Nanoporous Carbon Materials Derived from Zanthoxylum Bungeanum Peel and Seed for Electrochemical Supercapacitors.

In order to prepare biomass-derived carbon materials with high specific capacitance at a low activation temperature (≤700 °C), nanoporous carbon materials were prepared from zanthoxylum bungeanum peels and seeds via the pyrolysis and KOH-activation processes. The results show that the optimal activation temperatures are 700 °C and 600 °C for peels and seeds. Benefiting from the hierarchical pore structure (micropores, mesopores, and macropores), the abundant heteroatoms (N, S, and O) containing functional groups, and plentiful electrochemical active sites, the PAC-700 and SAC-600 derive the large capacities of ~211.0 and ~219.7 F g-1 at 1.0 A g-1 in 6 M KOH within the three-electrode configuration. Furthermore, the symmetrical supercapacitors display a high energy density of 22.9 and 22.4 Wh kg-1 at 7500 W kg-1 assembled with PAC-700 and SAC-600, along with exceptional capacitance retention of 99.1% and 93.4% over 10,000 cycles at 1.0 A g-1. More significantly, the contribution here will stimulate the extensive development of low-temperature activation processes and nanoporous carbon materials for electrochemical energy storage and beyond.

Transparent Cellulose/Multi-Walled Carbon Nanotube Hybrids with Improved Ultraviolet-Shielding Properties Prepared from Cotton Textile Waste.

Plastics offer many advantages and are widely used in various fields. Nevertheless, most plastics derived from petroleum are slow to degrade due to their stable polymer structure, posing serious threats to organisms and ecosystems. Thus, developing environmentally friendly and biodegradable plastics is imperative. In this study, biodegradable cellulose/multi-walled carbon nanotube (MCNT) hybrid gels and films with improved ultraviolet-shielding properties were successfully prepared using cotton textile waste as a resource. It was proven that MCNTs can be dispersed evenly in cellulose without any chemical or physical pretreatment. It was found that the contents of MCNTs had obvious effects on the structures and properties of hybrid films. Particularly, the averaged transmittance of cellulose/MCNT composite films in the range of 320-400 nm (T320-400) and 290-320 nm (T290-320) can be as low as 19.91% and 16.09%, when the content of MCNTs was 4.0%, much lower than those of pure cellulose films (T320-400: 84.12% and T290-320: 80.03%). Meanwhile, the water contact angles of the cellulose/MCNT films were increased by increasing the content of MCNTs. Most importantly, the mechanical performance of cellulose/MCNT films could be controlled by the additives of glycerol and MCNTs. The tensile strength of the cellulose/MCNT films was able to reach as high as 20.58 MPa, while the elongation at break was about 31.35%. To summarize, transparent cellulose/MCNT composites with enhanced ultraviolet-shielding properties can be manufactured successfully from low-cost cotton textile waste, which is beneficial not only in terms of environmental protection, but also the utilization of natural resources.

Cellulose/Grape-Seed-Extract Composite Films with High Transparency and Ultraviolet Shielding Performance Fabricated from Old Cotton Textiles.

Plastics displaying many merits have been indispensable in daily life and they still maintain the strong momentum of development. Nevertheless, petroleum-based plastics possess a stable polymer structure and most of them are incinerated or accumulated in the environment, leading to devastating impacts on our ecology system. Thus, exploiting renewable and biodegradable materials to substitute or replace these traditional petroleum-derived plastics is an urgent and important task. In this work, renewable and biodegradable all-biomass cellulose/grape-seed-extract (GSEs) composite films with high transparency and anti-ultraviolet performance were fabricated successfully from pretreated old cotton textiles (P-OCTs) using a relatively simple, green, yet cost-effective, approach. It is proved that the obtained cellulose/GSEs composite films exhibit good ultraviolet shielding performance without sacrificing their transparency, and their UV-A and UV-B blocking values can reach as high as nearly 100%, indicating the good UV-blocking performance of GSEs. Meanwhile, the cellulose/GSEs film show higher thermal stability and water vapor transmission rate (WVTR) than most common plastics. Moreover, the mechanical property of the cellulose/GSEs film can be adjusted by the addition of a plasticizer. Briefly, the transparent all-biomass cellulose/grape-seed-extracts composite films with high anti-ultraviolet capacity were manufactured successfully and they can be used as potential materials in the packaging field.

Transparent cellulose-based bio-hybrid films with enhanced anti-ultraviolet, antioxidant and antibacterial performance.

