Recent advances on COF-based single-atom and dual-atom sites for oxygen catalysis.

Designing cost-efffective electrocatalysts for the oxygen evolution reaction (OER) holds significant importance in the progression of clean energy generation and efficient energy storage technologies, such as water splitting and rechargeable metal-air batteries. In this work, an OER electrocatalyst is developed using Ni and Fe precursors in combination with different proportions of graphene oxide. The catalyst synthesis involved a rapid reduction process, facilitated by adding sodium borohydride, which successfully formed NiFe nanoparticle nests on graphene support (NiFe NNG). The incorporation of graphene support enhances the catalytic activity, electron transferability, and electrical conductivity of the NiFe-based catalyst. The NiFe NNG catalyst exhibits outstanding performance, characterized by a low overpotential of 292.3mV and a Tafel slope of 48mVdec-1, achieved at a current density of 10mAcm- 2. Moreover, the catalyst exhibits remarkable stability over extended durations. The OER performance of NiFe NNG is on par withthat of commercial IrO2 in alkaline media. Such superb OER catalytic performance can be attributed to the synergistic effect between the NiFe nanoparticle nests and graphene, which arises from their large surface area and outstanding intrinsic catalytic activity. The excellent electrochemical properties of NiFe NNG hold great promise for further applications in energy storage and conversion devices.

Covalent organic frameworks (COFs) are a family of crystalline porous networks having applications in various fields, including gas and energy storage. Despite respectable progress in the synthesis of such crystalline materials, examples of the use of template-free methods to construct COFs having hollow nano- and microstructures are rare. Furthermore, all reported methods for synthesizing these hollow structural COFs have involved [4 + 2] and [3 + 2] condensations. Herein, we report the synthesis of hollow microspherical and microtubular carbazole-based COFs through template-free, one-pot, [3 + 3] condensations of the novel triamine 9-(4-aminophenyl)-carbazole-3,6-diamine (Car-3NH2) and triformyl linkers with various degrees of planarity. Depending upon the monomer's planarity, a unique morphological variety was observed. A time-dependent study revealed that each COF formed through an individual mechanism depended on the degree of planarity of the triformyl linker; it also confirmed that the hollow structures of these COFs formed through inside-out Ostwald ripening. Our COFs exhibited high Brunauer-Emmett-Teller surface areas (up to ca. 1400 m2 g-1), excellent crystallinity, and high thermal stability. Moreover, the CO2 uptake capacities of these COFs were excellent: up to 61 and 123 mg g-1 at 298 and 273 K, respectively. The high surface areas facilitated greater numbers of strong interactions with CO2 molecules, leading to high CO2 uptake capacities. Moreover, the prepared COFs exhibited redox activity because of their redox-active triphenylamine and pyridine groups, which can be utilized in electrochemical energy storages. Accordingly, such hollow COFs having high surface areas appear to be useful materials for industrial and biological applications.

Covalent organic frameworks (COFs), which are constructed from organic linkers, are a new class of crystalline porous materials comprising periodically extended and covalently bound network structures. The intrinsic structures and the tailorable organic linkers endow COFs with a low density, large surface area, tunable pore size and structure, and facilely-tailored functionality, attracting increasing interests in different fields including membrane separations. Exciting research activities ranging from fabrication strategies to separation applications of COF-based membranes have appeared. This review analyzes the synthesis and applications of diverse continuous/discontinuous COF membranes, such as COF-based mixed matrix membranes (MMMs), COF-based thin film nanocomposite (TFN) membranes, and free-standing COF films. Special attention was given to pore size, stability, hydrophilicity/hydrophobicity and surface charge of COFs in view of determining proper COFs for membrane fabrication, along with the approaches to fabricate COF-based membranes, such as blending, in situ growth, layer-by-layer stacking and interfacial polymerization (IP). Moreover, applications of COF-based membranes in gas separation, water treatment (deaslination and dye removal), organic solvent nanofiltration (OSN), pervaporation and fuel cell are disscussed. Finally, we illustrate the advantages and disadvantages of COF-based membranes through a comparison with MOF-based membranes, and the remaining challenges and future opportunities in this field.

