Enhanced redox kinetics of Prussian blue analogues for superior electrochemical deionization performance.

Prussian blue analogues (PBAs), representing the typical faradaic electrode materials for efficient capacitive deionization (CDI) due to their open architecture and high capacity, have been plagued by kinetics issues, leading to insufficient utilization of active sites and poor structure stability. Herein, to address the conflict issue between desalination capacity and stability due to mismatched ionic and electronic kinetics for the PBA-based electrodes, a rational design, including Mn substitution and polypyrrole (ppy) connection, has been proposed for the nickel hexacyanoferrate (Mn-NiHCF/ppy), serving as a model case. Particularly, the theoretical calculation manifests the reduced bandgap and energy barrier for ionic diffusion after Mn substitution, combined with the increased electronic conductivity and integrity through ppy connecting, resulting in enhanced redox kinetics and boosted desalination performance. Specifically, the optimized Mn-NiHCF/ppy demonstrates a remarkable desalination capacity of 51.8 mg g-1 at 1.2 V, accompanied by a high charge efficiency of 81%, and excellent cycling stability without obvious degradation up to 50 cycles, outperforming other related materials. Overall, our concept shown herein provides insights into the design of advanced faradaic electrode materials for high-performance CDI.

Hierarchical Self-Assembly of Hyperbranched Polymer-Based Topological Supramolecular Amphiphiles.

Supramolecular polymers (SPs) are constructed through non-covalent interactions. The dynamic or reversible nature of SPs endows them unique physical and chemical properties, such as self-adaptive and stimuli-response abilities. The topological structures of SPs play an important role in determining the physicochemical properties and functionality. Hyperbranched polymers (HBPs) are highly branched 3D macromolecules with linear, dendritic, and terminal units, which makes them versatile candidates for the construction of SPs with fascinating architectures. The resultant HBP-based SPs perfectly integrated the dynamic/reversible nature of SPs and the 3D topological features and multifunctionality of HBP polymers. To date, various types of HBP-based SPs and their assemblies have been constructed, and their potential applications have been explored as well. This article overviews the current progress on self-assembly of HBP-based SPs. The strategies for construction of HBP-based SPs and their assemblies are discussed. Typical potential applications of the assemblies of HBP-based SPs are also introduced.

Fe3O4-doped mesoporous carbon cathode with a plumber's nightmare structure for high-performance Li-S batteries.

Shuttling of lithium polysulfides and slow redox kinetics seriously limit the rate and cycling performance of lithium-sulfur batteries. In this study, Fe3O4-dopped carbon cubosomes with a plumber's nightmare structure (SP-Fe3O4-C) are prepared as sulfur hosts to construct cathodes with high rate capability and long cycling life for Li-S batteries. Their three-dimensional continuous mesochannels and carbon frameworks, along with the uniformly distributed Fe3O4 particles, enable smooth mass/electron transport, strong polysulfides capture capability, and fast catalytic conversion of the sulfur species. Impressively, the SP-Fe3O4-C cathode exhibits top-level comprehensive performance, with high specific capacity (1303.4 mAh g-1 at 0.2 C), high rate capability (691.8 mAh gFe3O41 at 5 C), and long cycling life (over 1200 cycles). This study demonstrates a unique structure for high-performance Li-S batteries and opens a distinctive avenue for developing multifunctional electrode materials for next-generation energy storage devices.

Toward Ultrahigh Rate and Cycling Performance of Cathode Materials of Sodium Ion Battery by Introducing a Bicontinuous Porous Structure.

The emerging sodium-ion batteries (SIBs) are one of the most promising candidates expected to complement lithium-ion batteries and diversify the battery market. However, the exploitation of cathode materials with high-rate performance and long-cycle stability for SIBs has remained one of the major challenges. To this end, an efficient approach to enhance rate and cycling performance by introducing an ordered bicontinuous porous structure into cathode materials of SIBs is demonstrated. Prussian blue analogues (PBAs) are selected because they are recognized as a type of most promising SIB cathode materials. Thanks to the presence of 3D continuous channels enabling fast Na+ ions diffusion as well as the intrinsic mechanical stability of bicontinuous architecture, the resultant PBAs exhibit excellent rate capability (80 mAh g-1 at 2.5 A g-1) and ultralong cycling life (>3000 circulations at 0.5 A g-1), reaching the top performance of the reported PBA-based cathode materials. This study opens a new avenue for boosting sluggish ion diffusion kinetics in electrodes of rechargeable batteries and also provides a new paradigm for solving the dilemma that electrodes' failure due to high-stress concentration upon ion storage.

Construction of the single-diamond-structured titania scaffold-Recreation of the holy grail photonic structure.

As one of the most stunning biological nanostructures, the single-diamond (SD) surface discovered in beetles and weevils exoskeletons possesses the widest complete photonic bandgap known to date and is renowned as the "holy grail" of photonic materials. However, the synthesis of SD is difficult due to its thermodynamical instability compared to the energetically favoured bicontinuous double diamond and other easily formed lattices; thus, the artificial fabrication of SD has long been a formidable challenge. Herein, we report a bottom-up approach to fabricate SD titania networks via a one-pot cooperative assembly scenario employing the diblock copolymer poly(ethylene oxide)-block-polystyrene as a soft template and titanium diisopropoxide bis(acetylacetonate) as an inorganic precursor in a mixed solvent, in which the SD scaffold was obtained by kinetically controlled nucleation and growth in the skeletal channels of the diamond minimal surface formed by the polymer matrix. Electron crystallography investigations revealed the formation of tetrahedrally connected SD frameworks with the space group Fd [Formula: see text] m in a polycrystalline anatase form. A photonic bandgap calculation showed that the resulting SD structure has a wide and complete bandgap. This work solves the complex synthetic enigmas and offers a frontier in hyperbolic surfaces, biorelevant materials, next-generation optical devices, etc.

pH-Modulated 1D Hierarchical Self-Assembly of a Brush-Like Poly-Para-Phenylene Homopolymer.

