Conversion of carbon dioxide (CO₂) into value-added products is aimed to develop scalable technologies to promote a circular economy. While the electrochemical reduction of CO₂ to carbon monoxide (CO) and formic acid has advanced significantly, a major challenge remains achieving further reduced and more energy-dense products, such as methanol (MeOH), through sustainable pathways. Herein, we report a molecular electrode capable of direct six-electron reduction of CO₂ to MeOH using water as a proton source with a global Faradaic efficiency (FE_G) of 22% and product selectivity of 61% for MeOH. The design consists of an active copper-hydride center surrounded by two closely spaced benzimidazole–hydride units, facilitating the catalytic transfer of three hydrides to produce MeOH. The concurrent formation of formic acid and the absence of formaldehyde suggest that MeOH is generated via a formato pathway. DFT investigations revealed the complete mechanistic pathway, which supports the experimental observations. The morphology and stability of the electrode were evaluated before and after prolonged electrolysis (12 h) experiments using electron microscopic techniques.

Photonic crystals are optical materials that are often fabricated by assembly of particles into periodically arranged structures. However, assembly of lignin nanoparticles has been limited due to lacking methods and incomplete understanding of the interparticle forces and packing mechanisms. Here we show a centrifugation-assisted fabrication of photonic crystals with rainbow structural colors emitted from the structure covering the entire visible spectrum. Our results show that centrifugation is crucial for the formation of lignin photonic crystals, because assembly of lignin nanoparticles without centrifugation assistance leads to the formation of stripe patterns rather than photonic crystals. We further prove that the functions of centrifugation are to classify lignin nanoparticles according to their particle size and produce monodispersed particle layers that display gradient colors from red to violet. The different layers of lignin nanoparticles were assembled in a way that created semi-closed packing structures, which gave rise to coherent scattering. The diameter of the lignin nanoparticles in each color layer is smaller than that predicted by a modified Bragg’s equation. In situ optical microscope images provided additional evidence on the importance of dynamic rearrangement of lignin nanoparticles during their assembly into semi-closed packing structures. The preparation of lignin nanoparticles combined with the methodology for their classification and assembly pave the way for sustainable photonic crystals.

We hypothesized that the morphology of the hydrochar from hydrothermal carbonization of glucose would be affected by Fe²⁺; and indeed, with such ions, large pieces of hydrochar formed that comprised aggregated spherical particles and blue and thin films. Thin carbonized films formed at the bottom of the autoclave liners or on Teflon^TM tape used as a template. Free-standing films could be prepared by stretching the Teflon^TM tape after the synthesis. The carbonized films that formed at the bottom of the autoclave adhered to spherical hydrochar particles. The blueness was ascribed to thin-film interference under white-light irradiation and related to the film thickness, which was about 200 nm. Analysis of transmission electron microscopy (TEM) images showed that the films consisted of a layered amorphous carbon. The amorphous and thin films were more carbonized than the amorphous carbon of the TEM grid, as derived via electron energy loss spectroscopy (EELS). Additional analysis of one of the thin films by X-ray photoelectron spectral analysis showed a higher carbon fraction than for bulk hydrochar, supporting the EELS analysis. We believe that the synthesis of thin films of hydrochar can open up new colloidal processing pathways, which could be useful in the preparation of carbon-based materials and alike.

Single and multilayer films of La0.67Sr0.33MnO3 and CoFe2O4 were deposited by spin-coating. The all-alkoxide precursors allowed inorganic gel films of extreme homogeneity to be formed and converted to phase pure complex oxides at low temperatures. La0.67Sr0.33MnO3 films were made with La- and Ca-methoxy-ethoxides and Mn19O12(moe)(14)(moeH)(10) as precursors at 800 degrees C. The CoFe2O4 films were obtained at extremely low 275 degrees C, using a new CoFe2-methoxyethoxide precursor. The decomposition and microstructural development on heating was described by TG, TEM, XRD and IR spectroscopy. XRD showed no spurious phases and the unit-cell dimensions coincided quite well with literature values of the targeted phases. The structural, magnetic and electronic properties of these films established their phase purity and high quality with physical properties comparable to films deposited by physical deposition methods. The magnetic and magneto transport results are presented for single, bi- and tri- layer structures. The magnetically soft La0.67Sr0.33MnO3 layer was exchange coupled to the magnetically hard CoFe2O4 layer, giving rise to interesting switching behaviour in magnetism and magneto-transport properties.

Al1-xTixB2 particles extracted from Al-Ti-B alloys have been investigated by means of a transmission electron microscope equipped with an X-ray energy-dispersive spectroscopic analyser. The solid solubility Al1-xTixB2 was found to be unlimited (0 <= x <= 1). The composition of boride particles extracted from an Al-Ti-B alloy with a composition within the solid solubility range was widely spread, whereas it was close to TiB2 for Ti concentrations in excess of the TiB2 stoichiometry. The particle size varied from 0.02 to 2 mu m. The largest particles were almost pure TiB2 or AlB2, but the small ones were solid solutions of varying compositions. Those small particles tended to form relatively large agglomerates. Due to impurities in the master alloys, vanadium was present in some boride particles, implying that we actually have an Al1-x(Ti1-yVy)(x)B-2 solid solution (0 <= x + y <= 1). The y value was found to vary within the range 0 <= y <= 0.07. It was found that master alloys containing boride particles with a narrow size distribution and a composition close to TiB2 gives better grain refinement results than master alloys with wide distributions of particle size and composition.

