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Herein we report a hybrid organic–inorganic nanomaterial that combines the structural stability of colloidal lignin nanoparticles with the lubricant performance of MoS2 nanoparticles.

The development of sustainable valorization methods for lignin is a challenging task, because the vast majority of the reported methods require either harsh conditions or the use of expensive transition metal catalysts. Inspired from the natural-sunlight degradation of lignin, known as lignin yellowing, we report here the use of a commercially available cheap organic photocatalyst, namely, phenacyl bromide (PAB), for the efficient cleavage of lignin model compound 2-phenoxyacetophenone (2-PAP), and the depolymerization of soda pulped lignin (SL) under UV-A irradiation under ambient conditions. Real-time NMR investigations of the photoreaction between the model compound and PAB shed light on the possible reaction mechanisms involving different radical species, HBr, and molecular oxygen. Interestingly, combined spectral, chromatographic, powder X-ray diffraction and thermal studies of the photocatalytic reaction between PAB and SL indicated the formation of guaiacyl alcohol. The unprecedented catalytic performance of such a simple organic photocatalyst is attributed to the generation of phenacyl radicals, photolabile brominated species and HBr playing key roles in the cleavage of β-O-4 linkages. This study represents a new edge for lignin valorization under mild reaction conditions and offers the opportunity for large-scale environment-neutral production of valuable aromatics using technical lignins as feedstock.

Ruthenium containing molecular electrocatalyst onto pyridine modified, fluorine-doped carbon cloth represents an efficient, bifunctional, and regenerable electrode for water electrolysis at pH 7.

Direct hydroxylation via the functionalization of tertiary benzylic C(sp(3))-H bonds is of great significance for obtaining tertiary alcohols, which find wide applications in pharmaceuticals as well as in fine chemical industries. However, current synthetic procedures use toxic reagents, and therefore, the development of a sustainable strategy for the synthesis of tertiary benzylic alcohols is highly desirable. To solve this problem, herein, we report a metal-free heterogeneous photocatalyst to synthesize the hydroxylated products using oxygen as the key reagent. Various benzylic substrates were employed into our mild reaction conditions to afford the desirable products in good to excellent yields. More importantly, the gram-scale reaction was achieved via harvesting direct solar energy and exhibited high quantity of the product. The high stability of the catalyst was proved via recycling the catalyst and spectroscopic analyses. Finally, a possible mechanism was proposed based on electron paramagnetic resonance and other experimental evidence.

This mini-review focuses on up-to-date advances of hybrid materials consisting of organic and inorganic components and their applications in different chemical processes. The purpose of forming such hybrids is mainly to functionalize and stabilize inorganic supports by attaching an organic linker to enhance their performance towards a target application. The interface chemistry is present with the emphasis on the sustainability of their components, chemical changes in substrates during synthesis, improvements of their physical and chemical properties, and, finally, their implementation. The latter is the main sectioning feature of this review, while we present the most prosperous applications ranging from catalysis, through water purification and energy storage. Emphasis was given to materials that can be classified as green to the best in our consideration. As the summary, the current situation on developing hybrid materials as well as directions towards sustainable future using organic-inorganic hybrids are presented.

We report the first magic-angle spinning (MAS) nuclear magnetic resonance (NMR) study on Sn(NCN). In this compound the spatially elongated (NCN)2− ion is assumed to develop two distinct forms: either cyanamide (N≡C–N2−) or carbodiimide (−N=C=N−). Our 14N MAS NMR results reveal that in Sn(NCN) the (NCN)2− groups exist exclusively in the form of symmetric carbodiimide ions with two equivalent nitrogen sites, which is in agreement with the X-ray diffraction data. The 14N quadrupolar coupling constant | C Q | $\vert {C}_{\text{Q}}\vert $ ≈ 1.1 MHz for the −N=C=N− ion in Sn(NCN) is low when compared to those observed in molecular compounds that comprise cyano-type N≡C– moieties ( | C Q | $\vert {C}_{\text{Q}}\vert $ > 3.5 MHz). This together with the information from 14N and 13C chemical shifts indicates that solid-state NMR is a powerful tool for providing atomic-level insights into anion species present in these compounds. The experimental NMR results are corroborated by high-level calculations with quantum chemistry methods.

