Synthesis of Soluble High Molar Mass Poly(Phenylene Methylene)-Based Polymers.

Poly(phenylene methylene) (PPM) is a multifunctional polymer that is also active as an anticorrosion fluorescent coating material. Although this polymer was synthesized already more than 100 years ago, a versatile synthetic route to obtain soluble high molar mass polymers based on PPM has yet to be achieved. In this article, the influence of bifunctional bis-chloromethyl durene (BCMD) as a branching agent in the synthesis of PPM is reported. The progress of the reaction was followed by gel permeation chromatography (GPC) and NMR analysis. PPM-based copolymers with the highest molar mass reported so far for this class of materials (up to Mn of 205,300 g mol-1) were isolated. The versatile approach of using BCMD was confirmed by employing different catalysts. Interestingly, thermal and optical characterization established that the branching process does not affect the thermoplastic behavior and the fluorescence of the material, thus opening up PPM-based compounds with high molar mass for applications.

Self-Assembled Preparation of Porous Nickel Phosphide Superparticles with Tunable Phase and Porosity for Efficient Hydrogen Evolution.

Self-assembly of colloidal nanoparticles enables the easy building of assembly units into higher-order structures and the bottom-up preparation of functional materials. Nickel phosphides represent an important group of catalysts for hydrogen evolution reaction (HER) from water splitting. In this paper, the preparation of porous nickel phosphide superparticles and their HER efficiencies are reported. Ni and Ni2 P nanoparticles are self-assembled into binary superparticles via an oil-in-water emulsion method. After annealing and acid etching, the as-prepared Ni-Ni2 P binary superparticles change into porous nickel phosphide superparticles. The porosity and crystalline phase of the superparticles can be tuned by adjusting the ratio of Ni and Ni2 P nanoparticles. The resulting porous superparticles are effective in driving HER under acidic conditions, and the modulation of porosity and phase further optimize the electrochemical performance. The prepared Ni3 P porous superparticles not only possess a significantly enhanced specific surface area compared to solid Ni-Ni2 P superparticles but also exhibit an excellent HER efficiency. The calculations based on the density functional theories show that the (110) crystal facet exhibits a relatively lower Gibbs free energy of hydrogen adsorption. This work provides a self-assembly approach for the construction of porous metal phosphide nanomaterials with tunable crystalline phase and porosity.

Optimization of Mass and Light Transport in Nanoparticle-Based Titania Aerogels.

Aerogels composed of preformed titania nanocrystals exhibit a large surface area, open porosity, and high crystallinity, making these materials appealing for applications in gas-phase photocatalysis. Recent studies on nanoparticle-based titania aerogels have mainly focused on optimizing their composition to improve photocatalytic performance. Little attention has been paid to modification at the microstructural level to control fundamental properties such as gas permeability and light transmittance, although these features are of fundamental importance, especially for photocatalysts of macroscopic size. In this study, we systematically control the porosity and transparency of titania gels and aerogels by adjusting the particle loading and nonsolvent fraction during the gelation step. Mass transport and light transport were assessed by gas permeability and light attenuation measurements, and the results were related to the microstructure determined by gas sorption analysis and scanning electron microscopy. Mass transport through the aerogel network was found to proceed primarily via Knudsen diffusion leading to relatively low permeabilities in the range of 10-5-10-6 m2/s, despite very high porosities of 96-99%. While permeability was found to depend mainly on particle loading, the optical properties are predominantly affected by the amount of nonsolvent during gelation, allowing independent tuning of mass and light transport.

Superelastic Cobalt Silicate@Resorcinol Formaldehyde Resin Core-Shell Nanobelt Aerogel Monoliths with Outstanding Fire Retardant and Thermal Insulating Capability.

