A Molecular Adsorption Concept for Increasing Energy Density of Hybrid Supercapacitors.

In this report, we demonstrate that high-capacity hybrid supercapacitors can be realized by utilizing iron azaphthalocyanine (FeAzPc-4N) adsorbed activated carbons (ACs) as an electrode due to the combination of the electric double layer of activated carbon surfaces and redox reactions of FeAzPc-4N molecules. By increasing the mixing ratio of FeAzPc-4N with ACs, a maximum capacity of 907 F/gAC is achieved, also enabling rapid charging and discharging at 20 A/g. The revelation of the capacitor electrode's durability through 20 000 cycles of charging and discharging is realized, and the capacitor cell had sufficient output power to illuminate LEDs. This concept illustrates the potential for enhancing capacitor performance by immobilizing redox-active species.

Benchmarking pH-field coupled microkinetic modeling against oxygen reduction in large-scale Fe-azaphthalocyanine catalysts.

Molecular metal-nitrogen-carbon (M-N-C) catalysts with well-defined structures and metal-coordination environments exhibit distinct structural properties and excellent electrocatalytic performance, notably in the oxygen reduction reaction (ORR) for fuel cells. Metal-doped azaphthalocyanine (AzPc) catalysts, a variant of molecular M-N-Cs, can be structured with unique long stretching functional groups, which make them have a geometry far from a two-dimensional geometry when loaded onto a carbon substrate, similar to a "dancer" on a stage, and this significantly affects their ORR efficiency at different pH levels. However, linking structural properties to performance is challenging, requiring comprehensive microkinetic modeling, substantial computational resources, and a combination of theoretical and experimental validation. Herein, we conducted pH-dependent microkinetic modeling based upon ab initio calculations and electric field-pH coupled simulations to analyze the pH-dependent ORR performance of carbon-supported Fe-AzPcs with varying surrounding functional groups. In particular, this study incorporates large molecular structures with complex long-chain "dancing patterns", each featuring >650 atoms, to analyze their performance in the ORR. Comparison with experimental ORR data shows that pH-field coupled microkinetic modeling closely matches the observed ORR efficiency at various pH levels in Fe-AzPc catalysts. Our results also indicate that assessing charge transfer at the Fe-site, where the Fe atom typically loses around 1.3 electrons, could be a practical approach for screening appropriate surrounding functional groups for the ORR. This study provides a direct benchmarking analysis for the microkinetic model to identify effective M-N-C catalysts for the ORR under various pH conditions.

Bifunctional rare metal-free electrocatalysts synthesized entirely from biomass resources.

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are important processes for various energy devices, including polymer electrolyte fuel cells, rechargeable metal-air batteries, and water electrolyzers. We herein report the preparation of a rare metal-free and highly efficient ORR/OER electrocatalyst by calcination of a mixture of blood meal and ascidian-derived cellulose nanofibers. The obtained carbon alloys showed high ORR/OER performances and proved to be promising electrocatalysts. The carbon alloys synthesized entirely from biomass resources not only lead to a new electrocatalyst fabrication process but also contribute to CO2 reduction and the realization of a good life-cycle assessment value in fabrication of a sustainable energy device.

Effect of Pore Size of Honeycomb-Patterned Polymer Film on Spontaneous Formation of 2D Micronetworks by Coculture of Human Umbilical Vein Endothelial Cells and Mesenchymal Stem Cells.

The geometrical control of micronetwork structures ( µ NSs) formed by endothelial cells is an important topic in tissue engineering, cell-based assays, and fundamental biological studies. In this study, µ NSs are formed using human umbilical vein endothelial cells (HUVECs) by the coculture of HUVECs and human mesenchymal stem cells (MSCs) confined in a honeycomb-patterned poly-l-lactic acid film (honeycomb film (HCF)), which is a novel cell culture scaffold. The HCF is produced using the breath figure method, which uses condensed water droplets as pore templates. The confinement of the HUVECs and MSCs in the HCF along with the application of centrifugal force results in µ NS formation when the pore size is more than 20  µ m. Furthermore, µ NS development is geometrically restricted by the hexagonally packed and connected pores in the horizontal direction of the HCF. Network density is also controlled by changing the seeding density of the HUVECs and MSCs. The threshold pore size indicates that µ NSs can be formed spontaneously by using an HCF with a perfectly uniform porous structure. This result provides an important design guideline for the structure of porous cell culture scaffolds by applying a blood vessel model in vitro.

Micropatterned culture of HepG2 spheroids using microwell chip with honeycomb-patterned polymer film.

Microwell chip culture is a promising technique for the generation of homogenous spheroids. We investigated the relationship between the structure of the bottom surface of microwell chip and the properties of HepG2 spheroid. We developed a microwell chip, the bottom surface of which consisted of a honeycomb-patterned polymer film (honeycomb film) that had a regular porous structure (HF chip). The chip comprised 270 circular microwells; each microwell was 600 µm in diameter and 600 µm in depth. At the center of the honeycomb film, an area, 200 µm in diameter, was modified with collagen to facilitate cell adhesion. With the exception of the collagen-coated area, the entire microwell was modified with polyethylene glycol to eliminate cell adhesion. HepG2 cells formed uniform spheroids when cultured in the microwells of HF chip. Furthermore, the cells passed through the porous structure of honeycomb film and formed spheroids at its opposite side. The spheroid growth of HepG2 cells cultured in HF chip was greater than that when the cells were culture in a microwell chip, the bottom surface of which was made of poly-methylmethacrylate (PMMA chip). The albumin secretion activity of HepG2 spheroids in HF chip was equal to that in PMMA chip. These results indicate that the microwell bottom with a porous structure enhances the cell growth and maintains well the spheroid function. Thus, HF chip is a promising platform for spheroid cell culture.

Formation and control of line defects caused by tectonics of water droplet arrays during self-organized honeycomb-patterned polymer film formation.

This study describes the formation of macro-scale defects of the honeycomb-patterned polymer film and we discovered two types of new line defects which differ from the defects reported in the past studies. We examined the formation mechanisms of the line defects and clarified two types of formation mechanisms of the "Divergent" mode line defects and the "Convergent" mode line defects caused by the "tectonics" of water droplet arrays on polymer solutions. The regions causing the macro-scale line defects are made clear in the phase diagram represented by the radius and the density of the micro-scale water droplets. In addition, the results of our calculations made it possible to theoretically predict the water droplet growth time for the water droplets to grow to the ideal size for uniform packing that is necessary for fabrication of the defect-free honeycomb-patterned polymer film. With the use of these techniques, A4-sized, defect-free, honeycomb-patterned polymer films can be fabricated.