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. The high stability of OLNPs is attributed to the alkyl chains accumulated in the shell of the particle, which delays protonation/deprotonation of carboxylic acid and phenolic hydroxyl groups. Owing to the enhanced stability, acid‐ and base‐catalyzed functionalization of OLNPs at pH 2.0 and pH 12.0 via oxirane ring‐opening reactions were successfully performed. We also demonstrated these new functionalized particles as efficient pH‐switchable dye adsorbents and anticorrosive particulate coatings., Lignin oleate nanoparticles (OLNPs) are demonstrated for functionalization in aqueous dispersion under acidic (pH 2) and basic (pH 12) conditions owing to the hydration barrier effect provided by oleic acid chains in the shells of OLNPs. Covalent functionalization of these nanoparticles using robust chemistries opens new avenues such as functional anticorrosive coatings and pH‐switchable adsorbents for removal of organic dyes from wastewater.

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. However, this class of polymers usually has a high hydrophobic character, which limits cell attachment and proliferation, and therefore decreases biological interactions. In this way, functionalization of polyester-based materials is often performed in order to modify their interfacial free energy and achieve more hydrophilic surfaces. Herein, we report the preparation, characterization, and in vitro assessment of electrospun PLA fibers with low contents (0.1 wt %) of different curcuminoids featuring π-conjugated systems, and a central β-diketone unit, including curcumin itself. We evaluated the potential of these materials for photochemical and biomedical purposes. For this, we investigated their optical properties, water contact angle, and surface features while assessing their in vitro behavior using SH-SY5Y cells. Our results demonstrate the successful generation of homogeneous and defect-free fluorescent fibers, which are noncytotoxic, exhibit enhanced hydrophilicity, and as such greater cell adhesion and proliferation toward neuroblastoma cells. The unexpected tailoring of the scaffolds' interfacial free energy has been associated with the strong interactions between the PLA hydrophobic sites and the nonpolar groups from curcuminoids, which indicate its role for releasing hydrophilic sites from both parts. This investigation reveals a straightforward approach to produce photoluminescent 3D-scaffolds with enhanced biological properties by using a polymer that is essentially hydrophobic combined with the low contents of photoactive and multifunctional curcuminoids.

Zeitschrift für Naturforschung / B 76(5), 275-280 (2021). doi:10.1515/znb-2021-0031, Published by De Gruyter, Berlin

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-Si

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. Herein, levulinic acid was evaluated as a medium for the reductive electrochemical depolymerization of the lignin macromolecule. Copper was chosen as the electrocatalyst due to the economic feasibility and low activity towards the hydrogen evolution reaction. After depolymerization, high-resolution mass spectrometry and nuclear magnetic resonance spectroscopy revealed lignin-derived monomers and dimers. A predominance of aryl ether and phenolic groups was observed. Depolymerized lignin was further evaluated as an anti-corrosion coating, revealing enhancements on the electrochemical stability of the metal. Via a simple depolymerization process of biomass waste in a biomass-based solvent, a straightforward approach to produce high value-added compounds or tailored biobased materials was demonstrated.

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. Experimentally measured surface complex formation constants (logK) of the nucleotides were found to be in the range of 2.69-4.02, which is higher than that for the orthophosphate (2.39). Theoretically calculated nucleotide complexation energies for chitosan deposited on the surface range from 11.5 to 23.0 kcal.mol(-)(1), in agreement with experimental data. The adsorption of nucleotides was interpreted using their calculated speciation in an aqueous solution. Based on the structures of all optimized complexes determined from quantum-chemical PM6 calculations, electrostatic interactions between the surface-located NH3- groups and -PO3H--/-PO32- fragments of the nucleotides were identified to play the decisive role in the adsorption mechanism. The saccharide fragment of monophosphates also plays an important role in the binding of the nucleotides to chitosan through the creation of hydrogen bonds.

Inorganic chemistry 60(2), 919-929 (2021). doi:10.1021/acs.inorgchem.0c03041, Published by American Chemical Society, Washington, DC

Lubrication of an internal combustion engine is critical for energy and material losses. Engine lubricants contain a number of functional additives including zinc dialkyldithiophosphate, which is a...

