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. Herein, we present an unprecedented approach using electrocatalysis for the simultaneous depolymerization and dearomatization of lignin in aqueous medium under ambient conditions. By employing water/sodium carbonate as a solvent system, we demonstrated a pathway for selectively depolymerizing lignin under reductive electrochemical conditions using carbon as an electrocatalyst. After reductive electrocatalysis, the presence of aromatic compounds was no longer detected via nuclear magnetic resonance (NMR) spectroscopy. Further characterization by NMR, FTIR spectroscopy, and mass spectrometry revealed the major presences of sodium levulinate, sodium 4-hydroxyvalerate, sodium formate, and sodium acetate as products. By achieving a complete dearomatization, valuable aliphatic intermediates with enhanced reactivity were selectively obtained, opening new avenues for further synthesis of many different organic chemicals, and contributing to a more sustainable and circular economy.

MoS2 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, e.g., 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. Here, we present a novel and green material based on the combination of hydroxymethylated lignin nanoparticles (HLNPs) with molybdenum disulfide (MoS2) nanoflowers grown via a hydrothermal route. By bringing together the lubricant performance of MoS2 and the structural stability of biomass-based nanoparticles, a MoS2-HLNPs hybrid is presented as a bio-derived additive for superior tribological performances. While FT-IR analysis confirmed the structural stability of lignin after the hydrothermal growth of MoS2, TEM and SEM micrographs revealed a homogeneous distribution of MoS2 nanoflowers (average size of 400 nm) on the HLNPs (average size of 100 nm). Regarding the tribological tests, considering a pure oil as reference, only HLNPs as bio-derived additives led to a reduction in the wear volume of 18%. However, the hybrid of MoS2-HLNPs led to a considerably higher reduction (71%), pointing out its superior performance. These results open a new window of opportunity for a versatile and yet underexplored field that can pave the way for a new class of biobased lubricants.

Synthesis, Electronic Properties and Reactivity of [B12 X11 (NO2 )]2- (X=F-I) Dianions.

Nitro-functionalized undecahalogenated closo-dodecaborates [B12 X11 (NO2 )]2- were synthesized in high purities and characterized by NMR, IR, and Raman spectroscopy, single crystal X-diffraction, mass spectrometry, and gas-phase ion vibrational spectroscopy. The NO2 substituent leads to an enhanced electronic and electrochemical stability compared to the parent perhalogenated [B12 X12 ]2- (X=F-I) dianions evidenced by photoelectron spectroscopy, cyclic voltammetry, and quantum-chemical calculations. The stabilizing effect decreases from X=F to X=I. Thermogravimetric measurements of the salts indicate the loss of the nitric oxide radical (NO. ). The homolytic NO. elimination from the dianion under very soft collisional excitation in gas-phase ion experiments results in the formation of the radical [B12 X11 O]2-. . Theoretical investigations suggest that the loss of NO. proceeds via the rearrangement product [B12 X11 (ONO)]2- . The O-bonded nitrosooxy structure is thermodynamically more stable than the N-bonded nitro structure and its formation by radical recombination of [B12 X11 O]2-. and NO. is demonstrated.

Trivalent Actinide Ions Showing Tenfold Coordination in Solution.