The pursuit of efficient photocatalysts toward photocatalytic water splitting has attracted wide attention. However, the low efficiency of photocatalytic reactions due to the rapid electron-hole recombination and the time-consuming searching process hinder the development of high-performance photocatalysts. Here, we proposed a data-driven screening procedure for covalent organic frameworks (COFs) as overall solar water-splitting photocatalysts. Based on a COF database through assembling different Cores and Linkers, three COFs are predicted to be efficient photocatalysts for overall solar water splitting after high-throughput computational screening. We found that the photogenerated electrons and holes are well separated on single COF photocatalysts without material engineering, and both hydrogen and oxygen evolution reactions can occur spontaneously on the three screened COFs under visible light radiation. This kind of novel COF screened by a data-driven screening procedure offers new perspectives for advancing efficient photocatalysts.

The severe environmental issues triggered by the overuse of fossil energy have propelled the development of energy conversion and storage technologies. Oxygen electrocatalysis, including oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), has attracted widespread attention as the key reaction of many energy devices. Increasing research has demonstrated the exceptional potential of atomic iron catalysts in oxygen electrocatalysis, offering promising prospects for advancing these technologies. Building upon an analysis of the mechanisms underlying oxygen electrocatalysis and integrating insights from characterization techniques and theoretical calculations, this paper systematically summarizes the strategies for regulating the electronic structure of atomic iron catalysts, including coordination environment, metal active center, and substrate modulation. Then, given that the stability of Fe–N–C catalysts remains a fundamental bottleneck hindering their development, optimization strategies including adjusting the Fe─N bond length, reducing H 2 O 2 attack, and improving the graphitization degree of the carrier are proposed. Furthermore, the applications in energy storage and conversion devices are reviewed. Finally, the future challenges and opportunities for atomic iron catalysts are discussed, offering insights for the development of more advanced Fe‐based catalysts.

Polyamide⊥TpPa-PVDF membranes for aliphatic-aromatic solvent separations

Over the years the interest in developing an electrocatalyst that can be more efficient for oxygen evolution reaction (OER) has increased and various electrocatalysts have been developed after enormous efforts. Recently, large attention has been engrossed by covalent organic frameworks (COFs) which belong to porous organic materials due to their extraordinary properties like high crystallinity, adjustable pore size, unique structure, and large surface area. These COFs have been used for designing electrocatalysts for OER. As COFs building blocks are organic molecules, they have low electrocatalytic activity and poor conductivity. Therefore, to overcome this metal nanoparticles are combined to form COFs-based nanomaterials for better electrocatalytic activity. These COFs based nanomaterials have shown their potential as electrocatalysts for OER. Thus, this chapter involves a discussion on the development of COFs-based nanomaterials as OER electrocatalysts.

Covalent organic frameworks (COFs) are a promising class of metal-free catalysts, offering a high structural and functional variety. Here, we systematically study imine-linked COFs with donor (D) and acceptor (A) groups using density functional theory (DFT). Using water splitting as a model reaction, we analyze the effects of protonation of the catalyst, the orientation of the imine linkage leading to different constitutional isomers, and solvation. In agreement with experimental results, we show that protonation decreases the band gap. In addition, COFs in which the donor is closer to the nitrogen atom of the imine group (DNCA) have lower band gaps than those in which the donor is closer to the carbon atom (DCNA). Three different D/A COFs are compared in this work, for which energies for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) and corresponding electrochemical overpotentials are computed. We show that reaction energies are very similar for DCNA and DNCA COFs. The differences in hydrogen evolution rates between the constitutional isomers observed experimentally in (photocatalytic) HER (Yang et al., Nat. Commun., 2022, 13, 6317), are proposed to be at least in part a consequence of differences in charge distribution.

