Reaction pathways and selectivity in the chemo-catalytic conversion of cellulose and its derivatives to ethylene glycol:A review

Biomass-to-ethylene glycol is an effective means to achieve high-value utilisation of cellulose but is hindered by low conversion efficiency and poor catalyst activity and stability.Glucose and cellobiose are derivatives of cellulose conversion to ethylene glycol,and it is found that studying the reaction process of both can help to understand the reaction mechanism of cellulose.It is desirable to develop a reusable,highly active catalyst to convert cellulose into ethylene glycol.This ideal catalyst might have one or more active sites described the conversion steps above.Here,we discuss the catalyst development of celluloseto-ethylene glycol,including tungsten,tin,lanthanide,and other transition metal catalysts,and special attention is given to the reaction mechanism and kinetics for preparing ethylene glycol from cellulose,and the economic advantages of biomass-to-ethylene glycol are briefly introduced.The insights given in this review will facilitate further development of efficient catalysts,for addressing the global energy crisis and climate change related to the use of fossil fuels.

Phosphorylated cellulose nanofibers establishing reliable ion-sieving barriers for durable lithium-sulfur batteries

The shuttle effect is among the most characteristic and formidable challenges in the pursuit of high-performance lithium-sulfur(Li-S)batteries.Herein,phosphorylated cellulose nanofibers(pCNF)are intentionally engineered to establish an ion-sieving barrier against polysulfide shuttling and thereby improve battery performance.The phosphorylation,involving the grafting of phosphate groups onto the cellulose backbone,imparts an exceptional electronegativity that repels the polysulfide anions from penetrating through the separator.Moreover,the electrolyte wettability and Li^(+)transfer can be significantly promoted by the polar nature of pCNF and the facile Li^(+)disassociation.As such,rational ion management is realized,contributing to enhanced reversibility in both sulfur and lithium electrochemistry.As a result,Li-S cells equipped with the self-standing pCNF separator demonstrate outstanding long-term cyclability with a minimum fading rate of 0.013%per cycle over 1000 cycles at 1 C,and a decent areal capacity of 5.37 mA h cm^(-2) even under elevated sulfur loading of 5.0 mg cm^(-2) and limited electrolyte of 6.0 mL g^(-1).This work provides a facile and effective pathway toward the well-tamed shuttle effect and highly durable Li-S batteries.

Recent Progress in Improving Rate Performance of Cellulose-Derived Carbon Materials for Sodium-Ion Batteries

Cellulose-derived carbon is regarded as one of the most promising candidates for high-performance anode materials in sodium-ion batteries;however,its poor rate performance at higher current density remains a challenge to achieve high power density sodium-ion batteries.The present review comprehensively elucidates the structural characteristics of cellulose-based materials and cellulose-derived carbon materials,explores the limitations in enhancing rate performance arising from ion diffusion and electronic transfer at the level of cellulose-derived carbon materials,and proposes corresponding strategies to improve rate performance targeted at various precursors of cellulose-based materials.This review also presents an update on recent progress in cellulose-based materials and cellulose-derived carbon materials,with particular focuses on their molecular,crystalline,and aggregation structures.Furthermore,the relationship between storage sodium and rate performance the carbon materials is elucidated through theoretical calculations and characterization analyses.Finally,future perspectives regarding challenges and opportunities in the research field of cellulose-derived carbon anodes are briefly highlighted.

Leaf Morphology Genes SRL1 and RENL1 Co-Regulate Cellulose Synthesis and Affect Rice Drought Tolerance

The morphological development of rice(Oryza sativa L.)leaves is closely related to plant architecture,physiological activities,and resistance.However,it is unclear whether there is a co-regulatory relationship between the morphological development of leaves and adaptation to drought environment.In this study,a drought-sensitive,roll-enhanced,and narrow-leaf mutant(renl1)was induced from a semi-rolled leaf mutant(srl1)by ethyl methane sulfonate(EMS),which was obtained from Nipponbare(NPB)through EMS.Map-based cloning and functional validation showed that RENL1 encodes a cellulose synthase,allelic to NRL1/OsCLSD4.The RENL1 mutation resulted in reduced vascular bundles,vesicular cells,cellulose,and hemicellulose contents in cell walls,diminishing the water-holding capacity of leaves.In addition,the root system of the renl1 mutant was poorly developed and its ability to scavenge reactive oxygen species(ROS)was decreased,leading to an increase in ROS after drought stress.Meanwhile,genetic results showed that RENL1 and SRL1 synergistically regulated cell wall components.Our results revealed a theoretical basis for further elucidating the molecular regulation mechanism of cellulose on rice drought tolerance,and provided a new genetic resource for enhancing the synergistic regulation network of plant type and stress resistance,thereby realizing simultaneous improvement of multiple traits in rice.

