TBC

A porous organic cage crystal, α-CC2, shows unexpected adsorption of sulphur hexafluoride (SF6) in its cage cavities, which are formally occluded even to the smallest diatomic gas, H2, according to a pore analysis of the static crystal structure. In situ powder X-ray diffraction (PXRD) experiments provide unequivocal evidence for the presence of (SF6) inside the ‘occluded’ cage voids, pointing to a

To exploit the full potential of metal-organic frameworks as solid adsorbents in water-adsorption applications, many challenges remain to be solved. A more fundamental insight into the properties of the host material and the influence water exerts on them can be obtained by performing molecular simulations. In this work, the prototypical flexible MIL-53(Al) framework is modelled using advanced molecular

Controlling the assembly of molybdenum disulfide (MoS2) layers into static and dynamic superstrucutres can impact on their use in optoelectronics, energy, and drug delivery. Toward this goal, we present a strategy to drive the assembly of MoS2 layers via the hybridization of complementary DNA linkers. By functionalizing the MoS2 surface with thiolated DNA, MoS2 nanosheets were assembled into mulitlayered

The process combining heterogeneous catalysts and DC electric field can achieve high catalytic activities, even under mild conditions (<500 K) with less electrical energy consumption. Hydrogen production by steam reforming of methane, aromatics and alcohol, dehydrogenation of methylcyclohexane, dry reforming of methane, and ammonia synthesis are known to proceed at low temperatures in an electric field

The hydroformylation of 1-hexene with 12 bar of 1:1 H2/CO in the presence of the catalytic system [Rh(acac)(CO)2]/PPh3 was successfully studied by real-time multinuclear high-resolution FlowNMR spectroscopy at 50 °C. Quantitative reaction progress curves that yield rates as well chemo- and regioselectivities have been obtained with varying P/Rh loadings. Dissolved H2 can be monitored in solution to

Metal-organic frameworks (MOFs) provide a suitable platform for stable and efficient heterogeneous photoelectrochemical oxidation catalysis due to their highly ordered structure, large surface area, and synthetic tunability. Herein, a mixed-linker MOF comprising a photosentisizer [Ru(dcbpy)(bpy)2]2+ (bpy = 2,2'-bipyridine, dcbpy = 5,5′-dicarboxy-2,2′-bipyridine) and catalyst [Ru(tpy)(dcbpy)Cl]+ (tpy

Structural vivid colours can arise from the interference of light reflected from structures exhibiting periodicity on scales in the range of visible wavelengths. This effect is observed with light reflected from cell-walls of some plants and exoskeletons of certain insects. Sometimes the colour sequence observed for these structures consists of nearly circular concentric rings that vary in colour from

Supported liquid phase catalysis has great potential to unify the advantages from both, homogeneous and heterogeneous catalysis. Recently, we reported Supported Catalytically Active Liquid Metal Solutions (SCALMS) as a new class of liquid phase catalysts. SCALMS enable high temperature application due to the high thermal stability of liquid metals when compared to supported molten salts or ionic liquids

III-VI post-transition metal chalcogenides (InSe and GaSe) are a new class of layered semiconductors, which feature a strong variation of size and type of their band gaps as a function of number of layers (N). Here, we investigate exfoliated layers of InSe and GaSe ranging from bulk crystals down to monolayer, encapsulated in hexagonal boron nitride, using Raman spectroscopy. We present the N-dependence

Many framework materials such as metal-organic frameworks (MOF) or porous coordination polymers (PCPs) are synthesized as polycrystalline powders, which are too small for structure determination by single crystal X-ray diffraction (SCXRD). Here, we show that a three-dimensional (3D) electron diffraction method, namely continuous rotation electron diffraction (cRED), can be used for ab initio structure

Molecules in gas and liquid states, as well as in solution, exhibit significant and random Brownian motion. Molecules in the solid-state, although strongly immobilized, can still exhibit significant intramolecular dynamics. However, in most framework materials, these intramolecular dynamics are driven by temperature, and therefore are neither controlled nor spatially or temporarily aligned. In recent

The colour purity and versatility of fabrication of one-dimensional photonic crystals (1D PhCs) make them ideal candidates for colorimetric sensing of a variety of analytes. For instance, the detection of bacterial contaminants in food via colorimetric sensors can be highly appealing, as most of the existing detection techniques are in general time-consuming and whose read-out requires specialised

