In-situ synthesis of Pt nanoparticles/reduced graphene oxide/cellulose nanohybrid for nonenzymatic glucose sensing.

In recent years, nanocellulose-based bioinorganic nanohybrids have been exploited in numerous applications due to their unique nanostructure, excellent catalytic properties, and good biocompatibility. To the best of our knowledge, this is the first report on the simple and effective synthesis of graphene/cellulose (RGO/CNC) matrix-supported platinum nanoparticles (Pt NPs) for nonenzymatic electrochemical glucose sensing. The Pt/RGO/CNC nanohybrid presented a porous network structure, in which Pt NPs, RGO, and CNCs were integrated well. Here, cellulose nanocrystals act as a biocompatible framework for wrapped RGO and monodispersed Pt nanoparticles, effectively preventing the restacking of graphene during reduction. The superior glucose sensing performance of Pt/RGO/CNC modified glass carbon electrode (GCE) was achieved with a linear concentration range from 0.005 to 8.5 mM and a low detection limit of 2.1 µM. Moreover, the Pt/RGO/CNC/GCE showed remarkable sensitivity, selectivity, durability, and reproducibility. The obtained results indicate that the CNCs-based bioinorganic nanohybrids could be a promising electrode material in electrochemical biosensors.

Impact of Different Lignin Sources on Nitrogen-Doped Porous Carbon toward the Electrocatalytic Oxygen Reduction Reaction.

Lignin is an ideal carbon source material, and lignin-based carbon materials have been widely used in electrochemical energy storage, catalysis, and other fields. To investigate the effects of different lignin sources on the performance of electrocatalytic oxygen reduction, different lignin-based nitrogen-doped porous carbon catalysts were prepared using enzymolytic lignin (EL), alkaline lignin (AL) and dealkaline lignin (DL) as carbon sources and melamine as a nitrogen source. The surface functional groups and thermal degradation properties of the three lignin samples were characterized, and the specific surface area, pore distribution, crystal structure, defect degree, N content, and configuration of the prepared carbon-based catalysts were also analyzed. The electrocatalytic results showed that the electrocatalytic oxygen reduction performance of the three lignin-based carbon catalysts was different, and the catalytic performance of N-DLC was poor, while the electrocatalytic performance of N-ELC was similar to that of N-ALC, both of which were excellent. The half-wave potential (E1/2) of N-ELC was 0.82 V, reaching more than 95% of the catalytic performance of commercial Pt/C (E1/2 = 0.86 V) and proving that EL can be used as an excellent carbon-based electrocatalyst material, similar to AL.

Fast Pyrolysis of Cellulose and the Effect of a Catalyst on Product Distribution.

Fast pyrolysis of microcrystalline cellulose (MC) was carried out by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The effects of temperature, time, and a catalyst on the distribution of the pyrolysis products were analyzed. The reaction temperature and time can significantly affect the types and yields of compounds produced by cellulose pyrolysis. A pyrolysis temperature of 500-600 °C and pyrolysis time of 20 s optimized the yield of volatile liquid in the pyrolysis products of cellulose. In all catalytic experiments, the relative contents of alcohols (1.97%), acids (2.32%), and esters (4.52%) were highest when K2SO4 was used as a catalyst. HZSM-5 promoted the production of carbohydrates (92.35%) and hydrocarbons (2.20%), while it inhibited the production of aldehydes (0.30%) and ketones (1.80%). MCM-41 had an obvious catalytic effect on cellulose, increasing the contents of aldehydes (41.58%), ketones (24.51%), phenols (1.82%), furans (8.90%), and N-compounds (12.40%) and decreasing those of carbohydrates (5.38%) and alcohols (0%).

Effect of Evolution of Carbon Structure during Torrefaction in Woody Biomass on Thermal Degradation.

Torrefaction is an effective method for upgrading biomass. Cedar torrefaction is carried out in a fixed bed reactor at the temperature of 200-300 °C. The structural parameters are obtained from elemental analysis and 13C nuclear magnetic resonance (NMR). Thermal degradation behavior of raw and torrefied cedar is monitored by thermogravimetry analysis. The results show that carbon structure varied during torrefaction has a significant effect on thermal degradation of cedar. Some unstable oxygen functional groups, such as C1 of hemicellulose, ß-O-4 linked bonds, and amorphous C6 of cellulose, are decomposed at mild torrefaction of torrefied temperature ≤ 200 °C. The temperature of maximum weight loss rate increases from 348 °C of raw cedar to 373 °C of C-200. The amorphous cellulose is partly re-crystallized at moderate torrefaction of torrefied temperature 200-250 °C. The aromaticity of torrefied cedar increases from 0.45 of C-200 to 0.73 of C-250. The covalent bond in the side chain of aromatic rings in cedar was further broken during torrefaction at severe torrefaction of torrefied temperature 250-300 °C. The area percentage of DTG mainly signed at 387 °C of C-300. The proton aromatic carbon increases from 12.35% of C-250 to 21.69% of C-300. These results will further facilitate the utilization of biomass for replacing fossil fuel to drive carbon neutrality.

