Pure-Water-Fed Forward-Bias Bipolar Membrane CO2 Electrolyzer.

Coupling renewable electricity to reduce carbon dioxide (CO2) electrochemically into carbon feedstocks offers a promising pathway to produce chemical fuels sustainably. While there has been success in developing materials and theory for CO2 reduction, the widespread deployment of CO2 electrolyzers has been hindered by challenges in the reactor design and operational stability due to CO2 crossover and (bi)carbonate salt precipitation. Herein, we design asymmetrical bipolar membranes assembled into a zero-gap CO2 electrolyzer fed with pure water, solving both challenges. By investigating and optimizing the anion-exchange-layer thickness, cathode differential pressure, and cell temperature, the forward-bias bipolar membrane CO2 electrolyzer achieves a CO faradic efficiency over 80% with a partial current density over 200 mA cm-2 at less than 3.0 V with negligible CO2 crossover. In addition, this electrolyzer achieves 0.61 and 2.1 mV h-1 decay rates at 150 and 300 mA cm-2 for 200 and 100 h, respectively. Postmortem analysis indicates that the deterioration of catalyst/polymer-electrolyte interfaces resulted from catalyst structural change, and ionomer degradation at reductive potential shows the decay mechanism. All these results point to the future research direction and show a promising pathway to deploy CO2 electrolyzers at scale for industrial applications.

Colloidal Synthesis of Ultrathin and Se-Rich V2Se9 Nanobelts as High-Performance Anode Materials for Li-Ion Batteries.

In this study, the one-dimensional (1D) material V2Se9 was successfully synthesized using a colloidal method with VO(acac)2 and Se powder as precursors in a 1-octadecene solvent. The obtained colloidally synthesized V2Se9 (C-V2Se9) has an ultrathin nanobelt shape and a 4.5 times higher surface area compared with the bulk V2Se9, which is synthesized in a solid-state reaction as previously reported. In addition, all surfaces of C-V2Se9 are exposed to Se atoms, which is advantageous for storing Li through the conversion reaction into the Li2Se phase. Herein, the electrochemical performance of the C-V2Se9 anode material is evaluated; thus, the novelty of C-V2Se9 as a Se-rich 1D anode material is verified. The C-V2Se9 electrode exhibits a reversible capacity of 893.21 mA h g-1 and a Coulombic efficiency of 97.82% at the 100th cycle and excellent structural stability. Compared with the bulk V2Se9 electrode, the outstanding electrochemical performance of C-V2Se9 is attributed to its ultrathin nanobelt shape, high surface area, shorter Li diffusion length, and more electrochemically active sites. This work indicates the great potential of the Se-rich 1D material, C-V2Se9, as a post-transition metal dichalcogenide material for high-performance LIBs.

Peptide-Assembled Single-Chain Atomic Crystal Enhances Pluripotent Stem Cell Differentiation to Neurons.

Nanomaterials hybridized with biological components have widespread applications. among many candidates, peptides are attractive in that their peptide sequences can self-assemble with the surface of target materials with high specificity without perturbing the intrinsic properties of nanomaterials. Here, a 1D hybrid nanomaterial was developed through self-assembly of a designed peptide. A hexagonal coiled-coil motif geometrically matched to the diameter of the inorganic nanomaterial was fabricated, whose hydrophobic surface was wrapped along the axis of the hydrophobic core of the coiled coil. Our morphological and spectroscopic analyses revealed rod-shaped, homogeneous peptide-inorganic nanomaterial complexes. Culturing embryonic stem cells on surfaces coated with this peptide-assembled single-chain atomic crystal increased the growth and adhesion of the embryonic stem cells. The hybridized nanomaterial also served as an ECM for brain organoids, accelerating the maturation of neurons. New methods to fabricate hybrid materials through peptide assembly can be applied.

Ultrahigh-Porosity MgO Microparticles for Heat-Energy Storage.

Continuous industrial development has increased the demand of energy. Inevitably, the development of energy sources is steadily progressing using various methods. Rather than establishing a new energy source, a system for storing waste heat generated by industry has now been accepted as a useful strategy. Among such systems, the hydration and dehydration reactions of MgO/Mg(OH)2  are eco-friendly, have relatively low toxicity and risk, and have a large reserves. Therefore, it is a promising candidate for a heat-storage system. In this study, ultrahigh-porosity particles are used to maximize the heat-storage efficiency of pure MgO. Due to its large surface area, the heat storage rate is 90.3% of the theoretical value and the reaction rate is very high. In addition, as structural collapse, likely to be caused by volume changes between reactions, is blocked as the porous region is filled and emptied, the cycle stability is secured. Ultrahigh-porosity MgO microparticles can be used to build eco-friendly heat-storage systems.

