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In this study, we propose a complete biomass fractionation strategy where all three major biopolymers, namely, cellulose, hemicellulose, and lignin, are separated with higher efficiency and purity....

In this study, we report on the synthesis and evaluation of a sodium, magnesium, and aluminum (Na-Mg-Al) layered double hydroxide (LDH) based sorbent for hydrogen chloride (HCl) removal at concentrations found in lignocellulosic biomass derived syngas. The LDH was synthesized by a spontaneous self-assembly method and further calcined at 700 °C to produce a mixed metal oxide sorbent that we evaluated in the hot gas cleanup of hydrogen chloride at 100 parts per million. The performance of this sorbent was evaluated in a fixed bed reactor from 400 to 600 °C against that of a commercial magnesium and aluminum LDH (ComLDH) material that does not contain sodium in the matrix as well as two other commercial sorbents, sodium carbonate (Na2CO3) and sodium aluminate (NaAlO2). Our Na-Mg-Al LDH is thermally stable in the hot gas cleanup temperature range. During fixed bed experiments, our calcined LDH mixed metal oxide was effective in reducing hydrogen chloride’s concentration below the breakthrough concentration of 1 ppm from 400 to 600 °C for more than 14 h. The better performance of our calcined LDH compared to calcined commercial LDH supported our hypothesis that sodium incorporation in the LDH matrix enhances HCl sorption. Based on comparison against the commercial Na-based sorbents, the following rankings by temperature observed: LDH > NaAlO2 > Na2CO3 at 400 °C; LDH = NaAlO2 > Na2CO3 at 500 °C; and Na2CO3 = NaAlO2 = LDH at 600 °C.

The objective of this research was to investigate the presence of residual lignin in cellulose fibers on the efficiency and energy consumption during nanofibers processing. Four kinds of lignin-containing cellulose nanofibers (LCNFs) from switchgrass, yellow poplar, hybrid poplar, and pine, respectively, were isolated via organosolv fractionation coupling mechanical grinding. Nanofibrils were observed after organosolv fractionation. The details of their morphological features, chemical structures, water retention value (WRV), and thermal degradation characteristics were revealed and compared. Mean diameters of nanofibers separated from switchgrass, yellow poplar, hybrid poplar, and pine were 27.9 nm, 25.4 nm, 24.6 nm, and 21.5 nm, respectively. The presence of lignin for the four types of LCNFs led to a decrease in energy consumption and an increase in WRV, among which pine nanofibers show the best with an average energy consumption of 0.511 kWh/kg and a WRV of 537%. It was also demonstrated that increasing lignin content for LCNFs could contribute to the sample’s thermal stability. In conclusion, exact benefits of residual lignin for nanofiber will facilitate its preparation process and extend its application.

Production of nanocellulosic materials from loblolly pine (Pinus taeda) kraft pulp provides an opportunity to diversify the portfolio of traditional pulp and paper industries. In this study, pinewood was first subjected to dilute acid pre-extraction with 0.5% sulfuric acid in order to fractionate the hemicellulose, followed by kraft pulping and elemental chlorine free bleaching in order to obtain up to 97% pure cellulose fractions. CNCs (cellulose nanocrystals) were prepared by hydrolyzing the bleached kraft pulp with 64% sulfuric acid at 45 °C for 30 min; the resultant unhydrolyzed solid residues were homogenized using a microfluidizer in order to produce cellulose nanofibers (CNFs). The dilute acid pre-extraction step resulted in complete hydrolysis of galactan and arabinan from pinewood, as well as in partial removal of mannan (80%) and xylan (58%). As a result of pre-extraction, the CNC yield and crystallinity improved by 44% and 11%, respectively, from the corresponding kraft pulps. CNCs produced from the pre-extracted materials also exhibited 16% reduction in particle size, but a 70% increase in sulfur content as well as 20% increase in zeta potential. Higher purity of kraft pulps resulted in higher exposure of cellulose crystalline domains to sulfuric acid thereby resulting in the observed changes. Thus, pulp purity was found to play a significant role in determining the quantity and quality of nanocellulosic materials derived from loblolly pine.