Sustainable, thermoplastic and hydrophobic coating from natural cellulose and cinnamon to fabricate eco-friendly catering packaging

Non-degradable polymers cause serious environmental pollution problem,such as the widely-used while unrecyclable coatings which significantly affect the overall degradation performance of products.It is imperative and attractive to develop biodegradable functional coatings.Herein,we proposed a novel strategy to successfully prepare biodegradable,thermoplastic and hydrophobic coatings with high transparence and biosafety by weakening the interchain interactions between cellulose chain.The natural cellulose and cinnamic acid were as raw materials.Via reducing the degree of polymerization(DP)of cellulose and regulating the degree of substitution(DS)of cinnamate moiety,the obtained cellulose cinnamate(CC)exhibited not only the thermalflow behavior but also good biodegradability,which solves the conflict between the thermoplasticity and biodegradability in cellulose-based materials.The glass transition temperature(T_(g))and thermalflow temperature(T_(f))of the CC could be adjusted in a range of 150–200℃ and 180–210℃,respectively.The CC with DS<1.2 and DP≤100 degraded more than 60%after an enzyme treatment for 7 days,and degraded more than 80%after a composting treatment for 42 days.Furthermore,CC had no toxicity to human epidermal cells even at a high concentration(0.5 mg mL^(-1)).In addition,CC could be easily fabricated into multifunctional coating with high hydrophobicity,thermal adhesion and high transparence.Therefore,after combining with cellophane and paperboard,CC coating with low DP and DS could be used to prepare fully-biodegradable heat-sealing packaging,art paper,paper cups,paper straws and food packaging boxes.

Bacterial Cellulose/Zwitterionic Dual-network Porous Gel Polymer Electrolytes with High Ionic Conductivity

Bacterial cellulose(BC)was innovatively combined with zwitterionic copolymer acrylamide and sulfobetaine methacrylic acid ester[P(AM-co-SBMA)]to build a dual-network porous structure gel polymer electrolytes(GPEs)with high ionic conductivity.The dual network structure BC/P(AM-co-SBMA)gels were formed by a simple one-step polymerization method.The results show that ionic conductivity of BC/P(AM-co-SBMA)GPEs at the room temperature are 3.2×10^(-2) S/cm@1 M H_(2)SO_(4),4.5×10^(-2) S/cm@4 M KOH,and 3.6×10^(-2) S/cm@1 M NaCl,respectively.Using active carbon(AC)as the electrodes,BC/P(AM-co-SBMA)GPEs as both separator and electrolyte matrix,and 4 M KOH as the electrolyte,a symmetric solid supercapacitors(SSC)(AC-GPE-KOH)was assembled and testified.The specific capacitance of AC electrode is 173 F/g and remains 95.0%of the initial value after 5000 cycles and 86.2%after 10,000 cycles.

A Sustainable Dual Cross‑Linked Cellulose Hydrogel Electrolyte for High‑Performance Zinc‑Metal Batteries

Aqueous rechargeable Zn-metal batteries(ARZBs)are considered one of the most promising candidates for grid-scale energy storage.However,their widespread commercial application is largely plagued by three major challenges:The uncontrollable Zn dendrites,notorious parasitic side reactions,and sluggish Zn^(2+) ion transfer.To address these issues,we design a sustainable dual crosslinked cellulose hydrogel electrolyte,which has excellent mechanical strength to inhibit dendrite formation,high Zn^(2+) ions binding capacity to suppress side reaction,and abundant porous structure to facilitate Zn^(2+) ions migration.Consequently,the Zn||Zn cell with the hydrogel electrolyte can cycle stably for more than 400 h under a high current density of 10 mA cm^(−2).Moreover,the hydrogel electrolyte also enables the Zn||polyaniline cell to achieve high-rate and long-term cycling performance(>2000 cycles at 2000 mA g^(−1)).Remarkably,the hydrogel electrolyte is easily accessible and biodegradable,making the ARZBs attractive in terms of scalability and sustainability.

