On-Water Surface Synthesis of Two-Dimensional Polymer Membranes for Sustainable Energy Devices.

Abstract

ConspectusIon-selective membranes are key components for sustainable energy devices, including osmotic power generators, electrolyzers, fuel cells, and batteries. These membranes facilitate the flow of desired ions (permeability) while efficiently blocking unwanted ions (selectivity), which forms the basis for energy conversion and storage technologies. To improve the performance of energy devices, the pursuit of high-quality membranes has garnered substantial interest, which has led to the exploration of numerous candidates, such as polymeric membranes (e.g., polyamide and polyelectrolyte), laminar membranes (e.g., transition metal carbide (MXene) and graphene oxide (GO)) and nanoporous 2D membranes (e.g., single-layer MoS2 and porous graphene). Despite impressive progress, the trade-off effect between ion permeability and selectivity remains a major scientific and technological challenge for these membranes, impeding the efficiency and stability of the resulting energy devices.Two-dimensional polymers (2DPs), which represent monolayer to few-layer covalent organic frameworks (COFs) with periodicity in two directions, have emerged as a new candidate for ion-selective membranes. The crystalline 2DP membranes (2DPMs) are typically fabricated either by bulk crystal exfoliation followed by filtration or by direct interfacial synthesis. Recently, the development of surfactant-monolayer-assisted interfacial synthesis (SMAIS) method by our group has been pivotal, enabling the synthesis of various highly crystalline and large-area 2DPMs with tunable thicknesses (1 to 100 nm) and large crystalline domain sizes (up to 120 μm2). Compared to other membranes, 2DPMs exhibit well-defined one-dimensional (1D) channels, customizable surface charge, ultrahigh porosity, and ultrathin thickness, enabling them to overcome the permeability-selectivity trade-off challenge. Leveraging these attributes, 2DPMs have established their critical roles in diverse energy devices, including osmotic power generators and metal ion batteries, opening the door for next-generation technology aimed at sustainability with a low carbon footprint.In this Account, we review our achievements in synthesizing 2DPMs through the SMAIS method and highlight their selective-ion-transport properties and applications in sustainable energy devices. We initially provide an overview of the SMAIS method for producing highly crystalline 2DPMs by utilizing the programmable assembly and enhanced reactivity/selectivity on the water surface. Subsequently, we discuss the critical structural parameters of 2DPMs, including pore sizes, charged sites, crystallinity, and thickness, to elucidate their roles in selective ion transport. Furthermore, we present the burgeoning landscape of energy device applications for 2DPMs, including their use in osmotic power generators and as electrode coating in metal ion batteries. Finally, we conclude persistent challenges and future prospects encountered in synthetic chemistry, material science, and energy device applications within this rapidly evolving field.