Bioessential Inorganic Molecular Wire-Reinforced 3D-Printed Hydrogel Scaffold for Enhanced Bone Regeneration.

Materials with physicochemical properties and biological activities similar to those of the natural extracellular matrix are in high demand in tissue engineering. In particular, Mo3 Se3 - inorganic molecular wire (IMW) is a promising material composed of bioessential minerals and possess nanometer-scale diameters, negatively charged surfaces, physical flexibility, and nanotopography characteristics, which are essential for interactions with cell membrane proteins. Here, an implantable 3D Mo3 Se3 - IMW enhanced gelatin-GMA/silk-GMA hydrogel (IMW-GS hydrogel) is developed for osteogenesis and bone formation, followed by biological evaluations. The mechanical properties of the 3D printed IMW-GS hydrogel are improved by noncovalent interactions between the Mo3 Se3 - IMWs and the positively charged residues of the gelatin molecules. Long-term biocompatibility with primary human osteoblast cells (HOBs) is confirmed using the IMW-GS hydrogel. The proliferation, osteogenic gene expression, collagen accumulation, and mineralization of HOBs improve remarkably with the IMW-GS hydrogel. In in vivo evaluations, the IMW-GS hydrogel implantation exhibits a significantly improved new bone regeneration of 87.8 ± 5.9% (p < 0.05) for 8 weeks, which is higher than that from the gelatin-GMA/silk-GMA hydrogel without Mo3 Se3 - IMW. These results support a new improved strategy with in vitro and in vivo performance of 3D IMW enhanced scaffolds in tissue engineering.

Organic Dispersion of Mo3Se3- Single-Chain Atomic Crystals Using Surface Modification Methods.

In this study, single-chain atomic crystals (SCACs), Mo3Se3-, which can be uniformly dispersed, with an atomically thin diameter of ∼0.6 nm were modified to disperse in an organic solvent. Various surfactants were chosen to provide steric hindrance to aqueous-dispersed Mo3Se3- by modifying the surface of Mo3Se3-. The organic dispersions of surface-modified Mo3Se3- SCACs in nonpolar solvent (toluene, benzene, and chloroform) were stable with a uniform diameter of 2 nm, and they have enhanced stability from oxidation (>10 days). With the surfactants that have a polystyrene tail group (PS-NH2), the surface-modified Mo3Se3- SCAC showed high compatibility with a polystyrene polymer matrix. Using the surface-modified Mo3Se3- SCAC, a homogeneous Mo3Se3-/polystyrene/toluene organogel was prepared. More importantly, the Mo3Se3-/polystyrene organogel exhibits significantly enhanced mechanical properties, with the improvement of 202.27% and 279.52% for tensile strength and elongation, respectively, compared with that of the pure organogel. The surface-modified Mo3Se3- had a similar structure with a polymer matrix, and the properties of the polymer can be improved even with a small addition of Mo3Se3-.

Tunable mechanical properties of Mo3Se3-poly vinyl alcohol-based/silk fibroin-based nanowire ensure the regeneration mechanism in tenocytes derived from human bone marrow stem cells.

Silk fibroin (SF) and poly vinyl alcohol (PVA)-based nanomaterial has exceptional attention in regenerative medicine. However, the preparation of SF and PVA-based nanomaterials in the desired form is complex due to their poor mechanical strength, brittleness, and compatibility. To this end, Mo3Se3 is chosen as a bio-nanowire to fabricate by combining PVA and SF to improve the mechanical properties. Physicochemical and structural features of the Mo3Se3-PVA-SF nanowire hydrogel (Mo3Se3-PVA-SF-NWH) were characterized by field emission scanning electron microscope (FE-SEM). Mechanical properties, degradation ratio, hydrophilicity, water uptake capacity, biocompatibility, and biological activity of the hydrogel were also studied. Superior interactions were formed between the reinforcing molecules of Mo3Se3 and PVA/SF in the hydrogel network by introducing Mo3Se3 nanowire (NW) into the hydrogel. Conversely, Mo3Se3 NW imparts mechanical stability and robustness to the blends (hydrogel) with predictable long-term degradation characteristics. It was proven by in vitro biodegradable rate, and swelling behaviour was varied depending on the concentration of Mo3Se3 NW. Mo3Se3 reinforced the hydrogels and found high porosity with superior biocompatibility. Excellent cellular adaptation was analyzed by MTT assay, live/dead staining, western blot, and quantitative real-time polymerase chain reaction (qRT-PCR). It revealed moderate toxicity at a concentration of 0.02% among the control samples. There was no discernible difference in 0.01% and 0.005% of Mo3Se3-PVA-SF-NWH in tenocytes derived from human bone marrow mesenchymal stem cells (hBMSC). Hence, this Mo3Se3-PVA-SF-NWH might be considered biocompatible due to its biological activities and appropriate mechanical properties. Overall, the Mo3Se3-PVA-SF-NWH might be considered a biocompatible scaffold for the possible biomedical applications of tendon tissue engineering.