The practical applications of resorcinol formaldehyde resin (RFR) aerogels are prevented by their poor mechanical properties. Herein, a facile template-directed method is reported to produce macroscopic free-standing cobalt silicate (CS)@RFR core-shell nanobelt aerogels that display superelastic behavior and outstanding thermal insulating and fire-resistant capability. The synthesis relies on the polymerization of RFR on pre-formed CS nanobelts which leads to in situ formation of hydrogel monoliths that can be transformed to corresponding aerogels by a freeze-drying method. The composite nanobelt aerogel can withstand a compressive load of more than 4000 times of its own weight and fully recover after the removal of the weight. It can also sustain 1000 compressive cycles with 6.9% plastic deformation and 91.8% of the maximum stress remaining, with a constant energy loss coefficient as low as 0.16, at the set strain of 30%. The extraordinary mechanical properties are believed to be associated with the structural flexibility of the nanobelts and the RFR-reinforced joints between the crosslinked nanobelts. These inorganic-organic composite aerogels also show good thermal insulation and excellent fire-proof capability. This work provides an effective strategy for fabricating superelastic RFR-based aerogels which show promising applications in fields such as thermal insulation, energy storage, and catalyst support.

Metal Phosphorous Chalcogenide: A Promising Material for Advanced Energy Storage Systems.

The development of efficient and affordable electrode materials is crucial for clean energy storage systems, which are considered a promising strategy for addressing energy crises and environmental issues. Metal phosphorous chalcogenides (MPX3 ) are a fascinating class of two-dimensional materials with a tunable layered structure and high ion conductivity, making them particularly attractive for energy storage applications. This review article aims to comprehensively summarize the latest research progress on MPX3 materials, with a focus on their preparation methods and modulation strategies. Additionally, the diverse applications of these novel materials in alkali metal ion batteries, metal-air batteries, and all-solid-state batteries are highlighted. Finally, the challenges and opportunities of MPX3 materials are presented to inspire their better potential in energy storage applications. This review provides valuable insights into the promising future of MPX3 materials in clean energy storage systems.

Chitin Nanofibrils from Fungi for Hierarchical Gel Polymer Electrolytes for Transient Zinc-Ion Batteries with Stable Zn Electrodeposition.

Rechargeable batteries play an integral role toward carbon neutrality. Environmentally sustainable batteries should consider the trade-offs between material renewability, processability, thermo-mechanical and electrochemical performance, as well as transiency. To address this dilemma, we follow circular economy principles to fabricate fungal chitin nanofibril (ChNF) gel polymer electrolytes (GPEs) for zinc-ion batteries. These biocolloids are physically entangled into hierarchical hydrogels with specific surface areas of 49.5 m2 ·g-1 . Ionic conductivities of 54.1 mS·cm-1 and a Zn2+ transference number of 0.468 are reached, outperforming conventional non-renewable/non-biodegradable glass microfibre separator-liquid electrolyte pairs. Enabled by its mechanically elastic properties and large water uptake, a stable Zn electrodeposition in symmetric Zn|Zn configuration with a lifespan above 600 h at 9.5 mA·cm-2 is obtained. At 100 mA·g-1 , the discharge capacity of Zn/α-MnO2 full cells increases above 500 cycles when replacing glass microfiber separators with ChNF GPEs, while the rate performance remains comparable to glass microfiber separators. To make the battery completely transient, the metallic current collectors are replaced by biodegradable polyester/carbon black composites undergoing degradation in water at 70 °C. This work demonstrates the applicability of bio-based materials to fabricate green and electrochemically competitive batteries with potential applications in sustainable portable electronics, or biomedicine.

Oriented Porous NASICON 3D Framework via Freeze-Casting for Sodium-Metal Batteries.

Sodium-metal batteries are promising candidates for low-cost, large-format energy storage systems. However, sodium-metal batteries suffer from high interfacial resistance between the electrodes and the solid electrolyte, leading to poor electrochemical performance. We demonstrate a sodium superionic conductor (NASICON) with an oriented porous framework of sodium aluminum titanium phosphate (NATP) fabricated by the freeze-casting technique, which shows excellent properties as a solid electrolyte. Using X-ray computed tomography, we confirm the uniform low-tortuosity channels present along the thickness of the scaffold. We infiltrated the porous NATP scaffolds with sodium vanadium phosphate (NVP) cathode nanoparticles achieving mass loadings of ∼3-4 mg cm-2, which enables short sodium ion diffusion path lengths. For the resulting hybrid cell, we achieved a capacity of ∼90 mAh g-1 at a specific current of 50 mA g-1 (∼300 Wh kg-1) for over 100 cycles with ∼94% capacity retention. Our study offers valuable insights for the design of hybrid solid electrolyte-cathode active material structures to achieve improved electrochemical performance through low-tortuosity ion transport networks.

