Spontaneous-Spin-Polarized 2D π-d Conjugated Frameworks Towards Enhanced Oxygen Evolution Kinetics.

Alternative strategies to design sustainable-element-based electrocatalysts enhancing oxygen evolution reaction (OER) kinetics are demanded to develop affordable yet high-performance water-electrolyzers for green hydrogen production. Here, it is demonstrated that the spontaneous-spin-polarized 2D π-d conjugated framework comprising abundant elements of nickel and iron with a ratio of Ni:Fe = 1:4 with benzenehexathiol linker (BHT) can improve OER kinetics by its unique electronic property. Among the bimetallic NiFex:y-BHTs with various ratios with Ni:Fe = x:y, the NiFe1:4-BHT exhibits the highest OER activity. The NiFe1:4-BHT shows a specific current density of 140 A g-1 at the overpotential of 350 mV. This performance is one of the best activities among state-of-the-art non-precious OER electrocatalysts and even comparable to that of the platinum-group-metals of RuO2 and IrO2. The density functional theory calculations uncover that introducing Ni into the homometallic Fe-BHT (e.g., Ni:Fe = 0:1) can emerge a spontaneous-spin-polarized state. Thus, this material can achieve improved OER kinetics with spin-polarization which previously required external magnetic fields. This work shows that a rational design of 2D π-d conjugated frameworks can be a powerful strategy to synthesize promising electrocatalysts with abundant elements for a wide spectrum of next-generation energy devices.

Lateral Heterometal Junction Rectifier Fabricated by Sequential Transmetallation of Coordination Nanosheet.

Heterostructures of two-dimensional materials realise novel and enhanced physical phenomena, making them attractive research targets. Compared to inorganic materials, coordination nanosheets have virtually infinite combinations, leading to tunability of physical properties and are promising candidates for heterostructure fabrication. Although stacking of coordination materials into vertical heterostructures is widely reported, reports of lateral coordination material heterostructures are few. Here we show the successful fabrication of a seamless lateral heterojunction showing diode behaviour, by sequential and spatially limited immersion of a new metalladithiolene coordination nanosheet, Zn3 BHT, into aqueous Cu(II) and Fe(II) solutions. Upon immersion, the Zn centres in insulating Zn3 BHT are replaced by Cu or Fe ions, resulting in conductivity. The transmetallation is spatially confined, occurring only within the immersed area. We anticipate that our results will be a starting point towards exploring transmetallation of various two-dimensional materials to produce lateral heterojunctions, by providing a new and facile synthetic route.

Controlling Microstructure-Transport Interplay in Poly(ether-block-amide) Multiblock Copolymer Gas Separation Membranes.

In this study, we investigated the effect of morphology on the gas-transport properties of a poly(ether-block-amide) (PEBA) multiblock copolymer. We annealed the copolymer samples and varied the annealing temperature to evaluate the influence of changes in the microstructure on the gas transport properties of PEBA. In addition, we used time-resolved attenuated total reflection Fourier transform infrared spectroscopy to evaluate the diffusion coefficient of CO2 in PEBA based on the Fickian model. The effect of the annealing temperature on the microphase-separated structure of the multiblock copolymer is discussed in detail. Furthermore, the gas diffusivity was significantly affected by the purity of the soft domains. The annealed sample demonstrated a 38% increase in CO2 permeability while maintaining a high CO2/N2 permselectivity of approximately 53. The findings of this study provide valuable insight into the design and optimization of PEBA membranes for gas separation applications.

Superior Multielectron-Transferring Energy Storage by π-d Conjugated Frameworks.

Reversible multielectron-transfer materials are of considerable interest because of the potential impact to advance present electrochemical energy storage technology by boosting energy density. To date, a few oxide-based materials can reach an electron-transfer number per metal-cation (eM ) larger than 2 upon a (de)intercalation mechanism. However, these materials suffer from degradation due to irreversible rearrangements of the cation-oxygen bonds, and are based on precious metals, for example, Ir and Ru. Hence, a design of the non-oxide-based reversible multielectron-transfer materials with abundant elements can provide a promising alternative. Herein, it is demonstrated that the bis(diimino)copper framework can show eM  = 3.5 with cation/anion co-redox mechanism together with a dual-ion mechanism. In this study, the role of the cation-anion interactions is unveiled by using an experiment/theory collaboration applied to a series of the model non-oxide abundant electrode systems based on different metal-nitrogen bonds. These models provide designer multielectron-transfer due to the tunable π-d conjugated electronic structures. It is found that the Cu-nitrogen bonds show a unique reversible rearrangement upon Li-intercalation, and this process responds to acquire a significant reversible multielectron-transfer. This work provides new insights into the affordable multielectron-transfer electrodes and uncovers an alternative strategy to advance the electrochemical energy storage reactions.

