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Nature Communications volume 15, Article number: 4856 (2024 ) Cite this article 8 quinol structure and function
Developing highly active materials that efficiently utilize solar spectra is crucial for photocatalysis, but still remains a challenge. Here, we report a new donor-acceptor (D-A) covalent organic framework (COF) with a wide absorption range from 200 nm to 900 nm (ultraviolet-visible-near infrared light). We find that the thiophene functional group is accurately introduced into the electron acceptor units of TpDPP-Py (TpDPP: 5,5’-(2,5-bis(2-ethylhexyl)−3,6-dioxo-2,3,5,6-tetrahydropyrrolo [3,4-c]pyrrole-1,4-diyl)bis(thiophene-2-carbaldehyde), Py: 1,3,6,8-tetrakis(4-aminophenyl)pyrene) COFs not only significantly extends its spectral absorption capacity but also endows them with two-photon and three-photon absorption effects, greatly enhancing the utilization rate of sunlight. The selective coupling of benzylamine as the target reactant is used to assess the photocatalytic activity of TpDPP-Py COFs, showing high photocatalytic conversion of 99% and selectivity of 98% in 20 min. Additionally, the TpDPP-Py COFs also exhibit the universality of photocatalytic selective coupling of other imine derivatives with ~100% conversion efficiency. Overall, this work brings a significant strategy for developing COFs with a wide absorption range to enhance photocatalytic activity.
The development of efficient photocatalysts is crucial for solar-driven photocatalysis benefit owing to its clean, eco-friendly, and renewable advantages1,2,3. Conventional inorganic photocatalysts, such as TiO24,5, ZnO6,7, and CdS8,9 encounter constraints in modulating their broad-band gaps, thereby limiting their capability to harness sunlight. Organic small-molecule photocatalyst, on the other hand, grapple with stability concerns, which complicates the processes of separation and recycling, impacting their overall sustainability10. Covalent organic frameworks (COFs), one of new crystalline porous materials, exhibiting enormous advantages, including high porosity11, extended π conjugation12,13, adjustable bandgaps14, and good stability15. Significantly, the Pt-doped COFs reported by Lotch’s group for continuous hydrogen production exhibit excellent structure and chemical stability, which has ignited extensive research on COFs-based photocatalysts16. Recently, COFs have been widely studied and applied in photocatalysts fields, including carbon dioxide reduction17,18, photocatalytic hydrogen production19,20, hydrogen peroxide synthesis21,22, and organic synthesis23,24. The noteworthy importance of imines as crucial intermediates in chemical synthesis, pharmaceuticals, and biology has prompted extensive investigations into the use of COFs for achieving efficient photocatalytic imine production25,26,27,28. In this pursuit, researchers have consistently focused on designing and synthesizing COFs with high photocatalytic active.
The common effective strategies for enhancing photocatalytic active are to promote the separation of photogenerated electron-hole, such as metal doping, heterojunctions, regulating band gap or the position of conduction and valence band29. Recently, the triazine-structured monomers30,31, porphyrins32,33, or phenolic functional group-containing monomers such as 2,4,6-triformyl resorcinol have been used to synthesize COFs for promoting the charge separation efficiency27,34. However, most COFs have a narrow absorption range typically between 200 nm and 550 nm, leading to reduced photocatalytic efficiency. To solve this bottleneck, developing novel strategies to expand the absorption range of COFs is key for enhancing their photocatalytic efficiency, but it still remains grand challenges.
Herein, we developed a novel strategy to precisely incorporate thiophene into the electron acceptor units of TpDPP-Py COFs (TpDPP: 5,5’-(2,5-bis(2-ethylhexyl)−3,6-dioxo-2,3,5,6-tetrahydropyrrolo [3,4-c]pyrrole-1,4-diyl)bis(thiophene-2-carbaldehyde), Py: 1,3,6,8-tetrakis(4-aminophenyl)pyrene), which extends its π-conjugated framework structure, significantly increasing the sunlight harvesting capabilities. In addition, the extended π-conjugated framework structure facilitates substantial interactions among non-adjacent chromophores without inducing aggregation, resulting in multi-photon absorption35. The fabricated TpDpp-Py COFs exhibit a wide absorption wavelength range of 200–900 nm and two/three-photon absorption effects, which enormous enhance the utilization rate of solar energy, thus exhibiting excellent performance of photocatalytic benzylamine (BA) coupling with conversion of 99% and selectivity of 98% in 20 min. In addition, the TpDPP-Py COFs also exhibit the universality of photocatalytic selective coupling of other imine derivatives with ~100% photocatalytic conversion efficiency. Overall, this work presents a significant strategy for the development of COFs with a broad absorption range to enhance photocatalytic activity.
