Acta Phys. -Chim. Sin. ›› 2025, Vol. 41 ›› Issue (12): 100176.doi: 10.1016/j.actphy.2025.100176
• REVIEW • Previous Articles Next Articles
Yihong Shao1, Rongchen Shen1, Song Wang2,*(
), Shijie Li3,*(
), Peng Zhang4,*(
), Xin Li1,*(
)
Received:2025-08-08
Revised:2025-08-28
Accepted:2025-08-28
Published:2025-10-23
Contact:
Email: Xinli@scau.edu.cn (Xin Li)wangsong1984@hbuas.edu.cn (Song Wang)lishijie@zjou.edu.cn (Shijie Li)zhangp@zzu.edu.cn (Peng Zhang)
Supported by:Yihong Shao, Rongchen Shen, Song Wang, Shijie Li, Peng Zhang, Xin Li. Composition engineering in covalent organic frameworks for tailored photocatalysis[J]. Acta Phys. -Chim. Sin. 2025, 41(12), 100176. doi: 10.1016/j.actphy.2025.100176
Fig 1
Main progress of COFs in photocatalysis. Reprinted with permission from Ref. [83], Copyright 2005, The American Association for the Advancement of Science. Reprinted with permission from Ref. [99], Copyright 2014, Royal Society of Chemistry. Reprinted with permission from Ref. [105], Copyright 2018, American Chemical Society. Reprinted with permission from Ref. [106], Copyright 2020, American Chemical Society."
Fig 6
(a) and (b) Schematic diagram of in situ DRIFTS spectra of Bpy-COF and Cu-Bpy-COF. Reprinted with permission from Ref. [141], Copyright 2023, Wiley-VCH GmbH. (c) and (d) Schematic diagram of Temperature-dependent PL spectra of sp2c-py-bpy COF and Im-py-Bpy COF. Reprinted with permission from Ref. [142], Copyright 2025, Wiley-VCH GmbH."
Fig 7
(a) Schematic diagram of fs-TA spectra of DS-COF. (b) Schematic diagram of fs-TA spectra of X-COF at 620 nm. Reprinted with permission from Ref. [143], Copyright 2024, Wiley-VCH GmbH. (c) Schematic diagram of Gibbs free energy distribution calculated by DFT of COOH-COF, TP-COF, and AO-COF. (d) Schematic diagram of the CO2 conversion pathway. Reprinted with permission from Ref. [144], Copyright 2025, Wiley-VCH GmbH."
Fig 9
(a) Schematic diagram of the synthesis of Py-XTP-BT-COF. (b) Transient photocurrent. (c) Gibbs free energy. Reprinted with permission from Ref. [145], Copyright 2020, Wiley-VCH GmbH. (d) Schematic diagram of the synthesis of Nx-COF. (e) Photocatalytic hydrogen production performance. (f) Photon efficiencies at 400, 450, 500, and 550 nm. Reprinted with permission from Ref. [146], Copyright 2015, Springer. (g) Schematic diagram of the synthesis of COF-TPT-Azo. (h) Transient photocurrent. (i) Gibbs free energy diagram of ORR. Reprinted with permission from Ref. [147], Copyright 2024, Wiley-VCH GmbH."
Fig 10
(a) Schematic diagram of the synthesis of TD-COF and TT-COF. (b) The S atom in the thiophene ring of TD-COF and TT-COF is the active center of ORR. Reprinted with permission from Ref. [138], Copyright 2023, Wiley-VCH GmbH. (c) Schematic diagram of the synthesis of a series of thiophene-based COFs. (d) Gibbs free energy diagram of hydrogen evolution. (e) Transient photocurrent. Reprinted with permission from Ref. [150], Copyright 2025, Wiley-VCH GmbH. (f) Schematic diagram of the synthesis of trifluorenone-based COFs. (g) Gibbs free energy diagram of hydrogen evolution. (h) Photocatalytic hydrogen evolution performance. Reprinted with permission from Ref. [152], Copyright 2024, Springer."
