Two-dimensional Covalent Organic Frameworks Research Articles

Do the Hydrogen Evolution Reaction and Oxygen Reduction Reaction Really Need To Be Suppressed in O2-Tolerant CO2 Electroreduction Catalyzed by DAE-BPy-CoPor and Co-TAPP?

This letter chooses DAE-BPy-CoPor [DAE, 1,2-bis(5'-formyl-2'-methylthien-3'-yl)cyclopentene; BPy, 2,2'-bipyridine-5,5'-dicarbaldehyde; and CoPor, two-dimensional cobalt porphyrin-based covalent organic framework] and Co-TAPP [10,15,20-tetrakis(4-aminophenyl)porphinatocobalt] as two model catalysts to investigate the effect of the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) in the O2-tolerant CO2 electroreduction reaction (CO2RR). Both catalysts have been proven to have CO2RR activity at a potential range from -0.60 to -1.10 V when CO2 and O2 are co-feeding (Zhu, H.-J.; Si, D.-H.; Guo, H.; Chen, Z.; Cao, R.; Huang, Y.-B. Oxygen-tolerant CO2 electroreduction over covalent organic frameworks via photoswitching control oxygen passivation strategy. Nat. Commun. 2024, 15, 1479, DOI: 10.1038/s41467-024-45959-9). The calculated results by grand canonical density functional theory (GC-DFT) and microkinetic (MK) simulation show that the effect of HER could be categorized into two groups: (1) Positive *H formation energy: HER would have no effect on the turnover frequency (TOF) of the CO2RR. (2) Negative *H formation energy: HER would also have no effect to the TOF of CO2RR when the calculated limiting potential for HER is larger than that for CO2RR. Otherwise, all active sites would be covered by *H and poisoned before CO2RR can happen. The effect of ORR could be categorized into three types: (1) ORR would have no effect to the TOF of the CO2RR when ORR happened with the CO2RR at the same time. (2) ORR is suppressed; the active site is covered by an intermediate state (such as *OH); and the CO2RR is also suppressed because of the poisoned active site. (3) ORR is suppressed; the active site is not covered; and the TOF of the CO2RR is not affected.

Tuning structures and catalysis performance of two-dimensional covalent organic frameworks based on copper phthalocyanine building block and phenyl connector

Based on the experimentally reported stable and conductive two-dimensional covalent organic frameworks with copper phthalocyanine (CuPc) as building block and cyan substituted phenyl as connector (CuCOF-CN) as an electrocatalyst for CO2 reduction reaction (RR), first principle calculations were performed on CuCOF-CN and its analog with the CN being replaced by H (CuCOF). Comparatively studied on the crystal structures, electronic properties, and CO2RR performance of the two catalysts found that CuCOF has reduced crystal unit size, more positive charge on Cu and CuPc segments, smaller band gap, and lower reaction barrier for CO2 RR than CuCOF-CN. CuCOF is proposed to be good potential electrocatalyst with good environment friendliness. The substituent effect and structure-property-performance relationship would help for designing and fabricating new electrocatalysts.

Diketopyrrolopyrrole-Activated Dynamic Condensation Approach to Narrow-Band Gap Vinylene-Linked Covalent Organic Frameworks.

Vinyl units intrinsically featuring less steric, nonpolarity, and unsaturated character, are well-known π-bridge used in the synthesis of high-performance semiconducting materials. Two-dimensional (2D) vinylene-linked covalent organic frameworks (COFs) represent a promising class of π-conjugated structures, however, the range of available monomers for the reversible formation of carbon-carbon double bonds remains limited. In this study, a new class of 2D vinylene-linked COFs were synthesized using dimethyldiketopyrrolopyrrole(DM-DPP) as the key monomer. The strong electron deficiency of diketopyrrolopyrrole (DPP) makes its methyl substituents readily activated upon the cocatalysis of L-proline and 4-dimethylaminopyridine in aqueous solution to conduct dynamic condensation with tritopic aromatic aldehydes. The resulting COFs crystallized in an eclipsed AA stacking arrangement and featured abundant, regular nanochannels. Their robust vinyl DPP-linking mode enhanced donor-π-acceptor conjugation and promoted π-stacked alignment along the vertical direction. Consequently, the synthesized COFs exhibited band gaps as narrow as 1.02 eV and demonstrated excellent light-harvesting capability across the visible to near-infrared I (NIR-I) regions. Furthermore, the COFs could be converted into free-standing thin pellets through simple pressure casting, and show excellent photothermal response and cycling stability under different light sources.