Ionic liquids (ILs) can be used to sustainably convert lignocellulosic feedstocks into renewable bio-based materials and chemicals. To improve the prospects of commercialization, it is essential to investigate the fate of lignocellulosic biomass during IL-based processing and develop tools for designing and optimizing this “green” technology. In situ characterization during pretreatment and dissolution processes have shown that ILs reduced the inherent recalcitrance of lignocellulosic biomass via swelling of cellulose bundles and formation of fissures in the secondary cell wall layers. It subsequently enhanced the penetration of ILs into the plant cell wall leading to depolymerization and solubilization of matrix polysaccharides, mainly hemicellulose via deacetylation. Lignin also underwent dehydration or reduction reactions, depending on the IL type, with different mechanisms leading to the cleavage of inter-unit linkages. Following this process, the accessibility to cellulose microfibrils increased and induced delamination. Complementary X-ray diffraction analyses have elucidated that ILs also reduced cellulose crystallinity and altered cellulose polymorphs. High throughput in situ analyses, namely bright-field optical microscopy, nuclear magnetic resonance and Fourier transform infrared spectroscopies, have aided in monitoring the degree of swelling and chemical structural changes in lignocellulosic biomass during IL-based processing. Development of novel in situ analytical tools like IL-based gel permeation chromatography and rheometry will further shed light on molecular level changes in lignocellulose. Thus, an overall understanding of physico-chemical changes underwent by lignocellulosic biomass will help develop tools for monitoring and improving IL-based engineering of renewable materials and chemicals.

Biomass processing industries and modern society are both interested in environmentally friendly plant-based polymers, such as lignin, to replace petrochemical derivatives. In this study, an n-buta...

Huanglongbing (HLB), also known as citrus greening, is a bacterial disease that poses a devastating threat to the citrus industry worldwide. To manage this disease efficiently, we developed and characterized a ternary aqueous solution (TSOL) that contains zinc nitrate, urea, and hydrogen peroxide. We report that TSOL exhibits better antimicrobial activity than commercial bactericides for growers. X-ray fluorescence analysis demonstrates that zinc is delivered to citrus leaves, where the bacteria reside. FTIR and Raman spectroscopy, molecular dynamics simulations, and density functional theory calculations elucidate the solution structure of TSOL and reveal a water-mediated interaction between Zn2+ and H2O2, which may facilitate the generation of highly reactive hydroxyl radicals contributing to superior antimicrobial activity of TSOL. Our results not only suggest TSOL as a potent antimicrobial agent to suppress bacterial growth in HLB-infected trees, but also provide a structure-property relationship that explains the superior performance of TSOL.

Catalytic pyrolysis may serve as an alternative production strategy to petroleum-derived fuels and chemicals. Furthermore, red mud, a toxic industrial bauxite byproduct, could serve as a sustainable catalyst and overcome the need for more robust catalysts. To test this, in situ catalytic pyrolysis was run on a semi-pilot scale reactor with various ratios of red mud and switchgrass (Panicum virgatum). Authors hypothesized that the coking process would render red mud environmentally friendly, improve soil quality, and yield for bioenergy crop production, like biochar. Therefore, this work investigated red mud’s capability to enhance bio-oil quality, as well as, how the modified biochar produced from in situ pyrolysis affected switchgrass seedling vigor, and root/shoot mass. The results indicated that red mud was effective at increasing soil pH and biochar and bio-oil yields, while reducing the total acid number in bio-oil. While a high loading of reacted red mud had a negative impact on plant yield, the addition of uncatalyzed biochar to pure red mud considerably improved the seedling yield in marginal soils. These results suggest that this technology has potential for valorizing a waste stream and creating a soil amendment from red mud that closes nutrient and bioenergy production cycles while potentially reducing soil pollution.