Developing the biodegradable and eco-friendly materials to substitute for the traditional petroleum-derived plastics is significant, and cellulose is the most promising candidate to replace petroleum-derived plastics. However, the high-cost dissolving pulps are still the major raw materials in industry. Moreover, the traditional cellulose materials lack functions, limiting their application and service life. Herein, multi-functional cellulose/tea polyphenols (TPs) bio-hybrid films were fabricated successfully via employing low-cost waste cotton textiles as cellulose source. It was found that the cellulose/TPs films displayed high anti-ultraviolet capacity and irradiation stability without sacrificing their transparency, and UV-A and UV-B blocking values can reach 85.08 % and 99.97 %. Besides, cellulose/TPs films show up to 63 % of radical scavenging activity and possess obvious antibacterial capacity, due to the copious phenolic hydroxyls within TPs. Hence, the cellulose/TPs bio-hybrid films with enhanced anti-ultraviolet, antioxidant and antibacterial performance were manufactured successfully, which demonstrated great potentials in packaging fields.

2D Zinc-Based Metal-Organic Complexes Derived N-Doped Porous Carbon Nanosheets as Durable Air Cathode for Rechargeable Zn-Air Batteries.

The defect and N-doping engineering are critical to developing the highly efficient metal-free electrocatalysts for oxygen reduction reaction (ORR), mainly because they can efficiently regulate the geometric/electronic structures and sur-/interface properties of the carbon matrix. Herein, we provide a facile and scalable strategy for the large-scale synthesis of N-doped porous carbon nanosheets (NPCNs) with hierarchical pore structure, only involving solvothermal and pyrolysis processes. Additionally, the turnover frequency of ORR (TOFORR) was calculated by taking into account the electron-transfer number (n). Benefiting from the trimodal pore structures, high specific surface area, a higher pore volume, high-ratio mesopores, massive vacancies/long-range structural defects, and high-content pyridinic-N (~2.1%), the NPCNs-1000 shows an excellent ORR activity (1600 rpm, js = ~5.99 mA cm-2), a selectivity to four-electron ORR (~100%) and a superior stability in both the three-electrode tests (CP test for 7500 s at 0.8 V, Δjs = ~0.58 mA cm-2) and Zn-Air battery (a negligible loss of 0.08 V within 265 h). Besides, the experimental results indicate that the enhancement of ORR activity mainly originates from the defects and pyridinic-N. More significantly, this work is expected to realize green and efficient energy storage and conversion along with the carbon peaking and carbon neutrality goals.

Eco-Friendly and Complete Recycling of Waste Bamboo-Based Disposable Paper Cups for Value-Added Transparent Cellulose-Based Films and Paper Plastic Composites.

Disposable paper cups are widely used in daily life and most of them are landfilled or incinerated after use, resulting in a serious ecological hazard and significant waste of resources due to the usage of thin polyethylene (PE) as their inner coating. Hence, converting these common solid domestic wastes into high-value added materials is attractive and meaningful. In this study, transparent cellulose-based films were achieved from old bamboo-based disposable paper cups after pretreatment through using the room ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as solvent. The cellulose-based film with a dense texture demonstrated a relatively nice mechanical and UV-shielding performances, and its tensile strength was as high as 48 MPa, much higher than that of commercial polyethylene (PE, 12 MPa) film. Thus, the resultant cellulose-based film showed a great potential in the packaging field. Besides, the flexible paper plastic composites (PPC) were also fabricated from the rest thin PE coating with the stuck fibers, and it was found that PPC showed excellent mechanical property and hydrophobicity. Consequently, a feasible and eco-friendly process of recycling and reusing waste disposable paper cups was developed to achieve a complete utilization and valorization of waste disposable paper cups.

Fabrication and Characterization of Transparent and Uniform Cellulose/Polyethylene Composite Films from Used Disposable Paper Cups by the "One-Pot Method".

