Covalent organic frameworks with flexible side chains in hybrid PEMs enable highly efficient proton conductivity.

Electrochemical hydrogen compression (EHC) is an emerging energy conversion technology. Proton exchange membranes (PEMs) with high proton conductivity and high mechanical strength are highly required to meet the practical requirements of EHC. Herein, ionic covalent organic frameworks (iCOFs) with tunable side chains were synthesized and introduced into the sulfonated poly (ether ether ketone) (SPEEK) matrix to fabricate hybrid PEMs. In our membranes, the rigid iCOFs afford ordered proton conduction channels, whereas the flexible side chains on iCOFs afford abundant proton conduction sites, adaptive hydrogen bonding networks, and high local density short hydrogen bonds for highly efficient proton transport. Moreover, the hydrogen bond interactions between the side chains on iCOFs and the SPEEK matrix enhance the mechanical stability of membranes. As a result, the hybrid PEM acquires an enhanced proton conductivity of 540.4 mS cm-1 (80 °C, 100%RH), a high mechanical strength of 120.41 MPa, and a superior performance (2.3 MPa at 30 °C, 100%RH) in EHC applications.

Manipulation of Cationic Group Density in Covalent Organic Framework Membranes for Efficient Anion Transport.

Anion exchange membranes with high anion conductivity are highly desired for electrochemical applications. Increasing ion exchange capacity is a straightforward approach to enhancing anion conductivity but faces a challenge in dimensional stability. Herein, we report the design and preparation of three kinds of isoreticular covalent organic framework (COF) membranes bearing tunable quaternary ammonium group densities as anion conductors. Therein, the cationic groups are integrated into the backbones by flexible ether-bonded alkyl side chains. The highly quaternary ammonium-group-functionalized building units endow COF membranes with abundant cationic groups homogeneously distributed in the ordered channels. The flexible side chains alleviate electrostatic repulsion and steric hindrance caused by large cationic groups, ensuring a tight interlayer stacking and multiple interactions. As a result, our COF membranes achieve a high ion exchange capacity and exceptional dimensional stability simultaneously. Furthermore, the effect of the ionic group density on the ion conductivity in rigid COF channels is systematically explored. Experiments and simulations reveal that the ionic group concentration and side chain mobility jointly determine the ion transport behavior, resulting in the abnormal phenomenon that the anion conductivity is not positively correlated to the ionic group density. The optimal COF membrane achieves the ever-reported highest hydroxide ion conductivity over 300 mS cm-1 at 80 °C and 100% RH. This study offers insightful guidelines on the rational design and preparation of high-performance anion conductors.

3D covalent organic framework membrane with fast and selective ion transport.

3D ionic covalent organic framework (COF) membranes, which are envisioned to be able to break the trade-off between ion conductivity and ion selectivity, are waiting for exploitation. Herein, we report the fabrication of a 3D sulfonic acid-functionalized COF membrane (3D SCOF) for efficient and selective ion transport, using dual acid-mediated interfacial polymerization strategy. The 3D SCOF membranes possess highly interconnected ion transport channels, ultramicroporous pore sizes (0.97 nm), and abundant sulfonate groups (with a high ion exchange capacity of 4.1 mmol g-1), leading to high proton conductivity of 843 mS cm-1 at 90 °C. When utilized in osmotic energy conversion, a high power density of 21.2 W m-2, and a remarkable selectivity of 0.976 and thus an exceptional energy conversion efficiency of 45.3% are simultaneously achieved. This work provides an alternative approach to 3D ionic COF membranes and promotes the applications of 3D COFs in ion transport and separation.

Spacer-Engineered Ionic Channels in Covalent Organic Framework Membranes toward Ultrafast Proton Transport.

Side-chain engineering of covalent organic frameworks as advanced ion conductors is a critical issue to be explored. Herein, ionic covalent organic framework membranes (iCOFMs) with spacer-engineered ionic channel are de novo designed and prepared. The ionic channels are decorated with side chains comprising spacers having different carbon chain lengths and the -SO3 H groups at the end. Attributed to the synergistic contribution from the spacers and the -SO3 H groups, the iCOFM with moderate-length spacer exhibit the highest through-plane proton conductivity of 889 mS cm-1 at 90 °C.

