Electrochemical reduction of nitrate into ammonia is one potential strategy to valorize pollutants needed to close the nitrogen cycle. The understanding of carbonaceous materials as metal-free representatives of electrocatalysts is of high importance to ensure sufficient activity and target selectivity. We report on the role of defects in cellulose-derived nitrogen-doped carbon (NDC) materials, produced by ammonolysis at different temperatures, to obtain efficient electrocatalysts for the nitrate reduction reaction (NO₃RR). Carbon catalyst ammonolysis at 800 °C (NDC-800) yields the highest electrochemical performance, exhibiting 73.1% NH₄⁺ selectivity and nearly 100% NO₃⁻ reduction efficiency with a prolonged NO₃RR time (48 h) at −1.5 V vs. Ag/AgCl in a 0.1 M Na₂SO₄ electrolyte. We provide support to our findings by undertaking complementary structural analyses with scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, low-temperature N₂ adsorption, and theoretical studies based on multi-scale/level calculations. Atomistic molecular dynamics simulations based on a reactive force field combined with quantum chemistry (QC) calculations on representative model systems suggest possible realistic scenarios of the material structure and reaction mechanisms of the NO₃⁻ reduction routes.

Nanocellulose membranes based on tunicate-derived cellulose nanofibers, starch, and ~5% wood-derived lignin were investigated using three different types of lignin. The addition of lignin into cellulose membranes increased the specific surface area (from 5 to ~50 m²/g), however the fine porous geometry of the nanocellulose with characteristic pores below 10 nm in diameter remained similar for all membranes. The permeation of H₂, CO₂, N₂, and O₂ through the membranes was investigated and a characteristic Knudsen diffusion through the membranes was observed at a rate proportional to the inverse of their molecular sizes. Permeability values, however, varied significantly between samples containing different lignins, ranging from several to thousands of barrers (10⁻¹⁰ cm³ (STP) cm cm⁻² s⁻¹ cmHg⁻¹cm), and were related to the observed morphology and lignin distribution inside the membranes. Additionally, the addition of ~5% lignin resulted in a significant increase in tensile strength from 3 GPa to ~6–7 GPa, but did not change thermal properties (glass transition or thermal stability). Overall, the combination of plant-derived lignin as a filler or binder in cellulose–starch composites with a sea-animal derived nanocellulose presents an interesting new approach for the fabrication of membranes from abundant bio-derived materials. Future studies should focus on the optimization of these types of membranes for the selective and fast transport of gases needed for a variety of industrial separation processes.

The achievement of frictionless systems, known as superlubricity, has become of great importance concerning energy saving and emission reduction. In parallel, the drive toward sustainability and environmental aspects has led to intense advances in the research and development of biobased materials. From the standpoint of Green Chemistry principles, this review presents a critical overview of the latest findings and future perspectives on the application of biobased materials aiming at superlubricant pursuits. The progress in the use of biomacromolecules, such as chitosan, cellulose, and lignin, as additives to lubricants or coating materials, are addressed, as well as the advances on sustainable coatings based on diamond-like carbon (DLC). Deeper investigations on the development of non-hazardous processes dedicated to the tribological properties of DLC, such as electrochemical synthesis using environment-friendly solvents to generate molecular precursors, widen the perspectives to achieve sustainable materials. Besides, the exploration of the tribochemical interactions between the DLC surface and lubricants containing biobased materials arises as a promising strategy to achieve green superlubricity as a viable and scalable process, through different pathways: by hydrogen bonds between lubricant and additives, via surface passivation of the functional groups present in these biomacromolecules or by biomimicking natural joints.

Efficient treatment of domestic and industrial wastewater is one of the major challenges of the 21st century. Among the inorganic pollutants, nitrogen species are significant contaminants and the management of the nitrogen cycle is one the most crucial parts of wastewater purification. Herein, we report an integrated method that minimizes the amount of chemicals used, can be empowered by renewable energy, uses renewables materials for ammonia recovery, and is scalable. Complete denitrification of wastewater was achieved by combining electrochemical and adsorption treatment for real wastewater samples from the Stockholm water pilot plant. About 98% of nitrate was selectively converted to ammonia over abundant copper electrocatalysts in the presence of Na2SO4-supporting electrolyte at -0.6 V vs reversible hydrogen electrode (RHE) within 3 h. The valorized nitrate in the form of ammonia could be recovered by means of cheap kraft lignin-SiO2 sorbents to achieve total denitrification. The presented method is economically feasible, scalable, and contributes to sustainable recycling within a circular economy.