Disposable paper cups are usually composed of high-grade paper board and an inner polyethylene coatings and are extensively used in daily life. However, most disposable paper cups are only used for a short time and then incinerated or accumulated in landfill at the end of their service due to the difficulty in separating the components, leading to a serious threat to our ecosystem. Therefore, developing a facile and green method to recycle and reuse disposable paper cups is vital. By using ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as a solvent, transparent and homogenous cellulose/polyethylene composite films were successfully prepared from used bamboo-based disposable paper cups through the "one-pot method", without any pre-treatment. It was found that there was a transformation of cellulose I to II after the dissolution and regeneration processes, and the crystallinity degree of the regenerated cellulose-based materials decreased significantly, resulting in a change in thermal properties. Meanwhile, compared to traditional pure cellulose films, the composite films possessed good UV-shielding properties and hydrophobicity. Moreover, they also displayed good mechanical properties. Additionally, the size of the ground PE coatings displayed obvious effects on the structures and properties of the composite films, where the CPE100 (sieved with 100-200 mesh) possessed the most homogeneous texture and the highest tensile strength (82 Mpa), higher than that of commercial polyethylene film (9-12 MPa), showing superiority as packaging or wrapping materials. Consequently, the goals to fabricate uniform cellulose/polyethylene composite films and valorize the solid waste from disposable paper cups were simultaneously achieved by a facile and green "one-pot method".

Transparent Cellulose-Based Films Prepared from Used Disposable Paper Cups via an Ionic Liquid.

Paper cups are widely employed in daily life with many advantages, but most of the used paper cups are incinerated or landfilled, due to the great challenge of separating the thin inner polyethylene (PE) coating, causing the waste of energy and the pollution of our environment. Therefore, recycling and converting the used paper cups into high-value materials is meaningful and important. In this work, transparent cellulose-based films were successfully prepared from the used paper cups via 1-allyl-3-methylimidazolium chloride ionic liquid after simple pretreatment. Additionally, the difference in properties and structures of cellulose-based films regenerated in different coagulation baths (water or ethanol) was also explored. It was found that the cellulose-based film possessed good thermal property and displayed better hydrophobicity than the traditional pure cellulose film. Moreover, they also demonstrated good mechanical property and the tensile strength of cellulose-based film regenerated in water can reach 31.5 Mpa, higher than those of cellulose-based film regenerated in ethanol (25.5 Mpa) and non-degradable polyethylene film (9-12 MPa), indicating their great potential as the packaging materials. Consequently, valorization of the low cost used paper cups and preparation of high-valve cellulose-based films were realized simultaneously by a facile and green process.

Cellulose-Based Films with Ultraviolet Shielding Performance Prepared Directly from Waste Corrugated Pulp.

As the most important paper packaging materials, corrugated cartons with a tremendous amount of production demonstrate several advantages and have been widely used in daily life. However, waste corrugated cartons (WCCs) are usually recycled and reused to produce new corrugated cartons, and their properties are decreased dramatically after several cycles. Therefore, recycling and converting WCCs into cellulose-based film with high value is attractive and significant. Herein, without any pretreatment, the waste old corrugated cartons were directly dissolved in ionic liquid 1-allyl-3-methylimidazolium chloride, and semitransparent cellulose-based films were successfully fabricated. It was indicated that cellulose-based films displayed better UV-shielding property and hydrophobicity than traditional cellulose films. Interestingly, the cellulose-based films regenerated from deionized water displayed higher tensile strength, elongation at break, and toughness. Their tensile strength could reach 23.16 MPa, exhibiting enormous superiority as wrapping and packaging materials to replace the petrochemical polyethylene membrane (8.95 MPa). Consequently, these renewable, biodegradable, and high-valued cellulose-based films were successfully fabricated to simultaneously realize the valorization of old corrugated cartons and supplement the petrochemical plastics.

Transparent cellulose/aramid nanofibers films with improved mechanical and ultraviolet shielding performance from waste cotton textiles by in-situ fabrication.

Cellulose films with biodegradability and intrinsically antistatic property have many applications. However, conventional cellulose films show poor toughness and UV-shielding property, and the major sources are high-grade cotton linter or wood pulp. Herein, by using low-cost waste cotton textiles as the raw materials, we successfully fabricated transparent cellulose/aramid nanofibers (ANFs) films, in which in-situ retained ANFs had a diameter of 20-30 nm and a length of several micrometers. Because ANFs and cellulose chains formed strong hydrogen bonding interactions, the tensile strength and elongation of the resultant cellulose/ANFs film with 1.0 wt% ANFs could reach 54.4 MPa and 15.8%, respectively, increased by 63.4% and 154% compared to those of pure cellulose film (33.3 MPa and 6.2%). Meanwhile, the cellulose/ANFs films show excellent UV-shielding properties and irradiation stability. Hence, the novel cellulose/ANFs films with improved mechanical and UV-shielding performance were in-situ prepared leading to enhance the valorization of waste cotton textiles.

Facile and green fabrication of cellulosed based aerogels for lampblack filtration from waste newspaper.