Diketopyrrolopyrrolopyrrole dialdehyde is widely recognized as a favorable candidate for the construction of donor‒acceptor (D‒A) structured COFs with enhanced light absorption performance owing to its well-established chromophore36. In the synthesis pathway, the thiophene functional groups with strong aromaticity and enhanced photocatalytic activity were selected as the side chain electron acceptor unit37,38,39 (Fig. 1a, Supplementary Fig. 1–3). For comparison, the DPP (4,4’-(2,5-bis(2-ethylhexyl)−3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4-c]pyrrole-1,4 diyl)dibenzaldehyde) molecule with phenyl groups as the side chain was also synthesized (Fig. 1b, Supplementary Fig. 4, 5). Further, the Py (Py: 1,3,6,8-tetrakis(4-aminophenyl)pyrene) molecular with abundant conjugated electrons was chosen as the electronic donor unit40,41. A novel TpDPP-Py COFs with large π-conjugated system was synthesized by employing TpDPP as the electron acceptor and Py as the electron donor (Fig. 1c). The reference DPP-Py COFs were synthesized by employing DPP as the electron acceptor and Py as the electron donor (Fig. 1d).
a, b Synthetic route of TpDPP and DPP organic molecules. c, d Molecular structure of TpDPP-Py COFs and DPP-Py COFs.
To confirm the chemical bonding properties, Fourier transform infrared (FT-IR) and Raman spectroscopy were carried out. The FT-IR spectroscopy showed the disappearance of the amino group of Py (νN-H = 3370‒3346 cm–1) and aldehyde group of TpDPP (νHC=O = 1693 cm–1), accompanied by the presence of a new characteristic peak located at 1571 cm–1 divided to C = N imine bonds, indicating the formation of TpDPP-Py COFs connected by imine bonds (Fig. 2a). Similarly, Raman spectroscopy displayed pronounced peaks at 1571 cm–1, consistent with the presence of imine bonds observed in the FT-IR analysis (Fig. 2b). X-ray Photoelectron Spectroscopy (XPS) data further confirmed the formation of imine bonds in TpDPP-Py COFs (Supplementary Fig. 6). Additionally, the solid-state 13C NMR (ss NMR) spectroscopy was performed to reveal the molecular framework structure of TpDPP-Py COFs, showing a chemical shift at 150 ppm corresponding to the imine bond (C = N) (Fig. 2c). In addition, the 15N ssNMR spectroscopy showed that the chemical shift located 162 ppm could be attributed to imine bond (Supplementary Fig. 7). These results provided additional evidence for the formation of COFs42,43,44,45,46,47. Overall, the above results provided powerful evidence for the formation of imine bonded TpDPP-Py COFs. Further, The FT-IR spectra and 13C ssNMR also demonstrated the formation of DPP-Py COFs (Supplementary Fig. 8).
a FT-IR spectra of TpDPP, Py and TpDPP-Py COFs. b Raman spectra of Py, TpDPP and TpDPP-Py COFs. c Solid-state 13C CP-MAS NMR spectrum of TpDPP-Py COFs. d Experimental and simulated XRD pattern of TpDPP-Py COFs (purple). e Simulated TpDPP-Py COFs molecular structure. f Temperature dependent XRD pattern of TpDPP-Py COFs.
