Biodegradable and multifunctional black mulch film decorated with darkened lignin induced by iron ions for "green" agriculture.

High-value utilization of bleached lignin has been widely used in different fields, whereas the investigation on darkened lignin in composite materials was often ignored. In this work, a sort of eco-friendly and structurally robust sodium carboxymethyl cellulose (CMC)/polyvinyl alcohol (PVA)/sodium lignosulfonate (SLS) black composite mulch film was elaborately designed. The chelation and redox reaction effect between Fe ions and SLS lead to the formation of a more quinones structure on lignin, darkening both lignin and the mulch films. The chelation effect between Fe ions and biopolymer formed three-dimensional structures, which can be used as sacrifice bonds to dissipate energy and improve the mechanical properties of the composite films. In particular, the maximum elongation at break and toughness increased from 48.4 % and 1141 kJ/m3 for the CMC/PVA film to 210.9 % and 1426 kJ/m3 for the optimized CMC/PVA/SLS/Fe black mulch film, respectively. In addition, the optimized black mulch film also possesses good soil water retention, thermal preservation effect, controlled urea release, and well biodegradability. This work offered a novel strategy for designing eco-friendly black mulch with reinforced mechanical strength, slow-release urea, soil moisture retention, and heat preservation performances.

Synergistic cobalt­copper metal-organic framework anchored amino-functionalized cellulose for antibiotic degradation: Interfacial engineering and mechanism insight.

Improving electron transfer rate of Co species and inhibiting aggregation of metal-organic frameworks (MOFs) particles are essential prerequisites for activating advanced oxidation process in wastewater treatment field. Here, we exploit Cu species with variable valence states to accelerate electron transfer of Co species and then to boost the unsatisfactory degradation efficiency for refractory pharmaceuticals via in-situ growth of copper and cobalt species on l-lysine functionalized carboxylated cellulose nanofibers. Utilizing the synergistic interplay of Co sites and deliberately exposed Cu0/Cu1+ atoms, the subtly designed catalyst exhibited a surprising degradation efficiency (~100 %) toward tetracycline hydrochloride within 10 min (corresponding to a catalytic capacity of 267.71 mg/g) without adjusting temperature and pH. Meanwhile, the catalyst displays good recyclability, well tolerance for coexisting ions and excellent antibacterial performance derived from the intrinsic antibacterial property of Cu-MOF. This research provided a novel strategy to construct MOFs-cellulose materials toward degrading various stubborn antibiotic pollutants.

Carboxymethyl cellulose-based hydrogel with high-density crack microstructures inspired from the multi-tentacles of octopus for ultrasensitive flexible sensing microsystem.

Constructing high-density contact-separation sites on conductive materials highly determines the sensitivity of flexible resistance-type sensors relying on the crack microstructures. Herein, inspired from the multiple-tentacle structures on octopus, we demonstrated a sort of novel carbonized ZIF-8@loofah (CZL) as conductive material to develop ultrasensitivity flexible sensor, in which the carbonized ZIF-8 nanoparticles (~100 nm) served as tentacles. Originating from the formation of high-density contact-separation sites, the fabricated CZL-based strain sensor delivered ultrahigh sensitivity of GFmax = 15,901, short response time of 22 ms and excellent durability over 10,000 cycles. These features enable the sensor with efficient monitoring capacity for complex human activities, such as pulse rate and phonation. Moreover, when CZL was assembled into triboelectric nanogenerator (TENG), CZL-based TENG can effectively convert the irregular biomechanical energy into electric energy, providing sustainable power supply for the continuous operation of the sensing micro-system. Our findings established a novel platform to develop high-performance self-powered sensing systems of physiological parameter of human inspired from the nature.

Constructing high-density crack-microstructures within MXene interlayers for ultrasensitive and superhydrophobic cellulosic fibers-based sensors.

