Multiporous ZIF-8 carbon/cellulose composite beads: Highly efficient and scalable adsorbents for water treatment.

Metal-organic framework (MOF) particles are one of the most promising adsorbents for removing organic contaminants from wastewater. However, powder-type MOF particles face challenges in terms of utilization and recovery. In this study, a novel bead-type adsorbent was prepared using activated carbon based on the zeolitic imidazolate framework-8 (AC-ZIF-8) and a regenerated cellulose hydrogel for dye removal. AC-ZIF-8 particles with a large surface area were obtained by carbonization and chemical activation with KOH. The AC-ZIF-8 powders were efficiently immobilized in hydrophilic cellulose hydrogel beads via cellulose dissolution/regeneration. The prepared AC-ZIF-8/cellulose hydrogel (AC-ZIF-8/CH) composite beads exhibit a large specific surface area of 1412.8 m2/g and an excellent maximum adsorption capacity of 565.13 mg/g for Rhodamine B (RhB). Moreover, the AC-ZIF-8/CH beads were effective over a wide range of pH, temperatures and for different types of dyes. These composite beads also offer economic benefits through desorption of dyes for recycling. The AC-ZIF-8/CH beads can be produced in substantial amounts and used as fillers in a fixed-bed column system, which can purify the continuous inflow of dye solutions. These findings suggest that our simple approach for preparing high-performance adsorbent beads will broaden the application of dye adsorbents, oil-water separation, and catalysts.

Multiscale Porous Carbon Materials by In Situ Growth of Metal-Organic Framework in the Micro-Channel of Delignified Wood for High-Performance Water Purification.

Porous carbon materials are suitable as highly efficient adsorbents for the treatment of organic pollutants in wastewater. In this study, we developed multiscale porous and heteroatom (O, N)-doped activated carbon aerogels (CAs) based on mesoporous zeolitic imidazolate framework-8 (ZIF-8) nanocrystals and wood using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) oxidation, in situ synthesis, and carbonization/activation. The surface carboxyl groups in a TEMPO-oxidized wood (TW) can provide considerably large nucleation sites for ZIF-8. Consequently, ZIF-8, with excellent porosity, was successfully loaded into the TW via in situ growth to enhance the specific surface area and enable heteroatom doping. Thereafter, the ZIF-8-loaded TW was subjected to a direct carbonization/activation process, and the obtained activated CA, denoted as ZIF-8/TW-CA, exhibited a highly interconnected porous structure containing multiscale (micro, meso, and macro) pores. Additionally, the resultant ZIF-8/TW-CA exhibited a low density, high specific surface area, and excellent organic dye adsorption capacity of 56.0 mg cm-3, 785.8 m2 g-1, and 169.4 mg g-1, respectively. Given its sustainable, scalable, and low-cost wood platform, the proposed high-performance CA is expected to enable the substantial expansion of strategies for environmental protection, energy storage, and catalysis.

Hydrophobic, Sustainable, High-Barrier Regenerated Cellulose Film via a Simple One-Step Silylation Reaction.

With the increasing importance of environmental protection, high-performance biopolymer films have received considerable attention as effective alternatives to petroleum-based polymer films. In this study, we developed hydrophobic regenerated cellulose (RC) films with good barrier properties through a simple gas-solid reaction via the chemical vapor deposition of alkyltrichlorosilane. RC films were employed to construct a biodegradable, free-standing substrate matrix, and methyltrichlorosilane (MTS) was used as a hydrophobic coating material to control the wettability and improve the barrier properties of the final films. MTS readily coupled with hydroxyl groups on the RC surface through a condensation reaction. We demonstrated that the MTS-modified RC (MTS/RC) films were optically transparent, mechanically strong, and hydrophobic. In particular, the obtained MTS/RC films exhibited a low oxygen transmission rate of 3 cm3/m2 per day and a low water vapor transmission rate of 41 g/m2 per day, which are superior to those of other hydrophobic biopolymer films.

Toward millimeter thick cellulose nanofiber/epoxy laminates with good transparency and high flexural strength.