To further determine the ordered porous structure of TpDPP-Py COFs, N2 adsorption and desorption curves, X-ray diffraction (XRD) analysis and Cryogenic transmission electron microscopy (cryo-TEM) were conducted. N2 adsorption and desorption analysis revealed that the Brunauer-Emmett-Teller (BET) surface area and pore size of TpDPP-Py COFs were 408 m2 g–1 and 2.35 nm respectively, which was consistent with the theoretical simulations (Supplementary Fig. 9). The cell parameters of TpDPP-Py COFs and DPP-Py COFs are shown in Supplementary Tables 1, 2, respectively. The XRD pattern showed prominent peaks at 2.83°, 3.61°, 4.35° and 5.69°, corresponding to the crystal facets (110), (210), (120) and (310) respectively, with low-profile R-values of 5.2% and weighted-profile R-values of 6.9% (Fig. 2d, Supplementary Fig. 10). Compared to the A‒B stacking arrangement observed in TpDPP-Py COFs (Supplementary Fig. 11), the A‒A stacking arrangement aligns better with the experimental results (Fig. 2e). Additionally, temperature dependent XRD, Thermo-Gravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC) results demonstrate the excellent structural stability of TpDPP-Py COFs (Fig. 2f, Supplementary Fig. 12). Furthermore, SEM and TEM images were used to study the surface morphology of the TpDPP-Py COFs and DPP-Py COFs (Supplementary Fig. 13, Fig. 14). TEM images revealed the nanosheet morphology of TpDPP-Py COFs, displaying an average particle size of 650 nm (Supplementary Fig. 14). Additionally, cryo-TEM provided in-depth insights into the microstructural and lattice structure of the COF material (Fig. 3a). The crystal spacing of 3.11 nm was corresponded to the (110) crystal plane (Fig. 3b). The Fast Fourier Transform (FFT) patterns also exhibited a tetragonal structure, which was a match to the simulated molecular structure (Fig. 3c). Elemental mapping showed the uniform distribution of sulfur (S), oxygen (O), nitrogen (N), and carbon (C) on TpDPP-Py COFs (Fig. 3d). Thus, the above results confirmed the successful synthesis of TpDPP-Py COFs with ordered porous structure.
a Cryo-TEM images of TpDPP-Py COFs (scale bar, 50 nm). b High resolution Cryo-TEM of the TpDPP-Py COFs (scale bar, 20 nm). c FFT patterns of TpDPP-Py COFs. d HAADF-STEM image and the corresponding STEM-EDS elemental mapping images of TpDPP-Py COFs (scale bar, 100 nm) (d1, merge; d2, S; d3, O; d4, N; d5, C).
The optical band gap of TpDPP-Py COFs was calculated as 1.38 eV through the equation Eg (eV) = 1240 / λ (nm) (Fig. 4a). The UV-vis spectrum showed that TpDPP-Py COFs exhibited broad absorption peaks range from 200 to 900 nm, indicating a narrower optical bandgap and higher solar energy utilization efficiency compared to DPP-Py COFs (Fig. 4b, Supplementary Fig. 15). The photoluminescence fluorescence spectrum exhibited that TpDPP-Py COFs could be excited within the wavelength range from 300 nm to 700 nm, with an emission peak observed at 810 nm, signifying favorable absorption properties in the visible and near-infrared regions (Fig. 4c, Supplementary Fig. 16). The fluorescence decay of TpDPP-Py COFs exhibited a dual exponential decay model, with fluorescence decay times of 0.0595 ns and 0.299 ns (Fig. 4d, Supplementary Fig. 17), which were shorter than DPP-Py COFs (0.168 ns and 0.862 ns) (Supplementary Fig. 18), indicating more efficient charge separation efficiency and transport dynamics48,49.
a Kubelka-Munk function analysis of UV/Vis absorption spectra for TpDPP-Py COFs, TpDPP, and Py precursor materials, along with diffuse reflection spectra. b Kubelka-Munk Function UV/Vis Absorption Spectra of TpDPP-Py COFs and DPP-Py COFs. c Solid-state fluorescence spectra of TpDPP-Py COFs under different excitation wavelengths. d Time-resolved photoluminescence spectra of TpDPP-Py COFs (λex = 1200 nm). e Molecular orbital amplitude plots of HOMO and LUMO of the ligand and p-extended ligand calculated at the ωb97xd/6-31 G* basis set. f Two-photon induced solid-state fluorescence emission of TpDPP-Py COFs at different units (λex = 1200 nm). g three-photon induced solid-state fluorescence emission of TpDPP-Py COFs at different units (λex = 2100 nm). h transient photocurrent responses of the TpDPP-Py COFs and DPP-Py COFs.
The HOMO and LUMO energy levels of TpDPP Py COFs were calculated to be −4.67 eV and −3.39 eV, respectively (Fig. 4e), yielding a theoretical band gap of 1.28 eV. Moreover, compared with DPP-Py COFs, TpDPP-Py COFs exhibited excellent two-photon and three-photon absorption characteristics (Fig. 4f, g, Supplementary Fig. 19), implying more effectively utilization of sunlight. Figure 4h shows the photocurrent response curves of TpDPP-Py COFs and DPP-Py COFs. The TpDPP-Py COFs exhibited a photocurrent density of 0.054 μA cm‒2, which was significantly higher than that of DPP-Py COFs (0.035 μA cm‒2). The high photocurrent density of TpDPP-Py COFs mainly benefits from its excellent light absorption characteristics.
