An anthropocene-framed transdisciplinary dialog at the chemistry-energy nexus.

At the energy-chemistry nexus, key molecules include carbon dioxide (CO), hydrogen (H), methane (CH), and ammonia (NH). The position of these four molecules and that of the more general family of synthetic macromolecular polymer blends (found in plastics) were cross-analyzed with the planetary boundary framework, and as part of five scientific policy roadmaps for the energy transition. According to the scenarios considered, the use of some of these molecular substances will be drastically modified in the coming years.

Combined Covalent and Supramolecular Polymerization To Reinforce Perylenebisimide Photosynthetic "Quantasomes".

Invited for the cover of this issue are the groups of Marcella Bonchio at the University of Padova and Jérôme Canivet at the CNRS-University of Lyon. The image depicts the hierarchical self-organization of bio-inspired quantasomes, crosslinked within a polystyrene network to enchain their lateral and orthogonal proximity for long-lasting oxygen evolution using green photons. Read the full text of the article at 10.

Carbon-Supported Ru-Ni and Ru-W Catalysts for the Transformation of Hydroxyacetone and Saccharides into Glycol-Derived Primary Amines.

Nitrogen-containing molecules are used for the synthesis of polymers, surfactants, agrochemicals, and dyes. In the context of green chemistry, it is important to form such compounds from bioresource. Short-chain primary amines are of interest for the polymer industry, like 2-aminopropanol, 1-aminopropan-2-ol, and 1,2-diaminopropane.

Aqueous phase recycling: impact on microalgal lipid accumulation and biomass quality.

The potential success of microalgal biofuels greatly depends on the sustainability of the chosen pathway to produce them. Hydrothermal liquefaction (HTL) is a promising route to convert wet algal biomass into biocrude. Recycling the resulting HTL aqueous phase (AP) aims not only to recover nutrients from this effluent but also to use it as a substrate to close the photosynthetic loop and produce algal biomass again and process this biomass again into new biocrude.

Combined Covalent and Supramolecular Polymerization to Reinforce Perylenebisimide Photosynthetic "Quantasomes".

PSII-inspired quantasomes have emerged as promising artificial photosystems evolving oxygen from water due to their integrated multi-chromophore asset, hierarchical architecture, and efficient light-harvesting capabilities. In this study, we adopt a combined covalent and supramolecular strategy by implementing a poly-styrene backbone that reinforces proximity and pairing between adjacent perylenebisimide (PBI) quantasome units. The covalent fixation of the quantasome network results in a significant enhancement of the photoelectrocatalytic performance on engineered IO-ITO photoanodes, with up to 290 % photocurrent increase (J up to 100 μA cm, λ >450 nm, applied bias <1.

-Alkyl substituted triazenide-bridged homoleptic iron(II) dimers with an exceptionally short Fe-Fe bond.

Dinuclear transition metal complexes with direct metal-metal interactions have the potential to generate unique reactivities and properties. Using asymmetric triazine ligands HNBuR (R = Et, Pr, Bu) featuring different alkyl substituents at 1,3-N centers, we report here the first rational synthesis of 'tetragonal lantern' type Fe(II) triazenides [Fe(NBuR)] [R = Et (1), Pr (2), Bu (3)] having an exceptionally short Fe-Fe distance (2.167-2.

Quantitative synchrotron X-ray analysis of the ALD/MLD growth of transition metal dichalcogenide TiS ultrathin films.

We present the results of a full quantitative analysis of X-ray absorption spectroscopy (XAS) performed during the growth of ultrathin titanium disulfide (TiS) films an innovative two-step process, atomic layer deposition/molecular layer deposition (ALD/MLD) followed by annealing. This growth strategy aims at separating the growth process from the crystallization process by first creating an amorphous Ti-thiolate that is converted later to crystalline TiS thermal annealing. The simultaneous analysis of Ti and S K-edge XAS spectra, exploiting the insights from density functional theory calculations, allows us to shed light on the chemical and structural mechanisms underlying the main steps of growth.

How far the chemistry of self-assembled monolayers on gold surfaces affects their work function?

Self-assembled monolayers composed of various long-chain aliphatic molecules and different tail functional groups have been synthesized on the Au(111) surface and characterized by Kelvin probe force microscopy and ultraviolet photoelectron spectroscopy. Carboxy, amino, thio and methyl terminal groups have been considered in the design of self-assembled monolayers with different aliphatic chain lengths (from C6 to C16). Work function measurements by Kelvin probe force microscopy have been carried out under a controlled and room atmosphere.