Trivalent actinides generally exhibit ninefold coordination in solution. 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (nPr-BTP), a tridentate nitrogen donor ligand, is known to form ninefold coordinated 1:3 complexes, [An(nPr-BTP)3]3+ (An = U, Pu, Am, Cm) in solution. We report a Cm(III) complex with tenfold coordination in solution, [Cm(nPr-BTP)3(NO3)]2+. This species was identified using time-resolved laser fluorescence spectroscopy (TRLFS), vibronic side band spectroscopy (VSBS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). Adding nitrate to a solution of the [Cm(nPr-BTP)3]3+ complex in 2-propanol shifts the Cm(III) emission band from 613.1 to 617.3 nm. This bathochromic shift is due to a higher coordination number of the Cm(III) ion in solution, in agreement with the formation of the [Cm(nPr-BTP)3(NO3)]2+ complex. The formation of this complex exhibits slow kinetics in the range of 5 to 12 days, depending on the water content of the solvent. Formation of a complex [Cm(nPr-BTP)3(X)]2+ was not observed for anions other than nitrate (X- = NO2-, CN-, or OTf-). The formation of the [Cm(nPr-BTP)3(NO3)]2+ complex was studied as a function of NO3- and nPr-BTP concentrations, and slope analyses confirmed the addition of one nitrate anion to the [Cm(nPr-BTP)3]3+ complex. Experiments with varied nPr-BTP concentration show that [Cm(nPr-BTP)3(NO3)]2+ only forms at nPr-BTP concentrations below 10-4 mol/L whereas for concentrations greater than 10-4 mol/L the formation of the tenfold species is suppressed and [Cm(nPr-BTP)3]3+ is the only species present. The presence of the tenfold coordinated complex is supported by VSBS, XPS, and DFT calculations. The vibronic side band of the [Cm(nPr-BTP)3(NO3)]2+ complex exhibits a nitrate stretching mode not observed in the [Cm(nPr-BTP)3]3+ complex. Moreover, XPS on [M(nPr-BTP)3(NO3)](NO3)2 (M = Eu, Am) yields signals from both non-coordinated and coordinated nitrate. Finally, DFT calculations reveal that the energetically most favored structure is obtained if the nitrate is positioned on the C2 axis of the D3 symmetrical [Cm(nPr-BTP)3]3+ complex with a bond distance of 413 pm. Combining results from TRLFS, VSBS, XPS, and DFT provides sound evidence for a unique tenfold coordinated Cm(III) complex in solution-a novelty in An(III) solution chemistry.

A Complexation Study of 2,6-Bis(1-(p-tolyl)-1H-1,2,3-triazol-4-yl)pyridine Using Single-Crystal X-ray Diffraction and TRLFS.

To develop a selective ligand for the separation of lanthanides(III) and actinides(III) the coordination chemistry of the chelating N-donor ligand 2,6-bis(1-(p-tolyl)-1H-1,2,3-triazol-4-yl)pyridine (BTTP) was investigated. The two isostructural lanthanide compounds [Ln(BTTP)3(OTf)3] (Ln = Eu (1), Sm (2); OTf = trifluoromethanesulfonate) were synthesized and fully characterized. The solid-state structures of both compounds were established by single-crystal X-ray diffraction. The complexation of Cm(III) and Eu(III) with BTTP in acetonitrile was studied using time-resolved laser fluorescence spectroscopy. With increasing BTTP concentration Cm(III) 1:2 and 1:3 complexes and Eu(III) 1:1 and 1:3 complexes are identified. The conditional stability constants of the 1:3 complex species with BTTP are log ß3 = 14.0 for Cm(III) and log ß3 = 10.3 for Eu(III). Both M(III) 1:3 complexes are prone to decomplexation with increasing acidity.

NMR and TRLFS studies of Ln(iii) and An(iii) C5-BPP complexes.

C5-BPP is a highly efficient N-donor ligand for the separation of trivalent actinides, An(iii), from trivalent lanthanides, Ln(iii). The molecular origin of the selectivity of C5-BPP and many other N-donor ligands of the BTP-type is still not entirely understood. We present here the first NMR studies on C5-BPP Ln(iii) and An(iii) complexes. C5-BPP is synthesized with 10% 15N labeling and characterized by NMR and LIFDI-MS methods. 15N NMR spectroscopy gives a detailed insight into the bonding of C5-BPP with lanthanides and Am(iii) as a representative for trivalent actinide cations, revealing significant differences in 15N chemical shift for coordinating nitrogen atoms compared to Ln(iii) complexes. The temperature dependence of NMR chemical shifts observed for the Am(iii) complex indicates a weak paramagnetism. This as well as the observed large chemical shift for coordinating nitrogen atoms show that metal-ligand bonding in Am(C5-BPP)3 has a larger share of covalence than in lanthanide complexes, confirming earlier studies. The Am(C5-BPP)3 NMR sample is furthermore spiked with Cm(iii) and characterized by time-resolved laser fluorescence spectroscopy (TRLFS), yielding important information on the speciation of trace amounts of minor complex species.

6-(Tetrazol-5-yl)-2,2'-bipyridine: a highly selective ligand for the separation of lanthanides(III) and actinides(III).