To assess the photocatalytic properties, TpDPP-Py COFs were used for the selective photocatalytic coupling of benzylamine (BA) to N-benzylidenebenzylamine. The gas chromatogram (GC) was carried out to detect the conversion rate of N-benzylidenebenzylamine (Supplementary Fig. 20, 21). Figure 5a shows the activity and selectivity of converting BA to N-benzylidenebenzylamine over TpDPP-Py COFs. The TpDPP-Py COFs exhibit a high photocatalytic coupling conversion of BA of 99% and high selectivity of 98% in 20 min, which is significantly better than DPP-Py COFs (Fig. 5b). Meanwhile, the performance of TpDPP-Py COFs photocatalytic conversion of BA to N-benzylidenebenzylamine is also better than most reported photocatalysts (Fig. 5c, Supplementary Table 3). Figure 5d shows the activity and selectivity of different batches TpDPP-Py COFs for photocatalytic conversion of BA to N-benzylidenebenzylamine. No obvious attenuation indicates the excellent performance stability of TpDPP-Py COFs. Furthermore, XRD and FT-IR spectra confirm that the crystal structure of TpDPP-Py COFs does not undergo significant changes after the photocatalytic reaction (Supplementary Fig. 22), validating its excellent structural stability.
a Activity and selectivity of TPDPP-Py COFs photocatalytic conversion of BA to N-benzylidenebenzylamine. b Activity and selectivity of DPP-Py COFs photocatalytic conversion of BA to N-benzylidenebenzylamine. c performance comparison of TpDPP-Py COFs with reported photocatalyst. d Repeatability measurement of TpDPP-Py COFs photocatalytic conversion of BA to N-benzylidenebenzylamine. e EPR detection of the 1O2 trapped by TEMP over TpDPP-Py COFs under dark and light irradiation. f Comparison of EPR intensity of 1O2 between TpDPP-Py COFs and DPP-Py COFs. g EPR detection of the ∙O2– anion radical trapped by DMPO over TpDPP-Py COFs under dark and light irradiation. h Comparison of EPR intensity of ∙O2–anion radical between TpDPP-Py COFs and DPP-Py COFs. i EPR detection of the hole over TpDPP-Py COFs with and without BA.
Based on the above discussion, the mechanism of selective photocatalytic coupling of BA to generate N-benzylidenebenzylamine can be explained (Supplementary Fig. 25). Firstly, TpDPP-Py COFs are excited to produce photogenerated electron-hole pairs. And then, the 1O2 captures photogenerated electrons and is reduced to ∙O2– anion radical. Meanwhile, the α-carbon of BA is activated by the photogenerated hole. Further, the ∙O2– anion radical is used to react with activated BA molecule to generate benzaldehyde intermediate. Finally, the unstable benzaldehyde intermediates rapidly react with BA to synthesize N-benzylidenebenzylamine (Supplementary Fig. 25).
a 2-ethoxyaniline, b 3-ethoxyaniline, c 4-ethoxyaniline, d 2-thiophene methylamine, e 4-fluoroaniline, and f 4-Chlorobenzylamine.
In summary, we present a novel TpDPP-Py COFs for the first time by integrating thiophene into DPP organic ligands, resulting in a broad absorption range spanning from 200 nm to 900 nm (ultraviolet-visible-near infrared light). Our study illustrates that the extended π-conjugated framework structure not only enhances the absorption capacity but also confers multi-photon absorption effects, significantly improving sunlight utilization and photocatalytic activity. Utilizing the TpDPP-Py COFs for the selective photocatalytic coupling of benzylamine (BA) resulted in a high BA coupling conversion rate of 99% and a selectivity of 98% within a 20-min timeframe, surpassing that of most reported active materials. Furthermore, the TpDPP-Py COFs demonstrate a general applicability for the photocatalytic coupling of various amine derivatives. This work introduces a new strategy for the development of innovative COFs photocatalysts, which is of great significance for promoting the practical application of COFs in the field of photocatalysis.
