Two-Dimensional Covalent Organic Frameworks with Pentagonal Pores.

The pore shapes of two-dimensional covalent organic frameworks (2D COFs) significantly limit their practical applications in separation and catalysis. Although various 2D COFs with polygonal pores have been well developed, constructing COFs with pentagonal pores remains an enormous challenge. In this work, we developed one kind of pentagonal COFs with the mcm topological structure for the first time, through the rational combination of C4 and C2 symmetric building blocks. The resulting pentagonal COFs exhibit high crystallinity, excellent porosity, and strong robustness. Moreover, the inbuilt porphyrin units render these COFs as efficient electrocatalytic catalysts toward oxygen reduction reaction with a half-wave potential of up to 0.81 V, which ranks as one of the highest values among COFs-based electrocatalysts. This work not only verified the possibility of constructing 2D COFs with pentagonal pores but also developed a strategy for the construction of functional 2D COFs for interesting applications.

Lithiophilic Covalent Organic Framework as Anode Coating for High-Performance Lithium Metal Batteries.

The growth of disorganized lithium dendrites and weak solid electrolyte interphase greatly impede the practical application of lithium metal batteries. Herein, we designed and synthesized a new kind of stable polyimide covalent organic frameworks (COFs), which have a high density of well-aligned lithiophilic quinoxaline and phthalimide units anchored within the uniform one-dimensional channels. The COFs can serve as an artificial solid electrolyte interphase on lithium metal anode, effectively guiding the uniform deposition of lithium ions and inhibiting the growth of lithium dendrites. The unsymmetrical Li||COF-Cu battery exhibits a Coulombic efficiency of 99 % at a current density of 0.5 mA cm-2 , which can be well retained up to 400 cycles. Meanwhile, the Li-COF||LFP full cell shows a Coulombic efficiency over 99 % at a charge of 0.3 C. And its capacity can be well maintained up to 91 % even after 150 cycles. Therefore, the significant electrochemical cycling stability illustrates the feasibility of employing COFs in solving the disordered deposition of lithium ions in lithium metal batteries.

Two-Dimensional Covalent Organic Frameworks as Tailor-Made Scaffolds for Water Harvesting.

Developing materials to harvest water from the air is of great importance to alleviate the water shortage for people living in arid regions, where the annual average relative humidity (RH) is lower than 0.4. In this work, we report a general nitrogen atom incorporation strategy to prepare high-performance covalent organic frameworks (COFs) for water harvesting from the air in arid areas. A series of COFs, namely COF-W1, COF-W2, and COF-W3 were developed for this purpose. Different contents of nitrogen were embedded into COFs by incorporating pyridine units into the building blocks. With the increasing content of nitrogen from COF-W1 to COF-W3, the inflection points of their water isotherms shift distinctly from RH values from 0.65 to 0.25. Significantly, COF-W3 exhibits the lowest inflection point at a low RH value of 0.25 and reaches a high uptake capacity of 0.28 g g-1 at 25 °C with a low hysteresis loop. Moreover, the gram-scale COF-W3 retains its high performance, which renders it more attractive in water harvesting. This work demonstrates the feasibility of this nitrogen incorporation strategy to acquire high-performance COFs as water harvesters in the future.

Covalent Organic Frameworks for Water Harvesting from Air.

Despite approximately 70 % of the earth being covered by water, water shortage has emerged as an urgent social challenge. Sorbent-based atmospheric water harvesting stands out as a potent approach to alleviate the situation, particularly in arid regions. This method requires adsorbents with ample working capacity, rapid kinetics, low energy costs, and long-term stability under operating conditions. Covalent organic frameworks (COFs) are a novel class of crystalline porous materials and offer distinct advantages due to their high specific surface area, structural diversity, and robustness. These properties enable the rational design and customization of their water-harvesting capabilities. Herein, the basic concepts about the water sorption process within COFs, including the parameters that qualitatively or quantitatively describe their water isotherms and the mechanism are summarized. Then, the recent methods used to prepare COFs-based water harvesters are reviewed, emphasizing the structural diversity of COFs and presenting the common empirical understandings of these endeavors. Finally, challenges and research concepts are proposed to help develop next-generation COFs-based water harvesters.