The coordination structure in the solid state and solution complexation behavior of 6-(tetrazol-5-yl)-2,2'-bipyridine (HN4bipy) with samarium(III) was investigated as a model system for actinide(III)/lanthanide(III) separations. Two different solid 1:2 complexes, [Sm(N4bipy)2(OH)(H2O)2] (1) and [Sm(N4bipy)2(HCOO)(H2O)2] (2), were obtained from the reaction of samarium(III) nitrate with HN4bipy in isopropyl alcohol, resuspension in N,N-dimethylformamide (DMF), and slow crystallization. The formate anion coordinated to samarium in 2 is formed by decomposition of DMF to formic acid and dimethylamine. Time-resolved laser fluorescence spectroscopy (TRLFS) studies were performed with curium(III) and europium(III) by using HN4bipy as the ligand. Curium(III) is observed to form 1:2 and 1:3 complexes with increasing HN4bipy concentration; for europium(III), formation of 1:1 and 1:3 complexes is observed. Although the solid-state samarium complexes were confirmed as 1:2 species the 1:2 europium(III) solution complex in ethanol was not identified with TRLFS. The determined conditional stability constant for the 1:3 fully coordinated curium(III) complex species is more than 2 orders of magnitude higher than that for europium(III) (log ß3[Cm(N4bipy)3] = 13.8 and log ß3[Eu(N4bipy)3] = 11.1). The presence of added 2-bromodecanoic acid as a lipophilic anion source reduces the stability constant for formation of the 1:2 and 1:3 curium(III) complexes, but no ternary complexes were observed. The stability constants for the 1:3 metal ion-N4bipy complexes equate to a theoretical separation factor, SF(Cm(III)/Eu(III)) ≈ 500. However, the low solubility of the HN4bipy ligand in nonpolar solvents typically used in actinide-lanthanide liquid-liquid extractions prevents its use as a partitioning extractant until a more lipophilic HN4bipy-type ligand is developed.

Evidence for covalence in a N-donor complex of americium(III).

The molecular origin of the selectivity of N-donor ligands, such as alkylated bis-triazinyl pyridines (BTPs), for actinide complexation in the presence of lanthanides is still largely unclear. NMR investigations of an Am(nPrBTP)3(3+) complex with a (15)N labelled ligand showed that it exhibits large differences in (15)N chemical shift for coordinating N-atoms in comparison to both lanthanide(III) complexes and the free ligand. The temperature dependence of NMR chemical shifts observed for this complex indicates a weak paramagnetism. This fact and the observed large chemical shift for bound nitrogen atoms allow us to conclude that metal-ligand bonding in the reported Am(III) N-donor complex has a larger share of covalence than in lanthanide complexes. This may account for the observed selectivity.

A TRLFS study on the complexation of novel BTP type ligands with Cm(III).

Two BTP-type N-donor ligands with different numbers of aromatic nitrogen atoms (2,6-bis(4-ethyl-pyridazin-1-yl)pyridine, Et-BDP and 2,6-bis(4-(n)propyl-2,3,5,6-tetrazine-1-yl)pyridine, (n)Pr-Tetrazine) have been synthesized and characterized by NMR and MS techniques. The complexation with Cm(III) in 2-propanol-water (1 : 1, vol.) is studied for both ligands using time resolved laser-induced fluorescence spectroscopy (TRLFS) and the complexation properties are compared to (n)Pr-BTP. With increasing the ligand concentration three different species, the 1 : 1-, 1 : 2- and 1 : 3-complex, were found. Log ß3 values of 7.6 for the formation of Cm(Et-BDP)3 and 9.2 for the formation of Cm((n)Pr-Tetrazine)3 are determined. The complexation with (n)Pr-Tetrazine shows slow kinetics. Thermodynamic data of the complexation reactions are determined in a temperature range of 25 °C-60 °C. The complexation with Et-BDP is exothermic (ΔH = -16.3 ± 1.2 kJ mol(-1)) and exergonic (ΔG = -43.8 ± 2.6 kJ mol(-1)) whereas the complexation with (n)Pr-Tetrazine is endothermic (ΔH = 43.9 ± 3.1 kJ mol(-1)) and exergonic (ΔG = -51.7 ± 2.2 kJ mol(-1)). In the case of the latter the complexation is driven by a highly positive reaction entropy change (ΔS = 320.6 ± 15.4 J mol(-1) K(-1)). In comparison to (n)Pr-BTP, less negative ΔG values were found for the complexation of Cm(III) with both ligands.