Covalent organic frameworks (COFs) are a class of crystalline porous polymers that allow the atomically precise integration of organic units to create predesigned skeletons and nanopores. They have recently emerged as a new molecular platform for designing promising organic materials for gas storage, catalysis, and optoelectronic applications. The reversibility of dynamic covalent reactions, diversity of building blocks, and geometry retention are three key factors involved in the reticular design and synthesis of COFs. This tutorial review describes the basic design concepts, the recent synthetic advancements and structural studies, and the frontiers of functional exploration.

Covalent organic frameworks (COFs) have attracted growing interest by virtue of their structural diversity and tunability. Herein, we present a novel approach for the development of organic rechargeable battery cathodes in which three distinct redox-active COFs were successfully prepared and delaminated into 2D few-layer nanosheets. Compared with the pristine COFs, the exfoliated COFs with shorter Li diffusion pathways allow a significant higher utilization efficiency of redox sites and faster kinetics for lithium storage. Unlike diffusion-controlled manners in the bulk COFs, the redox reactions in ECOFs are mainly dominated by charge transfer process. The capacity and potential are further engineered by reticular design of COFs without altering the underlying topology. Specifically, DAAQ-ECOF exhibits excellent rechargeability (98% capacity retention after 1800 cycles) and fast charge-discharge ability (74% retention at 500 mA g as compared to at 20 mA g). DABQ-ECOF shows a specific capacity of 210 mA h g and a voltage plateau of 2.8 V.

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To the Editors-Electrochemical conversion of dinitrogen to ammonia in aqueous electrolyte solutions at high selectivity and rate requires a catalyst with unique properties. In particular, the surface of such a catalyst should exhibit higher affinity for nitrogen, as opposed to hydrogen, to facilitate the nitrogen reduction reaction (NRR) and suppress the hydrogen evolution reaction (HER). Detailed density functional theory (DFT) studies by Skúlason and co-workers 3 suggest that this is hardly possible with most metals traditionally considered in electrocatalytic research. One metal not included in the analysis in ref. 3 and long known to be a very poor HER catalyst 4 is bismuth, which was very recently introduced by Hao et al. 1 as an efficient NRR catalyst in their report in Nature Catalysis. However, DFT data reported in the same paper clearly indicate that N2 adsorption on various bismuth surfaces is highly thermodynamically unfavourable with an essentially insurmountable energy barrier of more than 2.7 eV. Nevertheless, despite this contradiction, the highly impressive experimental data on the Bicatalysed NRR reported by Hao et al. 1 present the best performances reported to date and therefore would represent important progress in this field. This prompted us to attempt to reproduce these experimental results. Details of our materials and equipment are provided