Fig 11
(a) Schematic diagram of the synthesis of TpBpy-Ni2%. (b) UV/Vis-DRS spectroscopy. (c) Photocatalytic hydrogen production performance. (d) Transient photocurrent response. (e) Time-resolved photoluminescence spectra. Reprinted with permission from Ref. [156], Copyright 2023, Wiley-VCH GmbH. (f) Schematic diagram of the synthesis of M SAS/Tr-COF. (g) Calculated Gibbs free energy for CO2 photoreduction. (h) The average rate of photocatalytic CO generation. (i) TON schematic. (j) Reaction mechanism of photocatalytic CO2 reduction. Reprinted with permission from Ref. [157], Copyright 2022, American Chemical Society."
Fig 12
(a) Schematic diagram of the synthesis of TPy-COF-Co. (b) Gibbs free energy for CO2 reduction. (c) FT-EXAFS fitting curves and Co coordination environment. (d) Co K-edge XANES spectra and 3D configuration of Co-N4Cl2. (e) Photocatalytic CO2 reduction reaction mechanism. Reprinted with permission from Ref. [160], Copyright 2025, Wiley-VCH GmbH. (f) Schematic diagram of the synthesis of Fe/PP-COF. (g) Schematic diagram of the latching effect and exciton behavior. (h) and (i) Schematic diagram of exciton binding energy. (j) and (k) Gibbs free energy schematic diagram of ORR and WOR. Reprinted with permission from Ref. [161], Copyright 2025, Wiley-VCH GmbH."
Fig 13
(a) Schematic diagram of the synthesis of Tp-nC/BPy2+-COF. (b) Transient photocurrent. (c) Photocatalytic hydrogen production performance. Reprinted with permission from Ref. [165], Copyright 2021, Wiley-VCH GmbH. (d) Schematic diagram of the synthesis PD2+-COF. (e) In situ DRIFTS spectra. (f) Photocatalytic H2O2 production performance. Reprinted with permission from Ref. [166], Copyright 2023, Wiley-VCH GmbH."
Fig 14
(a) Schematic diagram of the synthesis of Zi-VCOF-1 and Zi-VCOF-2. (b) Water contact angle. (c) Transient photocurrent. (d) Photocatalytic hydrogen production performance. Reprinted with permission from Ref. [169], Copyright 2023, American Chemical Society. (e) Schematic diagram of the synthesis of ZVCOF-1 and ZVCOF-2 (f) Reaction coordinates catalyzed by DMAP with or without the involvement of anhydrous molecules, (g) Photocatalytic hydrogen production performance, (h) PXRD profiles of ZVCOF-1 synthesized in different amounts of water Reprinted with permission from Ref. [170], Copyright 2023, American Chemical Society."
Fig 15
(a) Schematic diagram of the synthesis of thiadiazole bridging COF-ST. (b) Photocurrent density-time plot of COF-ST. (c) Photocatalytic hydrogen production performance of COF-ST. Reprinted with permission from Ref. [171], Copyright 2024, American Chemical Society. (d) Schematic diagram of the synthesis of vinyl-anchored DVA-COF. (e) Free energy of the ORR pathway of DVA-COF. (f) The photocatalytic mechanism of DVA-COF for hydrogen peroxide production. Reprinted with permission from Ref. [172], Copyright 2024, Wiley-VCH GmbH."
Fig 16
(a) Schematic diagram of the synthesis of TBTN-COF. (b) The CSS dynamic trajectory of TBTN-COF. (c) Free energy of the ORR pathway of TBTN-COF. (d) Schematic diagram of electron distribution calculations and active sites. Reprinted with permission from Ref. [173], Copyright 2024, Wiley-VCH GmbH. (e) Schematic diagram of the synthesis of COF-2CN. (f) Schematic diagram of the photocurrent response of COF-2CN. (g) Schematic diagram of the integrated PL intensity of COF-2CN. (h) Free energy of the WOR pathway of COF-2CN. Reprinted with permission from Ref. [174], Copyright 2024, Wiley-VCH GmbH."