The field of metal–organic frameworks (MOFs) is still heavily focused upon crystalline materials. However, solid-liquid transitions in both MOFs and their parent coordination polymer family are now receiving increasing attention due to the largely unknown properties of both the liquid phase and the glasses that may be formed upon quenching. Here, we argue that the commonly reported concept of ‘thermal

Nanographenes (NGs) and graphene nanoribbons (GNRs) are unique connectors between the domains of 1D-conjugated polymers and 2D-graphenes. They can be synthesized with high precision by oxidative flattening processes from dendritic or branched 3D-polyphenylene precursors. Their size, shape and edge type enable not only accurate control of classical (opto)electronic properties but also access to unprecedented

Acetic acid (CH3–COOH) is an important commodity chemical widely used in a myriad of industrial processes, whose production still largely depends on homogeneous catalysts based on expensive rare metals. Here, we report a computational study on the formation of CH3–COOH from carbon dioxide (CO2) as an alternative chemical feedstock on the {111} surface of the low-cost greigite Fe3S4 catalyst. We have

Graphite is spontaneously exfoliated within aqueous alkaline cellulose solutions, forming stable dispersions that can be used to coat cellulosic, ceramic and other substrates with continuous macroscopic layers. These are stable under various conditions and adhere strongly to wood, paper, cardboard, fabric, charcoal and brick. Coating morphology changes from highly smooth to porous and rough, depending

The production of methanol from glycerol over a basic oxide, such as MgO, using high reaction temperatures (320 °C) is a promising new approach to improving atom efficiency in the production of biofuels. The mechanism of this reaction involves the homolytic cleavage of the C3 feedstock, or its dehydration product hydroxyacetone, to produce a hydroxymethyl radical species which can then abstract an

The interaction of CO with an attapulgite-supported, KCl modified CuCl2 catalyst has previously been examined using a combination of XANES, EXAFS and DFT calculations. Exposing the catalyst to CO at elevated temperatures leads to the formation of CO2 as the only identifiable product. However, phosgene production can be induced by a catalyst pre-treatment stage, where the supported CuCl2 sample is exposed

Since inter- and intra-particle heterogeneities in catalyst particles are more the rule than exception, it is advantageous to perform high-throughput screening for the activity of single catalyst particles. A multiphase system (gas/liquid/solid) is developed, where droplet-based microfluidics and optical detection are combined for the analysis of single catalyst particles by safely performing a hydrogenation

Palladium-based catalysts are exploited in the industrial scale for selective hydrogenation of hydrocarbons. Formation of palladium carbide and hydride phases under reaction conditions changes the catalytic properties of the material, which points to the importance of operando characterization for determining a relation between the relative fraction of the two phases and the catalyst performance. We

The ability to distinguish molecular catalysis from nanoscale catalysis provides a key to success in the field of catalyst development, particularly for the transition to sustainable economies. Complex evolution of catalyst precursors, facilitated by dynamic interconversions and leaching, makes the identification of catalytically active forms an independent task, sometimes very difficult. We propose

In this study, the process economics of ammonia synthesis over Co3Mo3N was investigated by searching an optimum feed stoichiometry. By ammonia synthesis rate measurements at atmospheric pressure and 400 oC over Co3Mo3N, it was found that, the rate was independent of H2:N2 stoichiometries above 0.5:1. For H2:N2 stoichiometries below 0.5:1, there was a linear dependency of ammonia synthesis rate on the

Obtaining structural information for highly reactive metal-based species can provide valuable insight into important chemical transformations or catalytic processes. Trapping these metal-based species within the cavities of porous crystalline hosts, such as metal-organic frameworks (MOFs), can stabilise them, allowing detailed structural elucidation by single crystal X-ray diffraction. Previously,

Understanding the biodegradability of graphene materials by the action of oxidative enzymes secreted by the immune cells is essential for developing applicable biomedical products based on graphene materials. Herein, we demonstrate the biodegradation of graphene oxide (GO) by recombinant eosinophil peroxidase (EPO) enzyme extracted from human eosinophils in the presence of a low concentration of hydrogen

Selectivity to the products formation is strongly correlated with the nature of catalyst active centers. Therefore, the selective synthesis of active sites with certain structure is a big challenge in modern catalysis. Here the synthetic procedures are adopted for the formation of 1% Rh/TiO2 catalysts with different properties. It is shown that the nature of the precursor used for catalyst preparation