Synthesis of TpDPP-Py-COFs: 5,5’-(2,5-bis(2-ethylhexyl)−3,6-dioxo-2,3,5,6-tetrahydropyrrolo [3,4-c]pyrrole-1,4-diyl)bis(thiophene-2-carbaldehyde) (TpDpp) (12 mg, 0.02 mmol), and 1,3,6,8-tetrakis(4-aminophenyl)pyrene (Py) (6 mg, 0.01 mmol) were weighed into a 10 mL glass tube. Afterwards, o-DCB: mesitylene = 4:1 = 1.0 mL was added and the mixture was sonicated for 5 min. After addition of 0.1 mL AcOH (6 M, aqueous), the tube was degassed by the three freeze-pump-thaw cycles and sealed with flame. Upon warming to room temperature, the sealed tube was heated at 120 °C for 72 h. The formed precipitate was collected by filtration, washed with methanol and tetrahydrofuran (THF) and further activated by Soxhlet extraction using methanol and THF for 72 h. Finally, the solid was collected and dried at 120 °C for 12 h under vacuum to give TpDPP-Py COFs as the dark purple powder (15 mg, 60% yield).
Synthesis of DPP-Py COFs: 4,4’-(2,5-bis(2-ethylhexyl)−3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4-c]pyrrole-1,4-diyl)dibenzaldehyde (DPP) (12 mg, 0.02 mmol), and1,3,6,8-tetrakis(4-aminophenyl)pyrene (Py) (6 mg, 0.01 mmol) were weighed into a 10 mL glass tube. Afterwards, 1.4-dioxane: mesitylene = 1:1 = 1.0 mL was added and the mixture was sonicated for 5 min. After addition of 0.1 mL AcOH (6 M, aqueous), the tube was degassed by the three freeze-pump-thaw cycles and sealed with flame. Upon warming to room temperature, the sealed tube was heated at 120 °C for 72 h. The formed precipitate was collected by filtration, washed with methanol and tetrahydrofuran (THF) and further activated by Soxhlet extraction using methanol and THF for 72 h. Finally, the solid was collected and dried at 120 °C for 12 h under vacuum to give DPP-Py COFs as shiny red powder (10 mg, 50% yield). The synthesis route of TpDPP and DPP is in Supplementary Fig. S1–5.
5 mg photocatalyst was added into acetonitrile solution containing 1% benzylamine in the Pyrex vessel reactor. the mixed solution was bubbled with oxygen for 30 min before light irradiation. And then, the suspension solution was irradiated by a 300 W Xe lamp (Microsolar300, Beijing Perfectlight) equipped with AM1.5 G solar intensity. The gas chromatography (GC-7890B) with a flame ionization detector (FID) detector was carried out to detect the conversion rate of N-benzylidenebenzylamine. The photocatalytic coupling of amine derivatives (2-ethoxyaniline, 3-ethoxyaniline, 4-ethoxyaniline, 2-thiophene methylamine, 4-fluoroaniline, 4-chlorobenzylamine) is similar to that of BA.
Powder X-ray diffraction (PXRD) patterns were recorded on PANalytical Empyrean diffractometer for Cu/Kα radiation (λ = 1.5416 nm) The samples were spread on the square recess of XRD sample holder as a thin layer. Variable temperature PXRD was recorded at a rate of 10 °C min‒1 and held for 2 min. Themis 300 (cryo-TEM) at an accelerating voltage of 200 KV. Imaging was conducted using low-dose techniques and the dose rate was <5.0 e/Å2/s. Disperse 2 mg of COF into 1 ml of ethanol and add dropwise in the microgrid. Nanosheets were observed at JEM-2100 (200KV). Scanning Electron Microscopy (SEM) images were recorded using a Zeiss Gemini 300 scanning electron microscopy. Infrared spectra were measured on Lambda 1050+ under vacuum. All spectra were background corrected. Thermogravimetric analysis (TGA) measurements were carried out on a PerkinElmer series 7 thermal analysis system under N2 at a heating rate of 10 °C min−1. 13C cross polarization magic angle spinning nuclear magnetic resonance (13C CP/MAS NMR) spectra was recorded on a Bruker NEO 600 WB spectrometer. Samples were packed in 4 mm ZrO2 rotors, which were spun at 8 kHz in a double resonance MAS probe. All spectra were background corrected. Absorption spectra were recorded by PerkinElmer Lambda 1050 + UV-vis-NIR. UV-vis spectrophotometer at room temperature. The absorption spectra of solid powder employed integrating sphere mode with Ba2SO4 background. Fluorescence spectra of COF powders was using fluorescence spectrometer FLS1000, and the transient photoluminescence decay lifetime profiles of COF powder was using Astrella.