Fig 17
(a) Schematic diagram of the synthesis of FS-COF. (b) Photocatalytic performance of FS-COF. (c) The optimal site for the adsorption energy of O2. (d) Free-energy diagrams for the reduction of O2 to H2O2. Reprinted with permission from Ref. [136], Copyright 2023, Wiley-VCH GmbH. (e) Schematic diagram of the synthesis of COF-TPDB-NO2. (f) Hirshfeld charge distribution of COF-TPDB-NO2. (g) Photocatalytic performance of COF-TPDB-NO2. (h) Energy profile for the reduction of O2 to H2O2. Reprinted with permission from Ref. [176], Copyright 2025, Elsevier."
Fig 18
(a) Schematic diagram of the synthesis of COOH-COF and SO3H-COF. (b) Contact angle measurement. (c) Photocatalytic production of H2O2 activity. (d) The adsorption energy of O2. (e) Gibbs free energy of ORR. Reprinted with permission from Ref. [177], Copyright 2024, Wiley-VCH GmbH. (f) Schematic diagram of the synthesis of TFBP-DHBD and TFBP-BD. (g) and (h) In situ DRIFT spectra of TFBP-DHBD. (i) and (j) Free energy diagram of ORR of TFBP-DHBD and TFBP-BD. Reprinted with permission from Ref. [178], Copyright 2025, Wiley-VCH GmbH."
Fig 19
(a) Schematic diagram of the synthesis of PyTz-COF. (b) Photoluminescence spectrum. (c) Time-resolved photoluminescence spectra. Reprinted with permission from Ref. [182], Copyright 2021, Wiley-VCH GmbH. (d) Schematic diagram of the synthesis of BD-COF and CYANO-COF. (e) Charge distribution. (f) and (g) Exciton binding energy of BD-COF and CYANO-COF. Reprinted with permission from Ref. [183], Copyright 2022, Springer. (h) Schematic diagram of the synthesis of FS-OHOMe-COF. (i‒k) Exciton binding energies of the three COFs. (l) Calculated interlayer interaction energy. Reprinted with permission from Ref. [184], Copyright 2024, Wiley-VCH GmbH."
Fig 20
(a) Schematic diagram of the synthesis of TAPB-PDA-R COFs. (b) XRD profile of TAPB-PDA-R COFs. Reprinted with permission from Ref. [188], Copyright 2023, American Chemical Society. (c) Schematic diagram of the synthesis of COF-C and COF-O. (d) Steady-state PL spectra of COF-C and COF-O (black: COF-C, red: COF-O). (e) Wavelength-dependent apparent quantum yield (AQY) of COF-O. (f) Free energy plots of different reaction sites under monolayer and AA stacking. Reprinted with permission from Ref. [189], Copyright 2024, Wiley-VCH GmbH. (g) Schematic diagram of the synthesis of BTz-COFs. (h) UV-Vis diffuse reflection absorption spectroscopy of BTz-COFs. (i) PL intensity of BTz-COFs. Reprinted with permission from Ref. [190], Copyright 2025, Wiley-VCH GmbH."
Fig 21
(a) Schematic diagram of the synthesis of PMCR-1. Reprinted with permission from Ref. [195], Copyright 2023, Wiley-VCH GmbH. (b) Schematic diagram of the synthesis of Cy-N3-COF. Reprinted with permission from Ref. [197], Copyright 2023, American Chemical Society. (c) Schematic diagram of the synthesis of LZU-520-LZU-530 Reprinted with permission from Ref. [198], Copyright 2024, American Chemical Society."
Fig 22
(a) Schematic diagram of DCNA COF and DNCA COF. (b) UV-Vis DRS spectra. (c) UV-Vis DRS spectra after protonation. (d) Photocatalytic performance of DCNA-1_AC and DNCA-1_AC. (e) Photocatalytic performance comparison of all DCNA_AC and DNCA_AC COFs. Reprinted with permission from Ref. [199], Copyright 2022, Springer. (f) Schematic diagram of the synthesis of COF-923 and COF-932. g) Electronic transfer pathways. (h) UV-Vis DRS spectra. (i) Photocatalytic hydrogen evolution performance for all COFs. Reprinted with permission from Ref. [200], Copyright 2023, Wiley-VCH GmbH."