Modulating Pore Wall Chemistry Empowers Sonodynamic Activity of Two-Dimensional Covalent Organic Framework Heterojunctions for Pro-Oxidative Nanotherapy.

Covalent organic frameworks (COFs) have garnered growing interest in the field of biomedicine; however, their application in sonodynamic therapy remains underexplored due to limited understanding of their intrinsic activity and structure-property relationships. Here, we present a pore wall chemistry modulation strategy for empowering sonodynamic activity to two-dimensional (2D) COF heterojunctions through in situ growth of COFs on bismuth oxycarbonate nanosheets (B NSs). Compared to the negligible sonodynamic effects observed in the pristine B NSs, the 2D heterojunction with vinyl-decorated COF pore walls demonstrates a 3.6-fold enhancement in sonocatalytic singlet oxygen generation. This performance also significantly outperforms that of isoreticular COFs functionalized with methoxy or non-substituted groups. Mechanistic studies reveal that the vinyl groups in the B@COF (BC) heterojunction facilitate the separation and transfer of charge carriers while also enhancing the adsorption of oxygen molecules. Furthermore, peroxymonosulfate (PMS) loading into the porous COFs boosts the therapeutic efficacy of antitumor nanotherapy via sonocatalytic dual oxidative species generation. These findings underscore the critical role of pore wall chemistry in modulating the sonocatalytic properties of COFs, and advance the development of COF-based sonosensitizers for pro-oxidative applications.

Photocarrier Dynamics of Two-Dimensional Aza-Fused Covalent Organic Frameworks as Bifunctional Photocatalysts toward Overall Water Splitting.

Designing high-efficiency bifunctional photocatalysts toward photoinduced overall water splitting is one of the most promising and challenging research directions for clean energy generation. By employing static electronic structure calculation and nonadiabatic molecular dynamics (NAMD) simulation, we herein established a recently synthesized two-dimensional (2D) aza-fused covalent organic framework (aza-COF) as a potential bifunctional photocatalyst toward overall water splitting reactions. Our calculated results reveal that the overpotentials for hydrogen evolution reaction and oxygen evolution reaction are only 0.06 and 0.31 V, respectively, at pH = 4. The dynamics of photoexcited charge carriers studied through NAMD simulation predicts the electron-hole recombination time (25.15 ns), and this confirms that the photogenerated electron and hole carriers migrate to the active sites for the occurrence of reaction before they recombine. Therefore, our results suggest that the 2D aza-COFs exhibit great potential as metal-free and single-material photocatalysts toward overall water splitting under visible light.

Carbazole and Triazine-Based D-A Covalent Organic Framework for Visible Light-Mediated Photocatalytic C-H Activation of Imidazopyridine and Indole.