In this study, the lightweight, hydrophobic and porous cellulose-based aerogels (CAGs) were synthesized through a freeze-drying process using waste newspaper as the only raw material. After crosslinking with glutaraldehyde and treatment with trimethylchlorosilane (TMCS) using a simple thermal chemical vapor deposition process, the resulting CAGs became hydrophobic and oleophilic. Furthermore, the as-prepared CAGs exhibited a low density (17.4-28.7mgcm-3) and mesoporous inner-structure. All these properties attributed the novel aerogel not only with a good adsorption capability of oils and organic solvents, including kerosene, nitrobenzene, and chloroform, but also an excellent filtration capacity of lampblack.

Cellulose-based films prepared directly from waste newspapers via an ionic liquid.

Waste newspapers, composed of cellulose (>60wt%), lignin (∼15wt%), hemicellulose (∼10wt%) and other additives, are one kind of low-cost, easily collected and abundant resources. In order to get value-added products from this waste, in this work an attempt was made to directly convert waste newspapers into cellulose-based films by employing an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as a solvent. Most of the organic substances in this waste were dissolved quickly in AmimCl under mild conditions, and then coagulated and dried. Although containing lignin, hemicellulose and inorganic additives, the regenerated cellulose-based films were smooth, compact and semi-transparent, and exhibited good mechanical properties. If the newspaper/AmimCl solution was filtered to remove undissolved inorganic substances, the regenerated films became transparent and had a tensile strength of 80MPa. Thus, this work provides a new, simple and highly efficient way to achieve a high-valued utilization of waste newspapers for packaging and wrapping.

Enhanced electroactive and mechanical properties of poly(vinylidene fluoride) by controlling crystallization and interfacial interactions with low loading polydopamine coated BaTiO3.

Poly(vinylidene fluoride) (PVDF) is a semi-crystalline polymer and the polar ß-phase of PVDF shows superb electroactive properties. In order to enhance the ß-phase of PVDF, extreme low content of BaTiO3 nanoparticles (BT-NPs) coated with polydopamine (Pdop) were incorporated into PVDF matrix by solution casting. The ß-phase of the resulting PVDF nanocomposites film was dramatically increased and the d33 value reached 34.3±0.4 pCN(-1). It is found that the Pdop layer could improve the dispersibility and stability of the BT NPs in solution and endow the BT NPs good dispersity in the PVDF matrix. Moreover, the interfacial interaction between PVDF chains and the surface of BT-Pdop nanoparticles (BT-Pdop NPs) were revealed, in which the CF2 groups on PVDF could interact with the electron-rich plane of aromatic ring of Pdop moiety. This interaction, led to the increase of the crystallization activation energy as derived from the DSC nonisothermal crystallization measurement. The α-ß crystal transformation, organization of interfacial interactions as well as the prevention of agglomeration of BT-NPs confer the improvement of mechanical and thermal properties of PVDF, such as toughness, tensile strength, elongation at break, and thermal conductivity.

Semi-crystalline polymethylene-b-poly(acrylic acid) diblock copolymers: aggregation behavior, confined crystallization and controlled growth of semicrystalline micelles from dilute DMF solution.

In this paper, we have systematically investigated the aggregation behavior, confined crystallization and controlled growth of a novel polyolefin analogue-containing block copolymers (BCPs), i.e., polymethylene-b-poly(acrylic acid) diblock copolymers (PM-b-PAA). On cooling from a homogenous DMF solution at 80 °C, PM-b-PAA was found to crystallize and aggregate with well-defined disk-like micelles. The aggregate behavior and in-plane morphology of PM-b-PAA could be easily controlled by modifying the block ratio, solution pH and solvent composition (DMF-water), by manipulating the crystallization of PM block and the stretching degree of solvated PAA corona. Further investigation of the crystalline feature of PM-b-PAA indicated that the crystallization of PM was retarded by tethered amorphous PAA segments. The crystalline micelle could construct a nano-confined environment with PM folding as the core into a thickness of the mono-layered polyethylene. Finally, when cultured in dilute DMF solution at 50 °C, the initial crystalline micelles, being as self-seeds, could follow a living growth mechanism and develop into single crystals, with well-defined lozenge-shaped morphology.

Porous chitosan doped with graphene oxide as highly effective adsorbent for methyl orange and amido black 10B.