Covalent organic frameworks (COFs) have been employed to catalyze the oxygen evolution reaction (OER). However, their catalytic activities have been limited, because their narrow interlayer space hindered the mass transport to the catalytic sites. Herein, we have demonstrated dimensional-controlled interlayer space of COFs for OER. The one dimensional (1D) catalytic COF had weaker stacking interaction between the 1D chains than that from two-dimensional COFs, which allowed for easier expansion of the interlayer distance in catalytic process, leading to enhanced catalytic activity. Moreover, the electronic states were well modulated with extending the length of conjugating units by integrating the alkynal units. The optimized catalyst achieved an overpotential of 225 mV and Tafel slope of 76 mV dec–1 in 1.0 M KOH, outperforming other 2D or 3D COFs. Theoretical calculations demonstrated that the alkynal units facilitated the OOH* desorption on the Fe sites, which further improved the activity.

Fine control over the physicochemical structures of carbon electrocatalysts is important for improving the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in rechargeable Zn–air batteries. Covalent organic frameworks (COFs) are considered good candidate carbon materials because their structures can be precisely controlled. However, it remains a challenge to impart bifunctional electrocatalytic activities for both the ORR and OER to COFs. Herein, a pyridine‐linked triazine covalent organic framework (PTCOF) with well‐defined active sites and pores is readily prepared under mild conditions, and its electronic structure is modulated by incorporating Co nanoparticles (CoNP‐PTCOF) to induce bifunctional electrocatalytic activities for the ORR and OER. The CoNP‐PTCOF exhibits lower overpotentials for both ORR and OER with outstanding stability. Computational simulations find that the p‐band center of CoNP‐PTCOF down‐shifted by charge transfer, compared to pristine PTCOF, facilitate the adsorption and desorption of oxygen intermediates on the pyridinic carbon active sites during the reactions. The Zn–air battery assembled with bifunctional CoNP‐PTCOF exhibits a small voltage gap of 0.83 V and superior durability for 720 cycles as compared with a battery containing commercial Pt/C and RuO2. This strategy for modulating COF electrocatalytic activities can be extended for designing diverse carbon electrocatalysts.

Using bimetallic Prussian blue analogue (PBA) as a precursor is effective for preparing electrocatalysts for the oxygen evolution reaction (OER); however, the role of these PBA-derived catalysts in the OER is still ambiguous. Herein, by simply controlling synthesis temperature, a bimetallic PBA-derived O,N-codoped Ni-Fe carbide, can be well tuned to optimize structure and OER performance. Importantly, by a series of ex situ and in situ investigations, real active species of NiFeOx Hy are in situ formed on the surface during the OER, which reveals a "pre-catalyst" role of O,N-codoped Ni-Fe carbides. Furthermore, it has been successfully applied to highly efficient Zn-air batteries and outplays its RuO2 counterpart. When applied to photoelectrocatalytic water oxidation as the co-catalyst, it improves the performance of the BiVO4 photoanode by enhancing hole collecting and transporting ability. We believe this research not only provides a highly efficient and low-cost electrocatalyst for the OER, but also unveils the "pre-catalyst" role of PBA-derived materials in energy-storage and conversion devices.

Synthesis of polyoxometalates derived bifunctional catalyst towards efficient overall water splitting in neutral and alkaline medium

Imine-based covalent organic frameworks (COFs) are a widely studied class of functional, crystalline, and porous nanostructures which combine a relatively facile crystallization with tuneable compositions and porosities. However, the imine linkage constitutes an intrinsic limitation due to its reduced stability in harsh chemical conditions and its unsuitability for in-plane π-conjugation in COFs. Urgent solutions are therefore required in order to exploit the full potential of these materials, thereby enabling their technological application in electronics, sensing, and energy storage devices. In this context, the advent of a new generation of linkages derived from the chemical conversion and locking of the imine bond represents a cornerstone for the synthesis of new COFs. A marked increase in the framework robustness is in fact often combined with the incorporation of novel functionalities including, for some of these reactions, an extension of the in-plane π-conjugation. This Minireview describes the most enlightening examples of one-pot reactions and post-synthetic modifications towards the chemical locking of the imine bond in COFs.

Design of two-dimensional porous covalent organic framework semiconductors for visible-light-driven overall water splitting: A theoretical perspective

Designing MOF-COF hybrid materials for energy, biomedical and environment applications