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.
This article overviews the progress of the studies on block copolymer self‐assembly guided synthesis of bicontinuous porous materials, with the emphases on their synthetic strategies, structural control, and potential applications in energy storage and conversion, metamaterials, photonic crystals, cargo delivery and release, nanoreactors, and biomolecule selection.
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) Ti3C2Tx 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.
This communication reports a bottom‐up approach to a two‐dimensional (2D) Ti3C2Tx MXene‐polydopamine heterostructure with ordered in‐plane cylindrical mesochannels. The resultant 2D heterostructure shows top‐level CDI performance in its application as electrode material for capacitive deionization.
Metal Organic Framework Cubosomes Li, Chen; Pan, Yi; Xiao, Tianyu ...
Angewandte Chemie International Edition,
March 6, 2023, Letnik:
62, Številka:
11
Journal Article
Recenzirano
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.
This study developed a general strategy for the synthesis of ordered metal organic framework (MOF) cubosomes with a single primitive bicontinuous structure by using polymer cubosomes as the template, and also investigated their growth mechanism and kinetics as well as potential proteolysis application.
Titania has received considerable attention as a promising anode material of Li-ion battery (LIB). Controlling the structure and morphology of titania nanostructures is crucial to govern their ...performance. Herein, we report a mesoporous titania scaffold with a bicontinuous shifted double diamond (SDD) structure for anode material of LIB. The titania scaffold was synthesized by the cooperative self-assembly of a block copolymer poly(ethylene oxide)-
block
-polystyrene template and titanium diisopropoxide bis(acetylacetonate) as the inorganic precursor in a mixture solvent of tetrahydrofuran and HCl/water. The structure shows tetragonal symmetry (space group
I
4
1
/amd
) comprising two sets of diamond networks adjoining each other with the unit cell parameter of
a
= 90 nm and
c
= 127 nm, which affords the porous titania a specific surface area (SSA) of 42 m
2
·g
−1
with a mean pore diameter of 38 nm. Serving as an anode material of LIB, the bicontinuous titania scaffold exhibits a high specific capacity of 254 mAh·g
−1
at the current density of 1 A·g
−1
and an alluring self-improving feature upon charge/discharge over 1,000 cycles. This study overcomes the difficulty in building up ordered bicontinuous functional materials and demonstrates their potential in energy storage application.
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.
This study reports the first formation of helical structures by the self‐assembly of an achiral rod−coil alternating copolymer. The copolymer self‐assembled into stable helical nanowires in solution via a hierarchical self‐assembly process from thin nanobelts with a uniform size to helical nanoribbons and finally to helical nanowires.
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.
A rechargeable Na/Cl2 battery with an ultrahigh rate capability (16,000 mA g−1) has been realized using a bicontinuous‐structured carbon cubosome with heteroatomic doping, which enables efficient Na+ and electron transport and promoted Cl2 adsorption and conversion. It provides a new paradigm to solve the dilemma between energy density and power density in energy storage devices.
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.
Covalent organic frameworks with an ordered bicontinuous mesostructure were synthesized through a block copolymer self‐assembly guided nanocasting method. The bicontinuous architecture enables efficient hole‐electron separation and smooth mass transport to the deep internal regions of the COFs, leading to high accessibility of their active catalytic sites and excellent NO removal capability.
Abstract Shuttling of lithium polysulfides and slow redox kinetics seriously limit the rate and cycling performance of lithium-sulfur batteries. In this study, Fe 3 O 4 -dopped carbon cubosomes with ...a plumber’s nightmare structure (SP-Fe 3 O 4 -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 Fe 3 O 4 particles, enable smooth mass/electron transport, strong polysulfides capture capability, and fast catalytic conversion of the sulfur species. Impressively, the SP-Fe 3 O 4 -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 gFe 3 O 4 1 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.
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.
This study developed a general strategy for the synthesis of ordered metal organic framework (MOF) cubosomes with a single primitive bicontinuous structure by using polymer cubosomes as the template, and also investigated their growth mechanism and kinetics as well as potential proteolysis application.
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.
A rechargeable Na/Cl2 battery with an ultrahigh rate capability (16,000 mA g−1) has been realized using a bicontinuous‐structured carbon cubosome with heteroatomic doping, which enables efficient Na+ and electron transport and promoted Cl2 adsorption and conversion. It provides a new paradigm to solve the dilemma between energy density and power density in energy storage devices.