Fig 23
(a) Schematic diagram of the synthesis of TpDz, TpMd and TpPz. (b) PL spectra. (c) Free energy diagram of the ORR pathway of TpDz. (d) Mechanism of photocatalytic production of H2O2 of TpDz. Reprinted with permission from Ref. [140], Copyright 2023, Wiley-VCH GmbH. (e) Schematic diagram of the synthesis of α-TTAN COFand β-TT-TDAN COF. (f) Electron distribution under excitation. (g) Exciton dissociation rate. (h) XANES spectrum. (i) and (j) Different active site distributions and free energy diagrams of ORR pathways. Reprinted with permission from Ref. [201], Copyright 2025, Wiley-VCH GmbH."
Fig 24
(a) Schematic diagram of the synthesis of BTT-PDA, BTT-NDA, BTT-AnthDA and BTT-BPhDA. (b) Transient photocurrents. (c) Photocatalytic hydrogen production performance. (d) Photoluminescence (PL) decay curves. (e) Calculated electron affinity (EAs). Reprinted with permission from Ref. [202], Copyright 2023, Wiley-VCH GmbH. (f) Schematic diagram of the synthesis of COF-1, COF-2 and COF-3. (g) Temperature-dependent PL spectra of four COFs. (h) Schematic diagram of dihedral angles. Reprinted with permission from Ref. [204], Copyright 2025, Wiley-VCH GmbH."
Fig 25
(a) Schematic diagram of the synthesis of PTCOF-OID. (b) Electrostatic surface potential (ESP) distribution and dipole moment of PTCOF-OID. (c) PL spectra of PTCOF-OID. (d) Transient photocurrent response of PTCOF-OID. Reprinted with permission from Ref. [206], Copyright 2023, Wiley-VCH GmbH. (e) Schematic diagram of the synthesis of FOOCOF-PDI. (f) Electrostatic surface potential (ESP) distribution of FOOCOF-PDI. (g) The built-in electric field strength of FOOCOF-PDI. (h) Transient photocurrent response of FOOCOF-PDI. Reprinted with permission from Ref. [207], Copyright 2025, Springer."
Fig 26
(a) Schematic diagram of the synthesis of UCOF-SCAU-2. (b) Steady-state fluorescence of UCOF-SCAU-2. (c) Photocurrent response of UCOF-SCAU-2. Reprinted with permission from Ref. [208], Copyright 2023, Wiley-VCH GmbH. (d) Schematic diagram of the synthesis of vertically expanded COFs. (e) The active center of vertically expanded COFs absorbs water molecules. (f) Gibbs free energy change of single-site path by vertically expanded COFs. Reprinted with permission from Ref. [209], Copyright 2025, Wiley-VCH GmbH."
Fig 27
(a) Schematic diagram of the synthesis of TSCOFW. (b) Calculation of the Gibbs free energy variation of intermediate states involved in illumination. (c) Transient absorption spectra of TSCOFW. (d) Photocurrent response of TSCOFW. Reprinted with permission from Ref. [215], Copyright 2023, Wiley-VCH GmbH. (e) Schematic diagram of the synthesis of COFIS. (f) Charge carrier transfer mechanism in S-scheme heterojunction. (g) fs-TA decay curve of 20COFIS. (h) Schematic diagram of electron dynamics of 20COFIS. Reprinted with permission from Ref. [221], Copyright 2024, Wiley-VCH GmbH."
Fig 28
(a) Schematic diagram of the synthesis of COF-JLU35 and COF-JLU36. (b) Photoluminescence decay traces of COF-JLU35. (c) Transient current density vs. time of COF-JLU35. (d) Comparison of photocatalytic performance. Reprinted with permission from Ref. [222], Copyright 2023, American Chemical Society. (e) Schematic diagram of the synthesis of USTB-COFs. (f) Schematic diagram of photocatalytic performance of USTB-COFs. (g) Photocurrent response of USTB-COFs. Reprinted with permission from Ref. [223], Copyright 2025, Elsevier."