The successive breakdown of the lignin macromolecule into smaller units is the key to generate high value-added products from this complex plant polyphenol. Obtaining well-defined aromatic compounds is, therefore, an important step towards the production of biobased chemicals for the fuel, coating and lubricant industries. Nevertheless, processes requiring lignin dissolution are always challenging. Dissolving this macromolecule in an environment-friendly way takes this challenge to a whole new level. Levulinic acid, an organic compound formed during the hydrothermal processing of lignocellulosic biomass, has been shown to efficiently dissolve lignin. Herein, we describe a system consisting of levulinic acid as a biobased solvent for the reductive electrochemical depolymerization of lignin. Copper was used as an electrocatalyst due to the economic feasibility and low activity towards the hydrogen evolution reaction. After depolymerization, high-resolution mass spectrometry and NMR structural characterization revealed lignin-derived monomers and dimers. A predominance of aryl ether and phenolic groups was observed. The effect of the depolymerized lignin as an anti-corrosion coating was assessed, revealing enhancements on the electrochemical stability of the metal. Via a simple depolymerization process of biomass waste in a biomass-based solvent, these results demonstrate a straightforward approach to produce high value-added compounds or tailored biobased materials.

Understanding of structural preferences and dynamics of water at the TiO2–H2O interface is fundamentally impor- tant in the perspective of broad range of TiO2 applications that extend from bio-adsorption for medical devices, photo- catalysis for energy production, to coatings with remarkable self-cleaning and anti-fogging properties. However, current knowledge on these systems under full hydration result almost entirely from modelling rather than direct experimental observations. Surface-sensitive techniques like electron microscopy (EM) or X-ray photoelectron spectroscopy (XPS) operate under high vacuum, therefore do not provide insights into phenomena underlying the real catalytic and bio-adsorption processes that take place under wet conditions. Herein, atomic-level characterization of TiO2 nanoparticles surface under full hydration was performed by a combination of 1H magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and molecular dynamics density functional theory (MD-DFT) simulations. Thanks to partial proton to deuteron exchange and fast MAS, resolved NMR signals from OH/H2O species at the TiO2–H2O interface could be observed and interpreted with chemical shifts calculations performed on system evolution trajectory frames. Presence of the recently debated atmospheric carboxylic acids was confirmed, however, the amount of these was small compared to OH/H2O surface species. Surface protonation and evolution of hydrogen-bonded network are shown to govern the surface chemistry of TiO2 under wet conditions.

The development of smart and sustainable photocatalysts is in high priority for the synthesis of H

Lignin is a renewable biopolymer, and its chemical functionalization renders it a prospective material for a plethora of applications. Within this respect, we present a method for lignin immobiliza...

Spherical mesoporous carbon (with a particle size in the range of 40–75 μm) was synthesized by nanoreplication of a hard silica template using sucrose as the carbon precursor. The mesoporous carbon...

The simultaneous removal of organic and inorganic pollutants from wastewater is a complex challenge and requires usually several sequential processes. Here, we demonstrate the fabrication of a hybrid material that can fulfill both tasks: (i) the adsorption of metal ions due to the negative surface charge, and (ii) photocatalytic decomposition of organic compounds. The bioinorganic hybrid membrane consists of cellulose fibers to ensure mechanical stability and of Bi4O5Br2/BiOBr nanosheets. The composite is synthesized at low temperature of 115 °C directly on the cellulose membrane (CM) in order to maintain the carboxylic and hydroxyl groups on the surface that are responsible for the adsorption of metal ions. The composite can adsorb both Co(II) and Ni(II) ions and the kinetic study confirmed a good agreement of experimental data with the pseudo-second-order equation kinetic model. CM/Bi4O5Br2/BiOBr showed higher affinity to Co(II) ions than to Ni(II) ions from diluted aqueous solutions. The bioinorganic composite demonstrates a synergistic effect in the photocatalytic degradation of rhodamine B (RhB) by exceeding the removal efficiency of single components. The fabrication of the biologic-inorganic interface was confirmed by various analytical techniques including scanning electron microscopy (SEM), scanning transmission electron microscopy with energy dispersive X-ray spectroscopy (STEM EDX) mapping, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The presented approach for controlled formation of the bioinorganic interface between natural material (cellulose) and nanoscopic inorganic materials of tailored morphology (Bi–O–Br system) enables the significant enhancement of materials functionality.