Fast pyrolysis of pine wood was carried out to yield a liquid bio-oil mixture that was separated into organic and aqueous phases. The organic phase (ORG-bio-oil) was characterized by gas chromatography–mass spectroscopy, 31P-nuclear magnetic resonance spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. It was further used as a raw material for producing a mixture of biphenolic compounds (ORG-biphenol). ORG-bio-oil, ORG-biphenol, and bisphenol-A were reacted with cyanogen bromide to yield cyanate ester monomers. Cyanate esters were characterized using FTIR spectroscopy and were thermally cross-linked to develop thermoset materials. Thermomechanical properties of cross-linked cyanate esters were assessed using dynamic mechanical analysis and compared with those of cross-linked bisphenol-A-based cyanate ester. ORG-biphenol cyanate ester was observed to have a superior glass transition temperature (350–380°C) as compared to bisphenol-A cyanate ester (190–220°C). Cyanate esters derived from bio-oil have the potential to be a sustainable alternative to the bisphenol-A-derived analog.

The recalcitrance bottleneck of lignocellulosic materials presents a major challenge for biorefineries, including second-generation biofuel production. Because of their abundance in the northern hemisphere, softwoods, such as Norway spruce, are of major interest as a potential feedstock for biorefineries. In nature, softwoods are primarily degraded by basidiomycetous fungi causing brown rot. These fungi employ a non-enzymatic oxidative system to depolymerize wood cell wall components prior to depolymerization by a limited set of hydrolytic and oxidative enzymes. Here, it is shown that Norway spruce pretreated with two species of brown-rot fungi yielded more than 250% increase in glucose release when treated with a commercial enzyme cocktail and that there is a good correlation between mass loss and the degree of digestibility. A series of experiments was performed aimed at mimicking the brown-rot pretreatment, using a modified version of the Fenton reaction. A small increase in digestibility after pretreatment was shown where the aim was to generate reactive oxygen species within the wood cell wall matrix. Further experiments were performed to assess the possibility of performing pretreatment and saccharification in a single system, and the results indicated the need for a complete separation of oxidative pretreatment and saccharification. A more severe pretreatment was also completed, which interestingly did not yield a more digestible material. It was concluded that a biomimicking approach to pretreatment of softwoods using brown-rot fungal mechanisms is possible, but that there are additional factors of the system that need to be known and optimized before serious advances can be made to compete with already existing pretreatment methods.

Materials generated from renewable resources are promising and attractive substitutes for petroleum-based materials. Recently, regeneration of cellulose fibers using ionic liquids (ILs) as green solvents has been a topic of interest to both industrial and academic sectors. However, extraction of cellulose from lignocellulosic biomass requires numerous energy intensive processing steps. Additionally, the deconstruction and removal of lignin and hemicellulose components from lignocellulosic biomass usually involve corrosive pretreatment and the solvation of specific biomass components. Instead, utilization of the whole biomass—particularly woody residues—to manufacture high-performance materials offers an attractive value-proposition. In this study, we demonstrated fiber regeneration of whole hybrid poplar (HP) biomass by a sustainable method. We developed an environmentally friendly approach by partially auto-hydrolyzing the biomass with water before its dissolution in 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) ionic liquid, for large-scale, roll-to-roll production of fibers by solution spinning. We report, for the first time, a fundamental understanding of the inter- and intramolecular interactions in HP biomass–IL solutions, as well as their corresponding spinnability, structural reformation, and mechanical performance of the regenerated fibers. Particularly, the molecular alignment, recrystallization, and crystallinity of the spun fibers were correlated to the chain entanglement, molecular relaxation, and rheological properties of the HP biomass–IL solutions. A window of entangled concentration (4–6.5 wt%) of biomass in the IL was determined to be favorable for fiber spinning.