Short hydrogen-bond network confined on COF surfaces enables ultrahigh proton conductivity.

The idea of spatial confinement has gained widespread interest in myriad applications. Especially, the confined short hydrogen-bond (SHB) network could afford an attractive opportunity to enable proton transfer in a nearly barrierless manner, but its practical implementation has been challenging. Herein, we report a SHB network confined on the surface of ionic covalent organic framework (COF) membranes decorated by densely and uniformly distributed hydrophilic ligands. Combined experimental and theoretical evidences have pointed to the confinement of water molecules allocated to each ligand, achieving the local enrichment of hydronium ions and the concomitant formation of SHBs in water-hydronium domains. These overlapped water-hydronium domains create an interconnected SHB network, which yields an unprecedented ultrahigh proton conductivity of 1389 mS cm-1 at 90 °C, 100% relative humidity.

Covalent organic framework membranes for efficient separation of monovalent cations.

Covalent organic frameworks (COF), with rigid, highly ordered and tunable structures, can actively manipulate the synergy of entropic selectivity and enthalpic selectivity, holding great potential as next-generation membrane materials for ion separations. Here, we demonstrated the efficient separation of monovalent cations by COF membrane. The channels of COF membrane are decorated with three different kinds of acid groups. A concept of confined cascade separation was proposed to elucidate the separation process. The channels of COF membrane comprised two kinds of domains, acid-domains and acid-free-domains. The acid-domains serve as confined stages, rendering high selectivity, while the acid-free-domains preserve the pristine channel size, rendering high permeation flux. A set of descriptors of stage properties were designed to elucidate their effect on selective ion transport behavior. The resulting COF membrane acquired high ion separation performances, with an actual selectivity of 4.2-4.7 for K+/Li+ binary mixtures and an ideal selectivity of ~13.7 for K+/Li+.

Assembling covalent organic framework membranes with superior ion exchange capacity.

Ionic covalent organic framework membranes (iCOFMs) hold great promise in ion conduction-relevant applications because the high content and monodispersed ionic groups could afford superior ion conduction. The key to push the upper limit of ion conductivity is to maximize the ion exchange capacity (IEC). Here, we explore iCOFMs with a superhigh ion exchange capacity of 4.6 mmol g-1, using a dual-activation interfacial polymerization strategy. Fukui function is employed as a descriptor of monomer reactivity. We use Brønsted acid to activate aldehyde monomers in organic phase and Brønsted base to activate ionic amine monomers in water phase. After the dual-activation, the reaction between aldehyde monomer and amine monomer at the water-organic interface is significantly accelerated, leading to iCOFMs with high crystallinity. The resultant iCOFMs display a prominent proton conductivity up to 0.66 S cm-1, holding great promise in ion transport and ionic separation applications.

Tight Covalent Organic Framework Membranes for Efficient Anion Transport via Molecular Precursor Engineering.

Fabricating covalent organic frameworks (COFs) membranes with tight structure, which can fully utilize well-defined framework structure and thus achieve superior conduction performance, remains a grand challenge. Herein, through molecular precursor engineering of COFs, we reported the fabrication of tight COFs membrane with the ever-reported highest hydroxide ion conductivity over 200 mS cm-1 at 80 °C, 100 % RH. Six quaternary ammonium-functionalized COFs were synthesized by assembling functional hydrazides and different aldehyde precursors. In an organic-aqueous reaction system, the impact of the aldehyde precursors with different size, electrophilicity and hydrophilicity on the reaction-diffusion process for fabricating COFs membranes was elucidated. Particularly, more hydrophilic aldehydes were prone to push the reaction zone from the interface region to the aqueous phase of the reaction system, the tight membranes were thus fabricated via phase-transfer polymerization process, conferring around 4-8 times the anion conductivity over the loose membranes via interfacial polymerization process.

Scalable Fabrication of Crystalline COF Membranes from Amorphous Polymeric Membranes.