While cellulose nanofiber-based bioplastics are of great interest for replacing synthetic polymer and glass materials, the main limitation is their low thickness, which makes them difficult for various applications. In this study, we fabricated millimeter-scale thick bioplastic composites, based on 2,2,6,6-tetramethylpiperidine-1-oxy-oxidized cellulose nanofibers (TEMPO-CNF) and epoxy resin, via sequential lamination processes. The glycerol as softener was added to TEMPO-CNF dispersion to prepare a thick TEMPO-CNF layer without shrinkage. It was discovered that the total thickness of TEMPO-CNF/epoxy laminates can be easily controlled by changing the thickness and number of TEMPO-CNF layers and the total thickness can also be easily increased up to 2.4 mm. Furthermore, these TEMPO-CNF/epoxy laminates have high flexural strength (272 MPa) as well as good transmittance (85% % at 600 nm). We anticipate that our approach will significantly broaden the strategies for fabricating nanocellulose-based bioplastics for use as a replacement for transparent synthetic polymers and glass materials.

Anti-Counterfeiting Tags Using Flexible Substrate with Gradient Micropatterning of Silver Nanowires.

Anti-counterfeiting technologies for small products are being developed. We present an anti-counterfeiting tag, a grayscale pattern of silver nanowires (AgNWs) on a flexible substrate. The anti-counterfeiting tag that is observable with a thermal imaging camera was fabricated using the characteristics of silver nanowires with high visible light transmittance and high infrared emissivity. AgNWs were patterned at microscale via a maskless lithography method using UV dicing tape with UV patterns. By attaching and detaching an AgNW coated glass slide and UV dicing tape irradiated with multiple levels of UV, we obtained AgNW patterns with four or more grayscales. Peel tests confirmed that the adhesive strength of the UV dicing tape varied according to the amount of UV irradiation, and electrical resistance and IR image intensity measurements confirmed that the pattern obtained using this tape has multi-level AgNW concentrations. When applied for anti-counterfeiting, the gradient-concentration AgNW micropattern could contain more information than a single-concentration micropattern. In addition, the gradient AgNW micropattern could be transferred to a flexible polymer substrate using a simple method and then attached to various surfaces for use as an anti-counterfeiting tag.

Facile preparation of nanocellulose/Zn-MOF-based catalytic filter for water purification by oxidation process.

Sulfate radical (SO4•-)-based advanced oxidation processes (SR-AOPs) have recently attracted much attention due to their potential in degrading organic pollutants. Metal-organic frameworks (MOFs) have been reported as effective materials to generate SO4•-. However, it is challenging to separate and recover the dispersed MOF particles from the reaction solution when MOFs are used alone. We used cellulose nanofibers (CNFs) as a porous filter template to immobilize Zn-based MOF, zeolitic imidazolate framework-8 (ZIF-8), and obtained a catalytic composite membrane having peroxymonosulfate (PMS) activating function to produce SO4•-. The CNF was effective in holding ZIF-8 nanoparticle and making a durable porous filter. The activated PMS-produced •OH and SO4•- radicals from ZIF-8 play an important role in the catalytic reaction. More than 90% of methylene blue and rhodamine B was degraded by ZIF-8/CNFs composite membrane in the PMS environment within 60 min. The ZIF-8/CNFs catalytic filters can be used several times without performance reduction for organic dye degradation. The results show that ZIF-8/CNFs catalytic membrane can be separated from organic pollution system quickly and used for the efficient separation and recovery of MOF particle-based catalytic materials. Therefore, this study provides a new perspective for fabricating the MOFs particles-immobilized catalytic filter by biomass nanocellulose-based materials for water purification. This method can be used for facile fabrication of the cellulose-based porous functional filter and open diverse applications.

Detection of nanoplastics based on surface-enhanced Raman scattering with silver nanowire arrays on regenerated cellulose films.

Plastic pollution has steadily become a global issue due to its ubiquity and degradation into micro and nanoparticles. Herein, we report the construction of surface-enhanced Raman scattering (SERS)-active array substrates with regenerated cellulose (RC) and plasmonic nanoparticles (AuNRs and AgNWs) via a simple vacuum-assisted filtration method using a silicon mask for rapid nanoplastic detection. The AgNWs/RC film exhibited a SERS intensity of crystal violet approximately six times higher than that of the AuNRs/RC film with a high enhancement factor of 1.8 × 107. Moreover, the AgNWs/RC film exhibits a better SERS activity for polystyrene nanoplastic detection than the AuNRs/RC film because the dense AgNW network structures are well suited for nanoplastic detection. The AgNWs/RC film can detect PS nanoplastics down to 0.1 mg/mL with a good reproducibility of the SERS signal. The low-cost, flexible, and highly sensitive AgNWs/RC films could provide an efficient and rapid SERS-based method for nanoplastic detection.

Double-crosslinked cellulose nanofiber based bioplastic films for practical applications.