The water–gas shift (WGS) reaction is an attractive process for producing hydrogen gas from lignocellulosic biomass conversion applications. The goal of this study was to investigate hydrogen production via the WGS reaction using carbon monoxide (CO), one of the significant non-condensable gases formed during biomass fast pyrolysis, as reactant over the range of the intermediate-temperature shift (ITS). WGS reaction is typically carried out as a low-temperature shift (LTS;150–300 °C) or a high-temperature shift (HTS; 300–500 °C) with each shift using a different catalyst. In this study, the WGS was conducted at an intermediate temperature range (200–400 °C) relevant to lignocellulosic biomass fast pyrolysis hydrodeoxygenation over a copper (Cu) based catalyst in a CO-lean environment (70 vol% steam, 20 vol% He, and 10 vol% CO). The experimental temperatures were tested over three different weight hourly space velocities (WHSV = 1220, 2040, and 6110 cm3 g−1 min−1). CO conversion increased with increasing temperature and catalyst weight, with a maximum CO conversion of 94% achieved for temperatures greater than 300 °C. We evaluated four models including two mechanistic Langmuir–Hinshelwood (LH) models, one redox mechanistic model, and one reduced order model (ROM). The first (LH1) and second (LH2) Langmuir–Hinshelwood models differ by the intermediate formed on the catalyst surface. LH1 forms product complexes while LH2 produces a formate complex intermediate. LH2 best described our experimental kinetic data, based on statistical and regression analysis, and provided apparent activation energies between 60 and 80 kJ mol−1 at different space velocities. Furthermore, the ROM fit the experimental data well and, due to its simplicity, has potential for incorporation into computationally expensive simulations for similar experimental conditions.

Recurring outbreaks linked to Escherichia coli O157:H7-contaminated lettuce and Salmonella enterica-contaminated sprouts highlight the need for improved food safety measures. The aim of this study was to determine the ability of a bio-based antimicrobial extract prepared from switchgrass, a dedicated energy crop, to reduce E. coli O157:H7 and S. Typhimurium populations on Formica coupons, a model food-contact surface. Overnight cultures of ~7 log CFU/mL E. coli O157:H7 and S. Typhimurium, air-dried on Formica coupons were treated with 0.625% NaClO, 70% ethanol, sterile water or different batches of switchgrass extractives (SE1, SE2, and SE3) for up to 30 min. E. coli O157:H7 was reduced by 4.43 log CFU/mL after 1 min by SE3, and to non-detectable levels after 1 min by all other treatments. Populations of S. Typhimurium LT2 (15-min drying) were reduced by 3.30 log CFU/mL with 70% ethanol, 5.38 log CFU/mL with SE1, and to non-detectable levels with 0.625% NaClO after 1 min, while S. Typhimurium ATCC 23564 (1-h drying) was non-detectable after 1 min by all treatments. Under soiled conditions, 10-min treatment with SE1 and 70% ethanol reduced both bacteria to non-detectable levels. Studies with concentrated switchgrass extractives combined with various other natural disinfectants or in hurdle approaches warrant further investigation.

Development of cross-linked, soft polymeric materials from biomass has been a focus of research. The aqueous phase of biomass pyrolysis oil (bio-oil) has been used as a precursor for monomer synthe...

A statistical response surface methodology (RSM) using a central composite design (CCD) model was applied to identify the optimum thermal desorption conditions for maximum recovery of preservative from copper naphthenate (CuNap) treated wood and subsequent production of a high quality pyrolytic vapor from the thermally treated wood. From the designed experiment, 94% of the total preservative present in the ties was desorbed at temperatures higher than 250 °C and residence times longer than 30 min. Elevating the temperature from 215 °C to 285 °C for 45 min residence time generated a weight loss of 12–36 wt%, an increase in higher heating value (HHV) from 20.1 to 21.9 MJ/kg, and a reduction of energy yield from 90.4 to 71.5% of the resulting thermally treated biomass. Pyrolysis at 450 °C of this material produced a vapor rich in sugars- and lignin-derived compounds. The predicted optimum conditions in terms of a maximum preservative recovery, minimum energy yield loss of the wood, and production of thermally treated biomass that generates a high proportion of sugars- and lignin-derived compounds during pyrolysis were found to be 265 °C and 51 min. Under these optimum conditions, the predicted maximum preservative recovery was 95% while the predicted thermally treated solid retained 77% of the original energy yield and produced high portions of levoglucosan and lignin-derived compounds during subsequent pyrolysis, similar to torrefied wood.