Covalent organic framework (COF) membranes hold potential for widespread applicability, but scalable fabrication is challenging. Here, we demonstrate the disorder-to-order transformation from amorphous polymeric membrane to crystalline COF membrane via monomer exchange. Solution processing is used to prepare amorphous membrane and the replacing monomer is selected based on the chemical and thermodynamical stability of the final framework. Reversible imine bonds allow the extraneous monomers to replace the pristine monomers within amorphous membrane, driving the transformation from disordered network to ordered framework. Incorporation of intramolecular hydrogen bonds enables the crystalline COF to imprint the amorphous membrane morphology. The COF membranes harvest proton conductivity up to 0.53 S cm-1 at 80 °C. Our strategy bridges amorphous polymeric and crystalline COF membranes for large-scale fabrication of COF membranes and affords guidance on materials processing.

Analogous Mixed Matrix Membranes with Self-Assembled Interface Pathways.

The implementation of mixed matrix membranes (MMMs) for sub-angstrom scale gas separations remains a grand challenge. Herein, a series of analogous mixed matrix membrane (AMMMs) were constructed via molecular-level hybridization by utilizing a reactive ionic liquid (RIL) as the continuous phase and graphene quantum dots (GQD) as nanofiller for sub-angstrom scale ethylene/ethane (0.416 nm/0.443 nm) separation. With a small number of GQDs (3.5 wt%) embedded in GQD/RIL AMMMs, ethylene permeability soared by 3.1-fold, and ethylene/ethane selectivity simultaneously boosted by nearly 60 % and reached up to 99.5, which outperformed most previously reported state-of-the-art membranes. Importantly, the interfacial pathway structure was visualized and their self-assembly mechanism was revealed, where the non-covalent interactions between RIL and GQDs induced the local arrangement of IL chains to self-assemble into plenty of compact and superfast interfacial pathways, contributing to the combination of superhigh permeability and selectivity.

Weakly Humidity-Dependent Proton-Conducting COF Membranes.

State-of-the-art proton exchange membranes (PEMs) often suffer from significantly reduced conductivity under low relative humidity, hampering their efficient application in fuel cells. Covalent organic frameworks (COFs) with pre-designable and well-defined structures hold promise to cope with the above challenge. However, fabricating defect-free, robust COF membranes proves an extremely difficult task due to the poor processability of COF materials. Herein, a bottom-up approach is developed to synthesize intrinsic proton-conducting COF (IPC-COF) nanosheets (NUS-9) in aqueous solutions via diffusion and solvent co-mediated modulation, enabling a controlled nucleation and in-plane-dominated IPC-COF growth. These nanosheets allow the facile fabrication of IPC-COF membranes. IPC-COF membranes with crystalline, rigid ion nanochannels exhibit a weakly humidity-dependent conductivity over a wide range of humidity (30-98%), 1-2 orders of magnitude higher than that of benchmark PEMs, and a prominent fuel cell performance of 0.93 W cm-2 at 35% RH and 80 °C arising from superior water retention and Grotthuss mechanism-dominated proton conduction.

De Novo Design of Covalent Organic Framework Membranes toward Ultrafast Anion Transport.

The emergence of all-organic frameworks is of fundamental significance, and designing such structures for anion conduction holds great promise in energy conversion and storage applications. Herein, inspired by the efficient anion transport within organisms, a de novo design of covalent organic frameworks (COFs) toward ultrafast anion transport is demonstrated. A phase-transfer polymerization process is developed to acquire dense and ordered alignment of quaternary ammonium-functionalized side chains along the channels within the frameworks. The resultant self-standing COFs membranes exhibit one of the highest hydroxide conductivities (212 mS cm-1 at 80 °C) among the reported anion exchange membranes. Meanwhile, it is found that shorter, more hydrophilic side chains are favorable for anion conduction. The present work highlights the prospects of all-organic framework materials as the platform building blocks in designing ion exchange membranes and ion sieving membranes.

Metal-Organic Nanogel with Sulfonated Three-Dimensional Continuous Channels as a Proton Conductor.

