Stephen C. Chmely

Lignin depolymerisation by nickel supported layered-double hydroxide catalysts

Lignin depolymerisation is traditionally facilitated with homogeneous acid or alkaline catalysts. Given the effectiveness of homogeneous basic catalysts for lignin depolymerisation, here, heterogeneous solid-base catalysts are screened for C–O bond cleavage using a model compound that exhibits a common aryl–ether linkage in lignin. Hydrotalcite (HTC), a layered double hydroxide (LDH), is used as a support material as it readily harbours hydroxide anions in the brucite-like layers, which are hypothesised to participate in catalysis. A 5 wt% Ni/HTC catalyst is particularly effective at C–O bond cleavage of a model dimer at 270 °C without nickel reduction, yielding products from C–O bond cleavage identical to those derived from a base-catalysed mechanism. The 5% Ni-HTC catalyst is shown to depolymerise two types of biomass-derived lignin, namely Organosolv and ball-milled lignin, which produces alkyl-aromatic products. X-ray photoelectron spectroscopy and energy dispersive X-ray spectroscopy show that the nickel is well dispersed and converts to a mixed valence nickel oxide upon loading onto the HTC support. The structure of the catalyst was characterised by scanning and transmission electron microscopy and X-ray diffraction, which demonstrates partial dehydration upon reaction, concomitant with a base-catalysed mechanism employing hydroxide for C–O bond cleavage. However, the reaction does not alter the overall catalyst microstructure, and nickel does not appreciably leach from the catalyst. This study demonstrates that nickel oxide on a solid-basic support can function as an effective lignin depolymerisation catalyst without the need for external hydrogen and reduced metal, and suggests that LDHs offer a novel, active support in multifunctional catalyst applications.

Classical versus bridged allyl ligands in magnesium complexes: the role of solvent.

Magnesium allyl complexes are regularly isolated with classical, sigma-bonded ligands, and this has been thought to be their preferred mode of bonding. Density functional theory calculations confirm that such bonding is the most stable mode when coordinated bases are present, but in their absence, pi-bonded forms are expected to be lower in energy. The isolation of the unsolvated [Mg{C(3)(SiMe(3))(2)H(3)}(2)](2) complex supports this prediction, as it is a dinuclear species in which two allyl ligands bridge the metals and display cation-pi interactions with them.

Solution Interaction of Potassium and Calcium Bis(trimethylsilyl)amides; Preparation of Ca[N(SiMe3)2]2 from Dibenzylcalcium

Ca[N(SiMe(3))(2)](2) (1) is isolated in nearly quantitative yield from the room temperature reaction of Ca(CH(2)Ph)(2)(THF) and HN(SiMe(3))(2) in toluene. A commonly used preparation of 1 involving the reaction of potassium bis(trimethylsilyl)amide, K[N(SiMe(3))(2)] (2), with CaI(2) can produce material that contains substantial amounts of potassium, probably in the form of a calciate such as K[Ca{N(SiMe(3))(2)}(3)]. The favorable formation of K[Ca{N(SiMe(3))(2)}(3)] from 1 and 2 was confirmed with density functional theory calculations. Deliberate doping of solutions of 1 with 2 initially causes only an upfield shift in the single (1)H NMR resonance observed for 1; not until K/Ca ratios exceed 1:1 is the presence of the added potassium obvious by the appearance of an additional peak in the spectrum.

Lignin-coated cellulose nanocrystal filled methacrylate composites prepared via 3D stereolithography printing: Mechanical reinforcement and thermal stabilization

Various contents of lignin-coated cellulose nanocrystals (L-CNC) were incorporated into methacrylate (MA) resin and their mixture was used to prepare nanocomposites via 3D stereolithography (3D-SL) printing. Gaps were found between the L-CNC and MA matrix in 3D-SL printed nanocomposites before postcure. However, gaps decreased after postcure due to interactions between the L-CNC and MA molecules. Mechanical properties increased with the addition of 0.1% and 0.5% L-CNC after postcure, and the thermal stability was improved at 0.5% L-CNC. Dynamic mechanical analysis demonstrated that incorporation of L-CNC increased the storage modulus in the rubbery plateau. The loss factor had two transition regions, which gradually changed by merging together with increasing L-CNC content, and a broadening of the transition region was observed after postcure. In particular, the mechanical and thermal properties of 3D-SL printed nanocomposites, after postcure, exhibited higher improvement than those before postcure.

Structural Distortions in M[E(SiMe3)2]3 Complexes (M = Group 15, f-Element; E = N, CH): Is Three a Crowd?

The tris(bistrimethylsilylamido) species P[N(SiMe3)2]3 (1) and As[N(SiMe3)2]3 (2) have been prepared through halide metathesis in high yield. Their single crystal X-ray structures, along with that of Sb[N(SiMe3)2]3 (3), complete the series of structurally authenticated group 15 M[N(SiMe3)2]3 complexes (the bismuth analogue (4) has been previously reported). All four complexes possess the expected pyramidal geometries, with progressively longer M-N bond distances from P to Bi but closely similar N-M-N angles (107-104°). The structures of 1-4 also display distortions that are similar to those in f-element M[N(SiMe3)2]3 and M[CH(SiMe3)2]3 complexes, in which M···(β-Si-C) interactions have been identified. Such structural features include distorted M-(N,CH)-Si and (N,CH)-Si-C angles and close M···C and M···Si contacts. DFT calculations confirm that there are no M···(β-Si-C) interactions in 1-4; the bond distortions appear to result from the particular steric crowding that arises in pyramidal M[(N,CH)(SiMe3)2]3 complexes. This is likely the source of the most of the distortions in the structures of the f-element analogues as well, even though the latter possess attractive M···Si-C interactions.