The controllable self-assembly of conjugated homopolymers, especially homopolymers without other segments (a prerequisite for phase separation), which can afford chances to achieve tunable optical/electronic properties, remains a great challenge due to their poor solubility and has remained rarely documented. Herein, a conjugated homopolymer (DPPP-COOH) is synthesized, which has a unique brush-like structure with a conjugated dendritic poly-para-phenylene (DPPP) backbone and alkyl-carboxyl side chains at both edges of the backbone. The introduction of carboxyl makes the brush-like homopolymer exhibit pH-modulated 1D hierarchical self-assembly behavior in dilute solution, and allows for flexible morphological regulation of the assemblies, forming some uncommon superstructures including ultralong nanowires (at pH 7), superhelices (at pH 10) and "single-wall" nanotubes (at pH 13), respectively. Furthermore, the good aqueous dispersibility and 1D feature endow the superstructures formed in a high-concentration neutral solution with high broad-spectrum antibacterial performance superior to that of many conventional 1D materials.

Increasing the Accessibility of Internal Catalytic Sites in Covalent Organic Frameworks by Introducing a Bicontinuous Mesostructure.

Introducing continuous mesochannels into covalent organic frameworks (COFs) to increase the accessibility of their inner active sites has remained a major challenge. Here, we report the synthesis of COFs with an ordered bicontinuous mesostructure, via a block copolymer self-assembly-guided nanocasting strategy. Three different mesostructured COFs are synthesized, including two covalent triazine frameworks and one vinylene-linked COF. The new materials are endowed with a hierarchical meso/microporous architecture, in which the mesochannels exhibit an ordered shifted double diamond (SDD) topology. The hierarchically porous structure can enable efficient hole-electron separation and smooth mass transport to the deep internal of the COFs and consequently high accessibility of their active catalytic sites. Benefiting from this hierarchical structure, these COFs exhibit excellent performance in visible-light-driven catalytic NO removal with a high conversion percentage of up to 51.4 %, placing them one of the top reported NO-elimination photocatalysts. This study represents the first case of introducing a bicontinuous structure into COFs, which opens a new avenue for the synthesis of hierarchically porous COFs and for increasing the utilization degree of their internal active sites.

Electronic Structure of Isolated Graphene Nanoribbons in Solution Revealed by Two-Dimensional Electronic Spectroscopy.

Structurally well-defined graphene nanoribbons (GNRs) are nanostructures with unique optoelectronic properties. In the liquid phase, strong aggregation typically hampers the assessment of their intrinsic properties. Recently we reported a novel type of GNRs, decorated with aliphatic side chains, yielding dispersions consisting mostly of isolated GNRs. Here we employ two-dimensional electronic spectroscopy to unravel the optical properties of isolated GNRs and disentangle the transitions underlying their broad and rather featureless absorption band. We observe that vibronic coupling, typically neglected in modeling, plays a dominant role in the optical properties of GNRs. Moreover, a strong environmental effect is revealed by a large inhomogeneous broadening of the electronic transitions. Finally, we also show that the photoexcited bright state decays, on the 150 fs time scale, to a dark state which is in thermal equilibrium with the bright state, that remains responsible for the emission on nanosecond time scales.

Hyperbranched polyphthalocyanine micelles with dual PTT/PDT functions for bacteria eradication under an NIR window.

A Zinc phthalocyanine-based (ZnPc-PA) polymeric micelle around 70 nm and with dual-modal PTT/PDT functions for non-antibiotic bacteria eradication was developed. It showed an excellent bacterial killing efficiency of 95.2% and 96.7% in vitro against Methicillin-resistant Staphylococcus aureus (MRSA) and its biofilm, respectively. Furthermore, the in vivo experiments proved its great potential for implant-associated infection (IAI).

Nitrogen-Doped Carbon Cubosomes as an Efficient Electrocatalyst with High Accessibility of Internal Active Sites.

Porous carbon particles (PCPs) present considerable potential for applications across a wide range of fields, particularly within the realms of energy and catalysis. The control of their overall morphologies and pore structures has remained a big challenge. Here, using metal-organic frameworks (MOFs) as the precursor and polymer cubosomes (PCs) as the template, nitrogen-doped carbon cubosomes (SP-NCs) with a single primitive bicontinuous architecture are prepared. SP-NCs inherit the high porosity of MOFs, generating a high specific surface area of 825 m2 g-1 and uniformly distributed active sites with a 5.9 at % nitrogen content. Thanks to the presence of three-dimensional continuous mesochannels that enable much higher accessibility of internal active sites over those of their porous counterparts' lack of continuous channels, SP-NCs exhibit superior electrocatalytic performance for oxygen reduction reaction with a half-wave potential of 0.87 V, situating them in the leading level of the reported carbon electrocatalysts. Serving as an air cathode catalyst of the Zn-air battery, SP-NCs exhibit excellent performance, outperforming the commercial Pt/C catalysts.