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 N-15 NMR (ssNMR) spectroscopy is a powerful tool for the determination of such positions in N-doped carbon at natural N-15 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. N-doped carbon (NH3) was obtained by the oxidation of cellulose with HNO3 followed by ammonolysis at 800 degrees C. It had a N content of 6.5 wt% and a surface area of 557 m(2) g(-1), and N-15 ssNMR spectroscopy provided evidence for graphitic nitrogen besides regular pyrrolic and pyridinic nitrogen. This structural determination allowed probing the role of graphitic nitrogen in electrocatalytic reactions, such as the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and nitrite reduction reaction. The N-doped carbon catalyst (NH3) showed higher electrocatalytic activities in the OER and HER under alkaline conditions and higher activity for nitrite reduction, as compared with a catalyst prepared by the carbonization of HNO3-treated cellulose in N-2. The electrocatalytic selectivity for nitrite reduction of the N-doped carbon catalyst (NH3) was directly related to the graphitic nitrogen functions. Complementary structural analyses by means of C-13 and H-1 ssNMR, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and low-temperature N-2 adsorption were performed and provided support to the findings. The results show that directly-excited N-15 ssNMR spectroscopy at natural N-15 abundance is generally capable of providing information on N-doped carbon materials if relaxation properties are favorable. It is expected that this approach can be applied to a wide range of solids with an intermediate concentration of N atoms.

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/Bi₄O₅Br₂/BiOBr bio-inorganic composites consisting of a lignin substrate that is coated by semiconducting nanosheets. The XPS analysis reveals that growing these nanosheets on lignin instead on cellulose prevents the formation of Bi⁵⁺ ions at the surface region, yielding thus a modified heterojunction Bi₄O₅Br₂/BiOBr. The material contains 18.9% of Bi₄O₅Br₂/BiOBr and is effective for the photocatalytic degradation of cationic methylene blue (MB) and zwitterionic rhodamine B (RhB) dyes under light irradiation. Lignin/Bi₄O₅Br₂/BiOBr decreases the dye concentration from 80 mg L⁻¹ to 12.3 mg L⁻¹ for RhB (85%) and from 80 mg L⁻¹ to 4.4 mg L⁻¹ for MB (95%). Complementary to the dye degradation, the lignin as a main component of the composite, was found to be efficient and rapid biosorbent for nickel, lead, and cobalt ions. The low cost, stability and ability to simultaneously photo-oxidize organic dyes and adsorb metal ions, make the photoactive lignin/Bi₄O₅Br₂/BiOBr composite a prospective material for textile wastewaters remediation and metal ions recycling.

A series of hybrid adsorbents were produced by surface modification with amino polycarboxylate ligands of industrially available microparticles (MP) of Kromasil (R) mesoporous nanostructured silica beads, bearing grafted amino propyl ligands. Produced materials, bearing covalently bonded functions as EDTA and TTHA, original Kromasil (R), bearing amino propyl ligands, and bare particles, obtained by thermal treatment of Kromasil (R) in air, were characterized by SEM-EDS, AFM, FTIR, TGA and gas sorption techniques. Adsorption kinetics and capacity of surface-modified particles to adsorb Rare Earth Elements (REE), crucial for extraction in recycling processes, were evaluated under dynamic conditions, revealing specificity matching the ligand nature and the size of REE cations. A detailed comparison with earlier reported adsorbents for REE extraction was presented. The cytotoxicity was assessed using four different types of healthy cells, human skeletal muscles derived cells (SKMDC), fibroblast cells, macrophage cells (RAW264.7), and human umbilical vein endothelial cells (HUVECs), indicating lower toxicity of ligand-free MP than MP bearing amino poly-carboxylate functions. Internalization of the MP inside the cells and release of nitric oxide were observed. In addition, zebrafish embryos were exposed to high concentrations of MP and did not show any pronounced toxicity.

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^––/–PO₃^2– 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.

The growing demand for Li-ion batteries (LIBs) has made their postconsumer recycling an imperative need toward the recovery of valuable metals, such as cobalt and nickel. Nevertheless, their recovery and separation from active cathode materials in LIBs, via an efficient and environmentally friendly process, have remained a challenge. In this work, we approach a simple and green method for the selective separation of nickel ions from mixed cobalt-nickel aqueous solutions under mild conditions. We discovered that the bioinspired microporous metal-organic framework (MOF) SU-101 is a selective sorbent toward Ni2+ ions at pH 5-7 but does not adsorb Co2+ ions. According to the Freundlich isotherm, the adsorption capacity toward Ni2+ reached 100.9 mg.g(-1), while a near-zero adsorption capacity was found for Co2+ ions. Ni2+ removal from aqueous solutions was performed under mild conditions (22 degrees C and pH 5), with a high yield up to 96%. The presence of Ni2+ ions adsorbed on the surface of the material has been proven by solid-state H-1 nuclear magnetic resonance spectroscopy. Finally, the separation of Ni2+ from Co2+ from binary solutions was obtained with approximately 30% yield for Ni2+, with a near-zero adsorption of Co2+, which has been demonstrated by UV-vis spectroscopy. The ion adsorption process of Ni2+ and Co2+ ions was additionally studied by means of classical molecular dynamics calculations (force fields), which showed that the Ni2+ ions were more prone to enter the MOF canals by replacing some of their coordinated water molecules. These results offer a green pathway toward the recycling and separation of valuable metals from cobalt-containing LIBs while providing a sustainable route for waste valorization in a circular economy.

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.