Two-dimensional donor-acceptor covalent organic frameworks (COFs) show considerable promise for metal-free and heterogeneous photocatalysis due to their efficient charge carrier separation and exciton transport upon photoexcitation. To date, numerous photocatalysts have been developed. However, they encounter several challenges, such as inadequate sunlight harvesting ability, poor photostability, and nonreusability. Fortunately, the emergence of COFs presents a promising solution to these problems. Herein, we report an imine-linked CzTA-TAPT COF featuring carbazole as the electron donor and triazine as the electron acceptor. Compared to the previously reported C2-linker-derived CzDA-TAPT COF, this C3-linked COF exhibits good charge separation and charge carrier transport. As a consequence, it demonstrates excellent photocatalytic applicability in the C-3 thiocyanation of imidazo[1,2-a]pyridine and indole under ambient conditions under visible light. Moreover, its broad substrate compatibility and high recyclability provide a green and sustainable approach for the thiocyanation of imidazopyridine and indole. To the best of our knowledge, this is the first heterogeneous catalyst demonstrated for the thiocyanation of imidazo[1,2-a]pyridine. These findings will inspire further research in the development of high-performance D-A COFs as photocatalysts for organic transformations.

Two-Dimensional Covalent Organic Frameworks with Carbazole-Embedded Frameworks Facilitate Photocatalytic and Electrocatalytic Processes.

Catalytic technologies are pivotal in enhancing energy efficiency, promoting clean energy production, and reducing energy consumption in the chemical industry. The pursuit of novel catalysts for renewable energy is a long-term goal for researchers. In this work, we synthesized three two-dimensional covalent organic frameworks (COFs) featuring electron-rich carbazole-based architectures and evaluated their catalytic performance in photocatalytic organic reactions and electrocatalytic oxygen reduction reactions (ORRs). Pyrene-functionalized COF, termed as FCTD-TAPy, demonstrated excellent photocatalytic performance for amino oxidation coupling and showed a remarkable preference for substrates with electron-withdrawing groups (up to >99% Conv. and >99% Sel). Furthermore, FCTD-TAPy favored a four-electron transfer pathway during the ORR and exhibited favorable reaction kinetics (51.07 mV/dec) and a high turnover frequency (0.011 s-1). In contrast, the ORR of benzothiadiazole-based FCTD-TABT favored a two-electron transfer pathway, which exhibited a maximum double-layer capacitance of 14.26 mF cm-2, a Tafel slope of 53.01 mV/dec, and a hydrogen peroxide generation rate of 70.3 mmol g-1 h-1. This work underscores the potential of carbazole-based COFs as advanced catalytic materials and offers new insights into the design of metal-free COFs for enhanced catalytic performance.

Molecular Design of Two-Dimensional Antiaromatic Covalent Organic Frameworks for Solar-Driven Overall Water Splitting

Molecular Design of Two-Dimensional Antiaromatic Covalent Organic Frameworks for Solar-Driven Overall Water Splitting

Triazine-Based Large-Sized Single-Crystalline Two-Dimensional Covalent Organic Framework for High-Performance Lithium-Ion Batteries.

A large-sized single crystalline 2D COFs with excellent crystallinity and stability was prepared through the traditional thermal solvent method. The electrochemical performance can be significantly enhanced using a straightforward hybrid approach that involves in situ growth of the 2D COFs on multi-walled carbon nanotubes (MWCNTs). Both the advantages of COFs and CNTs are mutually enhanced. The single-crystalline feature of the obtained COFs improves the structural integrity and brings excellent chemical and electrochemical stabilities for lithium-ion battery applications. The resultant COF-CNT core-shell hybrids greatly improved the conductivity and demonstrated excellent lithium-ion storage performance with a high capacity of 228 mAh g-1 (0.2 A g-1).

Two-Dimensional Covalent Organic Frameworks: Structural Insights across Different Length Scales and Their Impact on Photocatalytic Efficiency.