Conducting ITO Nanoparticle-Based Aerogels-Nonaqueous One-Pot Synthesis vs. Particle Assembly Routes.

Indium tin oxide (ITO) aerogels offer a combination of high surface area, porosity and conductive properties and could therefore be a promising material for electrodes in the fields of batteries, solar cells and fuel cells, as well as for optoelectronic applications. In this study, ITO aerogels were synthesized via two different approaches, followed by critical point drying (CPD) with liquid CO2. During the nonaqueous one-pot sol-gel synthesis in benzylamine (BnNH2), the ITO nanoparticles arranged to form a gel, which could be directly processed into an aerogel via solvent exchange, followed by CPD. Alternatively, for the analogous nonaqueous sol-gel synthesis in benzyl alcohol (BnOH), ITO nanoparticles were obtained and assembled into macroscopic aerogels with centimeter dimensions by controlled destabilization of a concentrated dispersion and CPD. As-synthesized ITO aerogels showed low electrical conductivities, but an improvement of two to three orders of magnitude was achieved by annealing, resulting in an electrical resistivity of 64.5-1.6 kΩ·cm. Annealing in a N2 atmosphere led to an even lower resistivity of 0.2-0.6 kΩ·cm. Concurrently, the BET surface area decreased from 106.2 to 55.6 m2/g with increasing annealing temperature. In essence, both synthesis strategies resulted in aerogels with attractive properties, showing great potential for many applications in energy storage and for optoelectronic devices.

Bottom-Up Design of a Green and Transient Zinc-Ion Battery with Ultralong Lifespan.

Transient batteries are expected to lessen the inherent environmental impact of traditional batteries that rely on toxic and critical raw materials. This work presents the bottom-up design of a fully transient Zn-ion battery (ZIB) made of nontoxic and earth-abundant elements, including a novel hydrogel electrolyte prepared by cross-linking agarose and carboxymethyl cellulose. Facilitated by a high ionic conductivity and a high positive zinc-ion species transference number, the optimized hydrogel electrolyte enables stable cycling of the Zn anode with a lifespan extending over 8500 h for 0.25 mA cm-2 - 0.25 mAh cm-2 . On pairing with a biocompatible organic polydopamine-based cathode, the full cell ZIB delivers a capacity of 196 mAh g-1 after 1000 cycles at a current density of 0.5 A g-1 and a capacity of 110 mAh g-1 after 10 000 cycles at a current density of 1 A g-1 . A transient ZIB with a biodegradable agarose casing displays an open circuit voltage of 1.123 V and provides a specific capacity of 157 mAh g-1 after 200 cycles at a current density of 50 mA g-1 . After completing its service life, the battery can disintegrate under composting conditions.

The Role of Zn Ions in the Structural, Surface, and Gas-Sensing Properties of SnO2:Zn Nanocrystals Synthesized via a Microwave-Assisted Route.

Although semiconducting metal oxide (SMOx) nanoparticles (NPs) have attracted attention as sensing materials, the methodologies available to synthesize them with desirable properties are quite limited and/or often require relatively high energy consumption. Thus, we report herein the processing of Zn-doped SnO2 NPs via a microwave-assisted nonaqueous route at a relatively low temperature (160 °C) and with a short treatment time (20 min). In addition, the effects of adding Zn in the structural, electronic, and gas-sensing properties of SnO2 NPs were investigated. X-ray diffraction and high-resolution transmission electron microscopy analyses revealed the single-phase of rutile SnO2, with an average crystal size of 7 nm. X-ray absorption near edge spectroscopy measurements revealed the homogenous incorporation of Zn ions into the SnO2 network. Gas sensing tests showed that Zn-doped SnO2 NPs were highly sensitive to sub-ppm levels of NO2 gas at 150 °C, with good recovery and stability even under ambient moisture. We observed an increase in the response of the Zn-doped sample of up to 100 times compared to the pristine one. This enhancement in the gas-sensing performance was linked to the Zn ions that provided more surface oxygen defects acting as active sites for the NO2 adsorption on the sensing material.

Improving the Corrosion Protection of Poly(phenylene methylene) Coatings by Side Chain Engineering: The Case of Methoxy-Substituted Copolymers.

