Nitrogen-Doped Single Graphene Fiber with Platinum Water Dissociation Catalyst for Wearable Humidity Sensor.

Humidity sensors are essential components in wearable electronics for monitoring of environmental condition and physical state. In this work, a unique humidity sensing layer composed of nitrogen-doped reduced graphene oxide (nRGO) fiber on colorless polyimide film is proposed. Ultralong graphene oxide (GO) fibers are synthesized by solution assembly of large GO sheets assisted by lyotropic liquid crystal behavior. Chemical modification by nitrogen-doping is carried out under thermal annealing in H2 (4%)/N2 (96%) ambient to obtain highly conductive nRGO fiber. Very small (≈2 nm) Pt nanoparticles are tightly anchored on the surface of the nRGO fiber as water dissociation catalysts by an optical sintering process. As a result, nRGO fiber can effectively detect wide humidity levels in the range of 6.1-66.4% relative humidity (RH). Furthermore, a 1.36-fold higher sensitivity (4.51%) at 66.4% RH is achieved using a Pt functionalized nRGO fiber (i.e., Pt-nRGO fiber) compared with the sensitivity (3.53% at 66.4% RH) of pure nRGO fiber. Real-time and portable humidity sensing characteristics are successfully demonstrated toward exhaled breath using Pt-nRGO fiber integrated on a portable sensing module. The Pt-nRGO fiber with high sensitivity and wide range of humidity detection levels offers a new sensing platform for wearable humidity sensors.

Extending density functional theory with near chemical accuracy beyond pure water.

Density functional simulations of condensed phase water are typically inaccurate, due to the inaccuracies of approximate functionals. A recent breakthrough showed that the SCAN approximation can yield chemical accuracy for pure water in all its phases, but only when its density is corrected. This is a crucial step toward first-principles biosimulations. However, weak dispersion forces are ubiquitous and play a key role in noncovalent interactions among biomolecules, but are not included in the new approach. Moreover, naïve inclusion of dispersion in HF-SCAN ruins its high accuracy for pure water. Here we show that systematic application of the principles of density-corrected DFT yields a functional (HF-r2SCAN-DC4) which recovers and not only improves over HF-SCAN for pure water, but also captures vital noncovalent interactions in biomolecules, making it suitable for simulations of solutions.

Density-Corrected Density Functional Theory for Open Shells: How to Deal with Spin Contamination.

Density functional theory (DFT) is usually used self-consistently to predict chemical properties, but the use of the Hartree-Fock (HF) density improves energetics in certain, well-characterized cases. Density-corrected (DC) DFT provides the theory behind this, but unrestricted Hartree-Fock (UHF) densities yield poor energetics in cases of strong spin contamination. Here we compare with restricted open-shell HF (ROHF) across 13 different functionals and two DC-DFT methods. For significant spin contamination, ROHF densities outperform UHF densities by as much as a factor of 3, depending on the energy functional, and ROHF-DFT improves over self-consistent DFT for most of the tested functionals. We refine the DC(HF)-DFT algorithm to use ROHF densities in cases of severe spin contamination.

3-D porous cellulose nanofibril aerogels with a controllable copper nanoparticle loading as a highly efficient non-noble-metal catalyst for 4-nitrophenol reduction.

Nitrophenols(NPs) are highly toxic compounds that occur in various industrial effluents. Herein, we investigated Cu nanoparticle-loaded cellulose nanofibril (CNF/PEI-Cu) aerogels as a catalyst for degrading 4-nitrophenol (4NP) in the wastewater. Non-noble metal based low-cost catalyst material and easily scalable preparation method make CNF/PEI-Cu aerogel as an appropriate catalyst for practical application in 4NP wastewater treatment. Our strategy to improve the loading amount of homogeneously distributed Cu nanoparticles was to functionalize a CNF aerogel using polyethylene imine (PEI), which can bind Cu2+ ions. Porous CNF aerogels with homogenously distributed 20-40 nm Cu nanoparticles were obtained by adsorbing Cu2+ ions and chemically reducing them to Cu metal. The FTIR, XRD, SEM, XPS and ICP-OES analysis were used to confirm the in-situ formation of Cu nanoparticles. In the presence of the CNF/PEI-Cu aerogels, 4NP was effectively reduced to 4-aminophenol (4AP) without loss of the Cu nanoparticles. The activation energy (Ea) and reaction rate constant (kapp) of the catalytic 4NP reduction reaction by the CNF/PEI2-Cu aerogels were calculated to be Ea = 39.56 kJ mol-1 and kapp = 0.770 min-1, respectively. The Ea is similar or even smaller than the Ea values of the corresponding reactions involving noble-metal catalysts, demonstrating that the CNF/PEI-Cu aerogels developed in the present study have strong potential as practical and economical catalysts.

Wide-Range Size Fractionation of Graphene Oxide by Flow Field-Flow Fractionation.