Regular ordering of spherical microdomains in dewetted monolayer islands induced by thermal annealing of spin-coated ultrathin films of a triblock copolymer.

We report here spontaneous dewetting of a spin-coated, ultra-thin film of a sphere-forming block copolymer (BCP) upon thermal annealing, and that the dewetting resulted in the formation of plateau-shaped islands with a constant thickness consistent with the thickness of a monolayer, in which the spherical microdomains are regularly ordered two-dimensionally in a deformed hexagonal lattice. Thus, the spontaneous dewetting was ascribed to a mismatch between the initial spin-coated film thickness with respect to the monolayer thickness. Such dewetting of sphere-forming BCPs is considered to be deterministic compared to the cases of lamella- and cylinder-forming BCPs, as incommensuration in thickness is avoided by attaining perpendicular orientation without dewetting. We further quantitatively examined the ordering regularity of spherical microdomains in the dewetted monolayer islands to clarify the effect of confinement on sphere ordering. The degree of deformation of the hexagonal lattice was found to have an increasing tendency as a function of the degree of the deformation of the dewetted islands (the island shape), irrespective of the size of the island. Namely, islands with almost round shapes exhibit a well-ordered arrangement of the spherical microdomains in a perfect hexagonal lattice. Another notable finding is that the regular ordering of the spherical microdomains was found to be spoiled in the vicinity of the edge of the island. In other words, the spherical microdomains were well-ordered in a hexagonal lattice far from the edge of the island, while they were not regularly ordered in the vicinity of the edge, which may be due to mismatch between the curvature of the island's perimeter and the polygonal shape of ordered sphere grains.

Glassy Porphyrin/C60 Composites: Morphological Engineering of C60 Fullerene with Liquefied Porphyrins.

Morphological control of C60 fullerene using liquefied porphyrins (1 and 2) as the host matrices was explored. Slow evaporation of the solvent of the equimolar mixture of porphyrin and C60 in toluene afforded the porphyrin/C60 composite with a 3:1 molar ratio. The stoichiometric binding behaviors suggest that specific porphyrin-C60 interactions operate the formation of the porphyrin/C60 composites, as corroborated by spectroscopic and thermal properties, and glazing-incidence wide-angle X-ray diffraction. Under the bulk conditions, the conventional thermodynamic advantage of multiple binding cooperativity for molecular recognition is unlikely to explain the stoichiometric binding behaviors. Instead, we propose a size-matching effect on the porphyrin-C60 interaction in the bulk porphyrin matrices, i.e., "supramolecular solvation". The glassy nature of the porphyrin matrices was transmitted to C60 through the specific interaction, and the porphyrin/C60 composites adopted glassy states at room temperature.

Tailoring the Electrochemical Properties of Two-Dimensional Bis(diimino)metal Coordination Frameworks by Introducing Co/Ni Heterometallic Structures.

Bis(diimino)metal coordination frameworks (MDI, M = transition metal), which are a class of metal organic frameworks with two-dimensional anisotropy, high electric conductivity, and redox activity, are attractive platforms for tailoring electrochemical properties by introducing a heterometallic composition. In this study, we synthesized heterometallic CoxNi1-xDI coordination frameworks for electrochemical energy storage applications and investigated their electrochemical properties by experimental and theoretical techniques. Ni atoms were embedded into CoDI, and the crystal structure of CoxNi1-xDI was modified, especially along the interlayer axis, which activated the kinetically impeded redox reactions accompanied by PF6- insertion/extraction. Furthermore, upon charge/discharge with Li+ transport, CoxNi1-xDI with a specific composition exhibited higher specific capacity (248 mAh g-1) than CoDI and NiDI in the potential window of 1.0-3.5 V versus Li+/Li. Density functional theory calculations indicate that the energy levels of the antibonding orbitals around the metals and interlayer spaces are important factors in tailoring the electrochemical properties of CoxNi1-xDI.

Perfluorophenyl-Directed Giant Porphyrin J-Aggregates.

Quadrupolar interactions of porphyrin bearing two pentafluorophenylethynyl terminals (1) drove the formation of a successive one-dimensional staircase structure, i.e., J-aggregates, to yield millimeter-length needles with a single-crystalline character in methylcyclohexane solution. In contrast, π-stacked interactions of porphyrin bearing two nonfluorinated phenyl terminals (2) formed no aggregates in solution. A spin-cast film of 1 also showed bathochromic shift of the Soret and Q bands, indicating the formation of J-aggregates. The molecular arrangement of the J-aggregates was revealed by microbeam glazing-incidence wide-angle X-ray diffraction (GIWAXD), and was in good agreement with the optimized structure generated by density functional theory (DFT) calculations.