While green bioplastic based on carbohydrate polymers have showed considerable promise, the methods typically used to prepare them in a single material have remained a significant challenge. In this study, a simple approach is proposed to fabricate high performance cellulose films composed of chemically and physically dual-crosslinked 2,2,6,6-tetramethylpiperidine-1-oxy-oxidized cellulose nanofibers (DC TEMPO-CNFs). The hydroxyl groups of TEMPO-CNF suspensions were firstly crosslinked chemically with epichlorohydrin (ECH), and subsequently TEMPO-CNF matrices were crosslinked physically via the strong electrostatic interaction between carboxylate and Ca2+ ions. It was found that the optimized DC TEMPO-CNF films exhibit a good transmittance (90 %) and a high tensile strength (303 MPa). Furthermore, these DC TEMPO-CNF films revealed superior thermal stability and excellent water resistance compared to neat TEMPO-CNF films without crosslinked domains. We believe that these results will pave the way to preparing practical polysaccharide bioplastics with simple, environmentally-friendly manufacturing processes.

Vapor phase polymerization for electronically conductive nanopaper based on bacterial cellulose/poly(3,4-ethylenedioxythiophene).

Eco-friendly conductive polymer nanocomposites have garnered attention as an effective alternative for conventional conductive nanocomposites. Here, we report the fabrication and optimization of flexible, self-standing, and conductive bacterial cellulose/poly(3,4-ethylene dioxythiophene) (BC/PEDOT) nanocomposites using the vapor phase polymerization (VPP) method. Eco-friendly bacterial cellulose (BC) is used as a flexible matrix, and the highly conductive PEDOT polymer is introduced into the BC matrix to achieve electronic conductivity. We demonstrate that vapor phase polymerized BC/PEDOT composites exhibit more than 10 times lower sheet resistance (18 Ω/square) compared to solution polymerized BC/PEDOT (188 Ω/square). The resultant BC/PEDOT fabricated could be bent up to 100 times and completely rolled up without a notable decrease in electronic performance. Moreover, bent BC/PEDOT films enable operation of a green light-emitting diode (LED) light, indicating the flexibility and stability of conductive BC/PEDOT films. Overall, this study suggests a strategy for the development of eco-friendly, flexible, and conductive nanocomposite films.

Cellulose nanocrystal-coated TEMPO-oxidized cellulose nanofiber films for high performance all-cellulose nanocomposites.

High performance biopolymer films are of great interest as effective alternatives to non-biodegradable and petroleum-based polymer films. However, most natural biopolymer films possess weak mechanical and poor gas barrier properties, limiting their applicability. In this work, we developed all-cellulose nanocomposite films through a simple vacuum filtration process, using cellulose nanocrystals (CNCs) and 2,2,6,6-tetramethylpiperidine-1-oxy-oxidized cellulose nanofibers (TEMPO-CNFs). The TEMPO-CNFs were employed to construct a transparent, free-standing substrate matrix and the CNCs were used as a coating material to improve the mechanical and water vapor barrier properties of the final material. We have demonstrated that the top and bottom CNCs-coated TEMPO-CNF substrates (CNC/TEMPO-CNF/CNC) have excellent mechanical and good water vapor barrier properties. The resulting CNC/TEMPO-CNF/CNC films revealed a high tensile strength of 114 MPa and a low specific water vapor transmission rate (SWVTR) of 19 g∙mm/m2∙day. In addition, the CNC/TEMPO-CNF/CNC films were resistant to various solvents including water, ethanol, tetrahydrofuran (THF), and acetone. This type of high performance cellulose nanocomposite can be used as a renewable material for a broad range of potential applications.

Fabrication of Highly Conductive Porous Cellulose/PEDOT:PSS Nanocomposite Paper via Post-Treatment.

In this paper, we report the fabrication of highly conductive poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS)/cellulose nanofiber (CNF) nanocomposite paper with excellent flexibility through post-treatment with an organic solvent. The post-treated PEDOT:PSS/CNF porous nanocomposite papers showed a lower sulfur content, indicating the removal of residual PSS. The electrical conductivity of PEDOT:PSS/CNF porous nanocomposite paper was increased from 1.05 S/cm to 123.37 S/cm and 106.6 S/cm by post-treatment with dimethyl sulfoxide (DMSO) and ethylene glycol (EG), respectively. These values are outstanding in the development of electrically conductive CNF composites. Additionally, the highly conductive nanocomposite papers showed excellent bending stability during bending tests. Cyclic voltammetry (CV) showed a Faradaic redox reaction and non-Faradaic capacitance due to the redox activity of PEDOT:PSS and large surface area, respectively. Electrochemical energy storage ability was evaluated and results showed that capacitance improved after post-treatment. We believe that the highly conductive PEDOT:PSS/CNF porous nanocomposite papers with excellent flexibility described here are potential candidates for application in porous paper electrodes, flexible energy storage devices, and bioengineering sensors.