The authors declare that the experimental data supporting the results of this study can be found in the paper and its Supplementary Information file. The experimental results of the study along with other simulation data are provided in the Supplementary Information file. The detailed simulation files for the study are available from the corresponding author upon request. Source data are provided with this paper.
Wang, E. et al. Solar-driven photocatalytic reforming of lignocellulose into H2 and value-added biochemicals. ACS Catal. 12, 11206–11215 (2022).
Wang, Y. et al. Current understanding and challenges of solar-driven hydrogen generation using polymeric photocatalysts. Nat. Energy 4, 746–760 (2019).
Article ADS CAS Google Scholar
Wang, Z. et al. Recent developments in heterogeneous photocatalysts for solar-driven overall water splitting. Chem. Soc. Rev. 48, 2109–2125 (2019).
Article CAS PubMed Google Scholar
Belkessa, N. et al. Gaseous ethylbenzene removal by photocatalytic TiO2 nanoparticles immobilized on glass fiber tissue under real conditions: evaluation of reactive oxygen species contribution to the photocatalytic process. Environ. Sci. Pollut. Res. Int. 30, 35745–35756 (2023).
Article CAS PubMed Google Scholar
Jia Z.-M., et al. Adsorption kinetics of the photocatalytic reaction of nano-TiO2 cement-based materials: A review. Constr. Build. Mater. 370, 130462 (2023).
Dhull, P. et al. An overview on ZnO-based sonophotocatalytic mitigation of aqueous phase pollutants. Chemosphere 333, 138873 (2023).
Article CAS PubMed Google Scholar
Li, Z. et al. Blocking the reverse reactions of overall water splitting on a Rh/GaN–ZnO photocatalyst modified with Al2O3. Nat. Catal. 6, 80–88 (2023).
Dong, F. et al. A novel pathway toward efficient improvement of the photocatalytic activity and stability of CdS-based photocatalyst for light driven H2 evolution: The synergistic effect between CdS and SrWO4. Int. J. Hydrog. Energy 48, 13877–13889 (2023).
Xu, Z. et al. Rational synthesis of Au-CdS composite photocatalysts for broad-spectrum photocatalytic hydrogen evolution. ACS Nano 17, 11655–11664 (2023).
Article CAS PubMed Google Scholar
Prier, C. K. et al. Visible light photoredox catalysis with transition metal complexes: Applications in organic synthesis. Chem. Rev. 113, 5322–5363 (2013).
Article CAS PubMed PubMed Central Google Scholar
Glaser, F. et al. Multi-photon excitation in photoredox catalysis: concepts, applications, methods. Angew. Chem. Int. Ed. 59, 10266–10284 (2020).
Deng, M. et al. Extending the π-conjugation system of covalent organic frameworks for more efficient photocatalytic H2O2 production. Green. Chem. 25, 3069–3076 (2023).
Fan, Y. et al. Enhanced energy transfer in a π-conjugated covalent organic framework facilitates excited-state nickel catalysis. Angew. Chem. Int. Ed. 62, e202218908 (2023).
Li, Z. et al. Three-dimensional covalent organic framework with ceq topology. J. Am. Chem. Soc. 143, 92–96 (2021).
Article CAS PubMed Google Scholar
Lyu, H. et al. Porous crystalline olefin-linked covalent organic frameworks. J. Am. Chem. Soc. 141, 6848–6852 (2019).
Article CAS PubMed Google Scholar
Stegbauer, L. et al. A hydrazone-based covalent organic framework for photocatalytic hydrogen production. Chem. Sci. 5, 2789–2793 (2014).
Gao, S. et al. Ingenious artificial leaf based on covalent organic framework membranes for boosting CO2 photoreduction. J. Am. Chem. Soc. 145, 9520–9529 (2023).
Article CAS PubMed Google Scholar
Zhang, Y. et al. Engineering single Cu sites into covalent organic framework for selective photocatalytic CO2 reduction. Small 19, e2300035 (2023).
Li, Z. et al. Three-component donor-π-acceptor covalent-organic frameworks for boosting photocatalytic hydrogen evolution. J. Am. Chem. Soc. 145, 8364–8374 (2023).
Liu, Y. et al. Cu2O/2D COFs core/shell nanocubes with antiphotocorrosion ability for efficient photocatalytic hydrogen evolution. ACS Nano 17, 5994–6001 (2023).
