Fully Additively Manufactured Counter Electrodes for Dye-Sensitized Solar Cells.

In dye-sensitized solar cells (DSSCs), the counter electrode (CE) plays a crucial role as an electron transfer agent and regenerator of the redox couple. Unlike conventional CEs that are generally made of glass-based substrates (e.g., FTO/glass), polymer substrates appear to be emerging candidates, owing to their intrinsic properties of lightweight, high durability, and low cost. Despite great promise, current manufacturing methods of CEs on polymeric substrates suffer from serious limitations, including low conductivity, scalability, process complexity, and the need for dedicated vacuum equipment. In the present study, we employ and evaluate a fully additive manufacturing route that can enable the fabrication of CEs for DSSCs in a high-throughput and eco-friendly manner with improved performance. The proposed approach sequentially comprises: (1) material extrusion 3-D printing of polymer substrate; (2) conductive surface metallization through cold spray particle deposition; and (3) over-coating of a thin-layer catalyzer with a graphite pencil. The fabricated electrodes are characterized in terms of microstructure, electrical conductivity, and photo-conversion efficiency. Owing to its promising electrical conductivity (8.5 × 104 S·m-1) and micro-rough surface structure (Ra ≈ 6.32 µm), the DSSCs with the additively manufactured CEs led to ≈2.5-times-higher photo-conversion efficiency than that of traditional CEs made of FTO/glass. The results of the study suggest that the proposed additive manufacturing approach can advance the field of DSSCs by addressing the limitations of conventional CE manufacturing platforms.

The complete chloroplast genome of Philodendron hederaceum (Jacq.) Schott 1829 (Alismatales: Araceae).

Philodendron hederaceum (Jacq.) Schott 1829, a species of the Araceae family, is a foliage plant of ornamental value. The complete chloroplast genome sequence of Philodendron hederaceum was obtained by the de novo assembly of NovaSeq 6000 (Illumina Co., San Diego, CA) paired-end short reads and Oxford Nanopore long reads. The complete chloroplast genome of P. hederaceum was 168,609 bp in length, with a large single-copy (LSC) region of 94,393 bp, a small single-copy (SSC) region of 25,774 bp, and a pair of identical inverted repeat regions (IRs) of 24,221 bp. The genome contained a total of 129 genes, including 85 protein-coding genes, 36 transfer RNA (tRNA) genes, and eight ribosomal RNA (rRNA) genes. The phylogenetic analysis of P. hederaceum with 19 related species and two outgroup species revealed the closest taxonomical relationship with Philodendron lanceolatum in the Araceae family.

Robust anion exchange membranes based on ionic liquid grafted chitosan/polyvinyl alcohol/quaternary ammonium functionalized silica for polymer electrolyte membrane fuel cells.

In this study, 1-bromohexyl-1methylpiperidinium bromide (Br-6-MPRD) ionic liquid grafted quaternized chitosan (QCS) and polyvinyl alcohol (PVA) blends were composited with glycidyl trimethyl ammonium chloride (GTMAC) quaternized silica (QSiO2) at different dosages. Glutaraldehyde (GA) crosslinked the membranes and then processed into hydroxide form with an aqueous potassium hydroxide solution. The resultant IL-QCS/PVA/QSiO2 membranes exhibit significantly improved ionic conductivity, moderate water absorption and swelling ratio compared with the pristine IL-QCS/PVA anion exchange membrane (AEM). Among them, the hydroxide ion conductivity and power density of IL-QCS/PVA/QSiO2-7 membrane can reach up to 78 mS cm-1 at 80 °C and 115 mW cm-2 at 60 °C respectively. In addition, IL-QCS/PVA/QSiO2 membranes have excellent thermal, mechanical, and chemical stabilities, which can meet the application requirements of AEM for fuel cells.

Investigation of the Relationship between Genetic and Breeding Characteristics of WBPH Behavior according to Resistant Materials in Rice.