Incorporating biopolymers into two-dimensional transition metal carbides and/or nitrides (2D MXene) has been demonstrated as an effective strategy to improve the mechanical behaviors of MXene-based composites. However, the insulate nature of biopolymers inevitably deteriorated the electrical conductivity and the sensitivity of assembled sensors. Herein, a novel cellulose nanofiber (CNF)/MXene/carbon black (CB) composite was demonstrated as the conductive layer in eco-friendly cellulose paper-based sensors by intercalating the CB into the MXene/CNF interlayer, followed by coating hydrophobic SiO2 for encapsulation. Befitting from the high-density crack-microstructures between CB and MXene, the fabricated superhydrophobic paper CB/CNF/MXene/SiO2 sensor delivered ultrahigh sensitivity of 729.52 kPa-1, low detect limit of 0.29 Pa, rapid response time of 80 ms and excellent stability over 10,000 cycles. Moreover, the fabricated sensor was capable of detecting the physiological parameter of human (e.g. huge/subtle movements) and spatial pressure distribution. Furthermore, the presence of SiO2 layer endowed the sensor with superhydrophobic performance (water contact angle ∼158.2 o) and stable electrical signals under high moisture conditions or even under water. Our work proposed a novel strategy to boost the sensitivity of MXene-based conductive layer in flexible electronic devices.

Bioconversion of spray corn husks into L-lactic acid with liquid hot water pretreatment.

Agricultural by-products like rice husk, bran, and spray corn husks, often utilized as feed, are considered less desirable. This study aims to enhance the utilization rate of these materials by subjecting then to liquid hot water (LHW) pretreatment, followed by enzymatic hydrolysis to produce fermentable sugars. We investigated the production of L-lactic acid using two methods: simultaneous saccharification fermentation (SSF) and separate hydrolysis fermentation (SHF), following varying intensities of LHW pretreatment. The results showed that the optimal enzymatic hydrolysis efficiency was achieved from spray corn husks under the pretreatment conditions of 155 °C and 15 min. SHF was generally more effective than SSF. The glucose L-lactic acid conversion rate in SHF using spray corn husks can reach more than 90 %. Overall, this work proposed a novel, environmental-friendly strategy for efficient and for L- lactic acid production from spray corn husks.

Porous carbon with the synergistic effect of cellulose fibers and MOFs as the anode for high-performance Li-ion batteries.

The commercial graphene for Li ion batteries (LIBs) has high cost and low capacity. Therefore, it is necessary to develop a novel carbon anode. The cellulose nanowires (CNWs), which has advantages of low cost, high carbon content, is thought as a good carbon precursor. However, direct carbonization of CNWs leads to low surface area and less mesopores due to its easy aggregation. Herein, the metal-organic frameworks (MOFs) have been explored as templates to prepare porous carbon due to their 3D open pore structures. The porous carbon was developed with the coordination effect of CNWs and MOFs. The precursor of MOFs coordinates with the -OH and - COOH groups in the CNWs to provide stable structure. And the MOFs was grown in situ on CNWs to reduce aggregation and provide higher porosity. The results show that the porous carbon has high specific capacity and fast Li+/electronic conductivity. As anode for LIBs, it displays 698 mAh g-1 and the capacity retention is 85 % after 200 cycles. When using in the full-battery system, it exhibits energy density of 480 Wh kg-1, suggesting good application value. This work provides a low-cost method to synthesize porous carbon with fast Li+/electronic conductivity for high-performance LIBs.

Bioconversion of cellulose and hemicellulose in corn cob into L-lactic acid and xylo-oligosaccharides.

With the banning of antibiotic chemical feed additives, multi-functional bioactive feed additives have been extensively sought after by the feed industry. In this study, low-cost and renewable corn cobs were treated with liquid hot water and converted into bioactive xylo-oligosaccharides and L-lactic acid after enzymatic hydrolysis, strain activation, and fermentation under mild conditions, which achieved a full utilization of cellulose and hemicellulose in corn cobs. Simultaneous saccharification fermentation after strain activation with enzymatic hydrolysate delivered the highest conversion rate of glucose to L-lactic acid (93.00 %) and yielded 17.38 g/L L-lactic acid and 2.68 g/L xylo-oligosaccharides. On this basis, batch-feeding fermentation resulted in a 78.03 % conversion rate of glucose to L-lactic acid, 18.99 g/L L-lactic acid, and 2.84 g/L xylo-oligosaccharides. This work not only provided a green and clean bioconversion strategy to produce multi-functional feed additives but can also boost the full utilization of renewable and cheap biomass resources.