Calcium carbonate is an abundant biomineral that is of great importance in industrial or geological contexts. In recent years, many studies of the precipitation of CaCO3 have shown that amorphous precursors and intermediates are widespread in the biomineralization processes and can also be exploited in bio-inspired materials chemistry. In this work, the thorough investigation of a urinary stone of a guinea pig suggests that amorphous calcium carbonate (ACC) can play a role in pathological mineralization. Importantly, certain analytical techniques that are often applied in the corresponding analyses are sensitive only to crystalline CaCO3 and can misleadingly exclude the relevance of calcium carbonate during the formation of urinary stones. Our analyses suggest that ACC is the major constituent of the particular stone studied, which possibly precipitated on struvite nuclei. Minor amounts of urea, other stable inorganics, and minor organic inclusions are observed as well.

The influence of operating condition on particle formation during pressurized, oxygen blown gasification of wood powder with an ash content of 0.4 wt% was investigated. The investigation was performed with a pilot scale gasifier operated at 7 bar(a). Two loads, 400 and 600 kW were tested, with the oxygen equivalence ratio (A) varied between 0.25 and 0.50. Particle concentration and mass size distribution was analyzed with a low pressure cascade impactor and the collected particles were characterized for morphology, elemental composition, nanostructure, and reactivity using scanning electron microscopy/high resolution transmission electron microscopy energy dispersive spectroscopy, and thermogravimetric analysis. In order to quantify the nanostructure of the particles and identify prevalent sub-structures, a novel image analysis framework was used. It was found that the process temperature, affected both by A and the load of the gasifier, had a significant influence on the particle formation processes. At low temperature (1060 degrees C), the formed soot particles seemed to be resistant to the oxidation process; however, when the oxidation process started at 1119 degrees C, the internal burning of the more reactive particle core began. A further increase in temperature ( > 1313 degrees C) lead to the oxidation of the less reactive particle shell. When the shell finally collapsed due to severe oxidation, the original soot particle shape and nanostructure also disappeared and the resulting particle could not be considered as a soot anymore. Instead, the particle shape and nanostructure at the highest temperatures ( > 1430 degrees C) were a function of the inorganic content and of the inorganic elements the individual particle consisted of. All of these effects together lead to the soot particles in the real gasifier environment having less and less ordered nanostructure and higher and higher reactivity as the temperature increased; i.e., they followed the opposite trend of what is observed during laboratory-scale studies with fuels not containing any ash-forming elements and where the temperature was not controlled by A.

Two electrodes for anodic water oxidation made by direct synthesis of inorganic catalysts onto conductive carbon fibre sheets are evaluated. As catalysts two Co- and Sb-containing phases were tested, that is, Co3Sb4O6F6 and the new compound CoSbO4. The compounds express large differences in their morphology: CoSbO4 grows as thin needles whereas Co3Sb4O6F6 grows as larger facetted crystals. Despite the smaller surface area the latter compound shows a better catalytic performance. When the compound Co3Sb4O6F6 was used it gave a low increase of +0.028 mV h(-1) at an overpotential of eta = 472 mV after 10 h and a stability of +0.48 mV h(-1) at an overpotential of eta = 488 mV after 60 h. The leakages of Co and Sb were negligible and only <0.001 at% Co and approximately 0.02 at% Sb were detected in the electrolyte.

The representation of aerosol properties and processes in climate models is fraught with large uncertainties. Especially at high northern latitudes a strong underprediction of aerosol concentrations and nucleation events is observed and can only be constrained by in situ observations based on the analysis of individual aerosol particles. To further reduce the uncertainties surrounding aerosol properties and their potential role as cloud condensation nuclei this study provides observational data resolved over size on morphological and chemical properties of aerosol particles collected in the summer high Arctic, north of 80A degrees aEuro-N. Aerosol particles were imaged with scanning and transmission electron microscopy and further evaluated with digital image analysis. In total, 3909 aerosol particles were imaged and categorized according to morphological similarities into three gross morphological groups: single particles, gel particles, and halo particles. Single particles were observed between 15 and 800aEuro-nm in diameter and represent the dominating type of particles (82aEuro-%). The majority of particles appeared to be marine gels with a broad Aitken mode peaking at 70aEuro-nm and accompanied by a minor fraction of ammonium (bi)sulfate with a maximum at 170aEuro-nm in number concentration. Gel particles (11aEuro-% of all particles) were observed between 45 and 800aEuro-nm with a maximum at 154aEuro-nm in diameter. Imaging with transmission electron microscopy allowed further morphological discrimination of gel particles in 'aggregate' particles, 'aggregate with film' particles, and 'mucus-like' particles. Halo particles were observed above 75aEuro-nm and appeared to be ammonium (bi)sulfate (59aEuro-% of halo particles), gel matter (19aEuro-%), or decomposed gel matter (22aEuro-%), which were internally mixed with sulfuric acid, methane sulfonic acid, or ammonium (bi)sulfate with a maximum at 161aEuro-nm in diameter. Elemental dispersive X-ray spectroscopy analysis of individual particles revealed a prevalence of the monovalent ions Na+/K+ for single particles and aggregate particles and of the divalent ions Ca2+/Mg2+ for aggregate with film particles and mucus-like particles. According to these results and other model studies, we propose a relationship between the availability of Na+/K+ and Ca2+/Mg2+ and the length of the biopolymer molecules participating in the formation of the three-dimensional gel networks.

A new iridium N-heterocyclic carbene (NHC) metallolinker has been synthesised and introduced into a metal-organic framework (MOF), for the first time, via two different routes: direct synthesis and postsynthetic exchange (PSE). The two materials were compared in terms of the Ir loading and distribution using X-ray energy dispersive spectroscopy (EDS), the local Ir structure using X-ray absorption spectroscopy (XAS) and the catalytic activity. The materials showed good activity and recyclability as catalysts for the isomerisation of an allylic alcohol.