The effects of hot water extraction on the removal of inorganic impurities (N, S, Na, K, Mg and Ca) in biomass that are detrimental to gasification were investigated on switchgrass and loblolly pine bark. As hot water extraction severity increased from 13 to 141 h °C, the extraction liquor pH decreased from 6.0 to 4.5 for switchgrass and 3.6 to 3.1 for pine bark, thus resulting in 20.7–69.6% of ash reduction for switchgrass and 57.0–73.3% for pine bark, respectively. In addition, the nitrogen content which results in ammonia (NH3) formation was reduced by 9.3–22.9% for switchgrass and 1.0–6.8% for pine bark following increment of severity. Furthermore, sulfur which leads to hydrogen sulfide (H2S) formation was reduced from 48.3 to 62.5% and 5.6 to 17.3% for switchgrass and pine bark, respectively. The range of potassium, sodium, magnesium and calcium reductions were 94.9–98.8, 47.9–72.4, 58.7–83.5 and 8.5–13.0 for switchgrass and 50.8–67.5, 29.2–60.1, 9.7–50.8 and 3.3–33.0% for pine bark. Finally, statistical analysis was carried out on the statistical significance of the extraction temperature and time as well as their interaction on the removal of inorganic impurities. The extraction temperature, time, and the interaction differed in their effect on liquor pH, ash reduction, mass loss, and reduction of individual inorganics.

Synthesizing lignin-based copolymers would valorize a major coproduct stream from pulp and paper mills and biorefineries as well as reduce the dependence on petrochemical-based consumer goods. In this study, we used organosolv lignin isolated from hybrid poplar ( Populus trichocarpa × P. deltoides) to generate lignin-containing methacrylate hydrogels. The copolymer hydrogels were synthesized by first grafting 2-hydroxyethyl methacrylate (HEMA) onto lignin (OSLH) via esterification and then by free radical polymerization of OSLH with excess HEMA. The copolymer hydrogels were prepared with different stoichiometric ratios of OSLH (e.g., 0, 10, 20, and 40 wt %) with respect to HEMA. Copolymerization with OSLH led to an increase in cross-linking density, which in turn enhanced the hydrogel's material properties; we report up to 39% improvement in water retention, 20% increase in thermostability, and up to a 3 order increase in magnitude of the storage modulus ( G'). The copolymer's properties, such as water retention and glass transition temperature, could be tuned by altering the percent functionalization of lignin OH groups and the ratio of OSLH to HEMA.

© 2017 Elsevier B.V. In this work, FeB, NiB, and FeNiB nanomaterials were examined as catalysts for catalytic transfer hydrogenolysis (CTH) using supercritical ethanol (sc-EtOH) as the hydrogen donor and reaction solvent. The earth-abundant alloys were synthesized using simple aqueous chemical reductions and characterized using ICP-OES, XRD, and STEM-EDS. Using acetophenone to model the desired catalytic reactivity, FeNiB was identified as having superior reactivity (74% conversion) and selectivity for complete deoxygenation to ethylbenzene (84%) when compared to the monometallic materials. Given its high reactivity and selectivity for deoxygenation over ring saturation, FeNiB was screened as a lignin valorization catalyst. FeNiB mediates deoxygenation of aliphatic hydroxyl and carbonyls in organosolv lignin via CTH in sc-EtOH. A combination of gel permeation chromatography, GC/MS, and NMR spectroscopy was used to demonstrate the production of a slate of monomeric phenols with intact deoxygenated aliphatic side chains. In total, these results highlight the utility of CTH for the valorization of biorefinery-relevant lignin using an inexpensive, earth-abundant catalyst material and a green solvent system that can be directly derived from the polysaccharide fraction of lignocellulosic biomass.