Chitosan was deposited on fumed silica without the addition of cross-linkers or activating agents. The chitosan surface layer has a high affinity toward organic molecules, e.g., Acid Orange 8 (AO8) dye, robust to a broad range of simulated conditions (variance with respect to temperature, time, and concentration of solute). Experimental equilibrium data were analyzed by the generalized Langmuir equation taking into consideration the energetic heterogeneity of the adsorption system. The effect of temperature on dye uptake and adsorption rate was studied. According to the calculated thermodynamic functions ΔG°, ΔH°, and ΔS° from the equilibrium data at different temperatures, the adsorption of AO8 onto chitosan–fumed silica composite is exothermic and spontaneous. The studies of temperature effect on adsorption equilibrium show that the maximum adsorption capacity (determined from the Langmuir–Freundlich equation) of synthesized composite toward AO8 is about one-third higher in the case of an isotherm measured at 5 °C than this value obtained for the isotherm measured at 45 °C. The quantitative binding of dye molecules to chitosan coating on the surface of silica was proved by 1H MAS NMR. The deep kinetics study through the application of various theoretical models—the first-order equation, pseudo-first-order equation, second-order equation, pseudo-second-order equation, mixed first, second-order equation, and multiexponential equation—was applied for getting inside the mechanism of AO8 binding to the chitosan coating. Structural characteristics of chitosan-coated silica were obtained from the low-temperature adsorption/desorption isotherms of nitrogen and imaging by scanning electron microscopy. The effects of a synthetic route for polymer coating on thermal stability and the ability to degrade were studied by differential scanning calorimetry.

Anatase TiO2 nanoparticles with an average crystallite size of ~ 20 nm are synthesized through a sol-gel method. A composite anode for Li-ion batteries is prepared with the synthesized TiO2 nanoparticles and reduced graphite oxide (RGO) as the conductive carbon source. After the preparation of TiO2/RGO nanocomposite, a novel surface modification is carried out by the employment of H2O2 to enhance the overall electrochemical performance of nanocomposite anode (TiO2/RGO-P composite). The physical and chemical characterizations of the surface modified TiO2/RGO-P composites are performed with X-ray powder diffraction (XRPD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and atomic force microscopy (AFM) analyses. The electrochemical performance of TiO2/RGO-P composite electrodes is investigated via galvanostatic charge-discharge cycling tests in a potential window of 1.0–3.0 V. Compared to the plain TiO2/RGO composite anode, the TiO2/RGO-P composite anode has higher reversible capacities and better cycling performance due to the enhanced and stable formation of 3D channels of TiO2 nanoparticles with RGO stemming from the surface modification with H2O2. The TiO2/RGO-P composite anode delivers reversible discharge capacities around 291 mA h g−1 at a rate of 100 mA g−1, whereas the value stays at 214 and 143 mA h g−1 for the plain TiO2/RGO composite and TiO2 nanoparticle without any RGO, respectively.

The effect of bimetallic monodisperse CoPd nanoparticles on the microstructure and the shear strength of the Cu/ SAC305/Cu solder joint was investigated. The nanocomposite Sn–3.0Ag–0.5Cu (SAC305) solders with 0.1, 0.3, 0.5, and 1.0 wt% nanoCoPd were prepared through a paste mixing method. The employed bimetallic nanoparticles were produced via a modified oleylamine method. The microstructural analysis of as-solidified Cu/solder/Cu joints was performed by scanning electron microscopy. The results showed that initial additions of CoPd nanoparticles into the SAC305 solder promoted the growth of the interfacial planar-type Cu3Sn IMC layer; while the average thickness of the interfacial scallop-type Cu6Sn5 IMC layer slightly decreased. Further additions of the nanosized CoPd admixtures to the SAC305 solder paste lead to a significant increase of the average thickness of the Cu6Sn5 intermetallic compound layer up to 40%. The shear strength measurements were performed to investigate a relationship between the microstructure and mechanical properties of the investigated solder joints. The results indicated a decrease in the shear strength of the SAC305 solder joint by addition of 0.1 wt% CoPd NPs, while a difference in absolute values between solder joints with 0.3, 0.5, and 1.0 wt% nanoCoPd was practically insignificant.