This work aims to improve the corrosion protection features of poly(phenylene methylene) (PPM) by sidechain engineering inserting methoxy units along the polymer backbone. The influence of side methoxy groups at different concentrations (4.6% mol/mol and 9% mol/mol) on the final polymer properties was investigated by structural and thermal characterization of the resulting copolymers: co-PPM 4.6% and co-PPM 9%, respectively. Then, coatings were processed by hot pressing the polymers powder on aluminum alloy AA2024 and corrosion protection properties were evaluated exposing samples to a 3.5% w/v NaCl aqueous solution. Anodic polarization tests evidenced the enhanced corrosion protection ability (i.e., lower current density) by increasing the percentage of the co-monomer. Coatings made with co-PPM 9% showed the best protection performance with respect to both PPM blend and PPM co-polymers reported so far. Electrochemical response of aluminum alloy coated with co-PPM 9% was monitored over time under two "artificially-aged" conditions, that are: (i) a pristine coating subjected to potentiostatic anodic polarization cycles, and (ii) an artificially damaged coating at resting condition. The first scenario points to accelerating the corrosion process, the second one models damage of the coating potentially occurring either due to natural deterioration or due to any accidental scratching of the polymer layer. In both cases, an intrinsic self-healing phenomenon was indirectly argued by the time evolution of the impedance and of the current density of the coated systems. The degree of restoring to the "factory conditions" by co-polymer coatings after self-healing events is eventually discussed.

Robust Antibacterial Activity of Xanthan-Gum-Stabilized and Patterned CeO2-x-TiO2 Antifog Films.

Increased occurrence of antimicrobial resistance leads to a huge burden on patients, the healthcare system, and society worldwide. Developing antimicrobial materials through doping rare-earth elements is a new strategy to overcome this challenge. To this end, we design antibacterial films containing CeO2-x-TiO2, xanthan gum, poly(acrylic acid), and hyaluronic acid. CeO2-x-TiO2 inks are additionally integrated into a hexagonal grid for prominent transparency. Such design yields not only an antibacterial efficacy of ∼100% toward Staphylococcus aureus and Escherichia coli but also excellent antifog performance for 72 h in a 100% humidity atmosphere. Moreover, FluidFM is employed to understand the interaction in-depth between bacteria and materials. We further reveal that reactive oxygen species (ROS) are crucial for the bactericidal activity of E. coli through fluorescent spectroscopic analysis and SEM imaging. We meanwhile confirm that Ce3+ ions are involved in the stripping phosphate groups, damaging the cell membrane of S. aureus. Therefore, the hexagonal mesh and xanthan-gum cross-linking chains act as a reservoir for ROS and Ce3+ ions, realizing a long-lasting antibacterial function. We hence develop an antibacterial and antifog dual-functional material that has the potential for a broad application in display devices, medical devices, food packaging, and wearable electronics.

Smart Anticorrosion Coatings Based on Poly(phenylene methylene): An Assessment of the Intrinsic Self-Healing Behavior of the Copolymer.

Poly(phenylene methylene) (PPM) is a multifunctional polymer featuring hydrophobicity, high thermal stability, fluorescence and thermoplastic processability. Accordingly, smart corrosion resistant PPM-based coatings (blend and copolymer) were prepared and applied by hot pressing on aluminum alloy AA2024. The corrosion protection properties of the coatings and their dependence on coating thickness were evaluated for both strategies employed. The accelerated cyclic electrochemical technique (ACET), based on a combination of electrochemical impedance spectroscopy (EIS), cathodic polarizations and relaxation steps, was used as the main investigating technique. At the coating thickness of about 50 µm, both blend and copolymer PPM showed effective corrosion protection, as reflected by |Z|0.01Hz of about 108 Ω cm2 over all the ACET cycles. In contrast, when the coating thickness was reduced to 30 µm, PPM copolymer showed neatly better corrosion resistance than blended PPM, maintaining |Z|0.01Hz above 108 Ω cm2 with respect to values below 106 Ω cm2 of the latter. Furthermore, the analysis of many electrochemical key features, in combination with the optical investigation of the coating surface under 254 nm UV light, confirms the intrinsic self-healing ability of the coatings made by PPM copolymer, contrary to the reference specimen (i.e., blend PPM).