Novel Sustainable Cellulose Acetate Based Biosensor for Glucose Detection

In this study,green zinc oxide(ZnO)/polypyrrole(Ppy)/cellulose acetate(CA)film has been synthesized via solvent casting.This film was used as supporting material for glucose oxidase(GOx)to sensitize a glucose biosensor.ZnO nanoparticles have been prepared via the green route using olive leaves extract as a reductant.ZnO/Ppy nanocomposite has been synthesized by a simple in-situ chemical oxidative polymerization of pyrrole(Py)monomer using ferric chloride(FeCl3)as an oxidizing agent.The produced materials and the composite films were characterized using X-ray diffraction analysis(XRD),scanning electron microscope(SEM),Fourier transform infrared(FTIR)and thermogravimetric analysis(TGA).Glucose oxidase was successfully immobilized on the surface of the prepared film and then ZnO/Ppy/CA/GOx composite was sputtered with platinum electrode for the current determination at different initial concentrations of glucose.Current measurements proved the suitability and the high sensitivity of the constructed biosensor for the detection of glucose levels in different samples.The performance of the prepared biosensor has been assessed by measuring and comparing glucose concentrations up to 800 ppm.The results affirmed the reliability of the developed biosensor towards real samples which suggests the wide-scale application of the proposed biosensor.

Unraveling the Rheology of Nanocellulose Aqueous Suspensions:A Comprehensive Study on Biomass-Derived Nanofibrillated Cellulose

The rheological properties of nanocellulose aqueous suspensions play a critical role in the development of nanocellulose-based bulk materials.High-crystalline,high-aspect ratio,and slender nanofibrillated cellulose(NFC)were extracted from four biomass resources.The cellulose nanofibrils and nanofibril bundles formed inter-connected networks in the NFC aqueous suspensions.The storage moduli of the suspensions with different concentrations were higher than their corresponding loss moduli.As the concentration increased,the storage and loss modulus of NFC dispersion increased.When the shear rate increased to a certain value,there were differences in the changing trend of the rheological behavior of NFC aqueous suspensions derived from different biomass resources and the suspensions with different solid concentrations.NFC dispersion’s storage and loss modulus increased when the temperature rose to nearly 80℃.We hope this study can deepen the understanding of the rheological properties of NFC colloids derived from different biomass resources.

Characterization and Selection of Microcrystalline Cellulose from Oil Palm Empty Fruit Bunches for Strengthening Hydrogel Films

Microcrystalline cellulose(MCC)is one of the cellulose derivatives produced as a result of the depolymerization of a part of cellulose to achieve high crystallinity.When implemented in other polymers,high crystallinity correlates with greater strength and stiffnes,but it can reduce the water-holding capacity.The acid concentration and hydrolysis time will affect the acquisition of crystallinity and water absorption capacity,both of which have significance as properties of hydrogel filler.The study aimed to evaluate the properties and select the MCC generated from varying the proportion of hydrochloric acid(HCl)and the appropriate hydrolysis time as a filler for film hydrogel.MCC was produced by hydrolyzing cellulose of oil palm empty fruit bunches(OPEFB)with the HCl solution at varied concentrations and periods.The results show that the longer hydrolysis times and higher HCl concentrations increase crystallinity and density while lowering yield and water absorption.The extensive acid hydrolysis reduces the amorphous area significantly,allowing the depolymerization to occur and extend the crystalline area.The morphological properties of the MCC,which are smaller but compact,indicate the presence of disintegrating and diminishing structures.A 2.5 N HCl concentration and a 45-min hydrolysis time succeed in sufficient crystallinity as well as maintaining good water absorption capacity.The treatment produced MCC with absorption capacity of 4.03±0.26 g/g,swelling capacity of 5.03±0.26 g/g,loss on drying of 1.44%±0.36,bulk and tapped density of 0.27±0.031 g/cm^(3) and 0.3±0.006 g/cm^(3),respectively,with a crystallinity index of 88.89%±4.76 and a crystallite size of 4.23±0.70 nm.The MCC generated could potentially be utilized as a hydrogel film filler,since a given proportion will be able to maintain the strength of the hydrogel,not readily dissolve but absorb water significantly.

