Silver-Catalyzed Aqueous Electrochemical Valorization of Soda Lignin into Aliphatics and Phenolics.

Transitioning from crude oil to renewable sources of carbon-based chemicals is critical for advancing sustainable development. Lignin, a wood-derived biomacromolecule, holds great potential as a renewable feedstock, but efficient depolymerization and dearomatization methods are required to fully unlock its potential. In this investigation, we present a silver-catalyzed aqueous electrocatalytic method for the selective depolymerization and partial dearomatization of soda lignin under mild, ambient conditions.

Synthesis of Benzoic Acids from Electrochemically Reduced CO Using Heterogeneous Catalysts.

A method for the synthesis of benzoic acids from aryl iodides using two of the most abundant and sustainable feedstocks, carbon dioxide (CO) and water, is disclosed. Central to this method is an effective and selective electrochemical reduction of CO (eCORR) to CO, which mitigates unwanted dehalogenation reactions occurring when H is produced via the hydrogen evolution reaction (HER). In a 3-compartment set-up, CO was reduced to CO electrochemically by using a surface-modified silver electrode in aqueous electrolyte.

Perovskite-Like Carbodiimides (NCN): Synthesis and Characterization of MnHf(NCN) and FeHf(NCN).

Two novel ternary air-stable transition-metal carbodiimides, MnHf(NCN) and FeHf(NCN), were synthesized via solid-state metathesis using either ZnNCN or NaNCN as the carbodiimide source and the corresponding binary metal chlorides. These two phases are the first examples of transition-metal carbodiimides with an (NCN) composition, akin to ubiquitous O perovskite oxides. The crystal structure of MnHf(NCN) was determined and refined from powder X-ray diffraction (XRD) data in the non-centrosymmetric space group 622 allowing for chirality, the assignment of which is supported by second-harmonic generation (SHG) measurements.

Thallium-Fluorides Revisited: Crystal Chemistry of TlHF, Tl[MF]·2TlF, and Tl[MF]·TlCl (M = Si and Ge).

Although the formation of thallium hydrogen fluorides TlHF ( = 1, 1.5, 2, 3, 5, 6.5, and 7) from TlF and HF was reported in the 1970s, little is known about the corresponding crystal structures.

Synthesis and Properties of Cobalt Complexes with [BH] Ligands.

The unusually high oxidation state + IV of cobalt is stabilized by ligands based on [BH] in dark blue colored Cs[Co(BH(OH))]·4.56HO, K[Co(BH(OH))]·2HO, Cs[Co{(BH)(O)(OBOH)}]·4HO and K[Co{(BH)(OBOH)}]·7HO. These compounds were obtained by reacting Co salts with [BH] under alkaline conditions.

A Water-Promoted Mars-van Krevelen Reaction Dominates Low-Temperature CO Oxidation over Au-FeO but Not over Au-TiO.

We provide experimental evidence that is inconsistent with often proposed Langmuir-Hinshelwood (LH) mechanistic hypotheses for water-promoted CO oxidation over Au-FeO. Passing CO and HO, but no O, over Au-γ-FeO at 25 °C, we observe significant CO production, inconsistent with LH mechanistic hypotheses. Experiments with HO further show that previous LH mechanistic proposals cannot account for water-promoted CO oxidation over Au-γ-FeO.

Organic Chemicals from Wood: Selective Depolymerization and Dearomatization of Lignin via Aqueous Electrocatalysis.

Replacing crude oil as the primary industrial source of carbon-based chemicals has become crucial for both environmental and resource sustainability reasons. In this scenario, wood arises as an excellent candidate, whilst depolymerization approaches have emerged as promising strategies to unlock the lignin potential as a resource in the production of high-value organic chemicals. However, many drawbacks, such as toxic solvents, expensive catalysts, high energy inputs, and poor product selectivity have represented major challenges to this task.

MoS nanoflower-decorated lignin nanoparticles for superior lubricant properties.

Lignin has been, for a long time, treated as a low-value waste product. To change this scenario, high-value applications have been recently pursued, , the preparation of hybrid materials with inorganic components. Although hybrid inorganic-based materials can benefit from the reactive lignin phenolic groups at the interface, often responsible for optimizing specific properties, this is still an underexplored field.