Rice accounts for most of the calories consumed by the world's population. However, the whitebacked planthopper (WBPH), Sogatella furcifera (Horvath), is an insect that can cause rice yield loss. WBPH sucks the stems of rice and negatively affects yield and grain quality. Therefore, numerous insecticides have been developed to control WBPH in rice fields. However, chemical pesticides cause serious problems such as environmental pollution and ecosystem disturbance. Here, we research the possibility of using previously reported rice extracts obtained using methanol, Chrysoeriol 7(C7) and Cochlioquinone-9 (cq-9), as potential insect repellents. WBPH was caged with C7 or cq-9 and monitored, and the WBPH behavior was recorded. The number of WBPHs approaching the periphery of the C7 and cq-9 was very low. In cages containing the C7 and cq-9, only 13 and 7 WBPHs out of 100, respectively, walked around the material. In addition, foliar spraying with C7 and cq-9 did not negatively affect the plant height. The expression level of genes related to resistance was maintained at a high level in the resistant lines when treated with WBPHs alone, but was at a similar level to those of the controls when treated with C7 or cq-9. Interfering with WBPH access did not adversely affect the plant phenotype. Recently, people's interest in the environment has increased, and the use of plant-derived materials is also increasing. There is a new trend towards using plant extracts as an environmentally friendly means of managing resistance to WBPH during the rice cultivation period, while also avoiding environmental pollution.

Amorphous Fluorinated Acrylate Polymer Dielectrics for Flexible Transistors and Logic Gates with High Operational Stability.

Fluorinated amorphous polymeric gate-insulating materials for organic thin-film transistors (OTFTs) not only form hydrophobic surfaces but also significantly reduce traps at the interface between the organic semiconductor and gate insulator. Therefore, these polymeric materials can enhance the OTFT's operation stability. In this study, we synthesized a new polymeric insulating material series composed of acrylate and fluorinated functional groups (with different ratios) named MBHCa-F and used them as gate insulators for OTFTs and in other applications. The insulating features of the MBHCa-F polymers, including surface energy, surface atomic content properties, dielectric constant, and leakage current, were clearly analyzed with respect to the content of the fluorinated functional groups. At higher fluorine-based functional group content, the polymeric series exhibited higher fluorine-based contents at the surface and superior electrical properties, such as field-effect mobility and driving stability, at OTFTs. Therefore, we believe that this study provides a substantial method for synthesizing polymeric insulating materials to enhance the operational stability and electrical performance of OTFTs.

Biodegradation Studies of Polyhydroxybutyrate and Polyhydroxybutyrate-co-Polyhydroxyvalerate Films in Soil.

Due to increased environmental pressures, significant research has focused on finding suitable biodegradable plastics to replace ubiquitous petrochemical-derived polymers. Polyhydroxyalkanoates (PHAs) are a class of polymers that can be synthesized by microorganisms and are biodegradable, making them suitable candidates. The present study looks at the degradation properties of two PHA polymers: polyhydroxybutyrate (PHB) and polyhydroxybutyrate-co-polyhydroxyvalerate (PHBV; 8 wt.% valerate), in two different soil conditions: soil fully saturated with water (100% relative humidity, RH) and soil with 40% RH. The degradation was evaluated by observing the changes in appearance, chemical signatures, mechanical properties, and molecular weight of samples. Both PHB and PHBV were degraded completely after two weeks in 100% RH soil conditions and showed significant reductions in mechanical properties after just three days. The samples in 40% RH soil, however, showed minimal changes in mechanical properties, melting temperatures/crystallinity, and molecular weight over six weeks. By observing the degradation behavior for different soil conditions, these results can pave the way for identifying situations where the current use of plastics can be replaced with biodegradable alternatives.

Mesoscale Simulation Based on the Dynamic Mean-Field Density Functional Method on Block-Copolymeric Ionomers for Polymer Electrolyte Membranes.

