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.

Metal Organic Framework Cubosomes.

We demonstrate a general strategy for the synthesis of ordered bicontinuous-structured metal organic frameworks (MOFs) by using polymer cubosomes (PCs) with a double primitive structure (Im 3 ‾ ${\bar{3}}$ m symmetry) as the template. The filling of MOF precursors in the open channel of PCs, followed by their coordination and removal of the template, generates MOF cubosomes with a single primitive topology (Pm 3 ‾ ${\bar{3}}$ m) and average mesopore diameters of 60-65 nm. Mechanism study reveals that the formation of ZIF-8 cubosomes undergoes a new MOF growth process, which involves the formation of individual MOF seeds in the template, their growth and eventual fusion into the cubosomes. Their growth kinetics follows the Avrami equation with an Avrami exponent of n=3 and a growth rate of k=1.33×10-4 , indicating their fast 3D heterogeneous growth mode. Serving as a bioreactor, the ZIF-8 cubosomes show high loading of trypsin enzyme, leading to a high catalytic activity in the proteolysis of bovine serum albumin.

Ultrahigh-Rate Na/Cl2 Batteries Through Improved Electron and Ion Transport by Heteroatom-Doped Bicontinuous-Structured Carbon.

Rechargeable sodium/chlorine (Na/Cl2 ) batteries are emerging candidates for sustainable energy storage owing to their superior energy densities and the high abundance of Na and Cl elements. However, their practical applications have been plagued by the poor rate performance (e.g., a maximum discharge current density of 150 mA g-1 ), as the widely used carbon nanosphere cathodes show both sluggish electron-ion transport and reaction kinetics. Here, by mimicking the sufficient mass and energy transport in a sponge, we report a bicontinuous-structured carbon cubosome with heteroatomic doping, which allows efficient Na+ and electron transport and promotes Cl2 adsorption and conversion, thus unlocking ultrahigh-rate Na/Cl2 batteries, e.g., a maximum discharge current density of 16,000 mA g-1 that is more than two orders of magnitude higher than previous reports. The optimized solid-liquid-gas (carbon-electrolyte-Cl2 ) triple interfaces further contribute to a maximum reversible capacity and cycle life of 2,000 mAh g-1 and 250 cycles, respectively. This study establishes a universal approach for improving the sluggish kinetics of conversion-type battery reactions, and provides a new paradigm to resolve the long-standing dilemma between high energy and power densities in energy storage devices.

Porous Polymer Cubosomes with Ordered Single Primitive Bicontinuous Architecture and Their Sodium-Iodine Batteries.

Bicontinuous porous materials, which possess 3D interconnected pore channels facilitating a smooth mass transport, have attracted much interest in the fields of energy and catalysis. However, their synthesis remains very challenging. We report a general approach, using polymer cubosomes as the template, for the controllable synthesis of bicontinuous porous polymers with an ordered single primitive (SP) cubic structure, including polypyrrole (SP-PPy), poly-m-phenylenediamine (SP-PmPD), and polydopamine (SP-PDA). Specifically, the resultant SP-PPy had a unit cell parameter of 99 nm, pore diameter of 45 nm, and specific surface area of approximately 60 m2·g-1. As a proof of concept, the I2-adsorbed SP-PPy was employed as the cathode materials of newly emerged Na-I2 batteries, which delivered a record-high specific capacity (235 mA·h·g-1 at 0.5 C), excellent rate capability, and cycling stability (with a low capacity decay of 0.12% per cycle within 400 cycles at 1 C). The advantageous contributions of the bicontinuous structure and I3- adsorption mechanism of SP-PPy were revealed by a combination of ion diffusion experiments and theoretical calculations. This study opens a new avenue for the synthesis of porous polymers with new topologies, broadens the spectrum of bicontinuous-structured materials, and also develops a novel potential application for porous polymers.

One-Dimensional Helical Nanostructures from the Hierarchical Self-Assembly of an Achiral "Rod-Coil" Alternating Copolymer.