Cellulose nanocrystal driven microphase separated nanocomposites: Enhanced mechanical performance and nanostructured morphology.

The interest in the modification of cellulose nanocrystals (CNCs) lies in the potential to homogenously disperse CNCs in hydrophobic polymer matrices and to promote interfacial adhesion. In this work, poly(methyl methacrylate) (PMMA) and poly(butyl acrylate) (PBA) were grafted onto CNCs, thereby imparting their hydrophobic traits. The successful grafting modification led to the increased thermal stability of modified CNCs (MCNCs), and the hydrophobic surface modification was integrated with crystalline structure and morphology of CNCs. The nanocomposites with 7 wt% MCNCs/PBA-co-PMMA had an increase in Young's modulus of >25-fold and in tensile strength at about 3 times compared to these of neat PBA-co-PMMA copolymer. In addition, a micro-phase separated morphology (PBA soft domains, and PMMA and CNC hard domains) of MCNCs/PBA-co-PMMA nanocomposites was observed. The large increase in the storage moduli (glass transition temperatures) and organized morphology of MCNCs/PBA-co-PMMA nanocomposites also elucidated the relationship between mechanical properties and micro-phase separated morphology. Therefore, the MCNCs are effective reinforcing agents for the PBA-co-PMMA thermoplastic elastomers, opening up opportunities for their wide-spread applications in polymer composites.

Cooking with Active Oxygen and Solid Alkali: A Promising Alternative Approach for Lignocellulosic Biorefineries.

Lignocellulosic biomass, a matrix of biopolymers including cellulose, hemicellulose, and lignin, has gathered increasing attention in recent years for the production of chemicals, fuels, and materials through biorefinery processes owing to its renewability and availability. The fractionation of lignocellulose is considered to be the fundamental step to establish an economical and sustainable lignocellulosic biorefinery. In this Minireview, we summarize a newly developed oxygen delignification for lignocellulose fractionation called cooking with active oxygen and solid alkali (CAOSA), which can fractionate lignocellulose into its constituents and maintain its processable form. In the CAOSA approach, environmentally friendly chemicals are applied instead of undesirable chemicals such as strong alkalis and sulfides. Notably, the alkali recovery for this process promises to be relatively simple and does not require causticizing or sintering. These features make the CAOSA process an alternative for both lignocellulose fractionation and biomass pretreatment. The advantages and challenges of CAOSA are also discussed to provide a comprehensive perspective with respect to existing strategies.

Green Processing of Lignocellulosic Biomass and Its Derivatives in Deep Eutectic Solvents.

The scientific community has been seeking cost-competitive and green solvents with good dissolving capacity for the valorization of lignocellulosic biomass. At this point, deep eutectic solvents (DESs) are currently emerging as a new class of promising solvents that are generally liquid eutectic mixtures formed by self-association (or hydrogen-bonding interaction) of two or three components. DESs are attractive solvents for the fractionation (or pretreatment) of lignocellulose and the valorization of lignin, owing to the high solubility of lignin in DESs. DESs are also employed as effective media for the modification of cellulose to afford functionalized cellulosic materials, such as cellulose nanocrystals. More interestingly, biomassderived carbohydrates, such as fructose, can be used as one of the constituents of DESs and then dehydrated to 5-hydroxymethylfurfural in high yield. In this review, a comprehensive summary of recent contribution of DESs to the processing of lignocellulosic biomass and its derivatives is provided. Moreover, further discussion about the challenges of the application of DESs in biomass processing is presented.

Porous Carbon Nanofibers from Electrospun Biomass Tar/Polyacrylonitrile/Silver Hybrids as Antimicrobial Materials.

A novel route to fabricate low-cost porous carbon nanofibers (CNFs) using biomass tar, polyacrylonitrile (PAN), and silver nanoparticles has been demonstrated through electrospinning and subsequent stabilization and carbonization processes. The continuous electrospun nanofibers had average diameters ranging from 392 to 903 nm. The addition of biomass tar resulted in increased fiber diameters, reduced thermal stabilities, and slowed cyclization reactions of PAN in the as-spun nanofibers. After stabilization and carbonization, the resultant CNFs showed more uniformly sized and reduced average diameters (226-507 nm) compared to as-spun nanofibers. The CNFs exhibited high specific surface area (>400 m(2)/g) and microporosity, attributed to the combined effects of phase separations of the tar and PAN and thermal decompositions of tar components. These pore characteristics increased the exposures and contacts of silver nanoparticles to the bacteria including Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli, leading to excellent antimicrobial performances of as-spun nanofibers and CNFs. A new strategy is thus provided for utilizing biomass tar as a low-cost precursor to prepare functional CNFs and reduce environmental pollutions associated with direct disposal of tar as an industrial waste.