Block copolymers generally have peculiar morphological characteristics, such as strong phase separation. They have been actively applied to polymer electrolyte membranes for proton exchange membrane fuel cells (PEMFCs) to obtain well-defined hydrophilic regions and water channels as a proton pathway. Although molecular simulation tools are advantageous to investigate the mechanism of water channel formation based on the chemical structure and property relationships, classical molecular dynamics simulation has limitations regarding the model size and time scale, and these issues need to be addressed. In this study, we investigated the morphology of sulfonated block copolymers synthesized for PEM applications using a mesoscale simulation based on the dynamic mean-field density functional method, widely applied to investigate macroscopic systems such as polymer blends, micelles, and multi-block/grafting copolymers. Despite the similar solubility parameters of the monomers in our block-copolymer models, very different morphologies in our 3D mesoscale models were obtained. The model with sulfonated monomers, in which the number of sulfonic acid groups is twice that of the other model, showed better phase separation and water channel formation, despite the short length of its hydrophilic block. In conclusion, this unexpected behavior indicates that the role of water molecules is important in making PEM mesoscale models well-equilibrated in the mesoscale simulation, which results in the strong phase separation between hydrophilic and hydrophobic regions and the ensuing well-defined water channel. PEM synthesis supports the conclusion that using the sulfonated monomers with a high sulfonation degree (32.5 mS/cm) will be more effective than using the long hydrophilic block with a low sulfonation degree (25.2 mS/cm).

Potential Applications of Thermoresponsive Poly(N-Isoproplacrylamide)-Grafted Nylon Membranes: Effect of Grafting Yield and Architecture on Gating Performance.

This study illustrated the potential applications of thermoresponsive poly(N-isopropylacrylamide) (PNIPAm) grafted nylon membranes with different grafting yields and grafting architecture. The thermoresponsive gating performance at temperatures below and above the lower critical solution temperature (LCST) of PNIPAm (32 °C) were demonstrated. The linear PNIPAm-grafted nylon membrane exhibited a sharp response over the temperature range 20-40 °C. The grafting yield of 25.5% and 21.9%, for linear and crosslinked PNIPAm respectively, exhibited highest thermoresponsive gating function for water flux and had a stable and repeatable "open-closed" switching function over 5 cycle operations. An excellent oil/water separation was obtained at T < 32 °C, at which the hydrophilic behavior was observed. The linear PNIPAm-grafted nylon membrane with 35% grafting yield had the highest separation efficiency of 99.7%, while PNIPAm structures were found to be independent of the separation efficiency. In addition, the membranes with thermoresponsive gas permeability were successfully achieved. The O2 and CO2 transmission rates through the PNIPAm-grafted nylon membranes decreased when the grafting yield increased, showing the better gas barrier property. The permeability ratio of CO2 to O2 transmission rates of both PNIPAm architectures at 25 °C and 35 °C were around 0.85 for low grafting yields, and approximately 1 for high grafting yields. Ultimately, this study demonstrated the possibility of using these thermoresponsive smart membranes in various applications.

A Review of Recent Chitosan Anion Exchange Membranes for Polymer Electrolyte Membrane Fuel Cells.

Considering the critical energy challenges and the generation of zero-emission anion exchange membrane (AEM) sources, chitosan-based anion exchange membranes have garnered considerable interest in fuel cell applications owing to their various advantages, including their eco-friendly nature, flexibility for structural modification, and improved mechanical, thermal, and chemical stability. The present mini-review highlights the advancements of chitosan-based biodegradable anion exchange membranes for fuel cell applications published between 2015 and 2022. Key points from the rigorous literature evaluation are: grafting with various counterions in addition to crosslinking contributed good conductivity and chemical as well as mechanical stability to the membranes; use of the interpenetrating network as well as layered structures, blending, and modified nanomaterials facilitated a significant reduction in membrane swelling and long-term alkaline stability. The study gives insightful guidance to the industry about replacing Nafion with a low-cost, environmentally friendly membrane source. It is suggested that more attention be given to exploring chitosan-based anion exchange membranes in consideration of effective strategies that focus on durability, as well as optimization of the operational conditions of fuel cells for large-scale applications.

Polymer Electrolyte Membranes Containing Functionalized Organic/Inorganic Composite for Polymer Electrolyte Membrane Fuel Cell Applications.

To mitigate the dependence on fossil fuels and the associated global warming issues, numerous studies have focused on the development of eco-friendly energy conversion devices such as polymer electrolyte membrane fuel cells (PEMFCs) that directly convert chemical energy into electrical energy. As one of the key components in PEMFCs, polymer electrolyte membranes (PEMs) should have high proton conductivity and outstanding physicochemical stability during operation. Although the perfluorinated sulfonic acid (PFSA)-based PEMs and some of the hydrocarbon-based PEMs composed of rationally designed polymer structures are found to meet these criteria, there is an ongoing and pressing need to improve and fine-tune these further, to be useful in practical PEMFC operation. Incorporation of organic/inorganic fillers into the polymer matrix is one of the methods shown to be effective for controlling target PEM properties including thermal stability, mechanical properties, and physical stability, as well as proton conductivity. Functionalization of organic/inorganic fillers is critical to optimize the filler efficiency and dispersion, thus resulting in significant improvements to PEM properties. This review focused on the structural engineering of functionalized carbon and silica-based fillers and comparisons of the resulting PEM properties. Newly constructed composite membranes were compared to composite membrane containing non-functionalized fillers or pure polymer matrix membrane without fillers.