Unravelling the Molecular Structure and Confining Environment of an Organometallic Catalyst Heterogenized within Amorphous Porous Polymers.

The catalytic activity of multifunctional, microporous materials is directly linked to the spatial arrangement of their structural building blocks. Despite great achievements in the design and incorporation of isolated catalytically active metal complexes within such materials, a detailed understanding of their atomic-level structure and the local environment of the active species remains a fundamental challenge, especially when these latter are hosted in non-crystalline organic polymers. Here, we show that by combining computational chemistry with pair distribution function analysis, Xe NMR, and Dynamic Nuclear Polarization enhanced NMR spectroscopy, a very accurate description of the molecular structure and confining surroundings of a catalytically active Rh-based organometallic complex incorporated inside the cavity of amorphous bipyridine-based porous polymers is obtained.

Basic Properties of MgAl-Mixed Oxides in CO Adsorption at High Temperature.

The increase of consciousness towards global warming and the need to reduce greenhouse gas emissions lead to the necessity of finding alternative applications based on easy-to-use materials in order to control and reduce global CO emissions. Layered Double Hydroxides (LDHs) and LDH-derived materials are potentially good adsorbents for CO, thanks to their low cost, easy synthesis, high sorption capacity, and surface basicity. They have been intensively studied in CO capture at high temperature, presenting variable sorption capacities for MgAl LDHs with the same composition, but prepared under different synthesis conditions.

Porphyrin-Based MOF Thin Film on Transparent Conducting Oxide: Investigation of Growth, Porosity and Photoelectrochemical Properties.

Synthesizing metal-organic frameworks (MOFs) composites with a controlled morphology is an important requirement to access materials of desired patterning and composition. Since the last decade, MOF growth from sacrificial metal oxide layer is increasingly developed as it represents an efficient pathway to functionalize a large number of substrates. In this study, porphyrin-based Al-PMOF thin films were grown on conductive transparent oxide substrates from sacrificial layers of ALD-deposited alumina oxide.

Improved Visible Emission from ZnO Nanoparticles Synthesized via the Co-Precipitation Method.

Since ZnO nanoparticles (NPs) possess a variety of intrinsic defects, they can provide a wide spectrum of visible emission, without adding any impurity or any doping atoms. They are attracting more and more interest as a material for light sources and energy downshifting systems. However, defect emission with a high luminescence quantum efficiency (PL QY) is difficult to obtain.

ZIF-8 thin films by a vapor-phase process: limits to growth.

Metal-organic frameworks are a class of porous materials that show promising properties in the field of microelectronics. To reach industrial use of these materials, gas phase techniques are often preferred and were recently introduced. However, the thicknesses achieved are not sufficient, limiting further development.

Ultra-Small YPO -YAG:Ce Composite Nanophosphors with a Photoluminescence Quantum Yield Exceeding 50.

Synthesis of high quality colloidal Cerium(III) doped yttrium aluminum garnet (Y Al O :Ce , "YAG:Ce") nanoparticles (NPs) meeting simultaneously both ultra-small size and high photoluminescence (PL) performance is challenging, as generally a particle size/PL trade-off has been observed for this type of nanomaterials. The glycothermal route is capable to yield ultra-fine crystalline colloidal YAG:Ce nanoparticles with a particle size as small as 10 nm but with quantum yield (QY) no more than 20%. In this paper, the first ultra-small YPO -YAG:Ce nanocomposite phosphor particles having an exceptional QY-to-size performance with an QY up to 53% while maintaining the particle size ≈10 nm is reported.

Luminescent and sustainable d coinage metal thiolate coordination polymers for high-temperature optical sensing.

The d coinage metal coordination polymers (CPs) are known to display photophysical properties which can be tuned depending on the functionality of the ligand. Three new CPs made of d coinage metals and methyl thiosalicylate, [M(-SPhCOMe)] (M = Cu, Ag, Au), are reported. They are all constructed from one-dimensional metal-sulfur networks, in which Cu and Ag are three-coordinated to sulfur atoms, whereas Au is only two-coordinated.

Influence of Surface-Active Substances and Substrates on the Wettability of Individual Aerosol Particles during Condensation by Environmental Scanning Electron Microscopy.