Developing novel proton conductors is crucial to the electrochemical technology for energy conversion and storage. Metal-organic frameworks (MOFs), with a highly ordered and controllable structure, have been widely explored to prepare high-performance proton conductors. Albeit the prominent merits and great potential of the MOF-based materials such as MOF pellets or composite polymer electrolytes, constructing well-defined proton-transfer channels with much lower grain boundary resistance and more homogeneous distribution deserves extensive explorations. Herein, a kind of nanostructured metal-organic gel (MOG) with a three-dimensional (3D) interconnected proton-conductive network is prepared by a facile sol-gel method using Cr3+ and sulfonated terephthalic as the metal source and organic ligand, respectively. During the gelation process, the primary metal-organic nanoparticles are cross-linked through mismatched growth and aggregate into the 3D well-percolated gel network. The resultant MOG features in the tunable hierarchical structure and long-range continuous proton-transfer channels, leading to remarkably reduced energy barrier for proton conduction. Attributed to the sulfonated ligand and well-interconnected proton-conductive pathways, MOG exhibits intrinsic proton conductivity that is about one order of magnitude higher than that of MIL-101-SO3H pellet (MIL, Matérial Institut Lavoisier). The method in this study can be extended to construct long-range continuous ionic channels for a number of solid electrolytes.

Two-dimensional nanochannel membranes for molecular and ionic separations.

Two-dimensional (2D) nanosheets have emerged as promising functional materials owing to their atomic thickness and unique physical/chemical properties. By using 2D nanosheets as building blocks, diverse kinds of two-dimensional nanochannel membranes (2DNCMs) are being actively explored, in which mass transport occurs in the through-plane and interlayer channels of 2D nanosheets. The rational construction and physical/chemical microenvironment regulation of nanochannels are of vital significance for translating these 2D nanosheets into molecular separation membranes and ionic separation membranes. Focusing on the recent advances of 2DNCMs, in this review, various porous/nonporous 2D nanosheets and their derived nanochannels are first briefly introduced. Then we discuss the emerging top-down and bottom-up methods to synthesize high-quality 2D nanosheets and to prepare high-performance 2DNCMs. As the major part of this review, we focus on three types of nanochannels, which are based on nonporous nanosheets, intrinsically porous nanosheets and perforated nanosheets. The strategies for regulating the physical and chemical microenvironments in the nanochannels are emphasized. The representative applications of 2DNCMs in molecular separations (gas separation, liquid separation) and ionic separations are presented. Finally, the current challenges and future perspectives are highlighted.

Supramolecular Calix[n]arenes-Intercalated Graphene Oxide Membranes for Efficient Proton Conduction.

Graphene oxide (GO) membranes with 2D interlaminar channels have triggered intensive interest as ion conductors. Incorporating abundant ion-conducting sites into GO interlayers is recognized as an effective strategy to facilitate ion conduction. Herein, we designed supramolecular compounds, para-sulphonato-calix[n]arenes (p-SC[n]As), as versatile intercalators to acquire highly conductive and robust GO membranes. The SC[n]A with ultrahigh ionic exchange capacity (IECw, 5.37 mmol g-1) imparts sufficient proton donors, and its rigid framework imparts strong support of adjacent nanosheets. We designed three kinds of SC[n]As with the same IECw but different sizes as intercalators, endowing the GO/SC[n]A membranes with increasing ion concentration and d-spacing in the order of GO/SC[4]A < GO/SC[6]A < GO/SC[8]A. Therefore, the interlayers of GO/SC[8]A membranes afforded higher density of proton donors and could accommodate more water molecules to construct more continuous H-bond networks for proton transfer. Accordingly, the proton conductivities exhibited the same increasing trend, up to 327.0 mS cm-1 of GO/SC[8]A-30% at 80 °C, 100% RH, which was 2.80 times higher than that of the GO membrane. Moreover, the GO/SC[n]A membranes remained stable in wet state, along with a 66% elevation in mechanical performance compared to the GO membrane.

Control of Edge/in-Plane Interactions toward Robust, Highly Proton Conductive Graphene Oxide Membranes.