Design of amphoteric MOFs-cellulose based composite for wastewater remediation: Adsorption and catalysis.

Water pollution remains a serious problem for aquatic organism and human beings. Developing an efficient material which can simultaneously remove and convert pollutants into low or no harmful compounds is an essential issue. Targeting at this goal, a multifunctional and amphoteric wastewater treatment material of Co-MOF and functionalized cellulose-based composite (CMC/SA/PEI/ZIF-67) was designed and prepared. Carboxymethyl cellulose (CMC) and sodium alginate (SA) were selected as support to construct an interpenetrating network structure and made it crosslinked with polyethyleneimine (PEI) for further in situ growth of ZIF-67 with good dispersion. The material was characterized using an appropriate set of spectroscopic and analytical techniques. When applied in the adsorption of heavy metal oxyanions with no adjustment of pH, the adsorbent could completely decontaminate Cr(VI) at both low and high initial concentrations with good reduction rates. The adsorbent maintained good reusability after five cycles. Meanwhile, the cobalt species of CMC/SA/PEI/ZIF-67 can activate peroxymonosulfate to generate high oxidizing substances (such as SO4-· and ·OH- radicals) to degrade cationic rhodamine B dye within 120 min, thus indicating the amphoteric and catalytic nature of our CMC/SA/PEI/ZIF-67 adsorbent. The mechanism of the adsorption and catalytic process was also discussed based with the assistance of different characterization analysis.

Advances in Application of Cellulose-MOF Composites in Aquatic Environmental Treatment: Remediation and Regeneration.

Metal organic frameworks (MOFs) have gained remarkable interest in water treatment due to their fascinating characteristics, such as tunable functionality, large specific surface area, customizable pore size and porosity, and good chemical and thermal stability. However, MOF particles tend to easily agglomerate in nanoscale, thus decreasing their activity and processing convenience. It is necessary to shape MOF nanocrystals into maneuverable structures. The in situ growth or ex situ incorporation of MOFs into inexpensive and abundant cellulose-family materials can be effective strategies for the stabilization of these MOF species, and therefore can make available a range of enhanced properties that expand the industrial application possibilities of cellulose and MOFs. This paper provides a review of studies on recent advances in the application of multi-dimensional MOF-cellulose composites (e.g., aerogels, membranes, and bulk materials) in wastewater remediation (e.g., metals, dyes, drugs, antibiotics, pesticides, and oils) and water regeneration by adsorption, photo- or chemocatalysis, and membrane separation strategies. The advantages brought about by combining MOFs and cellulose are described, and the performance of MOF-cellulose is described and compared to its counterparts. The mechanisms of relative MOF-cellulose materials in processing aquatic pollutants are included. Existing challenges and perspectives for future research are proposed.

Waterproof and ultrasensitive paper-based wearable strain/pressure sensor from carbon black/multilayer graphene/carboxymethyl cellulose composite.

Huge electronic wastes motivated the flourishing of biodegradable electrically conductive cellulosic paper-based functional materials as flexible wearable devices. However, the relatively low sensitivity and unstable output in combination with poor wet strength under high moisture circumstances impeded the practical application. Herein, a superhydrophobic cellulosic paper with ultrahigh sensitivity was proposed by innovatively employing ionic sodium carboxymethyl cellulose (CMC) as bridge to reinforce the interfacial interaction between carbon black (CB) and multilayer graphene (MG) and SiO2 nanoparticles as superhydrophobic layer. The resultant paper-based (PB) sensor displayed excellent strain sensing behaviors, wide working range (-1.0 %-1.0 %), ultrahigh sensitivity (gauge factor, GF = 70.2), and satisfied durability (>10,000 cycles). Moreover, the superhydrophobic surface offered well waterproof and self-cleaning properties, even stable running data without encapsulation under extremely high moisture conditions. Impressively, when the fabricated PB sensor was applied for electronic-skin (E-skin), the signal capture of spatial strain of E-skin upon bodily motion was breezily achieved. Thus, our work not only provides a new pathway for reinforcing the interfacial interaction of electrically conductive carbonaceous materials, but also promises a category of unprecedentedly superhydrophobic cellulosic paper-based strain sensors with ultra-sensitivity in human-machine interfaces field.