The formation of liquid cloud droplets from aerosol particles in the Earth atmosphere is still under debate particularly because of the difficulties to quantify the importance of bulk and surface effects in these processes. Recently, single-particle techniques have been developed to access experimental key parameters at the scale of individual particles. Environmental scanning electron microscopy (ESEM) has the advantage to provide in situ monitoring of the water uptake of individual microscopic particles deposited on solid substrates.

Insight into the Varying Reactivity of Different Catalysts for CO Cycloaddition into Styrene Oxide: An Experimental and DFT Study.

The cycloaddition of CO into epoxides to form cyclic carbonates is a highly sought-after reaction for its potential to both reduce and use CO, which is a greenhouse gas. In this paper, we present experimental and theoretical studies and a mechanistic approach for three catalytic systems. First, as Lewis base catalysts, imidazole and its derivatives, then as a Lewis acid catalyst, ZnI alone, and after that, the combined system of ZnI and imidazole.

Deciphering strontium sulfate precipitation via Ostwald's rule of stages: From prenucleation clusters to solution-mediated phase tranformation.

Multiple-step nucleation pathways have been observed during mineral formation in both inorganic and biomineral systems. These pathways can involve precursor aqueous species, amorphous intermediates, or metastable phases. Despite the widespread occurrence of these processes, elucidating the precise nucleation steps and the transformation mechanisms between each step remains a challenging task.

TiO Catalyzed Dihydroxyacetone (DHA) Conversion in Water: Evidence That This Model Reaction Probes Basicity in Addition to Acidity.

In this paper, evidence is provided that the model reaction of aqueous dihydroxyacetone (DHA) conversion is as sensitive to the TiO catalysts' basicity as to their acidity. Two parallel pathways transformed DHA: while the pathway catalyzed by Lewis acid sites gave pyruvaldehyde (PA) and lactic acid (LA), the base-catalyzed route afforded fructose. This is demonstrated on a series of six commercial TiO samples and further confirmed by using two reference catalysts: niobic acid (NbOH), an acid catalyst, and a hydrotalcite (MgAlO), a basic catalyst.

Substitution pattern in ruthenium octa-n-butoxyphthalocyanine complexes influence their reactivity in N-H carbene insertions.

Ruthenium phthalocyanine complexes bearing -OBu substituents in the peripheral or non-peripheral positions are efficient catalysts for the selective double or single carbene insertion to the amine N-H bonds. This complementary reactivity of two Ru complexes can be used for the synthesis of asymmetric tertiary amines and diamines bearing different substituents and has been demonstrated by two examples of readily available primary amines using different carbene precursors in successive reactions.

Ultra-mild synthesis of nanometric metal chalcogenides using organyl chalcogenide precursors.

Bis(trialkylsilyl) monochalcogenides and diorganyl dichalcogenides, (RSi)E and RE (E = S, Se or Te and R = alkyl, aryl or allyl group), have emerged in the past decade as excellent reagents for the synthesis of metal chalcogenide nanoparticles (NPs) and clusters owing to their ability to transfer the chalcogenide anion (E) under ultra-mild conditions and versatility in reacting even with non-conventional metal reagents or being employed in a variety of synthetic methods. In comparison, the related non-silylated diorganyl monochalcogenides RE have received attention only recently for the solution phase synthesis of metal chalcogenide NPs. In spite of sharing many similarities, these three families of organyl chalcogenides are different in their coordination ability and decomposition behavior, and therefore in reactivities towards metal reagents.

Sustainable oxygen evolution electrocatalysis in aqueous 1 M HSO with earth abundant nanostructured CoO.

Earth-abundant electrocatalysts for the oxygen evolution reaction (OER) able to work in acidic working conditions are elusive. While many first-row transition metal oxides are competitive in alkaline media, most of them just dissolve or become inactive at high proton concentrations where hydrogen evolution is preferred. Only noble-metal catalysts, such as IrO, are fast and stable enough in acidic media.

A chiral 3D silver(I)-benzenedithiolate coordination polymer exhibiting photoemission and non-linear optical response.

A new tridimensional metal-organic chalcogenolate, made of a 1,3-benzenedithiolate bridging ligand and Ag(I), [Ag(1,3-BDT)], is reported. This coordination polymer has good thermal stability in air and displays both photoluminescence properties and a second harmonic generation response.