Lead cyanamide PbNCN was synthesized by solid-state metathesis between PbCl2 and Na2NCN in a 1 : 1 molar ratio, and its structure was confirmed from Rietveld refinement of X-ray data. Electronic-structure calculations of HSE06 density-functional type reveal PbNCN to be an indirect semiconductor with a band gap of 2.4 eV, in remarkable quantitative agreement with the measured value. Mott-Schottky experiments demonstrate PbNCN to be a p-type semiconductor with a flat-band potential of 2.3 eV vs. the reversible hydrogen electrode (RHE) which is commonly used to estimate the value of the valence band edge position. Moreover, thin films of powderous PbNCN were assembled into a photoelectrode for photoelectrochemical water splitting. On the example of p-type PbNCN, this study provides the first experimental evidence that MNCN compounds can be applied as photocathodes for reductive reactions in photoelectrochemical cells.

Cobalt-based Li-ion batteries are produced globally on a massive scale, but most are discarded to landfill at the end of their useful lifetime. In this work, an efficient cobalt catalyst for the hydrolysis of sodium borohydride to dihydrogen was prepared from lithium ion battery waste, providing a second life for valuable minerals. This material is composed of a mixed metal cobalt–aluminium oxide supported on graphene, as elucidated by a combined FTIR, Raman, SEM, scanning transmission electron microscopy with electron energy loss spectroscopy (STEM-EELS) and energy-dispersive X-ray spectroscopy (EDS) study. The obtained metal oxide material, which exhibits an average oxidation state for Co of 2.45, is a languid catalyst at room temperature, but rapid hydrogen production of up to 49 L(H2) min−1 g−1(Co) was observed in catalytic runs heated to 70 °C. This carbon-supported cobalt catalyst is competitive with designed cobalt nanostructured catalysts prepared from pure precursors. This work is illustrative of the opportunities which arise when e-waste is utilised as a mineral resource within the scope of a circular economy.

Catalysis science & technology (2022). doi:10.1039/d2cy00050d, Published by RSC Publ., London

The development of smart and sustainable photocatalysts is in high priority for the synthesis of H2O2 because the global demand for H2O2 is sharply rising. Currently, the global market share for H2O2 is around 4 billion US$ and is expected to grow by about 5.2 billion US$ by 2026. Traditional synthesis of H2O2 via the anthraquinone method is associated with the generation of substantial chemical waste as well as the requirement of a high energy input. In this respect, the oxidative transformation of pure water is a sustainable solution to meet the global demand. In fact, several photocatalysts have been developed to achieve this chemistry. However, 97% of the water on our planet is seawater, and it contains 3.0-5.0% of salts. The presence of salts in water deactivates the existing photocatalysts, and therefore, the existing photocatalysts have rarely shown reactivity toward seawater. Considering this, a sustainable heterogeneous photocatalyst, derived from hydrolysis lignin, has been developed, showing an excellent reactivity toward generating H2O2 directly from seawater under air. In fact, in the presence of this catalyst, we have been able to achieve 4085 ?M of H2O2. Expediently, the catalyst has shown longer durability and can be recycled more than five times to generate H2O2 from seawater. Finally, full characterizations of this smart photocatalyst and a detailed mechanism have been proposed on the basis of the experimental evidence and multiscale/level calculations.

Quaternary tantalum-based oxynitrides ATa(O,N)3, with electronic band gaps between 1.8 and 2.4 eV, are promising materials for photochemical water-splitting. The tailoring of their surface properties is a critical aspect to obtain efficient hole extraction. We report on the origin of improved photoelectrochemical (PEC) water oxidation by means of acidic treatment for this class of compounds on the example of cubic CaTaO2N particles. We address the effect of acidic treatment by using complementary physical characterization techniques, such as X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS), 1H and 14N solid-state nuclear magnetic resonance (NMR) spectroscopy, electron microscopy and electronic band structure calculations at the density functional theory (DFT) level. In combination with photoelectrochemical measurements, solid-state NMR indicates that the restructured surface displays a meaningfully higher concentration of terminating OH groups. Subsequent deposition of a nickel borate (NiBi) catalyst on the acid-treated surface yields a higher percentual upsurge of photocurrent in comparison to pristine CaTaO2N. Our results highlight the application of solid-state NMR spectroscopy for understanding of the semiconductor-catalyst interface in photochemical devices.