Lignocellulosic biomass is an alternative source of energy that can reduce our dependency on fossil fuels and limit greenhouse gas emissions. Several techno-economic analyses have consistently shown that all the steps in biomass-to-bioproduct processes needs improvement. Simultaneous assessment of genotypes for multiple productivity characteristics and integrating information across production stages has seldom been the focus of research efforts. To address this gap, we first determined the agronomic performance of 10 poplar genotypes. Differences between genotypes in height, diameter at breast height (DBH), tree mass and yield were consistently observed. Correlation analyses revealed that height and DBH are positively correlated with tree mass and yield, whereas bark content is negatively correlated with tree mass, yield and disease incidence. Four highest-yielding genotypes were subjected to proximate, ultimate, targeted chemical analyses, along with assessment of sugar production by acid hydrolysis and enzymatic saccharification. Despite having only marginal changes in overall chemistry, the genotypes showed differential conversion efficiencies of enzymatic saccharification. Interestingly, the genotype that showed highest cellulose conversion efficiency had the lowest estimated sugar yields due to its low biomass yield, whereas the genotype with lowest conversion efficiency had the highest estimated sugar yields. These results show the importance of integrating information across the stages of biomass production and bioconversion. These results also demonstrate the complexity of biomass feedstock production and the need for future studies to assess whether these tradeoffs can be genetically separated to guide the selection of genotypes that can maximize the overall biomass feedstock production efficiency.

The ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([EMIM]Acetate) has been widely used for biomass processing, i.e., to pretreat, activate, or fractionate lignocellulosic biomass to produce soluble sugars and lignin. However, this IL does not achieve high biomass solubility, therefore minimizing the efficiency of biomass processing. In this study, [EMIM]Acetate and three other ILs composed of different 3-methylimidazolium cations and carboxylate anions ([EMIM]Formate, 1-allyl-3-methylimidazolium ([AMIM]) formate, and [AMIM]Acetate) were analyzed to relate their physicochemical properties to their biomass solubility performance. While all four ILs are able to dissolve hybrid poplar under fairly mild process conditions (80 °C and 100 RPM stirring), [AMIM]Formate and [AMIM]Acetate have particularly increased biomass solubility of 40 and 32%, respectively, relative to [EMIM]Acetate. Molecular dynamics simulations suggest that strong interactions between IL and specific plant biopolymers may contribute to this enhanced solubilization, as the calculated second virial coefficients between ILs and hemicellullose are most favorable for [AMIM]Formate, matching the trend of the experimental solubility measurements. The simulations also reveal that the interactions between the ILs and hemicellulose are an important factor in determining the overall biomass solubility, whereas lignin-IL interactions were not found to vary significantly, consistent with literature. The combined experimental and simulation studies identify [AMIM]Formate as an efficient biomass solvent and explain its efficacy, suggesting a new approach to rationally select ionic liquid solvents for lignocellulosic deconstruction.

The sorption/desorption of gallic acid, a simple phenolic compound, was studied experimentally in a batch system. The motivation for this project was to provide insight into the recovery of phenolic compounds from switchgrass. Recovery of phenolic compounds could enhance the sustainability and economics of biorefining facilities. The sorption/desorption of gallic acid was shown to be qualitatively similar to that of phenolics extracted from switchgrass; so more extensive studies were made using gallic acid as a surrogate for the complex mixtures of phenolic compounds leached from switchgrass. The kinetics indicate that an approximation of equilibrium was reached within 48 h. Activated carbon was demonstrated to sorb gallic acid and phenolics from water and aqueous switchgrass leachate. The loading capacity of activated carbon for the gallic acid–water-activated carbon system increased with temperature for 20 to 60 °C. Ethanol was shown to be a preferable elution agent for desorbing gallic acid from activa...