Theoretical Study of Anisotropic Carrier Mobility for Two-Dimensional Nb2Se9 Material.

Finding new materials with satisfying all the desired criteria for nanodevices is an extremely difficult work. Here, we introduce a novel Nb2Se9 material as a promising candidate, capable of overcoming some physical limitations, such as a suitable band gap, high carrier mobility, and chemical stability. Unlike graphene, it has a noticeable band gap and no dangling bonds at surfaces that deteriorate transport properties, owing to its molecular chain structure. Using density functional theory (DFT) calculations with deformation potential (DP) theory, we find that the electron mobility of 2D Nb2Se9 across the axis direction reaches up to 2.56 × 103 cm2 V-1 s-1 and is approximately 2.5-6 times higher than the mobility of other 2D materials, such as MoS2, black phosphorous, and InSe, at room temperature. Moreover, the mobility of 2D Nb2Se9 is highly anisotropic (µ a /µ c ≈ 6.5). We demonstrate the potential of 2D Nb2Se9 for applications in nanoscale electronic devices and, possibly, mid-infrared photodetectors.

One-dimensional van der Waals stacked p-type crystal Ta2Pt3Se8 for nanoscale electronics.

Recently, ternary transition metal chalcogenides Ta2X3Se8 (X = Pd or Pt) have attracted great interest as a class of emerging one-dimensional (1D) van der Waals (vdW) materials. In particular, Ta2Pd3Se8 has been actively studied owing to its excellent charge transport properties as an n-type semiconductor and ultralong ballistic phonon transport properties. Compared to subsequent studies on the Pd-containing material, Ta2Pt3Se8, another member of this class of materials has been considerably less explored despite its promising electrical properties as a p-type semiconductor. Herein, we demonstrate the electrical properties of Ta2Pt3Se8 as a promising channel material for nanoelectronic applications. High-quality bulk Ta2Pt3Se8 single crystals were successfully synthesized by a one-step vapor transport reaction. Scanning Kelvin probe microscopy measurements were used to investigate the surface potential difference and work function of the Ta2Pt3Se8 nanoribbons of various thicknesses. Field-effect transistors fabricated on exfoliated Ta2Pt3Se8 nanoribbons exhibited moderate p-type transport properties with a maximum hole mobility of 5 cm2 V-1 s-1 and an Ion/Ioff ratio of >104. Furthermore, the charge transport mechanism of Ta2Pt3Se8 was analyzed by temperature-dependent transport measurements in the temperature range from 90 to 320 K. To include Ta2Pt3Se8 in a building block for modern 1D electronics, we demonstrate p-n junction characteristics using the electron beam doping method.

High Breakdown Current Density in Quasi-1D van der Waals Layered Material Ta2NiSe7.

We synthesized ternary composition chalcogenide Ta2NiSe7, a quasi-one-dimensional (Q1D) material with excellent crystallinity. To utilize the excellent electrical conductivity property of Ta2NiSe7, the breakdown current density (JBD) according to thickness change through mechanical exfoliation was measured. It was confirmed that as the thickness decreased, the maximum breakdown voltage (VBD) increased, and at 18 nm thickness, 35 MA cm-2 of JBD was measured, which was 35 times higher than that of copper, which is commonly used as an interconnect material. By optimization of the exfoliation process, it is expected that through a theoretical model fitting, the JBD can be increased to about 356 MA cm-2. It is expected that the low-dimensional materials with ternary compositions proposed through this experiment can be used as candidates for current-carrying materials that are required for the miniaturization of various electronic devices.

Ta2 Ni3 Se8 : 1D van der Waals Material with Ambipolar Behavior.