The complete chloroplast genome of Echeveria lilacina Kimnach & Moran 1980 (Saxifragales: Crassulaceae).

Echeveria lilacina Kimnach & Moran 1980 is a succulent plant having ornamental and ecological importance. In this study, the first complete chloroplast genome of Echeveria lilacina, a species belonging to the Crassulaceae family, was characterized from the de novo assembly of Illumina NovaSeq 6000 paired-end sequencing data. The chloroplast genome of E. lilacina is 150,080 bp in length, which includes a large single-copy (LSC) region of 81,741 bp, a small single-copy (SSC) region of 16,747 bp, and a pair of identical inverted repeat regions (IRs) of 25,796 bp each. The genome annotation revealed a total of 138 genes, including 87 protein-coding genes, 41 transfer RNA (tRNA) genes, and 10 ribosomal RNA (rRNA) genes. The phylogenetic analysis with 15 complete chloroplast genome sequences including outgroup showed that E. lilacina formed the closest taxonomical relationship with Graptopetalum amethystinum in the Crassulaceae family.

Effect of Cross-Linking and Surface Treatment on the Functional Properties of Electrospun Polybenzimidazole Separators for Lithium Metal Batteries.

In this work, electrospun PBI separators with a highly porous structure and nanofiber diameter of about 90-150 nm are prepared using a multi-nozzle under controlled conditions for lithium metal batteries. Cross-linking with α, α-dibromo-p-xylene and surface treatment using 4-(chloromethyl) benzoic acid successfully improve the electrochemical as well as mechanical properties of the separators. The resulting separator is endowed with high thermal stability and excellent wettability (1080 to 1150%) with commercial liquid electrolyte than PE and PP (Celgard 2400) separators. Besides, attractive cycling stability and rate capability in LiFePO4/Li cells are attained with the modified separators. Prominently, CROSSLINK PBI exhibits a stable Coulombic efficiency of more than 99% over 100 charge-discharge cycles at 0.5 C, which is superior to the value of cells using commercial PE and PP (Celgard 2400) separators. The half cells assembled using the CROSSLINK PBI separator can deliver a discharge capacity of 150.3 mAh g-1 at 0.2 C after 50 cycles corresponding to 88.4% of the theoretical value of LiFePO4 (170 mAh g-1). This work offers a worthwhile method to produce thermally stable separators with noteworthy electrochemical performances which opens new possibilities to improve the safe operation of batteries.

Self-Humidifying Membrane for High-Performance Fuel Cells Operating at Harsh Conditions: Heterojunction of Proton and Anion Exchange Membranes Composed of Acceptor-Doped SnP2O7 Composites.

Here we suggest a simple and novel method for the preparation of a high-performance self-humidifying fuel cell membrane operating at high temperature (>100 °C) and low humidity conditions (<30% RH). A self-humidifying membrane was effectively prepared by laminating together proton and anion exchange membranes composed of acceptor-doped SnP2O7 composites, Sn0.9In0.1H0.1P2O7/Sn0.92Sb0.08(OH)0.08P2O7. At the operating temperature of 100 °C, the electrochemical performances of the membrane electrode assembly (MEA) with this heterojunction membrane at 3.5% RH were better than or comparable to those of each MEA with only the proton or anion exchange membranes at 50% RH or higher.

Study on Control of Polymeric Architecture of Sulfonated Hydrocarbon-Based Polymers for High-Performance Polymer Electrolyte Membranes in Fuel Cell Applications.