ConspectusCovalent organic frameworks (COFs) are a rapidly emerging class of crystalline porous polymers, characterized by their highly defined, predictable, and tunable structure, porosity, and properties. COFs can form both two-dimensional (2D) and three-dimensional (3D) architectures, each with unique characteristics and potential applications. 2D COFs have attracted particular interest due to their favorable structural and optoelectronic properties. They can be equipped with a range of different functional moieties in their backbone, ranging from acidic to basic, from hydrophilic to hydrophobic, and from metal-coordinating to redox-active functions. In addition, their crystallinity, high specific surface area, and remarkable thermal and chemical stability make them attractive for a variety of applications, including gas separation, catalysis, energy storage, and optoelectronics.This Account provides a detailed overview of our recent efforts to synthesize and apply 2D COFs. First, various synthesis routes are discussed, focusing on methods that involve reversible and irreversible linkage reactions. Reversible reactions, such as imine or boronate ester formation, are advantageous for producing highly crystalline COFs because they allow for error correction during synthesis. In contrast, irreversible reactions, such as carbon-carbon or carbon-nitrogen bond formation, yield COFs with greater chemical stability, although controlling crystallinity can be more challenging. Our group has contributed significantly to refining these methods to balance crystallinity and stability, enhancing the performance of the resulting 2D COFs.In addition to different binding patterns, we have also developed strategies to control the micro- and macromorphologies of COFs, which is crucial for optimizing their properties for specific applications. For example, we have explored the synthesis of hierarchical porous COFs by using templating techniques or by forming composites with other functional materials. These strategies enable us to fine-tune the porosity and surface properties of COFs, thereby improving their performance in applications like catalysis. Hierarchical structures in particular enhance photocatalytic efficiency by providing a larger surface area for light absorption and facilitating the transport of photogenerated charge carriers.We further examine the practical applications of 2D COFs, with a primary focus on photocatalysis. Photocatalysis uses light to enable or accelerate chemical reactions, and 2D COFs are ideal for this purpose due to their tunable band gaps and large surface areas. Our research has shown that 2D COFs are highly versatile photocatalysts that can effectively catalyze reactions such as water splitting, carbon dioxide reduction, hydrogen peroxide formation, and cross-coupling reactions. By exploiting the unique properties of 2D COFs, we have achieved significant improvement in many photocatalytic reactions.With this comprehensive overview, we aim to contribute to the further development and understanding of 2D COFs and encourage further research and innovation in this promising field.

Synergistic effect of 2D covalent organic frameworks confined 0D carbon quantum dots film: Toward molecularly imprinted cathodic photoelectrochemical platform for detection of tetracycline

The development of high photoactive cathode materials combined with the formation of a stable interface are considered important factors for the selective and sensitive photoelectrochemical (PEC) detection of tetracycline (TC). Along these lines, in this work, a novel type II heterostructure composed of two-dimensional (2D) covalent organic frameworks confined to zero-dimensional (0D) carbon quantum dots (CDs/COFs) film was successfully synthesized using the rapid in-situ polymerization method at room temperature. The PEC signal of CDs/COFs was significantly amplified by improving the light absorption and electron transfer capabilities. Furthermore, a cathodic molecularly imprinted PEC sensor (MIP-PEC) for the detection of TC was constructed through fast in-situ Ultraviolet (UV) photopolymerization on the electrode. Finally, a “turn-off” PEC cathodic signal was achieved based on the selective recognition of the imprinted cavity and the mechanism of steric hindrance increase. Under optimal conditions, the proposed sensor demonstrated a wide linear relationship with TC in the concentration range of 5.00 × 10−12–1.00 × 10−5 M, with a detection limit as low as 6.00 × 10−13 M. Meanwhile, excellent stability, selectivity, reproducibility, and applicability in real river samples was recorded. Our work provides an effective and rapid in situ construction method for fabricating highly photoactive cathode heterojunctions and uniform stable selective MIP-PEC sensing interfaces, yielding accurate antibiotics detection in the environment.

Dynamic Two-Dimensional Covalent Organic Frameworks with Large Solvent-Induced Lattice Expansion.