Multielectron-Transfer-based Rechargeable Energy Storage of Two-Dimensional Coordination Frameworks with Non-Innocent Ligands.

The metallically conductive bis(diimino)nickel framework (NiDI), an emerging class of metal-organic framework (MOF) analogues consisting of two-dimensional (2D) coordination networks, was found to have an energy storage principle that uses both cation and anion insertion. This principle gives high energy led by a multielectron transfer reaction: Its specific capacity is one of the highest among MOF-based cathode materials in rechargeable energy storage devices, with stable cycling performance up to 300 cycles. This mechanism was studied by a wide spectrum of electrochemical techniques combined with density-functional calculations. This work shows that a rationally designed material system of conductive 2D coordination networks can be promising electrode materials for many types of energy devices.

Crystalline Graphdiyne Nanosheets Produced at a Gas/Liquid or Liquid/Liquid Interface.

Synthetic two-dimensional polymers, or bottom-up nanosheets, are ultrathin polymeric frameworks with in-plane periodicity. They can be synthesized in a direct, bottom-up fashion using atomic, ionic, or molecular components. However, few are based on carbon-carbon bond formation, which means that there is a potential new field of investigation into these fundamentally important chemical bonds. Here, we describe the bottom-up synthesis of all-carbon, π-conjugated graphdiyne nanosheets. A liquid/liquid interfacial protocol involves layering a dichloromethane solution of hexaethynylbenzene on an aqueous layer containing a copper catalyst at room temperature. A multilayer graphdiyne (thickness, 24 nm; domain size, >25 µm) emerges through a successive alkyne-alkyne homocoupling reaction at the interface. A gas/liquid interfacial synthesis is more successful. Sprinkling a very small amount of hexaethynylbenzene in a mixture of dichloromethane and toluene onto the surface of the aqueous phase at room temperature generated single-crystalline graphdiyne nanosheets, which feature regular hexagonal domains, a lower degree of oxygenation, and uniform thickness (3.0 nm) and lateral size (1.5 µm).

Liquid/Liquid Interfacial Synthesis of a Click Nanosheet.

A liquid/liquid interfacial synthesis is employed, for the first time, to synthesize a covalent two-dimensional polymer nanosheet. Copper-catalyzed azide-alkyne cycloaddition (CuAAC) between a three-way terminal alkyne and azide at a water/dichloromethane interface generates a 1,2,3-triazole-linked nanosheet. The resultant nanosheet, with a flat and smooth texture, has a maximum domain size of 20 µm and minimum thickness of 5.3 nm. The starting monomers in the organic phase and the copper catalyst in the aqueous phase can only meet at the liquid/liquid interface as a two-dimensional reaction space; this allows them to form the two-dimensional polymer. The robust triazole linkage generated by irreversible covalent-bond formation allows the nanosheet to resist hydrolysis under both acidic and alkaline conditions, and to endure pyrolysis up to more than 300 °C. The coordination ability of the triazolyl group enables the nanosheet to act as a reservoir for metal ions, with an affinity order of Pd2+ >Au3+ >Cu2+ .

Observation of an Orientation Change in Highly Oriented Layer-by-Layer Films of a Ruthenium Complex upon Oxidation Reaction.

Layer-by-layer films composed of redox-active ruthenium dimer and Zr(IV) ions were fabricated on an indium tin oxide electrode. The fabricating behavior was monitored by cyclic voltammetry and UV-vis absorption spectral measurements. The orientation of the film was also monitored by grazing-incidence small-angle and wide-angle X-ray scattering (GISAXS) measurements, and it has been clarified that this film has a crystalline structure. The peaks obtained by GISAXS were changed upon oxidation reaction, which indicates that a change in the orientation of the ruthenium dimer occurred in the film.

Use of extension-deformation-based crystallisation of silk fibres to differentiate their functions in nature.

