The on-surface synthesis of two-dimensional (2D) polymers from monomers represents a useful strategy for designing lattice, orbital and spin symmetries. Like other 2D materials, the ordered stacking of 2D polymers into bilayers may allow developing unique optoelectronic, charge transport and magnetic properties not found in the individual layers. However, controlling layer stacking of 2D polymers remains challenging. Here we describe a method for synthesizing 2D polymer bilayers or bilayer 2D covalent organic frameworks at the liquid–substrate interface through the direct condensation of monomers. More importantly, we also show how factors such as monomer structure and solvent mixture influence the bilayer stacking modes and how, under certain conditions, large-area moiré superlattices emerge from the twisted bilayer stacking. This finding offers new opportunities for the design of bilayer stacked framework materials with tunable electronic and structural properties.

Mixed-matrix membranes (MMMs) possess the unique properties and inherent characteristics of their component polymer and inorganic fillers, or other possible types of additives. However, the successful fabrication of compact and defect-free MMMs with a homogeneous filler distribution poses a major challenge, due to poor filler/polymer compatibility. In this study, we use two-dimensional multi-layered Ti₃C₂T_x MXene nanofillers to improve the compatibility and CO₂/CH₄ separation performance of cellulose triacetate (CTA)-based MMMs. CTA-based MMMs with TiO₂-based 1D (nanotubes) and 0D (nanofillers) additives were also fabricated and tested for comparison. The high thermal stability, compact homogeneous structure, and stable long-term CO₂/CH₄ separation performance of the CTA-2D samples suggest the potential application of the membrane in bio/natural gas separation. The best results were obtained for the CTA-2D sample with a loading of 3 wt.%, which exhibited a 5-fold increase in CO₂ permeability and 2-fold increase in CO₂/CH₄ selectivity, compared with the pristine CTA membrane, approaching the state-of-the-art Robeson 2008 upper bound. The dimensional (shape) effect on separation performance was determined as 2D > 1D > 0D. The use of lamellar stacked MXene with abundant surface-terminating groups not only prevents the aggregation of particles but also enhances the CO₂ adsorption properties and provides additional transport channels, resulting in improved CO₂ permeability and CO₂/CH₄ selectivity.

We systematically study the electronic structure, carrier mobility and work function of imine based 2D-COFs. The bandgaps of these semiconducting materials can be tailored by doping with nitrogen for tunable electronic/optoelectronic properties.