The self-assembly of alternating copolymers (ACPs) has attracted considerable interest due to their unique alternating nature. However, compared with block copolymers, their self-assembly behavior remains much less explored and their reported self-assembled structures are limited. Here, the formation of supramolecular helical structures by the self-assembly of an achiral rod-coil alternating copolymer named as poly(quarter(3-hexylthiophene)-alt-poly(ethylene glycol)) (P(Q3HT-alt-PEG)), is reported. The copolymer exhibits an interesting hierarchical self-assembly process, driven by the π-π stacking of the Q3HT segments and the solvophobic interaction of the alkyl chains in tetrahydrofuran (THF)-isopropanol mixed solvents. The copolymer first self-assembled into thin nanobelts with a uniform size, then grows to helical nanoribbons and eventually twisted into helical nanowires with an average diameter of 25 ± 9 nm and a mean pitch of 80 ± 10 nm. Dissipative particle dynamics (DPD) simulation supports the formation course of the helical nanowires. Furthermore, the addition of (S)-ethyl lactate and (R)-ethyl lactate in the self-assembly of P(Q3HT-alt-PEG) results in the formation of left-handed and right-handed chiral nanowires, respectively, demonstrating the tunability of the chirality of the helical wires. This study expands the library of ordered self-assembled structures of ACPs, and also brings a new strategy and mechanism to construct helical supramolecular structures.

Two-Dimensional MXene-Polymer Heterostructure with Ordered In-Plane Mesochannels for High-Performance Capacitive Deionization.

The application of traditional electrode materials for high-performance capacitive deionization (CDI) has been persistently limited by their low charge-storage capacities, excessive co-ion expulsion and slow salt removal rates. Here we report a bottom-up approach to the preparation of a two-dimensional (2D) Ti3 C2 Tx MXene-polydopamine heterostructure having ordered in-plane mesochannels (denoted as mPDA/MXene). Interfacial self-assembly of mesoporous polydopamine (mPDA) monolayers on MXene nanosheets leads to the mPDA/MXene heterostructure, which exhibits several unique features: (1) MXene undergoes reversible ion intercalation/deintercalation and possesses high conductivity; (2) mPDA layers establish redox capacitive characteristics and Na+ selectivity, and also help to prevent self-stacking and oxidation of MXene; (3) in-plane mesochannels enable the smooth transport of ions at the internal spaces of this stacked 2D material. When applied as an electrode material for CDI, mPDA/MXene nanosheets exhibit top-level CDI performance and cycling stability compared to those of the so far reported 2D materials. Our study opens an avenue for the rational construction of MXene-organic hybrid heterostructures, and further motivates the development of high-performance CDI electrode materials.

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.

Block Copolymer Self-Assembly Directed Synthesis of Porous Materials with Ordered Bicontinuous Structures and Their Potential Applications.

Porous materials with their ordered bicontinuous structures have attracted great interest owing to ordered periodic structures as well as 3D interconnected network and pore channels. Bicontinuous structures may favor efficient mass diffusion to the interior of materials, thus increasing the utilization ratio of active sites. In addition, ordered bicontinuous structures confer materials with exceptional optical and magnetic properties, including tunable photonic bandgap, negative refraction, and multiple equivalent magnetization configurations. The attractive structural advantages and physical properties have inspired people to develop strategies for preparing bicontinuous-structured porous materials. Among a few synthetic approaches, the self-assembly of block copolymers represents a versatile strategy to prepare various bicontinuous-structured functional materials with pore sizes and lattice parameters ranging from 1 to 500 nm. This article overviews progress in this appealing area, with an emphasis on the synthetic strategies, the structural control (including topologies, pore sizes, and unit cell parameters), and their potential applications in energy storage and conversion, metamaterials, photonic crystals, cargo delivery and release, nanoreactors, and biomolecule selection.

A general synthetic method towards conjugated microporous polymers with ordered bicontinuous mesostructures.

This work demonstrates a universal approach, based on the self-assembly of block copolymers, for the synthesis of novel conjugated microporous polymers (CMPs) with bicontinuous mesostructures. Three hexaazatriphenylene (Aza)-fused CMPs (Aza-CMPs) with double diamond structures were synthesized. The study broadens the spectrum of bicontinuous porous materials and opens a new route for synthesizing CMPs with new topologies.