Ammonia and sodium sulfite synergistically pretreat reed to enhance enzymatic saccharification.

Pretreatment is important to overcome the structural recalcitrance of reed (a viable energy grass) to produce fermentable sugar. Herein, the study reported the pretreatment of reed using different alkali chemicals (sodium hydroxide/anthraquinone, sodium hydroxide/sodium sulfite, sodium hydroxide/sodium sulfide, ammonia/hydrogen peroxide, triethanolamine, and ammonia/sodium sulfite). The comparative study showed that the pretreatment using ammonia and sodium sulfite (NS) performed the best among them. The NS pretreatment of reed was further optimized using the Response Surface Methodology (RSM). The results showed that about 90.36% lignin was removed when reed was pretreated with 10 wt% of ammonia and 10% of sodium sulfite at 172 °C for 20 min. The excellent lignin removal performance was attributable to the synergistic effects between ammonia and sodium sulfite. The NS pretreated reed achieved 85.6% of enzymatic hydrolysis efficiency and 64.83% of total sugar yield.

Superhydrophobic modification of cellulosic paper-based materials: Fabrication, properties, and versatile applications.

Cellulose is the cheapest and mostly widespread green raw material on earth. Due to the easy and versatile developed modification of cellulose, many cellulosic paper-based sustainable materials and their multifunctional applications have attained increasing interest under the background of the implementation of the "plastic ban" policy. However, intrinsic cellulose paper is hydrophilic and non-water-proof, which highly limited its application, thus becoming a bottleneck for the development of "cellulosic paper-based plastic replacement". Unquestioningly, the superhydrophobic modification of cellulosic paper-based materials and the extension of their high value-added applications are highly desired, which is the main content of this review. More importantly, we presented the comprehensive discussion of the functionalized applications of superhydrophobic cellulosic paper-based materials ranging from conventional products to high value-added functional materials such as paper straw and paper mulch film for the first time, which have great industrialization potential and value. This review would offer the valuable guidance and insightful information for the rational construction of sustainable superhydrophobic cellulosic paper for advanced functional devices.

High-performance carboxymethyl cellulose-based composite film tailored by versatile zeolitic imidazolate framework.

Robust biopolymer-based composite film with multifunctional performances significantly contributes to the packaging field. Herein, we proposed a sort of carboxymethyl cellulose (CMC) based composite film via incorporating versatile zeolitic imidazolate framework (ZIF) materials. Compared to pristine CMC film, the OTR, WVTR, and tensile strength of CMC/ZIF composite film with 1 wt ‰ Zn/Co-ZIF were improved from 64.89 cm3*µm/(m2*d*kPa), 1579.21 g/(m2*24h) and 16.9 MPa to 20.79 cm3*µm/(m2*d*kPa), 1209.58 g/(m2*24h) and 70.1 MPa, respectively. Notably, owing to the reduced band gap and intrinsic chemical and thermal stability of Zn/Co-ZIF, the fabricated Zn/Co-ZIF/CMC composite film presented well UV protection capability within the whole UV region and excellent UV-blocking durability after being exposed to UV-light at 365 nm for 12 h. In practice, the photocatalytic degradation of RhB solutions under UV light could be effectively suppressed when using Zn/Co-ZIF/CMC film as UV protection layer. Our findings proposed the potential application of these versatile ZIF materials as functional nanofiller within biopolymer substances for UV protection and transparent packaging area.

Biosurfactant promoted enzymatic saccharification of alkali­pretreated reed straw.