Eu- and Tb-adsorbed SiN and GeN: tuning the colours with one luminescent host.

Phosphor-converted white light emitting diodes (pc-LEDs) are efficient light sources for applications in lighting and electronic devices. Nitrides, with their wide-ranging applicability due to their intriguing structural diversity, and their auspicious chemical and physical properties, represent an essential component in industrial and materials applications. Here, we present the successful adsorption of Eu and Tb at the grain boundaries of bulk β-SiN and β-GeN by a successful combustion synthesis.

Synthetic Engineering in NaMSn(NCN) (M = Mn, Fe, Co, and Ni) Based on Electronic Structure Theory.

Quaternary transition metal cyanamides NaMSn(NCN) with M = Mn, Fe, Co, and Ni were prepared via solid-state metathesis reactions between NaSn(NCN) and binary transition metal fluorides MF in a 2:1 molar ratio. All phases crystallize isotypically in [NiAs]-derived structures (1) with inter- and intra-layer cation ordering over the octahedral sites. This leads to a highly asymmetric coordination of the NCN anion, resulting in a strong degree of cyanamide character, which is confirmed via IR measurements.

Electrochemical Depolymerization of Lignin in a Biomass-based Solvent.

Invited for this month's cover is the group of Adam Slabon at the University of Wuppertal. The image illustrates the reductive depolymerization of lignin into monomers using copper as electrocatalyst. The Research Article itself is available at 10.

Electrochemical Depolymerization of Lignin in a Biomass-based Solvent.

Breaking down lignin into smaller units is the key to generate high value-added products. Nevertheless, dissolving this complex plant polyphenol in an environment-friendly way is often a challenge. Levulinic acid, which is formed during the hydrothermal processing of lignocellulosic biomass, has been shown to efficiently dissolve lignin.

Closing the yellow gap with Eu- and Tb-doped GaN: one luminescent host resulting in three colours.

Gallium nitride (GaN) is a key material when it comes to light-emitting diodes (LEDs) and has pushed the LED revolution in lighting and displays. The concept of down-conversion of a GaN-based blue LED offers the possibility to provide efficient generation of monochromatic, high-color purity light resulting in a highly efficient warm-white all-nitride phosphor-converted light emitting diode (pc-LED). Although the down conversion of blue light from InGaN LEDs has become a dominant technique for producing white light, there are still some technical challenges, e.

Lignin-Supported Heterogeneous Photocatalyst for the Direct Generation of HO from Seawater.

The development of smart and sustainable photocatalysts is in high priority for the synthesis of HO because the global demand for HO is sharply rising. Currently, the global market share for HO is around 4 billion US$ and is expected to grow by about 5.2 billion US$ by 2026.

Unravelling the Hydration Barrier of Lignin Oleate Nanoparticles for Acid- and Base-Catalyzed Functionalization in Dispersion State.

Lignin nanoparticles (LNPs) are promising renewable nanomaterials with applications ranging from biomedicine to water purification. However, the instability of LNPs under acidic and basic conditions severely limits their functionalization for improved performance. Here, we show that controlling the degree of esterification can significantly improve the stability of lignin oleate nanoparticles (OLNPs) in acidic and basic aqueous dispersions.

Curcuminoid-Tailored Interfacial Free Energy of Hydrophobic Fibers for Enhanced Biological Properties.

The ability of mimicking the extracellular matrix architecture has gained electrospun scaffolds a prominent space into the tissue engineering field. The high surface-to-volume aspect ratio of nanofibers increases their bioactivity while enhancing the bonding strength with the host tissue. Over the years, numerous polyesters, such as poly(lactic acid) (PLA), have been consolidated as excellent matrices for biomedical applications.

Graphitic nitrogen in carbon catalysts is important for the reduction of nitrite as revealed by naturally abundant N NMR spectroscopy.

Metal-free nitrogen-doped carbon is considered as a green functional material, but the structural determination of the atomic positions of nitrogen remains challenging. We recently demonstrated that directly-excited solid state 15N NMR (ssNMR) spectroscopy is a powerful tool for the determination of such positions in N-doped carbon at natural 15N isotope abundance. Here we report a green chemistry approach for the synthesis of N-doped carbon using cellulose as a precursor, and a study of the catalytic properties and atomic structures of the related catalyst.