In this study, high-purity and centimeter-scale bulk Ta2 Ni3 Se8 crystals are obtained by controlling the growth temperature and stoichiometric ratio between tantalum, nickel, and selenium. It is demonstrated that the bulk Ta2 Ni3 Se8 crystals could be effectively exfoliated into a few chain-scale nanowires through simple mechanical exfoliation and liquid-phase exfoliation. Also, the calculation of electronic band structures confirms that Ta2 Ni3 Se8 is a semiconducting material with a small bandgap. A field-effect transistor is successfully fabricated on the mechanically exfoliated Ta2 Ni3 Se8 nanowires. Transport measurements at room temperature reveal that Ta2 Ni3 Se8 nanowires exhibit ambipolar semiconducting behavior with maximum mobilities of 20.3 and 3.52 cm2 V-1 s-1 for electrons and holes, respectively. The temperature-dependent transport measurement (from 90 to 295 K) confirms the carrier transport mechanism of Ta2 Ni3 Se8 nanowires. Based on these characteristics, the obtained 1D vdW material is expected to be a potential candidate for additional 1D materials as channel materials.

Bio-essential Inorganic Molecular Nanowires as a Bioactive Muscle Extracellular-Matrix-Mimicking Material.

Many physiochemical properties of the extracellular matrix (ECM) of muscle tissues, such as nanometer scale dimension, nanotopography, negative charge, and elasticity, must be carefully reproduced to fabricate scaffold materials mimicking muscle tissues. Hence, we developed a muscle tissue ECM-mimicking scaffold using Mo6S3I6 inorganic molecular wires (IMWs). Composed of bio-essential elements and having a nanofibrous structure with a diameter of ∼1 nm and a negative surface charge with high stability, Mo6S3I6 IMWs are ideal for mimicking natural ECM molecules. Once Mo6S3I6 IMWs were patterned on a polydimethylsiloxane surface with an elasticity of 1877.1 ± 22.2 kPa, that is, comparable to that of muscle tissues, the proliferation and α-tubulin expression of myoblasts enhanced significantly. Additionally, the repetitive one-dimensional patterns of Mo6S3I6 IMWs induced the alignment and stretching of myoblasts with enhanced α-tubulin expression and differentiation into myocytes. This study demonstrates that Mo6S3I6 IMWs are promising for mimicking the ECM of muscle tissues.

A study on the bio-applicability of aqueous-dispersed van der Waals 1-D material Nb2Se9 using poloxamer.

In this research, dispersion of a new type of one-dimensional inorganic material Nb2Se9, composed of van der Waals bonds, in aqueous solution for bio-application study were studied. To disperse Nb2Se9, which exhibits hydrophobic properties in water, experiments were carried out using a block copolymer (poloxamer) as a dispersant. It was confirmed that PPO, the hydrophobic portion of Poloxamer, was adsorbed onto the surface of Nb2Se9, and PEO, the hydrophilic portion, induced steric hinderance to disperse Nb2Se9 to a size of 10 nm or less. To confirm the adaptability of muscle cells C2C12 to the dispersed Nb2Se9 using poloxamer 188 as dispersant, a MTT assay and a live/dead assay were performed, demonstrating improvement in the viability and proliferation of C2C12 cells.

Edge Defect-Free Anisotropic Two-Dimensional Sheets with Nearly Direct Band Gaps from a True One-Dimensional Van der Waals Nb2Se9 Material.

Dangling-bond-free two-dimensional (2D) materials can be isolated from the bulk structures of one-dimensional (1D) van der Waals materials to produce edge-defect-free 2D materials. Conventional 2D materials have dangling bonds on their edges, which act as scattering centers that deteriorate the transport properties of carriers. Highly anisotropic 2D sheets, made of 1D van der Waals Nb2Se9 material, have three planar structures depending on the cutting direction of the bulk Nb2Se9 crystal. To investigate the applications of these 2D Nb2Se9 sheets, we calculated the band structures of the three planar sheets and observed that two sheets had nearly direct band gaps, which were only slightly greater (0.01 eV) than the indirect band gaps. These energy differences were smaller than the thermal energy at room temperature. The 2D Nb2Se9 plane with an indirect band gap had the shortest interchain distance for selenium ions among the three planes and exhibited significant interchain interactions on the conduction band. The interchain strain induced an indirect-to-direct band gap transition in the 2D Nb2Se9 sheets. These 2D sheets of Nb2Se9 with direct band gaps also had different band structures because of different interactions between chains, implying that they can have different charge mobilities. We expect these dangling-bond-free 2D Nb2Se9 sheets to be applied in optoelectronic devices because they allow for nearly direct band gaps. They can also be used in mechanical sensors because the band gaps can be controlled by varying the interchain strain.

Aqueous Dispersion of One-Dimensional van der Waals Material Mo6S3I6 with the Charge Type of the Hydrophobic Dispersant Tail.