Fig 29
(a) Schematic diagram of the synthesis of FOOBr-COF, FOOMe-COF and FOOPh-COF. (b) Electrostatic potential of FOOBr-COF, FOOMe-COF and FOOPh-COF. (c) fs-TA decay curves of FOOBr-COF, FOOMe-COF and FOOPh-COF. (d) Electron-hole distribution in the excited state. Reprinted with permission from Ref. [225], Copyright 2024, Elsevier. (e) Schematic diagram of the synthesis of ED-ER type COFs. (f) Decay kinetic curves of ED-ER type COFs. (g) Photogenerated electron transfer pathway. Reprinted with permission from Ref. [226], Copyright 2025, Wiley-VCH GmbH."
Fig 30
(a) Schematic diagram of the synthesis of Cu4-COF. (b) Free energy plot of CO2 photoreduction to CO on Cu4 and Cu4COF-2. (c) Transient photocurrent response. (d) PL emissions. (e) Photocatalytic CO2-to-CO performance and selectivity. Reprinted with permission from Ref. [227], Copyright 2025, Wiley-VCH GmbH. (f) Schematic diagram of the synthesis of Co-Btt-Bpy COF. (g) Transient photocurrent response. h) Performance diagram of photocatalytic CO production. (i) Performance diagram of photocatalytic O2 production. (j) Gibbs free energy for CO2 photoreduction and WOR. Reprinted with permission from Ref. [228], Copyright 2025, American Chemical Society."
Table 1
COFs for efficient photocatalytic hydrogen production."
| COFs | Cocatalyst | Sacrificial reagent | HER (µmol g−1 h−1) | Ref. |
| COF-JLU100 | Pt (3 wt.%) | TEOA | 107380 | [ |
| COF-ST | Pt (3 wt.%) | TEOA | 21.5 | [ |
| SP2c-Py-BT COF | Pt | TEOA | 891.5 | [ |
| Py-ClTP-BT-COF | Pt (5 wt.%) | AA | 8875 | [ |
| BTT-NDA | Pt (3 wt.%) | AA | 5220 | [ |
| TpBpy-Ni2% | Pt | AA | 51300 | [ |
| PyTz-COF | Pt (3 wt.%) | AA | 2072.4 | [ |
| COF-JLU35 | Pt (1 wt.%) | AA | 70800 ± 1900 | [ |
| Tp-2C/BPy2+-COF | Pt (3 wt.%) | AA | 34600 | [ |
| ODA-COF | Pt (9 wt.%) | TEOA | 2615 | [ |
| COF-954 | Pt (5 wt.%) | AA | 137230 | [ |
| PY-DHBD-COF | Pt (1 wt.%) | AA | 42432 | [ |
| Tz-COF-3 | Pt (3 wt.%) | AA | 43200 | [ |
| PABZ-TP | Pt (0.5 wt.%) | AA | 115000 | [ |
| PTT-COF-FC | Pt (3 wt.%) | AA | 79610 | [ |
| TMT-BO-COF | Pt (5 wt.%) | AA | 23700 | [ |
| TeTpb-COF | Pt (3 wt.%) | AA | 21600 | [ |
| COF-923-AC | Pt | AA | 23400 | [ |
| COF-F NKCOF-113-M | Pt (3 wt.%) Pt (5 wt.%) | AA TEOA | 10580 13100 | [ [ |
Fig 31
(a) Schematic diagram of ODA-COF. (b) Photocatalytic hydrogen production performance. (c) Photocatalytic hydrogen production under monochromatic light irradiation. Reprinted with permission from Ref. [235], Copyright 2022, Wiley-VCH GmbH. (d) Schematic diagram of COF-JLU100. (e) Photocatalytic hydrogen production performance. (f) Apparent quantum yield (AQY)at different wavelengths of incident light. Reprinted with permission from Ref. [233], Copyright 2022, Wiley-VCH GmbH."
Fig 32
(a) Schematic diagram of COF-JLU45. (b) Schematic diagram of photocatalytic hydrogen production of COF-JLU45. (c) Schematic diagram of photocatalytic hydrogen production of different amounts of COF-JLU45. Reprinted with permission from Ref. [244], Copyright 2025, Wiley-VCH GmbH. (d) Schematic diagram of COF-OMe-3. (e) Schematic diagram of photocatalytic hydrogen production of COF-OMe-3. (f) AQY of COF-OMe-3. Reprinted with permission from Ref. [245], Copyright 2025, Wiley-VCH GmbH."