LignoPhot: Conversion of hydrolysis lignin into the photoactive hybrid lignin/BiOBr/BiOBr composite for simultaneous dyes oxidation and Co and Ni recycling.

Valorization of lignin is still an open question and lignin has therefore remained an underutilized biomaterial. This situation is even more pronounced for hydrolysis lignin, which is characterized by a highly condensed and excessively cross-linked structure. We demonstrate the synthesis of photoactive lignin/BiOBr/BiOBr bio-inorganic composites consisting of a lignin substrate that is coated by semiconducting nanosheets.

Nucleotide Interaction with a Chitosan Layer on a Silica Surface: Establishing the Mechanism at the Molecular Level.

The growing interest in gene therapy is coupled with the strong need for the development of safe and efficient gene transfection vectors. A composite based on chitosan and fumed silica has been found to be a prospective gene delivery carrier. This study presents an investigation of the nature of the bonds between a series of nucleotides with a chitosan layer deposited on a fumed silica surface.

Structural Properties of NdTiON and Its Application as Photoanode.

Mixed-anion inorganic compounds offer diverse functionalities as a function of the different physicochemical characteristics of the secondary anion. The quaternary metal oxynitrides, which originate from substituting oxygen anions (O) in a parent oxide by nitrogen (N), are encouraging candidates for photoelectrochemical (PEC) water splitting because of their suitable and adjustable narrow band gap and relative negative conduction band (CB) edge. Given the known photochemical activity of LaTiON, we investigated the paramagnetic counterpart NdTiON.

Sensibilization of p-NiO with ZnSe/CdS and CdS/ZnSe quantum dots for photoelectrochemical water reduction.

Core/shell quantum dots (QDs) paired with semiconductor photocathodes for water reduction have rarely been implemented so far. We demonstrate the integration of ZnSe/CdS and CdS/ZnSe QDs with porous p-type NiO photocathodes for water reduction. The QDs demonstrate appreciable enhancement in water-reduction efficiency, as compared with the bare NiO.

Dissecting complex nanoparticle heterostructures via multimodal data fusion with aberration-corrected STEM spectroscopy.

With nanostructured materials such as catalytic heterostructures projected to play a critical role in applications ranging from water splitting to energy harvesting, tailoring their properties to specific tasks requires an increasingly comprehensive characterization of their local chemical and electronic landscape. Although aberration-corrected electron spectroscopy currently provides sufficient spatial resolution to study this space, an approach to concurrently dissect both the electronic structure and full composition of buried metal/oxide interfaces remains a considerable challenge. In this manuscript, we outline a statistical methodology to jointly analyze simultaneously-acquired STEM EELS and EDX datasets by fusing them along their shared spatial factors.

Converting cellulose nanocrystals into photocatalysts by functionalisation with titanium dioxide nanorods and gold nanocrystals.

Cellulose nanocrystals (CNCs) are promising building blocks for water purification due to their high surface area, tuneability of surface charge and grafting of surface groups depending on the pollutants. In this report we have converted CNCs into photocatalysts, without altering the surface groups, by growth of TiO nanorods (NRs) and functionalization with Au nanocrystals (NCs) for enhanced light absorption. The control of the density of the NRs assures that the CNC surface and functionalities are accessible for the pollutant, followed by the photocatalytic degradation on the light absorption layer under solar illumination.

Semi-transparent quaternary oxynitride photoanodes on GaN underlayers.

Conformal atomic layer deposition (ALD) technique is employed to make semi-transparent TaON, providing the possibility to build semi-transparent oxy(nitride) heterojunction photoanodes on conductive substrates. A generalized approach was developed to manufacture semi-transparent quaternary metal oxynitrides on conductive substrates beyond semi-transparent binary TaN photoanodes aiming for wireless tandem photoelectrochemical (PEC) cells.

Trapping of different stages of BaTiO reduction with LiH.

We investigated the hydride reduction of tetragonal BaTiO using LiH. The reactions employed molar H : BaTiO ratios of 1.2, 3, and 10 and variable temperatures up to 700 °C.