The decrease of cellulase activity and unproductive adsorption of lignin are important obstructive factors for inefficient enzymatic hydrolysis. This paper applied five different kinds of biosurfactants including rhamnolipid, sophorolipid, chitin, tea saponin, and sodium lignosulfonate in the enzymatic hydrolysis process of alkali-pretreated reed straw (RS) to enhance the saccharification efficiency. When 8 g/L sophorolipid is added, the efficiency of enzymatic hydrolysis is 91.68 %, which is 30.65 % higher than that without using any biosurfactant. The efficiency of enzymatic hydrolysis can be further increased to 99.56 % when 7.5 g/L sophorolipid and 1.5 g/L tea saponin are added together. This is because the sophorolipid, rhamnolipid, and chitin can synergistically hamper the enzymatic inactivation during enzymatic hydrolysis, while tea saponin and sodium lignosulfonate can inhibit the non-productive adsorption of lignin. This work proposed a very effective method to improve the efficiency of enzymatic hydrolysis and reduce the dosage of the enzyme by adding biosurfactants.

High-performance carboxymethyl cellulose-based hydrogel film for food packaging and preservation system.

Most traditional food packaging and preservation films suffer from limited stretchability and relatively simple functionality, which severely restricts their practical application. In this study, a highly stretchable and versatile sodium carboxymethyl cellulose (CMC)/polyvinyl alcohol (PVA)/poly(ethylene imine) (PEI)/tannic acid (TA) hydrogel film was elaborately designed and demonstrated as an efficient food packaging and preservation system. The dynamic reversible non-covalent within three-dimensional (3D) network structures served as sacrificial bonds to dissipate the loaded energy and endowed the hydrogel film with excellent elongation ~400 %, which is much larger than that of conventional food packaging films (<50 %). Furthermore, the optimized CMC/PVA/PEI/TA3 hydrogel film delivers versatile performances, including self-healing, whole UV-blocking (<400 nm), strong adhesive strength (234.08 KPa), antioxidation virtues, oxygen barrier (32.64 cm3*µm/(m2*d*KPa)) and water vapor barrier (642.92 g/(m2*24 h)). Notably, the shelf life of fresh strawberries, mangoes, and cherries was prolonged by at least one week under ambient conditions when the packaging box was covered by the fabricated CMC/PVA/PEI/TA3 film. Thus, our work not only provides a highly stretchable and versatile hydrogel film but also boosts the in-depth comprehension and rational design of robust food packaging and preservation films.

All-biodegradable soy protein isolate/lignin composite cross-linked by oxidized sucrose as agricultural mulch films for green farming.

Microplastics produced from the discarded traditional non-degradable mulch film deteriorate the ecological environment and pose a great threat to human health. Developing eco-friendly and biodegradable materials to substitute traditional plastic mulch film highly contributed to the progress of green agriculture. Herein, a category of eco-friendly and all-biodegradable soy protein isolate (SPI)/oxidized sucrose (OS)/Lignin mulch film was innovatively proposed by employing OS as green cross-linker and lignin as nanofiller under chemical/physical interaction. The cross-linking effect and hydrogen bonds between biopolymers act as sacrificial bonds for energy dissipation and effectively reinforced the intermolecular interactions as well as tensile strength from 6.67 MPa of pristine SPI film to 8.45 MPa of SPI/OS/Lignin film. Moreover, the SPI/OS/Lignin mulch film also presented excellent UV-shielding, moisture retention, heat preservation effect and sustained urea release properties. Benefitting from the above-mentioned merits, higher germination rate of cabbage seed was achieved when the natural soil was covered by such multifunctional mulch film compared to traditional low-density PE film. Our findings paved a solid way in rational designing and fabricating eco-friendly, low-cost and all-biodegradable mulch film to facilitate the crops growth, boosting the development of green farming.

A porous carbon based on the surface and structural regulation of wasted lignin for long-cycle lithium-ion battery.

Lignin, as the second most abundant source in nature, is considered as a good precursor for hard carbon. However, direct carbonization of pure lignin leads to low surface area and porosity. Herein we develop a method to prepare lignin-based porous carbon by a self-template method assisted with surface modification. The oxygen-containing functional groups are introduced to regulate the surface chemistry of lignin. And the metal ions are chosen to coordinate with the oxygen-containing group in the lignin, which can form the carbonates to act as the self template to regulate the pores structure. The aromatic skeleton of lignin can also disperse the metal ions to bring uniform pore-forming sites. The results show that the carbonized lignin modified by chloroacetic acid (CCL) shows mesopores with surface area of 233.4384 m2 g-1. As anode for lithium-ion batteries (LIBs), the CCL shows a specific capacity of 500 mAh g-1 at 50 mA g-1. The capacity retention was 99 % after 1000 cycles at 1000 mA g-1, which are superior to most reported carbon anode. This work proposes a low-cost anode for LIBs and put forward a regulation strategy for bio-mass carbon. Besides, it would reduce the discard of lignin and alleviate the pollution.