Antibacterial poly (3,4-ethylenedioxythiophene):poly(styrene-sulfonate)/agarose nanocomposite hydrogels with thermo-processability and self-healing.

Recently, Near-infrared (NIR)-induced photothermal killing of pathogenic bacteria has received considerable attention due to the increase in antibiotic resistant bacteria. In this paper, we report a simple aqueous solution-based strategy to construct an effective photothermal nanocomposite composed of poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) and agarose with thermo-processability, light triggered self-healing, and excellent antibacterial activity. Our experiments revealed that PEDOT:PSS/agarose was easily coated on both a 2D glass substrate and 3D cotton structure. Additionally, PEDOT:PSS/agarose can be designed into free-standing objects of diverse shape as well as restored through an NIR light-induced self-healing effect after damage. Taking advantage of strong NIR light absorption, PEDOT:PSS/agarose exhibited a sharp temperature increase of 24.5 °C during NIR exposure for 100 s. More importantly, we demonstrated that the temperature increase on PEDOT:PSS/agarose via photothermal conversion resulted in the rapid and effective killing of nearly 100% of the pathogenic bacteria within 2 min of NIR irradiation.

High-Performance Resistive Pressure Sensor Based on Elastic Composite Hydrogel of Silver Nanowires and Poly(ethylene glycol).

Improved pressure sensing is of great interest to enable the next-generation of bioelectronics systems. This paper describes the development of a transparent, flexible, highly sensitive pressure sensor, having a composite sandwich structure of elastic silver nanowires (AgNWs) and poly(ethylene glycol) (PEG). A simple PEG photolithography was employed to construct elastic AgNW-PEG composite patterns on flexible polyethylene terephthalate (PET) film. A porous PEG hydrogel structure enabled the use of conductive AgNW patterns while maintaining the elasticity of the composite material, features that are both essential for high-performance pressure sensing. The transparency and electrical properties of AgNW-PEG composite could be precisely controlled by varying the AgNW concentration. An elastic AgNW-PEG composite hydrogel with 0.6 wt % AgNW concentration exhibited high transmittance including T550nm of around 86%, low sheet resistance of 22.69 Ω·sq-1, and excellent bending durability (only 5.8% resistance increase under bending to 10 mm radius). A flexible resistive pressure sensor based on our highly transparent AgNW-PEG composite showed stable and reproducible response, high sensitivity (69.7 kPa-1), low sensing threshold (~2 kPa), and fast response time (20⁻40 ms), demonstrating the effectiveness of the AgNW-PEG composite material as an elastic conductor.

Micropatterning Silver Nanowire Networks on Cellulose Nanopaper for Transparent Paper Electronics.

Transparent microelectrodes with high bendability are necessary to develop lightweight, small electronic devices that are highly portable. Here, we report a reliable fabrication method for transparent and highly bendable microelectrodes based on conductive silver nanowires (AgNWs) and 2,2,6,6-tetramethylpiperidine-1-oxy (TEMPO)-oxidized cellulose nanofibers (CNFs). The AgNW-based micropatterns were simply fabricated on glass via poly(ethylene glycol) photolithography and then completely transferred to transparent TEMPO-CNF nanopaper with high bendability via vacuum-assisted microcontact printing (µCP). The AgNW micropatterns were embedded in the surface layer of TEMPO-CNF nanopaper, enabling strong adhesion to the nanopaper substrate. The resulting AgNW micropatterns on the TEMPO-CNF nanopaper showed an optical transparency of 82% at 550 nm and a sheet resistance of 54 Ω/sq when the surface density of AgNWs was as low as 12.9 µg/cm2. They exhibited good adhesion stability and excellent bending durability. After 12 peeling test cycles and 60 s sonication time, the sheet resistance of the AgNW networks embedded on TEMPO-CNF nanopaper increased by only ∼0.12 and ∼0.07 times, respectively. Furthermore, no significant change in electrical resistance was observed even after 3 bending cycles to nearly 90° and 500 cycles of 80% bending strain. Moreover, the AgNW patterns on TEMPO-CNF paper were successfully applied for constructing a transparent electric circuit as well as a solid-state electrochromic device. Overall, we proposed an effective way to fabricate AgNW micropatterns on transparent nanopaper, which can be expanded to various conductive materials for high-performance paper-based electronics.