Article CAS PubMed Google Scholar
Luo, Y. et al. Sulfone-modified covalent organic frameworks enabling efficient photocatalytic hydrogen peroxide generation via one-Step two-electron O2 Reduction. Angew. Chem. Int. Ed. 62, e202305355 (2023).
Chen, D. et al. Covalent organic frameworks containing dual O2 reduction centers for overall photosynthetic hydrogen peroxide production. Angew. Chem. Int. Ed. 62, e202217479 (2023).
Article ADS CAS Google Scholar
Liu, Y. et al. A universal room‐temperature approach to large‐area continuous COFs film for photocatalytic coupling of amines. Adv. Funct. Mater. 33, 2302874 (2023).
Liu, X. et al. Triazine-porphyrin-based hyperconjugated covalent organic framework for high-performance photocatalysis. J. Am. Chem. Soc. 144, 23396–23404 (2022).
Article CAS PubMed Google Scholar
Kumar, N. et al. Selective aerobic coupling of amines to imines using solar spectrum-responsive flower-like Nen-graphene quantum dots (GQDs) decorated with 2,4-dinitrophenylhydrazine (PH) as a photocatalyst. Chemosphere 341, 139697 (2023).
Article CAS PubMed Google Scholar
Liu, H. et al. Photocatalytic hydrogen production coupled with selective benzylamine oxidation over MOF composites. Angew. Chem. Int. Ed. 57, 5379–5383 (2018).
Article ADS CAS Google Scholar
Yang, S. et al. Modulating the stacking model of covalent organic framework isomers with different generation efficiencies of reactive oxygen species. ACS Appl. Mater. Interfaces 13, 29471–29481 (2021).
Article CAS PubMed Google Scholar
Xiong, K. et al. Linker length-dependent photocatalytic activity of β-ketoenamine covalent organic frameworks. Appl. Catal. B Environ. 322, 122135 (2023).
Wang, H. et al. Covalent organic framework photocatalysts: structures and applications. Chem. Soc. Rev. 49, 4135–4165 (2020).
Article CAS PubMed Google Scholar
Qi, W. et al. Fluorinated covalent organic framework materials for photocatalytically driven benzylamine coupling and azo dyes degradation. J. Photochem. Photobiol. A Chem. 437, 114502 (2023).
Li, Q. et al. Structural and morphological engineering of benzothiadiazole-based covalent organic frameworks for visible light-driven oxidative coupling of amines. ACS Appl. Mater. Interfaces 13, 39291–39303 (2021).
Article CAS PubMed Google Scholar
Wu, S. et al. Hydrazone-linked 2D porphyrinic covalent organic framework photocatalysis for visible light-driven aerobic oxidation of amines to imines. J. Colloid Interface Sci. 610, 446–454 (2022).
Article ADS CAS PubMed Google Scholar
Shi, J. L. et al. 2D sp2 Carbon-conjugated porphyrin covalent organic framework for cooperative photocatalysis with TEMPO. Angew. Chem. Int. Ed. 59, 9088–9093 (2020).
Wu, Z. et al. Covalent-organic frameworks with keto-enol tautomerism for efficient photocatalytic oxidative coupling of amines to imines under visible light. Sci. Chi. Chem. 64, 2169–2179 (2021).
Article ADS CAS Google Scholar
Nath, S. et al. Covalent organic frameworks as emerging nonlinear optical materials. Angew. Chem. Int. Ed. 62, e202218974 (2023).
Jiang, W. et al. New synthetic approaches to N-aryl and π-expanded diketopyrrolopyrroles as new building blocks for organic optoelectronic materials. Angew. Chem. Int. Ed. 60, 10700–10708 (2021).
Yue, J. Y. et al. Thiophene-containing covalent organic frameworks for overall photocatalytic H2O2 synthesis in water and seawater. Angew. Chem. Int. Ed. 62, e202309624 (2023).
Shen, L. et al. Effects of aromatic substituents on the electronic structure and excited state energy levels of diketopyrrolopyrrole derivatives for singlet fission. Phys. Chem. Chem. Phys. 20, 22997 (2018).
Article CAS PubMed Google Scholar
Leenaers, P. J. et al. Impact of π‑conjugated linkers on the effective exciton binding energy of diketopyrrolopyrrole−dithienopyrrole copolymers. J. Phys. Chem. C. 124, 27403–27412 (2020).
A cricity, l. it old. SOLVATOCHROMIC COVALENT EARNIC FRAMEWERERS. A nat. Commune. 9, 3802 (2018).