In this study, the results from laboratory measurements of the devolatilization kinetics of switchgrass in a rapidly heated fixed bed reactor flushed with argon and operated at constant temperatures between 600 and 800°C was reported. Results indicate that switchgrass decomposes in two sequential stages during pyrolysis: stage I involves the evaporation and devolatilization of water and extractives and stage II involves that of hemicellulose, cellulose, and lignin. The estimated global activation energy for stage II increased from 52.80 to 59.39kJ/mol as the reactor temperature was increased from 600 to 800°C. The maximum conversion of carbon, hydrogen, oxygen, sulfur, and nitrogen ranged from 0.68 to 0.70, 0.90 to 0.95, 0.88 to 0.91, 0.70 to 0.80, and 0.55 to 0.66, respectively. The retention of alkali and alkaline earth metal (AAEM) species in the solid char after complete pyrolysis was significantly higher than in the original feed, indicating the importance of AAEM species in subsequent char processing.

A two-step thermochemical process combining a thermal desorption at 250–300 °C and a pyrolysis at 500 °C of used creosote-treated wooden railroad ties was carried out to recover preservative and produce a high quality bio-oil and biochar. Under optimal temperature between 280 and 300 °C, high preservative removal efficiency (70–74%) was achieved with a high proportion of polycyclic aromatic hydrocarbons (PAHs, 80–82%) and a large portion of the original wood mass (67–70%) was retained. This thermally treated biomass had higher heating value (HHV; 19.9–20 MJ/kg) than the starting material. The physical properties of the preservative, such as viscosity and density, and its toxic threshold against a common decay basidiomycete fungus were similar to those of commercially available P2-creosote. Pyrolysis of the thermally treated ties produced bio-oils with lower water content and total acid numbers, and a higher amount of lignin-derived compounds than that of untreated ties. Biochars derived from the thermally...

Reforming whole lignocellulosic biomass into value-added materials has yet to be achieved mainly due to the infusible nature of biomass and its recalcitrance to dissolve in common organic solvents. Recently, the solubility of biomass in ionic liquids (ILs) has been explored to develop all-lignocellulosic materials; however, efficient dissolution and therefore production of value-added materials with desired mechanical properties remain a challenge. This article presents an approach to producing high-performance lignocellulosic films from hybrid poplar wood. An autohydrolysis step that removes ≤50% of the hemicellulose fraction is performed to enhance biomass solvation in 1-ethyl-3-methyl imidazolium acetate ([C2mim][OAc]). The resulting biomass–IL solution is then cast into free-standing films using different coagulating solvents, yet preserving the polymeric nature of the biomass constituents. Methanol coagulated films exhibit a cocontinuous 3D-network structure with dispersed domains of less than 100 nm...

© 2017 American Chemical Society. We have prepared composite materials of hexagonal nickel phosphide and molybdenum carbide (Mo2C) utilizing a simple and scalable two-stage synthesis method composed of carbothermic reduction followed by hydrothermal incubation. We observe the monophasic hexagonal phosphide Ni2P in the composite at low phosphide-to-carbide (P:C) ratios. Upon an increase in the proportion of P:C, the carbide surface becomes saturated, and we detect the emergence of a second hexagonal nickel phosphide phase (Ni5P4) upon annealing. We demonstrate that vapor-phase upgrading (VPU) of whole biomass via catalytic fast pyrolysis is achievable using the composite material as a catalyst, and we monitor the resulting product slates using pyrolysis-gas chromatography/mass spectrometry. Our analysis of the product vapors indicates that variation of the P:C molar ratio in the composite material affords product slates of varying complexity and composition, which is indicated by the number of products and their relative proportions in the product slate. Our results demonstrate that targeted vapor product composition can be obtained, which can potentially be utilized for tuning of the composition of the bio-oil downstream.