Polymer electrolyte membrane fuel cell (PEMFC) is an eco-friendly energy conversion device that can convert chemical energy into electrical energy without emission of harmful oxidants such as nitrogen oxides (NOx) and/or sulfur oxides (SOx) during operation. Nafion®, a representative perfluorinated sulfonic acid (PFSA) ionomer-based membrane, is generally incorporated in fuel cell systems as a polymer electrolyte membrane (PEM). Since the PFSA ionomers are composed of flexible hydrophobic main backbones and hydrophilic side chains with proton-conducting groups, the resulting membranes are found to have high proton conductivity due to the distinct phase-separated structure between hydrophilic and hydrophobic domains. However, PFSA ionomer-based membranes have some drawbacks, including high cost, low glass transition temperatures and emission of environmental pollutants (e.g., HF) during degradation. Hydrocarbon-based PEMs composed of aromatic backbones with proton-conducting hydrophilic groups have been actively studied as substitutes. However, the main problem with the hydrocarbon-based PEMs is the relatively low proton-conducting behavior compared to the PFSA ionomer-based membranes due to the difficulties associated with the formation of well-defined phase-separated structures between the hydrophilic and hydrophobic domains. This study focused on the structural engineering of sulfonated hydrocarbon polymers to develop hydrocarbon-based PEMs that exhibit outstanding proton conductivity for practical fuel cell applications.

Blended Anion Exchange Membranes for Vanadium Redox Flow Batteries.

In this study, blended anion exchange membranes were prepared using polyphenylene oxide containing quaternary ammonium groups and polyvinylidene fluoride. A polyvinylidene fluoride with high hydrophobicity was blended in to lower the vanadium ion permeability, which increased when the hydrophilicity increased. At the same time, the dimensional stability also improved due to the excellent physical properties of polyvinylidene fluoride. Subsequently, permeation of the vanadium ions was prevented due to the positive charge of the anion exchange membrane, and thus the permeability was relatively lower than that of a commercial proton exchange membrane. Due to the above properties, the self-discharge of the blended anion exchange membrane (30.1 h for QA-PPO/PVDF(2/8)) was also lower than that of the commercial proton exchange membrane (27.9 h for Nafion), and it was confirmed that it was an applicable candidate for vanadium redox flow batteries.

In-situ thermal phase transition and structural investigation of ferroelectric tetragonal barium titanate nanopowders with pseudo-cubic phase.

Optimization and miniaturization of existing electronic devices require the development of advanced nanostructured materials with high phase and structural purity. Over the past decade, barium titanate (BaTiO3) has attracted considerable attention due to its outstanding ferroelectric and dielectric properties. The present study involved the investigation of the phase transition and structural stability of tetragonal BaTiO3 nanopowders with pseudo-cubic phase using an in-situ high resolution and high temperature X-ray diffraction method. Under ambient conditions, the coexistence the tetragonal and cubic phases with weight fractions of 75.7% and 24.3%, respectively, was determined in BaTiO3. In the temperature range of 25 °C-300 °C, phase boundaries of BaTiO3 (180 nm in size) exhibiting several phases were detected. The phase transformation behavior, relative crystal phase content, lattice parameters, crystallite size, and tetragonality of the BaTiO3 nanopowders were established by the Rietveld refinement method at the onset temperature from 25 °C to 300 °C. Up to 150 °C, the nanopowders exhibited a complete transition of the cubic phase. Additionally, a complete tetragonal to cubic transformation was accomplished by a decrease of tetragonality at 125 °C and an increase in the crystallite size at 300 °C.

Anion Exchange Composite Membranes Composed of Quaternary Ammonium-Functionalized Poly(2,6-dimethyl-1,4-phenylene oxide) and Silica for Fuel Cell Application.