Graphene oxide (GO) membrane, bearing well-aligned interlayer nanochannels and well-defined physicochemical properties, promises fast proton transport. However, the deficiency of proton donor groups on the basal plane of GO and weak interlamellar interactions between the adjacent nanosheets often cause low proton conduction capability and poor water stability. Herein, we incorporate sulfonated graphene quantum dots (SGQD) into  GO membrane to solve the above dilemma via synergistically controlling the edge electrostatic interaction and in-plane π-π interaction of SGQD with GO nanosheets. SGQD with three different kinds of electron-withdrawing groups are employed to modulate the edge electrostatic interactions and improve the water swelling resistant property of GO membranes. Meanwhile, SGQD with abundant proton donor groups assemble on the sp2 domain of GO via in-plane π-π interaction and confer the GO membranes with low-energy-barrier proton transport channels. As a result, the GO membrane achieves an enhanced proton conductivity of 324 mS cm-1, maximum power density of 161.6 mW cm-2, and superior water stability when immersed into water for one month. This study demonstrates a strategy for independent manipulation of conductive function and nonconductive function to fabricate high-performance proton exchange membranes.

Hydroxide Conduction Enhancement of Chitosan Membranes by Functionalized MXene.

In this study, imidazolium brushes tethered by ⁻NH2-containing ligands were grafted onto the surface of a 2D material, MXene, using precipitation polymerization followed by quaternization. Functionalized MXene was embedded into chitosan matrix to prepare a hybrid alkaline anion exchange membrane. Due to high interfacial compatibility, functionalized MXene was homogeneously dispersed in chitosan matrix, generating continuous ion conduction channels and then greatly enhancing OH- conduction property (up to 172%). The ability and mechanism of OH- conduction in the membrane were elaborated based on systematic tests. The mechanical-thermal stability and swelling resistance of the membrane were evidently augmented. Therefore, it is a promising anion exchange membrane for alkaline fuel cell application.

Graphene Oxide Membranes with Conical Nanochannels for Ultrafast Water Transport.

Membrane-based separations have been increasingly utilized to address global energy crisis and water scarcity. However, the separation efficiency often suffers from the trade-off between membrane permeability and selectivity. Although great efforts have been devoted, a membrane with both high permeability and high selectivity remains a distant prospect. Inspired by the hourglass structure and ultrafast water transport in aquaporins, we propose a novel approach to fabricating membranes with conical nanochannels to reduce the mass transfer resistance and to introduce Laplace pressure as the internal driving force, which successfully breaks the permeability/selectivity trade-off. First, sulfonated polyaniline (SPANI) nanorods were in situ-synthesized and vertically aligned on sulfonated graphene oxide (SGO) nanosheets, forming SGO-SPANI X composites. Then, the graphene oxide (GO) membranes were fabricated by assembling SGO-SPANI X composites through pressure-assisted filtration, in which the SPANI nanorods would bend and flatten on the SGO nanosheets under low shear force, forming stripe arrays on SGO nanosheets. The tilted stripe arrays between the adjacent SGO nanosheets form the conical nanochannels inside GO membranes. The conical nanochannels significantly decreased the steric hindrance and enabled the generation of Laplace pressure as the internal driving force within membranes. Consequently, the resulting membranes exhibit an ultrahigh water permeability of 1222.77 L·m-2·h-1·bar-1 and high efficiency in dye removal from water with a rejection of 90.44% and permeability of 528 L·m-2·h-1·bar-1.

A Regularly Channeled Lamellar Membrane for Unparalleled Water and Organics Permeation.

Lamellar membranes show exceptional molecular permeation properties of key importance for many applications. However, their design and development need the construction of regular and straight interlayer channels and the establishment of corresponding transport rate equation. The fabrication of a uniformly lamellar membrane is reported using double-layered Ti3 C2 Tx MXenes as rigid building blocks. This membrane possesses ordered and straight 2 nm channels formed via a direct self-stacking, in contrast to the conventional irregular ones from flexible sheets. Such channels permit precise molecular rejection and unparalleled molecular permeation. The permeance of water and organics by this membrane reached 2300 and 5000 L m-2 h-1 bar-1 , respectively. The molecular transfer mechanism in confined nanochannels, and the corresponding model equation are established, paving a way to nanoscale design of highly efficient channeled membranes for transport and separation applications.