Electrocatalytic Activity and Stability Enhancement through Preferential Deposition of Phosphide on Carbide

Phosphides and carbides are among the most promising families of materials based on earth‐abundant elements for renewable energy conversion and storage technologies such as electrochemical water splitting, batteries, and capacitors. Nickel phosphide and molybdenum carbide in particular have been extensively investigated for electrochemical water splitting. However, a composite of the two compounds has not been explored. Here, we demonstrate preferential deposition of nickel phosphide on molybdenum carbide in the presence of carbon by using a hydrothermal synthesis method. We employ the hydrogen evolution reaction in acid and base to analyze the catalytic activity of phosphide‐deposited carbide. The composite material also shows superior electrochemical stability in comparison to unsupported phosphide. We anticipate that the enhanced electrochemical activity and stability of carbide deposited with phosphide will stimulate investigations into the preparation of other carbide–phosphide composite materials.

Iron piano-stool complexes containing NHC ligands outfitted with pendent arms: synthesis, characterization, and screening for catalytic transfer hydrogenation

Two iron piano-stool complexes containing NHC ligands equipped with hydroxyl-containing pendent arms (aliphatic and aromatic) have been prepared via deprotonation of the imidazolium salts with a strong base. Access to the anionic ligand is afforded with an additional equivalent of base when the wingtip contains a bulky phenol group. X-ray crystallography and DFT calculations demonstrate an apparent delocalization of the resulting negative charge, which evidently stabilizes the complex. The strongly donating ligands affect the electronic environment at the Fe center to a degree measurable using FTIR spectroscopy. The complexes were screened for catalytic transfer hydrogenation of benzaldehyde, acetophenone and benzophenone using 2-propanol as a solvent and hydrogen donor. The molecular complexes under visible light do not show reactivity towards reduction of carbonyls. Attempts to boost catalyst turnover under in situ conditions using UV light resulted in an unwanted photo-induced pinacolization of acetophenone in both cases and decomposition of the aromatic-containing NHC complex to an iron mirror.

Structural changes in lignocellulosic biomass during activation with ionic liquids comprising 3-methylimidazolium cations and carboxylate anions

BackgroundLignocellulosic biomass requires either pretreatment and/or fractionation to recover its individual components for further use as intermediate building blocks for producing fuels, chemicals, and products. Numerous ionic liquids (ILs) have been investigated for biomass pretreatment or fractionation due to their ability to activate lignocellulosic biomass, thereby reducing biomass recalcitrance with minimal impact on its structural components. In this work, we studied and compared 1-allyl-3-methylimidazolium formate ([AMIM][HCOO]) to the commonly used 1-ethyl-3-methylimidazolium acetate ([EMIM][CH3COO]) for its potential to activate hybrid poplar biomass and enable high cellulose and hemicellulose enzymatic conversion. Although [EMIM][CH3COO] has been widely used for activation, [AMIM][HCOO] was recently identified to achieve higher biomass solubility, with an increase of 40% over [EMIM][CH3COO].ResultsSince IL activation is essentially an early stage of IL dissolution, we assessed the recalcitrance of [EMIM][CH3COO] and [AMIM][HCOO]-activated biomass through a suite of analytical tools. More specifically, Fourier transform infrared spectroscopy and X-ray diffraction showed that activation using [AMIM][HCOO] does not deacetylate hybrid poplar as readily as [EMIM][CH3COO] and preserves the crystallinity of the cellulose fraction, respectively. This was supported by scanning electron microscopy and enzymatic saccharification experiments in which [EMIM][CH3COO]-activated biomass yielded almost twice the cellulose and hemicellulose conversion as compared to [AMIM][HCOO]-activated biomass.ConclusionWe conclude that the IL [AMIM][HCOO] is better suited for biomass dissolution and direct product formation, whereas [EMIM][CH3COO] remains the better IL for biomass activation and fractionation.

Lignin-containing Photoactive Resins for 3D Printing by Stereolithography

Generating compatible and competitive materials that are environmentally sustainable and economically viable is paramount for the success of additive manufacturing using renewable materials. We report the successful application of renewable, modified lignin-containing photopolymer resins in a commercial stereolithography system. Resins were fabricated within operable ranges for viscosity and cure properties, using up to 15% modified lignin by weight. A 4-fold increase in ductility in cured parts with higher lignin concentration is noted compared to commercial stereolithography resins. Excellent print quality was seen in modified lignin resins, with good layer fusion, high surface definition, and visual clarity. These materials can be used to generate new products for additive manufacturing applications and help fill vacant material property spaces, where ductility, sustainability, and application costs are critical.

Beneficial effects of Trametes versicolor pretreatment on saccharification and lignin enrichment of organosolv-pretreated pinewood

While previous studies have shown that white-rot fungal pretreatment reduces the severity of chemical pretreatments and improves enzymatic saccharification yields, very few have investigated the synergistic effects of fungal pretreatment combined with organosolv pretreatment on lignin recovery and quality. In this study, loblolly pine chips were incubated with Trametes versicolor for 15, 30 and 45 days, prior to organosolv pretreatment and enzymatic saccharification. Fungal pretreatment for 15 days improved the saccharification yield by 23%, and higher amounts (56%) of lignin-enriched fractions were obtained. Fungal pretreatment for 45 days led to extensive depolymerization, structural modification and enrichment of lignin in the organosolv precipitates (OP). Characterization of the OP fraction showed that samples pretreated for 30 and 45 days contained higher amounts of hydroxyl groups and p-hydroxyphenyl (H) subunits, and showed increases in depolymerization of carbohydrates as well as decreases in G/H lignin ratio. It became apparent that further investigations are needed to explore the benefits of combining fungal and organosolv pretreatments for improving lignin yields from softwoods.