Dynamic covalent organic frameworks (COFs) can switch reversibly between crystalline phases with different unit cell parameters and porosities upon physisorption of guest molecules. While impressive changes in unit cell volumes have been realized for three-dimensional frameworks, the solvent-induced volume changes of two-dimensional (2D) COFs have remained comparably small. We have now developed a series of 2D COFs where we systematically varied the length of the interconnecting bridge units. The optimized materials achieve solvent-induced expansions of up to 85% relative to the volume of the solvent-free contracted COFs. These structural changes are fully reversible and the frameworks fully retain their high degree of crystalline order. This study introduces a versatile design strategy for dynamic 2D COFs, which could enable future applications of these materials in gas separation and sensing.

Engineering of Covalent Organic Framework Nanosheet Membranes for Fast and Efficient Ion Sieving: Charge-Induced Cation Confined Transport.

Artificial membranes with ion-selective nanochannels for high-efficiency mono/divalent ion separation are of great significance in water desalination and lithium-ion extraction, but they remain a great challenge due to the slight physicochemical property differences of various ions. Here, the successful synthesis of two-dimensional TpEBr-based covalent organic framework (COF) nanosheets, and the stacking of them as consecutive membranes for efficient mono/divalent ion separation is reported. The obtained COF nanosheet membranes with intrinsic one-dimensional pores and abundant cationic sites display high permeation rates for monovalent cations (K+, Na+, Li+) of ≈0.1-0.3mol m-2 h-1, while the value of divalent cations (Ca2+, Mg2+) is two orders of magnitude lower, resulting in an ultrahigh mono/divalent cation separation selectivity up to 130.4, superior to the state-of-the-art ion sieving membranes. Molecular dynamics simulations further confirm that electrostatic interaction controls the confined transport of cations through the cationic COF nanopores, where multivalent cations face i) strong electrostatic repulsion and ii) steric transport hindrance since the large hydrated divalent cations are retarded due to a layer of strongly adsorbed chloride ions at the pore wall, while smaller monovalent cations can swiftly permeate through the nanopores.

Facilitating Charge Transfer via Ti-Knot Pathway in Electrochromic Three-Dimensional Metalated Covalent Organic Frameworks.

Due to the ordered one-dimensional channel as well as accessible redox sites, two-dimensional covalent organic frameworks (2D COFs) have garnered extensive attention in the field of electrochromism. However, organic 2D frameworks impose limitations on charge transfer and the weak interlayer interactions in 2D COFs, adversely affecting the stability during switching processes. Herein, we introduced Ti knots to construct three-dimensional metalated covalent organic frameworks (3D MCOFs), denoted as Ti-DHTA-Py. The Ti knots not only serve as templates for organizing organic units into unique 3D topological structures in a controlled manner but also establish charge transfer pathways conducive to electron delocalization and transmission within the framework. As a result, the 3D Ti-DHTA-Py MCOFs electrode exhibited a reduced band gap and remarkable electrochromic (EC) performances: electrochemical cyclic stability of 93.6% retention after 500 cycles, switching times (2.5 s/0.5 s), and a high coloration efficiency (423 cm2 C-1). This research underscores the potential of 3D MCOFs as promising candidates for advancing EC technologies, surmounting the limitations associated with traditional 2D COFs.

Hydrogen-Bond-Regulated Mechanochemical Synthesis of Covalent Organic Frameworks: Cocrystal Precursor Strategy for Confined Assembly.

Two-dimensional imine covalent organic frameworks (2D imine-COFs) are crystalline porous materials with broad application prospects. Despite the efforts into their design and synthesis, the mechanisms of their formation are still not fully understood. Herein, a one-pot two-step mechanochemical cocrystal precursor synthetic strategy is developed for efficient construction of 2D imine-COFs. The mechanistic investigation demonstrated that the cocrystal precursors of 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trianiline (TAPT) and p-toluenesulphonic acid (PTSA) sufficiently regulate the crystalline structure of COF. Evidenced by characterizations and theoretical studies, a helical hydrogen-bond network was constructed by the N-H⋅⋅⋅O supramolecular synthons between amino and sulfonic groups in TAPT-PTSA, demonstrating the role of cocrystals in promoting the organized stacking of interlayer π-π interactions, layer arrangement, and interlayer spacing, thus facilitating the orderly assembly of COFs. Moreover, the protonation degree of TAPT amines, which tuned nucleophilic directionality, enabled the sequential progression of intra- and interlayer imine condensation reactions, inhibiting the formation of amorphous polymers. The transformation from cocrystal precursors to COFs was achieved through comprehensive control of hydrogen bond and covalent bond sites. This work significantly advances the concept of hydrogen-bond-regulated COF assembly and its mechanochemical method in the design and synthesis of 2D imine-COFs, further elucidating the mechanistic aspects of their mechanochemical synthesis.