ß-Sheet crystals play an important role in determining the stiffness, strength, and optical properties of silk and in the exhibition of silk-type-specific functions. It is important to elucidate the structural changes that occur during the stretching of silk fibres to understand the functions of different types of fibres. Herein, we elucidate the initial crystallisation behaviour of silk molecules during the stretching of three types of silk fibres using synchrotron radiation X-ray analysis. When spider dragline silk was stretched, it underwent crystallisation and the alignment of the ß-sheet crystals became disordered initially but was later recovered. On the other hand, silkworm cocoon silk did not exhibit further crystallisation, whereas capture spiral silk was predominantly amorphous. Structural analyses showed that the crystallisation of silks following extension deformation has a critical effect on their mechanical and optical properties. These findings should aid the production of artificial silk fibres and facilitate the development of silk-inspired functional materials.

Nano-ordered surface morphologies by stereocomplexation of the enantiomeric polylactide chains: specific interactions of surface-immobilized poly(D-lactide) and poly(ethylene glycol)-poly(L-lactide) block copolymers.

Both AB diblock and ABA triblock copolymers consisting of poly(L-lactide) (PLLA: A) and poly(ethylene glycol) (PEG: B) were deposited on a silicon surface on which poly(D-lactide) (PDLA) had been preimmobilized. The deposit of the diblock copolymer (PLLA-PEG) formed band structures similar to those observed when the same copolymer was directly deposited on the silicon surface. In contrast, the deposit of the triblock copolymer (PLLA-PEG-PLLA) formed many particulates scattering over the surface. When the PLLA-PEG deposit was subjected to water-soaking, the original band morphology was completely replaced by the particulate morphology that was identical to that of the PLLA-PEG-PLLA deposit. Their FT-IR analyses revealed that both copolymers had been bound through the stereocomplex (sc) formation between the preimmobilized PDLA chains and the PLLA blocks of the copolymers. Grazing-incidence small-angle X-ray scattering (GISAXS) also supported these surface morphologies. It was therefore evident that hydrophilic PEG chains can be immobilized on the PDLA-preimmobilized surface by the sc formation.

π-Conjugated nickel bis(dithiolene) complex nanosheet.

A π-conjugated nanosheet comprising planar nickel bis(dithiolene) complexes was synthesized by a bottom-up method. A liquid-liquid interfacial reaction using benzenehexathiol in the organic phase and nickel(II) acetate in the aqueous phase produced a semiconducting bulk material with a thickness of several micrometers. Powder X-ray diffraction analysis revealed that the crystalline portion of the bulk material comprised a staggered stack of nanosheets. A single-layer nanosheet was successfully realized using a gas-liquid interfacial reaction. Atomic force microscopy and scanning tunneling microscopy confirmed that the π-conjugated nanosheet was single-layered. Modulation of the oxidation state of the nanosheet was possible using chemical redox reactions.

X-ray photon correlation spectroscopy using a fast pixel array detector with a grid mask resolution enhancer.

The performance of a fast pixel array detector with a grid mask resolution enhancer has been demonstrated for X-ray photon correlation spectroscopy (XPCS) measurements to investigate fast dynamics on a microscopic scale. A detecting system, in which each pixel of a single-photon-counting pixel array detector, PILATUS, is covered by grid mask apertures, was constructed for XPCS measurements of silica nanoparticles in polymer melts. The experimental results are confirmed to be consistent by comparison with other independent experiments. By applying this method, XPCS measurements can be carried out by customizing the hole size of the grid mask to suit the experimental conditions, such as beam size, detector size and sample-to-detector distance.

Enhancing the bioactivity of melt electrowritten PLLA scaffold by convenient, green, and effective hydrophilic surface modification.

As an emerging additive manufacturing (AM) technique, melt electrospinning writing (MEW) is used to fabricate three-dimensional (3D) submicron filament-based scaffolds with adjustable pore size and customized structure for bone regeneration. Poly(L-lactic acid) (PLLA) scaffold with excellent biodegradability and biocompatibility is first successfully manufactured using our self-assembled MEW device. However, the ultralow cell affinity and poor bioactivity severely hamper their practical applications in bone tissue engineering. These issues are caused by the severe inherent biologically inert, hydrophobicity as well as the smooth surface of the MEW PLLA filaments. In this study, a green and robust alkaline method is applied to modify the scaffold surface and to improve the bioactivity of the MEW PLLA scaffold. Without deterioration in mechanical property but robust surface hydrophilicity, the optimal MEW PLLA scaffold shows promoted surface roughness, enhanced filament tensile modulus (~ 2 folds of the as-prepared sample), and boosted crystallizability (ultrahigh WAXD intensity). Moreover, after being cultured with KUSA-A1 cells, the 0.5 M NaOH, 2 h treated MEW PLLA scaffold exhibits higher osteoinductive ability and increased immature bone tissue amounts (3 times of controlled scaffold). Thus, the flexible surface functionalization by the specific alkaline treatment was found to be an effective method for the preparation of bioactivated MEW PLLA scaffolds with promoted bone regeneration.

