z2CuII towards these reactants in the absence of solvating NH3 molecules.Rechargeable batteries based on Li-ion and post Li-ion chemistry have come a long way since their inception in the early 1980s. The last four decades have witnessed steady development and discovery of myriads of cathode materials taking into account their processing, economy, and performance along with ecological sustainability. Though oxides rule the battery sector with their high energy and power density, polyanionic insertion compounds work as gold mines for designing insertion compounds with rich structural diversity leading to tuneable redox potential coupled with high structural/chemical/thermal stability. The scope of polyanionic compounds can be taken a step further by combining two or more different types of polyanions to get suites of mixed polyanionic materials. While most cathodes are built with metal polyhedra constituted by oxygen (MOm|XOm, M = 3d metals, X = P, S, Si, B, W, etc., m = 3-6), in some cases, selected oxygen sites can form bonding with hydrogen to form OH/H2O ligands. It can lead to the family of hydroxy-based mixed-polyanionic cathode materials. The presence of hydroxy components can affect the crystal structure, local chemical bonding, and electronic, magnetic, diffusivity and electrochemical properties. Employing a mineralogical survey, the current review renders a sneak peek on various hydroxy-based polyanionic cathode materials for Li-ion and post Li-ion batteries. Their crystal structure, and electrochemical properties have been overviewed to outline future research focus and scope for real-life application.This perspective article provides a comprehensive but organized tutorial introduction of the kinetics related to photon upconversion (UC) by triplet-triplet annihilation (TTA) (TTA-UC). The field of TTA-UC is multi-disciplinary and rapidly growing with the involvement of researchers from diverse backgrounds. TTA-UC consists of a series of tangled photophysical processes, so a solid understanding of the kinetic features and consequences is important to develop and evaluate materials for TTA-UC. This tutorial starts with an introduction of the standard model of TTA-UC along with the assumptions used in the model. The essential concept of the spin statistics for TTA and how this concept is related to the singlet branching ratio, which directly affects the efficiency of UC, are then explained through step-by-step analyses. Using these foundations, solutions for the steady-state behaviors are derived, featuring the universal curve that describes the excitation intensity dependence of the UC quantum yield for any sample type. Various useful functions for analyzing experimental data are also introduced and summarized. The transient behaviors of TTA-UC are then discussed along with their equations, and the usefulness for analyzing transient experimental data is explained using examples. In this article, self-consistent derivations and relevant references are provided for an easy understanding of the advanced discussion and analyses.A cooperative catalytic strategy is developed for a copper-catalyzed asymmetric intramolecular C-arylation reaction with ureas as the co-catalysts. By forming hydrogen bonds with 1,3-dicarbonyl structures, ureas can activate the substrates, stabilize the carbanion intermediates and the products, and fix the syn-configurations of 1,3-dicarbonyl structures. They help enhance the reactivity, prevent side reactions and improve the enantioselectivities.A visible-light-promoted olefinic C-H trifluoromethylation of enamides was developed by employing cheap and stable Langlois’ reagent as the CF3 source. A series of β-CF3 enamides were obtained in moderate to good yields with high E-isomer selectivity under mild conditions. Preliminary mechanistic studies suggest that molecular oxygen acts as the terminal oxidant for this net oxidative process, and the E isomer selectivity could be well explained by a base-assisted deprotonation of the cation intermediate.We report an Rh(iii)-catalyzed one-pot synthesis of trisubstituted furan derivatives through Cvinyl-H activation of α,β-unsaturated ketones with acrylates. The control study revealed that the Heck-type product obtained undergoes Paal-Knorr type cyclization in the presence of an Ag salt. Hence, the Ag salt plays a dual role of a halide scavenger and a Lewis acid catalyst for Paal-Knorr type cyclization. The furan product can be transferred into the respective alcohol and acid derivatives which are useful intermediates in synthesizing biologically active molecules.A Zn-PyBisulidine catalyzed asymmetric Mannich reaction of 3-acyloxy-2-oxindoles has been developed. Various quaternary substituted 3-acyloxy-2-oxindoles bearing vicinal amino alcohol motifs were obtained in good to excellent yields with moderate to excellent dr and excellent enantioselectivities. The utility of this reaction was demonstrated by the easy removal of the acyl group to give C3-hydroxy derivatives and their application as a key skeleton of the ligand for the Ni-catalyzed enantioselective Henry reaction.