Article ADS PubMed PubMed Central Google Scholar
Auras, F. et al. Synchronized offset stacking: a concept for growing large-domain and highly crystalline 2D covalent organic frameworks. J. Am. Chem. Soc. 138, 16703–16710 (2016).
Article CAS PubMed PubMed Central Google Scholar
Xu, J. et al. A Highly conductive COF@CNT electrocatalyst boosting polysulfide conversion for Li–S chemistry. ACS Energy Lett. 6, 3053–3062 (2021).
Gole, B. et al. Microtubular self-assembly of covalent organic frameworks. Angew. Chem. Int. Ed. 57, 846–850 (2018).
Mohata, S. et al. Selective metal-free CO2 photoreduction in water using porous nanostructures with internal molecular free volume. J. Am. Chem. Soc. 145, 23802–23813 (2023).
Article CAS PubMed Google Scholar
Majumder, P. et al. Proximity-enabled photochemical C−H functionalization using a covalent organic framework-confined Fe2IV−μ−oxo species in water. J. Am. Chem. Soc. 145, 18855–18864 (2023).
Article CAS PubMed Google Scholar
Bag, S. et al. Covalent organic framework thin-film photodetectors from solution-processable porous nanospheres. J. Am. Chem. Soc. 145, 1649–1659 (2023).
Article CAS PubMed Google Scholar
Koner, K. et al. Bottom-up synthesis of crystalline covalent organic framework nanosheets, nanotubes, and kippah vesicles: an odd−even effect induction. J. Am. Chem. Soc. 145, 14475–14483 (2023).
Article CAS PubMed Google Scholar
Tan, H. et al. Photocatalysis of water into hydrogen peroxide over an atomic Ga-N5 site. Nat. Synth. 2, 557–563 (2023).
Wei, P.-F. et al. Benzoxazole-linked ultrastable covalent organic frameworks for photocatalysis. J. Am. Chem. Soc. 140, 4623–4631 (2018).
Article CAS PubMed Google Scholar
This work was financially supported by the Strategic Priority Research Program of CAS (XDB0520101), the National Natural Science Foundation of China (U22A6002, 22173109, 52303363), the National Key R&D Program of China (2018YFA0703200), the CAS Project for Young Scientists in Basic Research (YSBR-053), the CAS-Croucher Scheme for Joint Laboratories, Lu Jiaxi international team (GJTD-2020-02), the CAS Cooperation Project (121111KYSB20200036), and the Beijing Nova Program (20220484173). The authors gratefully acknowledge the assistance of Ningning Wu in data collection for nuclear magnetic analysis. We also extend our appreciation to Jiling Yue and Kaiang Liu for their valuable contributions in characterizing the cryo-TEM experiments. Additionally, we would like to thank Meirong Liu for her help in operating the femtosecond laser spectrometer.
These authors contributed equally: Yuanding Fang, Youxing Liu.
Center for Advanced Optoelectronic Functional Materials Research, and Key Lab of UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, 130024, Changchun, China
Yuandaning Fang & Qingxin Tang
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry Chinese Academy of Sciences, 100190, Beijing, China
Yuanding Fang, Youxing Liu, Haojie Huang, Jianzhe Sun, Jiaxing Hong, Fan Zhang, Xiaofang Wei, Wenqiang Gao, Mingchao Shao, Yunlong Guo & Yunqi Liu
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Y.F. and Yo.L contributed equally to this work. Y.G., Q.T. and Yu.L proposed and supervised the project. Y.F., Yo.L conceived the idea and designed the experiments. H.H. conducted DFT calculations. J.S. conducted Raman spectroscopy characterization. J.H. conducted transient photocurrent response. W.G. and M.S. assisted in the synthesis of materials. Q.T., F.Z., X.W. and Y.G. assisted in the writing of the article. X.W. assisted in the spectral experiment. Y.F. and Yo.L wrote the manuscript and all authors reviewed it.
Correspondence to Yunlong Guo, Qingxin Tang or Yunqi Liu.
The authors declare no competing interests.
Nature Communications thanks Rahul Banerjee, Zhiguo Zhang and Xianjun Lang for their contribution to the peer review of this work. A peer review file is available.
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Fang, Y., Liu, Y., Huang, H. et al. Design and synthesis of broadband absorption covalent organic framework for efficient artificial photocatalytic amine coupling. Nat Commun 15, 4856 (2024). https://doi.org/10.1038/s41467-024-49036-z
DOI: https://doi.org/10.1038/s41467-024-49036-z
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