Many interesting properties of 2D materials and their assembled structures are strongly dependent on the lateral size and size distribution of 2D materials. Accordingly, effective size separation of polydisperse 2D sheets is critical for desirable applications. Here, we introduce flow field-flow fractionation (FlFFF) for a wide-range size fractionation of graphene oxide (GO) up to 100 µm. Two different separation mechanisms are identified for FlFFF, including normal mode and steric/hyperlayer mode, to size fractionate wide size-distributed GOs while employing a crossflow field for either diffusion or size-controlled migration of GO. Obviously, the 2D GO sheet reveals size separation behavior distinctive from typical spherical particles arising from its innate planar geometry. We also investigate 2D sheet size-dependent mechanical and electrical properties of three different graphene fibers produced from size-fractionated GOs. This FlFFF-based size selection methodology can be used as a generic approach for effective wide-range size separation for 2D materials, including rGO, TMDs, and MXene.

Modified cellulose nanofibril aerogel: Tunable catalyst support for treatment of 4-Nitrophenol from wastewater.

4-Nitrophenol (4-NP) is a hazardous aromatic compound widely used for various industries. Catalytic reduction of 4-NP using metal nanoparticles (NPs) is a highly effective method to treat 4-NP from waste effluent. Even though lots of methods have investigated to prepare efficient metal NPs composites, the nano and/or micro size of composites makes it hard to recover after wastewater treatment, limiting its practical use. Here, we fabricate 3-dimensional polyethylene imine grafted cellulose nanofibril (CNF-PEI) aerogel as a porous support material for platinum (Pt) NPs to practically and effectively treat 4-NP from wastewater. The Pt NPs are formed in-situ mode on cylindrical CNF-PEI aerogel by adsorption reaction with amine groups of PEI and subsequently reduction with NaBH4. Control of PEI grafting density and the initial concentration of Pt ions allows manipulation of the loading mass, size, and distribution of Pt NPs on 3D scaffold of CNF-PEI aerogel. The composite aerogel shows high catalytic activity for conversion of 4-NP. The 4-NP conversion activity is strongly affected by the size of Pt NPs and effective surface area of aerogels. The 2.74 nm size Pt NPs with even distribution in the aerogel show fast reaction kinetics (k = 0.12 min-1). Finally, 4-NP reduction efficiency does not decrease during 5 times reuse cycle of Pt NPs loaded CNF-PEI aerogel. This CNF-PEI aerogel loaded with Pt NPs is recovered easily from wastewater after treatment, so it is reusable and offers high potential as a practical recyclable environmental catalyst.

Mechanically enhanced graphene oxide/carboxymethyl cellulose nanofibril composite fiber as a scalable adsorbent for heavy metal removal.

Recently, graphene oxide(GO) has gained much attention for heavy metal removal due to its high surface area and lots of functional groups on the surface. However, GO itself in powder form is far away from practical adsorbents because it remains dispersed in liquid phase which causes difficulty in the separation from effluent. In this study, GO/carboxymethyl cellulose nanofibril (CMCNF) composite fiber(CF) is developed as an efficient and durable adsorbent. Cross-linked GO/CMCNF CF was continuously produced by employing Fe3+ ion as a coagulant during a typical wet-spinning process. Based on multiple interactions such as ionic bonding and electrostatic interactions between Fe3+ and carboxyl group on CMCNF, the CF exhibits enhanced mechanical property than pure GO fiber. GO/CMCNF-Fe3+ CF showed efficient lead (Pb2+) uptake with successful adsorbent recovery, which indicates durable and cost-competitive fiber type adsorbent for heavy metal ions.

Modified tunicate nanocellulose liquid crystalline fiber as closed loop for recycling platinum-group metals.

Rising demand and elemental rarity requires the recycling of precious metals such as platinum group elements (PGMs). Recently, biosorption has been focused on the capability of recovering precious metals, but in practice, recycling is inefficient or far away from a closed-loop material system. Here we use a polyethylenimine (PEI)-grafted spun-fiber made of cellulose nanofibril (CNF) extracted from a tunicate as a biosorbent for PGMs. Liquid crystallinity (LC) of TCNF suspension appears to contribute the generation of well-developed open porous structure in the fiber. We show the fiber has the selectivity and high capacity of Pt (120.2 mg/g, 86%) and Pd (26.5 mg/g, 74.2%) adsorption under the presence of other metals in simulated automobile waste. The adsorbed Pt and Pd with nano-scale clusters were uniformly distributed on the porous surface, which were directly applied as a catalyst. These results propose an easy approach to recover precious metals and reuse them directly, thereby closing loops of metal recycling.

Recovery of platinum from waste effluent using polyethyleneimine-modified nanocelluloses: Effects of the cellulose source and type.