Optimization of Cellulose Nanocrystal Isolation from Ayous Sawdust Using Response Surface Methodology

This study focuses on the extraction of cellulose nanocrystals (CNC), from microcrystalline cellulose (MCC), derived from Ayous sawdust. The process involves multiple steps and a large amount of chemical products. The objective of this research was to determine the effects of factors that impact the isolation process and to identify the optimal conditions for CNC isolation by using the response surface methodology. The factors that varied during the process were the quantity of MCC, the concentration of sulfuric acid, the hydrolysis time and temperature, and the ultrasonic treatment time. The response measured was the yield. The study found that with 5.80 g of microcrystalline cellulose, a sulfuric acid concentration of 63.50% (w/w), a hydrolysis time of 53 minutes, a hydrolysis temperature of 69˚C, and a sonication time of 19 minutes are the ideal conditions for isolation. The experimental yield achieved was (37.84 ± 0.99) %. The main factors influencing the process were the sulfuric acid concentration, hydrolysis time and temperature, with a significant influence (p < 0.05). Infrared characterization results showed that nanocrystals were indeed isolated. With a crystallinity of 35.23 and 79.74, respectively, for Ayous wood fiber and nanocrystalline cellulose were observed by X-ray diffraction, with the formation of type II cellulose, thermodynamically more stable than native cellulose type I.

Optimization of Methylene Blue Dye Adsorption onto Coconut Husk Cellulose Using Response Surface Methodology: Adsorption Kinetics, Isotherms and Reusability Studies

In this study, coconut husk cellulose was employed as a cost-effective and environmentally friendly adsorbent to eliminate methylene blue (MB) dye from aqueous solutions. The successful development of response surface methodology paired with a central composite design (RSM-CCD) enabled the optimization and modelling of the adsorption process. The study investigated the individual and combined effects of three variables (pH, contact time, and initial MB dye concentration) on the adsorption of MB dye onto coconut husk cellulose. The developed RSM-CCD model exhibited a remarkable degree of precision in predicting the removal efficiency of MB dye within the specified experimental parameters. This was demonstrated by the strong regression parameters, with an R2 value of 99.79% and an adjusted R2 value of 99.6%. The study depicted that the optimal parameters for attaining a 98.8827% removal of MB dye using coconut husk cellulose were as follows: an initial MB dye concentration of 30 mg∙L−1, contact time of 120 minutes, and pH 7 at a fixed adsorbent dose of 0.5 g. The Freundlich isotherm model provided the most satisfactory description of the equilibrium adsorption isotherms, suggesting that MB dye adsorption onto coconut husk cellulose occurs on a heterogeneous surface. The experimental results demonstrated a strong agreement with the pseudo-second-order kinetics model, indicating that the number of active sites present on the cellulose adsorbent predominantly influences the adsorption process of MB dye. Additionally, the adsorbent made from coconut husk cellulose exhibited the potential to be reused, as it retained its efficiency for a maximum of three cycles of adsorption of MB dye. The results of this study show that coconut husk cellulose has the potential to be an effective and sustainable adsorbent for removing MB dye from aqueous solutions.

Research Progress in Preparation of Oxidized Cellulose

Cellulose is the most abundant natural polymer material in the world.Cellulose is diffi-cult to dissolve because it contains a large number of inter molecular hydrogen bonds.Therefore,the modification of natural cellulose by chemical oxidation can expand its application field.The oxidation process of cellulose is focused on,the oxidation methods and research progress of cellulose are introduced,and further development direction of oxidized cellulose is prospected.

Research Progress of Environment Friendly Plasticizers for Cellulose Acetate Processing

Cellulose acetate(CA)is an important cellulose derivative that can undergo thermoplas-tic processing.Plasticizers can form stable hydrogen bonds with CA molecular chains,reducing intermolecular and intramolecular interactions,and play an important role in the melting processing of CA.In recent years,environmentally friendly plasticizers that are natural,non-toxic,odorless,low dissolution,and low migration have received increas-ing attention in plastic processing.This article reviews the research progress of environ-mentally friendly plasticizers such as natural plasticizers,ionic liquid plasticizers,citrate plasticizers,and polyethylene glycol plasticizers in the processing of cellulose acetate,and looks forward to the application prospects of environmentally friendly plasticizers.