Cell membrane-inspired COF/AAO hybrid nanofluidic membrane with ion current rectification properties for ultrasensitive detection of E. coli

Nanofluidic membranes hold great prospects in sensitive and rapid detection of bioanalysts, while remaining lacking robust and general approaches for specificity. In this work, we introduce a cell membrane-inspired nanofluidic membrane with excellent ion current rectification properties as a simple and robust platform for label-free and ultrasensitive biosensing. The asymmetric nanofluidic membrane is prepared by coupling a two-dimensional covalent organic framework (COF) membrane to an anodic aluminum oxide (AAO) nanochannel via hydrogen bonding. The prepared COF/AAO membrane presents selective ion transport due to the asymmetric structure and anion selectivity of COF. With the large surface area and abundant functional modification sites of COF, further grafting of the recognition unit can be easily achieved to mimic the recognition process of receptors and ligands on cell membranes. As a proof of concept, the application in bacterial detection is demonstrated by covalently bonded Concanavalin A as recognition units. The highly amplified ionic current based on ion current rectification properties of the COF/AAO membrane allows sensitive and selective bioanalysis. Specifically, the proposed asymmetric nanofluidic membrane presents a linear detection range from 10 to 106 CFU/mL with an ultralow detection limit of 7 CFU/mL for E. coli. This work reveals the great potential of COF/AAO hybrid nanofluidic membrane as a sensor for rapid and precise bioanalysis.

Efficient and highly selective photocatalytic reduction of Cr(VI) by an active two-dimensional covalent organic framework

In this paper, a two-dimensional covalent organic framework material (named HDU-27) with thiazole structure and π-π conjugation has been successfully synthesized using the ligands tri acetaldehyde-based methoxyphenyl and benzo [1,2-d:4,5-d]thiazole-2,6-diamine in an ammonia-formaldehyde condensation reaction and applied to the photocatalytic reduction study of chromium (Cr). The photocatalytic experiments showed that HDU-27 had an excellent photocatalytic reduction of Cr(VI) with a high Cr(VI) reduction efficiency of 99.5 ​% at pH ​= ​2 for 60 ​min. In the presence of interfering ions, HDU-27 exhibited excellent selectivity for Cr(VI). Mechanistic experiments and electron spin resonance characterization identified e− and ·O2− radicals as the main active species in Cr(VI) photocatalytic reduction. In addition, the photocatalytic rate of HDU-27 was significantly accelerated in the Cr(VI)/organic pollutant (RhB, MB, MO) mixed system due to the oxidation of the organic matter and the increase in the separation of photogenerated e−−h+. The cycling experiments demonstrated the excellent reduction stability and recyclability of HDU-27 in the photocatalytic reduction of Cr(VI). HDU-27 is an excellent photocatalyst with potential application for removing organic pollutants and heavy metal ions from contaminated wastewater.