Molecular motions taking place in the nanospace of metal–organic frameworks (MOFs) are an interesting research subject, although not yet fully investigated. In this work, we utilized in situ Raman spectroscopy in the ultralow-frequency region to investigate the libration motion (including the rotational motion of phenylene rings) of MOFs, in particular [Cu2(bdc)2(dabco)] (Cu-JAST-1), where bdc = 1

In this study, we investigate the effect of thermal treatment/calcination on the stability and activity of a Na-Mn-W/SiO2 catalyst for the oxidative coupling of methane reaction. The catalyst performance and characterisation measurements suggest that the W species are directly involved in the catalyst active site responsible for CH4 conversion. Under operating conditions, the active components, present

A series of structures based on graphitic carbon nitride (g-C3N4), a layered material composed of linked carbon-nitrogen heterocycles arranged in a plane, were investigated by density functional theory calculations. g-C3N4 is a semiconductor that absorbs UV light and visible light at the blue end of the visible spectrum, and is widely studied as a photocatalyst for water splitting; however, its photocatalytic

Manganese nitride related materials are of interest as two-stage reagents for ammonia synthesis via nitrogen chemical looping. However, unless doped with a co-cation, manganese nitrides are thermochemically stable and high temperature is required to produce ammonia under reducing conditions, thereby hindering their use as nitrogen transfer materials. Nevertheless, when lithium is used as dopant, ammonia

Extraction of proteins from blood biological fluids requires the removal of large aggregates or cells by membrane filtration. However, conventional filters, based on simple size exclusion, do not allow to remove small molecules such as antibiotics. Here, we demonstrate that a graphene oxide (GO) layer can be firmly immobilized either inside or outside polyethersulfone-polyvinylpirrolidinone hollow

In this work, we report the synthesis and characterization of mixed phase Nb1+xS2 nanoflakes prepared by chemical vapor deposition. The as-grown samples show high density of flakes (thickness ~50 nm) that form a continuous film. Raman and X-ray diffraction data show that the samples consist of both 2H and 3R phases with the 2H phase containing high concentration of Nb interstitials. These Nb interstitials

The mechanism of the low-temperature water–gas shift (LT-WGS) reaction over Au/CeO2 catalysts with different ceria terminations, i.e., (111), (110), and (100) facets, was investigated. Using combined operando Raman and UV-Vis spectroscopy as well as isotope exchange experiments, we are able to draw conclusions about the reducibility behaviour and the exchange of surface oxygen. Additional density functional

Density functional theory (DFT) has been considered as a powerful tool for the identification of reaction mechanisms. However, it is still unclear whether the error of DFT calculations would lead to misidentification of mechanisms. Here, taking the hydrogenation of acetylene and 1,3-butadiene as model reactions and employing a well-trained Bayesian error estimation functional with van der Waals correlation

Recent in-situ works have shown extensive evidence of the dramatic and reversible structure reconstructions of metal and alloy materials in reaction conditions. The reconstructions are of primary interest because they could lead to alternative catalytic mechanisms during real reactions. However, how the catalyst structure evolves under the pressures relevant to industrial applications (> 1 atm) is

The oxidation of alcohols plays a central role in the valorisation of biomass, in particular when performed with a non-toxic oxidant such as O2. Aerobic oxidation of methanol on gold has attracted attention lately and the main steps of its mechanism have been described experimentally. However, the exact role of O and OH on each elementary step and the effect of the interactions between adsorbates are

The use of hexagonal boron nitride quantum dots (hBN QDs) as an electrochemical sensor for ferritin is reported for the first time in this manuscript. These QDs were synthesized using simple method of liquid exfoliation. The synthesized material was characterized using analytical techniques such as UV-Visible, Fourier Transform Infrared (FTIR) and Raman spectroscopy, X-Ray Diffraction (XRD), and High-Resolution

Due to its excellent chemical/thermal stability and mechanical robustness, hexagonal boron nitride (hBN) is a promising solid matrix material for ionogels. While bulk hBN ionogels have been employed in macroscopic applications such as lithium-ion batteries, hBN ionogel inks that are compatible with high-resolution printing have not yet been realized. Here, we describe aerosol-jet-printable ionogels

Computational insight in the impact of cooperative phenomena and correlated spatial disorder on the macroscopic behaviour of metal-organic frameworks (MOFs) is essential to consciously engineer these phenomena for targeted applications. However, the spatial extent of these effects, ranging over hundreds of nanometres, limits the applicability of current state-of-the-art computational tools in this