The case-dependent lignin role in lignocellulose nanofibers preparation and functional application-A review

Lignocellulose nanofibers(LCNFs) as a new material is attracting extensive attention. The pretreatment and mechanical fibrillation are the two main stages involved in the preparation of LCNFs, and lignin plays the important role of these two stages. This review discussed the interaction between lignin and chemicals in the pretreatment stage, and discovered the general law of the effect of lignin in the mechanical fibrillation stage.Lignin exhibits both promotion and inhibition effects on mechanical fibrillation, and the mutual competition between the two effects ultimately affects the energy consumption, morphology and yield of LCNFs. Furthermore, the recent research progress related to the contributions of lignin on the functional application of LCNFs was summarized, aiming to provide profound guidance for the preparation and application of LCNFs.

Cellulose Nanopaper:Fabrication,Functionalization,and Applications

Cellulose nanopaper has shown great potential in diverse fields including optoelectronic devices,food packaging,biomedical application,and so forth,owing to their various advantages such as good flexibility,tunable light transmittance,high thermal stability,low thermal expansion coefficient,and superior mechanical properties.Herein,recent progress on the fabrication and applications of cellulose nanopaper is summarized and discussed based on the analyses of the latest studies.We begin with a brief introduction of the three types of nanocellulose:cellulose nanocrystals,cellulose nanofibrils and bacterial cellulose,recapitulating their differences in preparation and properties.Then,the main preparation methods of cellulose nanopaper including filtration method and casting method as well as the newly developed technology are systematically elaborated and compared.Furthermore,the advanced applications of cellulose nanopaper including energy storage,electronic devices,water treatment,and high-performance packaging materials were highlighted.Finally,the prospects and ongoing challenges of cellulose nanopaper were summarized.

Comparison of Nanofibrillated Cellulose and Hydroxyethyl Cellulose in Improving the Storage Stability of Waterborne Coatings

Waterborne coatings often delaminate and settle during long-term storage,requiring the addition of thickeners.The effects of nanofibrillated cellulose(NFC)and the commonly used thickener,hydroxyethyl cellulose(HEC),on the storage stability of waterborne coatings were compared in this study.The morphology of NFC was characterized using infrared spectroscopy(FT-IR)and scanning electron microscopy(SEM).The rotational viscosity and rheological properties of the waterborne coatings with NFC and HEC were tested.Stationary settling experiments were also conducted at different temperatures to compare the difference of NFC and HEC on improving the storage stability of the waterborne coatings.The results showed that the waterborne coating with NFC exhibited pseudoplastic fluid characteristics;a small addition of NFC can achieve the same improvement effect on the storage stability of waterborne coatings as HEC.Further,the improvement effect of NFC was not affected by temperature.The waterborne coating with NFC still exhibited good storage stability at high temperatures,which was significantly superior to that of HEC.Therefore,NFC is a feasible agent for improving the prolonged storage stability and warming-induced delamination of waterborne coatings.

Late sowing enhances lodging resistance of wheat plants by improving the biosynthesis and accumulation of lignin and cellulose

Delayed sowing mitigates lodging in wheat. However, the mechanism underlying the enhanced lodging resistance in wheat has yet to be fully elucidated. Field experiments were conducted to investigate the effects of sowing date on lignin and cellulose metabolism, stem morphological characteristics, lodging resistance, and grain yield. Seeds of Tainong 18,a winter wheat variety, were sown on October 8(normal sowing) and October 22(late sowing) during both of the 2015–2016 and 2016–2017 growing seasons. The results showed that late sowing enhanced the lodging resistance of wheat by improving the biosynthesis and accumulation of lignin and cellulose. Under late sowing, the expression levels of key genes(Ta PAL, Ta CCR, Ta COMT, TaCAD, and TaCesA1, 3, 4, 7, and 8) and enzyme activities(TaPAL and TaCAD) related to lignin and cellulose biosynthesis peaked 4–12 days earlier, and except for the TaPAL, TaCCR, and TaCesA1 genes and TaPAL, in most cases they were significantly higher than under normal sowing. As a result, lignin and cellulose accumulated quickly during the stem elongation stage. The mean and maximum accumulation rates of lignin and cellulose increased, the maximum accumulation contents of lignin and cellulose were higher, and the cellulose accumulation duration was prolonged. Consequently, the lignin/cellulose ratio and lignin content were increased from 0 day and the cellulose content was increased from 11 days after jointing onward. Our main finding is that the improved biosynthesis and accumulation of lignin and cellulose were responsible for increasing the stem-filling degree, breaking strength, and lodging resistance. The major functional genes enhancing lodging resistance in wheat that are induced by delayed sowing need to be determined.