Heterometallic Benzenehexathiolato Coordination Nanosheets: Periodic Structure Improves Crystallinity and Electrical Conductivity.

Coordination nanosheets are an emerging class of 2D, bottom-up materials having fully π-conjugated, planar, graphite-like structures with high electrical conductivities. Since their discovery, great effort has been devoted to expand the variety of coordination nanosheets; however, in most cases, their low crystallinity in thick films hampers practical device applications. In this study, mixtures of nickel and copper ions are employed to fabricate benzenehexathiolato (BHT)-based coordination nanosheet films, and serendipitously, it is found that this heterometallicity preferentially forms a structural phase with improved film crystallinity. Spectroscopic and scattering measurements provide evidence for a bilayer structure with in-plane periodic arrangement of copper and nickel ions with the NiCu2 BHT formula. Compared with homometallic films, heterometallic films exhibit more crystalline microstructures with larger and more oriented grains, achieving higher electrical conductivities reaching metallic behaviors. Low dependency of Seebeck coefficient on the mixing ratio of nickel and copper ions supports that the large variation in the conductivity data is not caused by change in the intrinsic properties of the films. The findings open new pathways to improve crystallinity and to tune functional properties of 2D coordination nanosheets.

Modification of decellularized vascular xenografts with 8-arm polyethylene glycol suppresses macrophage infiltration but maintains graft degradability.

Because acellular vascular xenografts induce an immunological reaction through macrophage infiltration, they are conventionally crosslinked with glutaraldehyde (GA). However, the GA crosslinking reaction inhibits not only the host immune reaction around the graft but also the graft's enzymatic degradability, which is one of the key characteristics of acellular grafts that allow them to be replaced by host tissue. In this study, we used an 8-arm polyethylene glycol (PEG) to successfully suppress macrophage infiltration, without eliminating graft degradation. Decellularized ostrich carotid arteries were modified with GA or N-hydroxysuccinimide-activated 8-arm PEG (8-arm PEG-NHS), which has a molecular weight of 17 kDa. To evaluate the enzymatic degradation in vitro, the graft was immersed in a collagenase solution for 12 hr. The 8-arm PEG-modified graft was degraded to the same extent as the unmodified graft, but the GA-modified graft was not degraded. The graft was transplanted into rat subcutaneous tissue for up to 8 weeks. Although CD68-positive cells accumulated in the unmodified graft, they did not infiltrate into either modified graft. However, the GA-modified grafts calcified, but the 8-arm PEG-modified graft did not calcify after transplantation. These data suggested that 8-arm PEG-NHS is a promising modification agent for biodegradable vascular xenografts, to suppress acute macrophage infiltration only.

Relationship between morphological change and crystalline phase transitions of polyethylene-poly(ethylene oxide) diblock copolymers. 3. Dependence of morphological transition phenomena on the PE/PEO segmental lengths and its possible origins.

By measurement of the small-angle and wide-angle X-ray scatterings and infrared and Raman spectra and thermal data, microphase separation phenomena have been investigated for a series of polyethylene-poly(ethylene oxide) diblock copolymer (PE-b-PEO) in both the heating and cooling processes and compared with the structural changes occurring inside the PE and PEO domains. The complicated morphological changes between lamella, perforated lamella, gyroid, cylinder, and sphere phases were detected for the copolymer with relatively short PE segments. The orthorhombic crystalline structure of PE was kept unchanged in the lamella-to-gyroid transition. When the PE orthorhombic phase transformed to the pseudohexagonal or rotator phase, the gyroid morphology changed to the cylinder. On the other hand, the diblock copolymer with relatively long PE segment was found to show only the lamellar morphology, in which the order-disorder structural transition between the orthorhombic and pseudohexagonal phases occurred in the PE crystal region. As a possibility, the large difference in morphological change between the copolymers with short and long PE segments has been ascribed to the difference in thermal mobility of PE segments, which is controlled by the conformation of chains and their packing mode, i.e., an extended chain or a folded chain. The extended chains may move thermally and actively along the interfacial boundary in addition to the librational motion around the chain axis, resulting in a variety of morphological changes, whereas the thermal motion of the folded chains may be suppressed because of the geometrical constraint and does not cause such a large-scale morphological change from the lamellar structure. This concept, a thermal activity and geometrical constraint, is considered to be quite important in the interpretation of complicated morphological changes observed for many crystalline-amorphous and crystalline-crystalline diblock copolymers when viewed from the molecular level.