Nanocellulose is a promising biosorbent for the recovery of precious metals from waste streams. A variety of nanocelluloses exhibit significant different properties that depend on the natural source and type. In this study, cellulose nanofibrils(P-CNF) and cellulose nanocrystals(P-CNC) obtained from hard wood pulp and CNF from tunicates(T-CNF) were evaluated for their ability to recover platinum(Pt) after modification with polyethyleneimine(PEI). The PEI grafting density on each nanocellulose was distinct, resulting in significant variations in the Pt adsorption performance. The Pt adsorption capacity of the PEI-modified nanocelluloses followed the order T-CNF>>P-CNC > P-CNF. The inherent characteristics of T-CNF, that is, the negative charge and high surface area caused by open porous structure, were found attributed to the grafting of ≈40% PEI and the excellent Pt adsorption capacity(≈600 mg/g). Also PEI-modified T-CNF exhibited high selectivity towards Pt in the presence of other metals. Finally, PEI modified T-CNF was applied for Pt recovery from simulated spent automobile catalyst leachate to prove feasibility in a real application.

Continuous Meter-Scale Synthesis of Weavable Tunicate Cellulose/Carbon Nanotube Fibers for High-Performance Wearable Sensors.

Weavable sensing fibers with superior mechanical strength and sensing functionality are crucial for the realization of wearable textile sensors. However, in the fabrication of previously reported wearable sensing fibers, additional processes such as reduction, doping, and coating were essential to satisfy both requirements. The sensing fibers should be continuously synthesized in a scalable process for commercial applications with high reliability and productivity, which was challenging. In this study, we first synthesize mass-producible wearable sensing fibers with good mechanical properties and sensing functionality without additional processes by incorporating carbon nanotubes (CNTs) into distinct nanocellulose. Nanocellulose extracted from tunicate (TCNF) is homogeneously composited with single-walled CNTs, and composite fibers (TCNF/CNT) are continuously produced in aligned directions by wet spinning, facilitating liquid-crystal properties. The TCNF/CNT fibers exhibit a superior gas (NO2)-sensing performance with high selectivity and sensitivity (parts-per-billion detection). In addition, the TCNF/CNT fibers can endure complex and harsh distortions maintaining their intrinsic sensing properties and can be perfectly integrated with conventional fabrics using a direct weaving process. Our meter-scale scalable synthesis of functional composite fibers is expected to provide a mass production platform of versatile wearable sensors.

Heterogeneous Metal Oxide-Graphene Thorn-Bush Single Fiber as a Freestanding Chemiresistor.

The development of freestanding fiber-type chemiresistors, having high integration ability with various portable electronics including smart clothing systems, is highly demanding for the next-generation wearable sensing platforms. However, critical challenges stemming from the irreversible chemical sensing kinetics and weak reliability of the freestanding fiber-type chemiresistor hinder their practical use. In this work, for the first time, we report on the potential suitability of the freestanding and ultraporous reduced graphene oxide fiber functionalized with WO3 nanorods (porous WO3 NRs-RGO composite fiber) as a sensitive nitrogen dioxide (NO2) detector. By employing a tunicate cellulose nanofiber (TCNF), which is a unique animal-type cellulose, the numerous mesopores are formed on a wet-spun TCNF-GO composite fiber, unlike a bare GO fiber with dense surface structure. More interestingly, due to the superior wettability of TCNF, the aqueous tungsten precursor is uniformly adsorbed on an ultraporous TCNF-GO fiber, and subsequent heat treatment results in the thermal reduction of a TCNF-GO fiber and hierarchical growth of WO3 NRs perpendicular to the porous RGO fiber (porous WO3 NRs-RGO fiber). The freestanding porous WO3 NRs-RGO fiber shows a notable response to 1 ppm NO2. Furthermore, we successfully demonstrate reversible NO2 sensing characteristics of the porous WO3 NRs-RGO fiber, which is integrated on a wrist-type wearable sensing device.

Mussel-Inspired Defect Engineering of Graphene Liquid Crystalline Fibers for Synergistic Enhancement of Mechanical Strength and Electrical Conductivity.

Inspired by mussel adhesive polydopamine (PDA), effective reinforcement of graphene-based liquid crystalline fibers to attain high mechanical and electrical properties simultaneously is presented. The two-step defect engineering, relying on bioinspired surface polymerization and subsequent solution infiltration of PDA, addresses the intrinsic limitation of graphene fibers arising from the folding and wrinkling of graphene layers during the fiber-spinning process. For a clear understanding of the mechanism of PDA-induced defect engineering, interfacial adhesion between graphene oxide sheets is straightforwardly analyzed by the atomic force microscopy pull-off test. Subsequently, PDA could be converted into an N-doped graphitic layer within the fiber structure by a mild thermal treatment such that mechanically strong fibers could be obtained without sacrificing electrical conductivity. Bioinspired graphene-based fiber holds great promise for a wide range of applications, including flexible electronics, multifunctional textiles, and wearable sensors.