Aqueous dispersion of van der Waals bonded one-dimensional materials Mo6S3I6 with hydrophobic surfaces has been studied. The surface charge of the dispersed Mo6S3I6 is controlled from negative to positive by the charge type of dispersant tail (anionic, SDS and NaDDBS; cationic, CTAB; nonionic, Poloxamer 407), and through this, it is possible to deposit the dispersed Mo6S3I6 in nanosized by electrophoretic deposition at a desired position. When a flexible device was manufactured by transferring Mo6S3I6, it was confirmed that electrical conductivity can be measured in 40% of elongation and more than 1000 times cyclic test.

Indirect-To-Direct Band Gap Transition of One-Dimensional V2Se9: Theoretical Study with Dispersion Energy Correction.

Recently, we synthesized a one-dimensional (1D) structure of V2Se9. The 1D V2Se9 resembles another 1D material, Nb2Se9, which is expected to have a direct band gap. To determine the potential applications of this material, we calculated the band structures of 1D and bulk V2Se9 using density functional theory by varying the number of chains and comparing their band structures and electronic properties with those of Nb2Se9. The results showed that a small number of V2Se9 chains have a direct band gap, whereas bulk V2Se9 possesses an indirect band gap, like Nb2Se9. We expect that V2Se9 nanowires with diameters less than ∼20 Šwould have direct band gaps. This indirect-to-direct band gap transition could lead to potential optoelectronic applications for this 1D material because materials with direct band gaps can absorb photons without being disturbed by phonons.

Design of dispersant for highly concentrated one-dimensional Nb2Se9 inorganic molecular chains from bulk crystal.

We determined the optimum dispersant to separate bulk Nb2Se9 material into 1D chain units. The Nb2Se9, which had a negative zeta potential (-43.3 mV), showed acidic characteristics and strongly bonded with the amine head of octadecyl amine through a charge transfer (from the amine to Se atoms) reaction. The steric hindrance of the octadecyl tail resulted in excellent dispersion of Nb2Se9 (down to nanometre-sized mono-chains).

Exceptional Mechanical Properties of Phase-Separation-Free Mo3Se3--Chain-Reinforced Hydrogel Prepared by Polymer Wrapping Process.

As Mo3Se3- chain nanowires have dimensions comparable to those of natural hydrogel chains (molecular-level diameters of ∼0.6 nm and lengths of several micrometers) and excellent mechanical strength and flexibility, they have large potential to reinforce hydrogels and improve their mechanical properties. When a Mo3Se3--chain-nanowire-gelatin composite hydrogel is prepared simply by mixing Mo3Se3- nanowires with gelatin, phase separation of the Mo3Se3- nanowires from the gelatin matrix occurs in the micronetwork, providing only small improvements in their mechanical properties. In contrast, when the surface of the Mo3Se3- nanowire is wrapped with the gelatin polymer, the chemical compatibility of the Mo3Se3- nanowire with the gelatin matrix is significantly improved, which enables the fabrication of a phase-separation-free Mo3Se3--reinforced gelatin hydrogel. The composite gelatin hydrogel exhibits significantly improved mechanical properties, including a tensile strength of 27.6 kPa, fracture toughness of 26.9 kJ/m3, and elastic modulus of 54.8 kPa, which are 367%, 868%, and 378% higher than those of the pure gelatin hydrogel, respectively. Furthermore, the amount of Mo3Se3- nanowires added in the composite hydrogel is as low as 0.01 wt %. The improvements in the mechanical properties are significantly larger than those for other reported composite hydrogels reinforced with one-dimensional materials.

Thickness-Dependence Electrical Characterization of the One-Dimensional van der Waals TaSe3 Crystal.

Needle-like single crystalline wires of TaSe3 were massively synthesized using the chemical vapor transport method. Since the wedged-shaped single TaSe3 molecular chains were stacked along the b-axis by weak van der Waals interactions, a few layers of TaSe3 flakes could be easily isolated using a typical mechanical exfoliation method. The exfoliated TaSe3 flakes had an anisotropic planar structure, and the number of layers could be controlled by a repeated peeling process until a monolayer of TaSe3 nanoribbon was obtained. Through atomic force and scanning Kelvin probe microscope analyses, it was found that the variation in the work function with the thickness of the TaSe3 flakes was due to the interlayer screening effect. We believe that our results will not only help to add a novel quasi-1D block for nanoelectronics devices based on 2D van der Waals heterostructures, but also provide crucial information for designing proper contacts in device architecture.