Studies on the Interaction of Poly(phenylene methylene) with Silver(I) and Hexacarbonylchromium(0).

Complexes of poly(phenylene methylene) (PPM) with silver(I) ions and tricarbonylchromium(0) moieties, respectively, were synthesized. 13C NMR spectra indicate interaction of phenylene groups with silver(I) and chromium(0), and peak broadening implies dynamic behavior of the silver(I) complexes, with all phenylene groups temporarily involved in coordination, in contrast to the chromium complexes. About 5-10% of the phenylene groups are coordinated to metal atoms. 1H NMR and IR spectra, in the case of chromium(0), and the solubility of silver salts in the presence of PPM provide further evidence of coordination. The complexes are soluble in chloroform, but the silver complexes decay in tetrahydrofuran (second-order kinetics were observed in an example). The photoluminescence (fluorescence) of PPM is maintained upon complexation, although coordination of silver(I) seems to favor the so-called blue phase of PPM relative to the green phase by a factor of approximately two in PL spectra. The pronounced absorption of the tricarbonylchromium(0) units interferes with the blue phase, which almost disappears at a concentration of 50 mg/mL in PLE spectra, whereas the emission maximum of the green phase is hardly affected. This leads to a confinement of the emitted wavelength range of PPM. Thus, the perceived optical emission of PPM can be modified by coordinated entities.

The Importance of the Macroscopic Geometry in Gas-Phase Photocatalysis.

Photocatalysis has the potential to make a major technological contribution to solving pressing environmental and energy problems. There are many strategies for improving photocatalysts, such as tuning the composition to optimize visible light absorption, charge separation, and surface chemistry, ensuring high crystallinity, and controlling particle size and shape to increase overall surface area and exploit the reactivity of individual crystal facets. These processes mainly affect the nanoscale and are therefore summarized as nanostructuring. In comparison, microstructuring is performed on a larger size scale and is mainly concerned with particle assembly and thin film preparation. Interestingly, most structuring efforts stop at this point, and there are very few examples of geometry optimization on a millimeter or even centimeter scale. However, the recent work on nanoparticle-based aerogel monoliths has shown that this size range also offers great potential for improving the photocatalytic performance of materials, especially when the macroscopic geometry of the monolith is matched to the design of the photoreactor. This review article is dedicated to this aspect and addresses some issues and open questions that arise when working with macroscopically large photocatalysts. Guidelines are provided that could help develop novel and efficient photocatalysts with a truly 3D architecture.

Hierarchical Nanocellulose-Based Gel Polymer Electrolytes for Stable Na Electrodeposition in Sodium Ion Batteries.

Sodium ion batteries (NIBs) based on earth-abundant materials offer efficient, safe, and environmentally sustainable solutions for a decarbonized society. However, to compete with mature energy storage technologies such as lithium ion batteries, further progress is needed, particularly regarding the energy density and operational lifetime. Considering these aspects as well as a circular economy perspective, the authors use biodegradable cellulose nanoparticles for the preparation of a gel polymer electrolyte that offers a high liquid electrolyte uptake of 2985%, an ionic conductivity of 2.32 mS cm-1 , and a Na+ transference number of 0.637. A balanced ratio of mechanically rigid cellulose nanocrystals and flexible cellulose nanofibers results in a mesoporous hierarchical structure that ensures close contact with metallic Na. This architecture offers stable Na plating/stripping at current densities up to ±500 µA cm-2 , outperforming conventional fossil-based NIBs containing separator-liquid electrolytes. Paired with an environmentally sustainable and economically attractive Na2 Fe2 (SO4 )3 cathode, the battery reaches an energy density of 240 Wh kg-1 , delivering 69.7 mAh g-1 after 50 cycles at a rate of 1C. In comparison, Celgard in liquid electrolyte delivers only 0.6 mAh g-1 at C/4. Such gel polymer electrolytes may open up new opportunities for sustainable energy storage systems beyond lithium ion batteries.

Transient Batteries: A Promising Step Towards Powering Green Electronics.