In the current study, porous chitosan aerogels doped with small amount of graphene oxide (CSGO aerogels) with high porosity (97.96-98.78%), extraordinarily high water absorption (5848-8917%) and low density (0.021-0.035 g cm(-3)) were prepared and used as adsorbents for two azo dyes methyl orange (MO) and amido black 10B (AB10B). The adsorption behavior of these CSGO aerogels and some influence factors such as pH value, graphene oxide (GO) loading, concentration of pollutants, as well as adsorption kinetics were studied. Specifically, the adsorption capacity for MO is 686.89 mg g(-1), the highest comparing with other publication results, and it is 573.47 mg g(-1) for AB10B. Since they are biodegradable, non-toxic, efficient, low-cost and easy to prepare, we believe that these porous CSGO aerogels will be a promising candidate for dye removal.

Microporous spongy chitosan monoliths doped with graphene oxide as highly effective adsorbent for methyl orange and copper nitrate (Cu(NO3)2) ions.

In the current study, microporous spongy chitosan monoliths doped with small amount of graphene oxide (CSGO monoliths) with high porosity (96-98%), extraordinary high water absorption (more than 2000%) and low density (0.0436-0.0607 g cm(-3)) were prepared by the freeze-drying method and used as adsorbents for anionic dyes methyl orange (MO) and Cu(2+) ions. The adsorption behavior of the CSGO monoliths and influencing factors such as pH value, graphene oxide (GO) content, concentration of pollutants as well as adsorption kinetics were studied. Specifically, the saturated adsorption capacity for MO is 567.07 mg g(-1), the highest comparing with other publication results, and it is 53.69 mg g(-1) for Cu(2+) ions. Since they are biodegradable, non-toxic, efficient, low-cost and easy to prepare, we believe that these microporous spongy CSGO monoliths will be the promising candidates for water purification.

Modification of polymorphisms in polyvinylidene fluoride thin films via water and hydrated salt.

In this study, the effects of solvent and magnesium chloride hexahydrate (MgCl2·6H2O) on the polymorphism of polyvinylidene fluoride (PVDF) thin films were systematically investigated. Wherein, N,N-dimethylformamide (DMF) and water with different volume ratio were used as mixed solvents to obtain the solution casting films, P series. In addition, MgCl2·6H2O was comparatively added to prepare PVDF/MgCl2·6H2O hybrid films, P-M series. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and differential scanning calorimeter (DSC) were utilized to study the influence of the water content in the mixed solvents and the hydrated salt on crystallization behavior of PVDF. Further, the morphologic images from scanning electronic microscopy (SEM) and polarized optical microscopy (POM), as well as the pizoelectirc d33 test also supplies the corresponding evidences. As indicated, the water in the mixed solvent shows different effect on main crystal forms of PVDF. At low water content, the solvents may favor the polar phase (ß- and γ-phase) mainly by hydrogen bonds interactions between PVDF and water, together with dipolar interactions between PVDF and DMF. At high water content, the nonsolvent water will impose confinement effect on polymer chain diffusion and crystal growth which facilitate the formation of α-phase PVDF. Moreover, magnesium chloride hexahydrate mainly functioned as the nucleation sites for PVDF crystallization. The result of small-angle X-ray scattering (SAXS) implies the content of water or MgCl2·6H2O has little impact on the structure of the long period.

Unzipped multiwalled carbon nanotubes-incorporated poly(vinylidene fluoride) nanocomposites with enhanced interface and piezoelectric ß phase.

An improved method is described for the fabrication of poly(vinylidene fluoride) (PVDF)/carbon nanotubes (CNTs) hybrid materials to solve intrinsic limitation of CNTs. In this study, multiwalled carbon nanotubes (MWCNTs) were unzipped by an oxidative unzipping process before dispersing in PVDF matrix, and unzipped MWCNTs (µCNTs) with different unzipping degrees were obtained through controlling the amounts of oxidant (KMnO(4)). Due to the increased available interface area and specific interaction between the oxygen-containing groups (such as >C=O) in µCNTs and the >CF(2) group of PVDF, the dispersion of µCNTs in PVDF matrix is tremendously improved. The resulting PVDF/µCNTs nanocomposites were characterized by wide angle X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, scanning electron microscopy, and transmission electron microscopy. It is found that µCNTs nucleate PVDF crystallization and enhance piezoelectric ß phase with a concomitant decrease of α phase. This is particularly true for the nanocomposites including the µCNTs with higher unzipping degree, in which the mass crystallinity and content of ß phase (F(ß)) were enhanced, implied by the increased piezoelectric constant d(33). In addition, the increased storage modulus (E') tested by dynamic mechanical analysis confirmed that µCNTs were more effective than pristine MWNTs in terms of reinforcing polymers.