Interconnected and high cycling stability polypyrrole supercapacitors using cellulose nanocrystals and commonly used inorganic salts as dopants

Polypyrrole(PPy)is wildly used as electrode material in supercapacitors due to its high conductivity,low cost,ease of handling,and ease of fabrication.However,limited capacitance and poor cycling stability hinder its practical application.After developing carboxylated cellulose nanocrystals(CNC-COO^(-))as immobile dopants for PPy to improve its cycling stability,we investigated the effect of different commonly used salts(KCl,NaCl,KBr,and NaClO_(4))as dopants during electrode fabrication by electropolymerization.The film’s capacitance increased from 160.6 to 183.4 F g^(-1)after adding a combination of KCl and NaClO_(4) into the electrodeposition electrolyte.More importantly,the porous and interconnected PPy/CNC-COO^(-)-Cl-(Cl O_(4)^(-))_0.5 electrode film exhibited an excellent capacitance of 125.0 F g^(-1)(0.78 F cm^(-2))at a high current density of 2.0 Ag^(-1)(20 m A cm^(-2),allowing charging in less than 1 min),increasing almost 204%over PPy/CNC-COO-films.A symmetric PPy/CNC-COO^(-)-Cl-(ClO_(4)^(-))_0.5 supercapacitor retained its full capacitance after 5000 cycles,and displayed a high energy density of 5.2 Wh kg^(-1)at a power density of 25.4 W kg^(-1)(34.5μWh cm^(-2) at 1752.3μW cm^(-2)).These results reveal that the porous structure formed by doping with CNC-COO-and inorganic salts opens up more active reaction areas to store charges in PPy-based films as the stiff and ribbon-like CNC-COO-as permanent dopants improve the strength and stability of PPy-based films.Our demonstration provides a simple and practical way to deposit PPy based supercapacitors with high capacitance,fast charging,and excellent cycling stability.

Atmosphere-free activation methodology for holey graphene/cellulose nanofiber-based film electrode with highly efficient capacitance performance

An efficient chamber-induced activation method was applied for the preparation of holey graphene/cellulose nanofiber-based film with high specific surface area(SSA)and multiple channels through the graphene nanosheets.With the cellulose nanofiber(CNF)simultaneously serving as“dispersing agent,”“spacer,”and“activating agent,”the graphene oxide(GO)nanosheets are perforated by the pyrolysis gas from CNF in the confined space inside the hybrid films,uniformly dispersed,and sandwiched between CNF networks with less agglomeration and restacking.Additionally,we have proved that H2O and H2 are primarily responsible for the activation and etching of GO/CNF film.As the CNF content increases,the mesoporosity of the activated reduced GO/CNF(A-RGO/CNF)film increases,and the graphene nanosheets show more nanopore perforations.Benefitting from the high SSA,high density,moderate mesoporosity,and abundant channels for ion diffusion through the graphene nanosheets,the A-RGO/CNF film exhibits the highest specific capacitance of 323(236)F g^(−1)(F cm^(−3))at 1Ag^(−1).For the A-RGO5/CNF5 film containing half CNF and half GO,an excellent comprehensive electrochemical performance including superior rate performance(208(160)F g^(−1)(F cm^(−3))at 60Ag^(−1))is exhibited.Moreover,the A-RGO5/CNF5 electrode in an all-solid-state flexible symmetric supercapacitor delivers a high specific capacitance of 250(193)F g^(−1)(F cm^(−3))at 1Ag^(−1).This study provides a novel idea for the preparation of holey graphene-based film for supercapacitor electrodes.The strategy of simultaneously employing CNF as“dispersing agent,”“spacer,”and“activating agent”also offers a new vision for the assembly of homogeneous nanohybrid material and the utilization of pyrolysis gas.