Transient electronics is an emerging class of innovative technology wherein electronic devices undergo controlled degradation processes after a period of stable operation, leaving no toxic products behind. This technology offers exciting opportunities in research areas of green electronics, temporary biomedical implants, data-secure hardware systems, and many others. However, one major challenge with these devices is their rigid and bulky batteries that contain toxic chemicals and are not at all degradable. So, to realize autonomous and self-sufficient transient electronics, the development of transient batteries is a pre-requisite. This review provides an overview of the advancements in the field of transient batteries, their materials, output performance, transience behaviour, and a few potential applications.

Gas-Phase Nitrogen Doping of Monolithic TiO2 Nanoparticle-Based Aerogels for Efficient Visible Light-Driven Photocatalytic H2 Production.

The development of visible light-active photocatalysts is essential for increasing the conversion efficiency of solar energy into hydrogen (H2). Here, we present a facile method for nitrogen doping of monolithic titanium dioxide (TiO2) nanoparticle-based aerogels to activate them for visible light. Plasma-enhanced chemical vapor deposition at low temperature enables efficient incorporation of nitrogen into preformed TiO2 aerogels without compromising their advantageous intrinsic characteristics such as large surface area, extensive porosity, and nanoscale properties of the semiconducting building blocks. By balancing the dopant concentration and the defects, the nitridation improves optical absorption and charge separation efficiency. The nitrogen-doped TiO2 nanoparticle-based aerogels loaded with palladium (Pd) nanoparticles show a significant enhancement in visible light-driven photocatalytic H2 production (3.1 mmol h-1 g-1) with excellent stability over 5 days. With this method, we introduce a powerful tool to tune the properties of nanoparticle-based aerogels after synthesis for a specific application, as exemplified by visible light-driven H2 production.

3D Printed Scaffolds for Monolithic Aerogel Photocatalysts with Complex Geometries.

Monolithic aerogels composed of crystalline nanoparticles enable photocatalysis in three dimensions, but they suffer from low mechanical stability and it is difficult to produce them with complex geometries. Here, an approach to control the geometry of the photocatalysts to optimize their photocatalytic performance by introducing carefully designed 3D printed polymeric scaffolds into the aerogel monoliths is reported. This allows to systematically study and improve fundamental parameters in gas phase photocatalysis, such as the gas flow through and the ultraviolet light penetration into the aerogel and to customize its geometric shape to a continuous gas flow reactor. Using photocatalytic methanol reforming as a model reaction, it is shown that the optimization of these parameters leads to an increase of the hydrogen production rate by a factor of three from 400 to 1200 µmol g-1 h-1 . The rigid scaffolds also enhance the mechanical stability of the aerogels, lowering the number of rejects during synthesis and facilitating handling during operation. The combination of nanoparticle-based aerogels with 3D printed polymeric scaffolds opens up new opportunities to tailor the geometry of the photocatalysts for the photocatalytic reaction and for the reactor to maximize overall performance without necessarily changing the material composition.

Synthesis of Cu3N and Cu3N-Cu2O multicomponent mesocrystals: non-classical crystallization and nanoscale Kirkendall effect.

Mesocrystals are superstructures of crystallographically aligned nanoparticles and are a rapidly emerging class of crystalline materials displaying sophisticated morphologies and properties, beyond those originating from size and shape of nanoparticles alone. This study reports the first synthesis of Cu3N mesocrystals employing structure-directing agents with a subtle tuning of the reaction parameters. Detailed structural characterizations carried out with a combination of transmission electron microscopy techniques (HRTEM, HAADF-STEM-EXDS) reveal that Cu3N mesocrystals form by non-classical crystallization, and variations in their sizes and morphologies are traced back to distinct attachment scenarios of corresponding mesocrystal subunits. In the presence of oleylamine, the mesocrystal subunits in the early reaction stages prealign in a crystallographic fashion and afterwards grow into the final mesocrystals, while in the presence of hexadecylamine the subunits come into contact through misaligned attachment, and subsequently, to some degree, realign in crystallographic register. Upon prolonged heating both types of mesocrystals undergo chemical conversion processes resulting in structural and morphological changes. A two-step mechanism of chemical conversion is proposed, involving Cu3N decomposition and anion exchange driven by the nanoscale Kirkendall effect, resulting first in multicomponent/heterostructured Cu3N-Cu2O mesocrystals, which subsequently convert into Cu2O nanocages. It is anticipated that combining nanostructured Cu3N and Cu2O in a mesocrystalline and hollow morphology will provide a platform to expand their application potential.