Anion exchange membranes (AEMs) with good alkaline stability and ion conductivity are fabricated by incorporating quaternary ammonium-modified silica into quaternary ammonium-functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (QPPO). Quaternary ammonium with a long alkyl chain is chemically grafted to the silica in situ during synthesis. Glycidyltrimethylammoniumchloride functionalization on silica (QSiO2) is characterized by Fourier transform infrared and transmission electron microscopic techniques. The QPPO/QSiO2 membrane having an ion exchange capacity of 3.21 meq·g-1 exhibits the maximum hydration number (λ = 11.15) and highest hydroxide ion conductivity of 45.08 × 10-2 S cm-1 at 80 °C. In addition to the high ion conductivity, AEMs also exhibit good alkaline stability, and the conductivity retention of the QPPO/QSiO2-3 membrane after 1200 h of exposure in 1 M potassium hydroxide at room temperature is about 91% ascribed to the steric hindrance offered by the grafted long glycidyl trimethylammonium chain in QSiO2. The application of the QPPO/QSiO2-3 membrane to an alkaline fuel cell can yield a peak power density of 142 mW cm-2 at a current density of 323 mA cm-2 and 0.44 V, which is higher than those of commercially available FAA-3-50 Fumatech AEM (OCV: 0.91 V; maximum power density: 114 mW cm-2 at current density: 266 mA cm-2 and 0.43 V). These membranes provide valuable insights on future directions for advanced AEM development for fuel cells.

Crosslinked Pore-Filling Anion Exchange Membrane Using the Cylindrical Centrifugal Force for Anion Exchange Membrane Fuel Cell System.

In this study, novel crosslinked pore-filling membranes were fabricated by using a centrifugal force from the cylindrical centrifugal machine. For preparing these crosslinked pore-filling membranes, the poly(phenylene oxide) containing long side chains to improve the water management (hydrophilic), porous polyethylene support (hydrophobic) and crosslinker based on the diamine were used. The resulting membranes showed a uniform thickness, flexible and transparent because it is well filled. Among them, PF-XAc-PPO70_25 showed good mechanical properties (56.1 MPa of tensile strength and 781.0 MPa of Young's modulus) and dimensional stability due to the support. In addition, it has a high hydroxide conductivity (87.1 mS/cm at 80 °C) and low area specific resistance (0.040 Ω·cm2), at the same time showing stable alkaline stability. These data outperformed the commercial FAA-3-50 membrane sold by Fumatech in Germany. Based on the optimized properties, membrane electrode assembly using XAc-PPO70_25 revealed excellent cell performance (maximum power density: 239 mW/cm2 at 0.49 V) than those of commercial FAA-3-50 Fumatech anion exchange membrane (maximum power density: 212 mW/cm2 at 0.54 V) under the operating condition of 60 °C and 100% RH as well. It was expected that PF-XAc-PPO70_25 could be an excellent candidate based on the results superior to those of commercial membranes in these essential characteristics of fuel cells.

Electrochemical Performance Evaluation of Bipolar Membrane Using Poly(phenylene oxide) for Water Treatment System.

This study describes the use of poly(phenylene oxide) polymer-based ion-exchange polymers, polystyrene-based ion-exchange particles and a porous support for fabricating bipolar membranes and the results of an assessment of the applicability of these materials to water splitting. In order to achieve good mechanical as well as good ion-exchange properties, bipolar membranes were prepared by laminating poly(phenylene oxide) and polystyrene based ion-exchange membranes with a sulfonated polystyrene-block-(ethylene-ran-butylene)-block-polystyrene) (S-SEBS) modified interface. PE pore-supported ion-exchange membranes were also used as bipolar membranes. The tensile strength was 13.21 MPa for the bipolar membrane which utilized only a cation/anion-exchange membrane. When ion-exchange nanoparticles were introduced for high efficiency, a reduction in the tensile strength to 6.81 MPa was observed. At the same time, bipolar membrane in the form of a composite membrane using PE support exhibited the best tensile strength of 32.41 MPa. To confirm the water-splitting performance, an important factor for a bipolar membrane, pH changes over a period of 20 min were also studied. During water slitting using CA-P-PE-BPM, the pH at the CEM part and the AEM part changed from 5.4 to 4.18 and from 5.4 to 5.63, respectively.

Preparation and Characterization of Pore Filled Hybrid Composite Membrane Composed of Cation Exchange Materials and Polyethylene Support.

This study investigated ion exchange membranes for application to seawater desalination processes. This can provide better energy efficiency than the conventional reverse osmosis process. In this experiment, the problem of decreasing ion exchange performance when the ion exchange composite membrane was prepared could be improved through nanoparticles. The nanoparticle added ion exchange hybrid membrane showed ion exchange capacity similar to that of the conventional pristine film. In addition, the polymer having a high ion exchange capacity has poor mechanical strength, but has excellent mechanical strength of 30 MPa or more by the introduction of a polyethylene support.