The role of one-dimensional materials in modulating the selective mass transport of covalent organic framework membranes for nanofiltration

Two-dimensional covalent organic frameworks (2D COFs) membranes have well-ordered nanochannels for selective molecular sieving. One-dimensional (1D) materials have been proposed to link the loosely packed COFs nanosheet for enhancing the separation performance of COFs membranes. However, it remains unclear how the enhancement arises. Herein, we demonstrate the role of 1D materials in modulating the microstructure and interlayer force of 2D COFs membranes. The optimized composite membrane, assembled from 2D COFs and chitosan exhibits a 75% enhancement in permeance without sacrificing selectivity towards different dyes. Our results show that the interaction forces between COFs and 1D materials are directly correlated to the transport nanochannels. When the interaction forces are stronger, the microstructure is more densely packed. Meanwhile, the shielding effect of 1D materials on the intrinsic channels of 2D COFs is more significant, resulting in narrow transport channels for mass transfer. In contrast, the weaker interaction forces prevent the excessive shrinkage of nanochannels, facilitating fast mass transfer and maintaining the high molecular selectivity. The work unravels the interaction forces between 2D COFs and 1D materials leading to the shaping of mass transfer nanochannels, offering a new perspective for the advancement of COFs membrane for nanofiltration.

Sequence-Dependent Single-Molecule DNA Sensing Using Covalent Organic Framework Nanopores.

Enzyme-free single-molecule sequencing has the potential to significantly expand the application of nanopore technology to DNA, proteins, and saccharides. Despite their advantages over biological nanopores and natural suitability for enzyme-free single-molecule sequencing, conventional solid-state nanopores have not yet achieved single-molecule DNA sequencing. The biggest challenge for the accuracy of single-molecule sequencing using solid-state nanopores lies in the precise control of the pore size and conformity. In this study, we fabricated nanopore devices by covering the tip of a quartz nanopipette with ultrathin two-dimensional (2D) covalent organic framework (COF) nanosheets (pore size ≈ 1.1 nm). The size of the periodically arranged nanopores in COF is comparable to that of protein nanopores, and the structure of each COF nanopore is consistent at the atomic scale. The COF nanopore device could roughly distinguish dAMP, dCMP, dGMP, and dTMP. Furthermore, a certain percentage of the current blockades originating from 150 nucleotides model DNA molecules (13.5% for dA50dC50dA50 and 11.1% for dC50dA50dC50) show distinct DNA sequence-specific concave and convex resistive current patterns. The finite element simulation confirmed that the current blockade pattern of a DNA molecule passing through a COF nanopore is dependent on the relative location of the nanopore with respect to the wall of the nanopipette. Our study is a significant step toward single-molecule DNA sequencing by solid-state nanopores.

Harnessing the clean energy: Phosphorus-alkynyl covalent organic frameworks for photocatalytic hydrogen production

Given the diminishing reserves of fossil fuels, the development of renewable alternative energy sources is of global importance. Photocatalytic hydrogen (H2) evolution stands out as a promising and cost-effective method to harness sunlight for producing carbon-free H2 fuel. Recently, two-dimensional (2D) covalent organic frameworks (COFs) have garnered considerable research interest in photocatalysis on account of their exceptional surface area and predictable assembly of diverse molecules with adjustable electronic properties. Herein, six 2D COFs are constructed by topologically assembling phosphorus-alkynyl functional moieties and benzene-based building units, including benzene (COF-1), triazine (COF-2), heptazine (COF-3), triphenyl-benzene (COF-4), triphenyl-triazine (COF-5), and triphenyl-heptazine (COF-6), employing first-principles calculations. Our computational results illustrate that the variation of benzene-based building units significantly regulates the electronic structures of COFs, all of which possess semiconductor properties with tunable bandgaps spanning from 1.56 to 2.56 eV. Of particular importance, COF-1, COF-2, COF-4, COF-5, and COF-6 can spontaneously stimulate the hydrogen evolution reaction (HER) under their own light-induced bias without the need for sacrificial agents and co-catalysts. Among them, COF-4 and COF-5 show the best HER activity without light-induced bias, with ΔG values of 0.02 and −0.01 eV, respectively, whose excellent photocatalytic performance can be ascribed to their appropriate electronic band structures, pronounced optical absorption, and low work functions. This finding offers profound insights for exploring other highly efficient HER photocatalysts.