A degradable membrane based on lignin-containing cellulose for high-energy lithium-ion batteries.

Traditional polyolefin separator has the defects of non-degradation and poor wettability with the electrolyte. In this paper, we have designed the porous membrane based on the lignin-containing cellulose nanofibers (LCNFs) from the unbleached pulp by a facile method. In the designed membrane, the amorphous lignin can effectively adjust the dispersion of the cellulose to form a uniform mesoporous structure. And the abundant oxygen-containing functional groups both in cellulose and lignin can promote the affinity of the membrane with the electrolyte. Finally, the prepared the LCNF porous membrane shows a high electrolyte uptake of 276 % and high ionic conductivity of 1.86 mS cm-1. As the separator for LIBs, the batteries with high-voltage Li3V2(PO4)3 as cathode (up to 4.8 V), the batteries displayed 183 mAh g-1 with the energy density of 669 Wh kg-1, indicating the good application potential in high-energy LIBs. More importantly, the LCNF membrane made from the unbleached pulp has low cost and it can degraded in soil only after 16 days, which can largely reduce environment pollution of the LIBs. This research provided an efficient and low-cost method to fabricate a membrane with good biodegradability and high electrochemical performance for LIBs.

High-performance cellulose acetate-based gas barrier films via tailoring reduced graphene oxide nanosheets.

Improving the gas molecule barrier performance and structural stability of bio-plastic films dramatically contribute to packaging and protective fields. Herein, we proposed a novel nanocomposite film consisting of cellulose acetate (CA)/polyethyleneimine (PEI)/reduced graphene oxide (rGO)-NiCoFeOx) with high gas barrier property by applying "molecular glue" and "nano-patching" strategies. Systematical investigations demonstrated that the CA/rGO interfacial interaction was effectively enhanced due to the "molecular glue" role of PEI chains via physical/chemical bonds and the defective regions in rGO plane were nano-patched through hydrophilic interactions between edged oxygen-containing functional groups and ultrafine NiCoFeOx nanoparticles (~3 nm). As a result, the oxygen and moisture transmission rates of the prepared CA/PEI/rGO-NPs hybrid film were significantly reduced to 0.31 cm3 ∗ µm/(m2 ∗ d ∗ kPa) and 314.23 g/m2 ∗ 24 h, respectively, which were 99.60% and 54.69% lower than pristine CA films. Meanwhile, the tensile strength of hybrid film was increased from 25.90 MPa to 40.67 MPa. More importantly, the designed nanocomposite film possesses excellent structural stability without obvious GO layer shedding and hydrophobicity attenuation after persistent bending at least 100 times. The exceptional robust and high gas barrier film displays great promising application in food, agriculture, pharmaceuticals and electronic instruments packaging industry.

A Lignin-Based Carbon Anode with Long-Cycle Stability for Li-Ion Batteries.

Due to its wide source and low cost, biomass-based hard carbon is considered a valuable anode for lithium-ion batteries (LIBs). Lignins, as the second most abundant source in nature, are being intensively studied as candidate anode materials for next generation LIBs. However, direct carbonization of pure lignin usually leads to low specific surface area and porosity. In this paper, we design a porous carbon material from natural lignin assisted by sacrificing a metal-organic framework (MOF) as the template. The MOF nanoparticles can disperse the lignin particles uniformly and form abundant mesopores in the composites to offer fast transfer channels for Li+. The as-prepared carbon anode shows a high specific capacity of 420 mAh g-1 with the capacity retention of 99% after 300 cycles at 0.2 A g-1. Additionally, it keeps the capacity retention of 85% after long cycle of 1000 cycles, indicating the good application value of the designed anode in LIBs. The work provides a renewable and low-cost candidate anode and a feasible design strategy of the anode materials for LIBs.