Table 2
COFs for efficient production of H2O2."
| COFs | Reaction solution | H2O2 (µmol g−1 h−1) | AQY (%) | Reference |
| TBTN-COF | H2O/O2 | 11013 | 7.59 | [ |
| COF-2CN | H2O/O2 | 1601 | 6.8 | [ |
| TF50-COF | H2O: EtOH/O2 | 1739 | 5.1 | [ |
| TD-COF | H2O/O2 | 4060 | – | [ |
| FS-COF | H2O/O2 | 3904.2 | 6.21 | [ |
| Py-Py-COF | H2O: BA/O2 | 1242 | – | [ |
| TpDz | H2O/O2 | 7327 | 11.9 | [ |
| PD2+-COF | H2O: EtOH/O2 | 11965 | 12.9 | [ |
| PMCR-1 | H2O/O2 | 1445 | – | [ |
| TTF-BT-COF | H2O/O2 | 276000 | 11.19 | [ |
| COF-JLU52 | H2O: BA/O2 | 7624.7 | 18.2 | [ |
| COF-TfpBpy | H2O/air | 694.7 | 8.1 | [ |
| HEP-TAPT-COF | H2O/O2 | 1750 | 15.35 | [ |
| DMCR-1NH | H2O/O2 | 2588 | 10.2 | [ |
| Bpt-CTF | H2O/O2 | 3268.1 | 8.6 | [ |
| DETH-COF | H2O/air | 1665 | 0.063 | [ |
| TPB-DMTP-COF | H2O/O2 | 2882 | 18.4 | [ |
| COF-TpHt | H2O: BnOH/O2 | 11986 | – | [ |
| TAPT-PDA-COF | H2O: IPA/O2 | 706.2 | 1.69 | [ |
| COF-TPT-AZO | H2O/O2(PH=11) | 1498 | – | [ |
Fig 33
(a) Schematic diagram of TF50-COF. (b) Photocatalytic H2O2 production performance. (c) Wavelength dependent. Reprinted with permission from Ref. [250], Copyright 2022, Wiley-VCH GmbH. (d) Schematic diagram of HEP-TAPT-COF and HEP-TAPB-COF. (e) Photocatalytic H2O2 production performance. (f) AQY Photocatalytic H2O2 production performance. Reprinted with permission from Ref. [148], Copyright 2023, Wiley-VCH GmbH."
Fig 34
(a) Schematic diagram of D-A-π-D and D-A-π-A COF. (b) Schematic diagram of D-A system. (c) Schematic diagram of photocatalytic production of H2O2 of D-A-π-D COF. (d) Schematic diagram of the stability of H2O2 photosynthesis upon D-A-π-D COF. (e) Mechanism of D-A-π-D COF for photocatalytic H2O2 formation from ORR and WOR. Reprinted with permission from Ref. [257], Copyright 2025, Wiley-VCH GmbH."
Table 3
COF for efficient CO2 reduction."
| COFs | Sacrificial agent | CO2RR (µmol g−1 h−1) | Selectivity (%) | Reference |
| Re-COF | TEOA | 750 (CO) | 98 | [ |
| Re-Bpy-sp2c-COF | TEOA | 1400 (CO) | 86 | [ |
| COOH-COF | TEA | 3700 (CO) | – | [ |
| PI-COF-TT | – | 483.25 (CO) | 93 | [ |
| H-COF-Ni | TEOA | 2847 (CO) | 96 | [ |
| TTCOF-Zn | – | 12.33 (CO) | 100 | [ |
| Ni-TpBpy | TEOA | 811.4 (CO) | 96 | [ |
| Co-2,3-DHTA-COF | TEOA | 18000 (CO) | 95.7 | [ |
| Fe SAS/Tr-COF | TEOA | 980.3 (CO) | 96.4 | [ |
| LaNi-Phen/COF-5 | BIH | 605.8 (CO) | 98.2 | [ |
| N3-COF | – | 13.7 (CH3OH) | – | [ |
| Mo-COF | – | 3.57 (C2H4) | 42.92 | [ |
| CTF | – | 881.3 × 106 (HCOOH) | – | [ |
| TPy-COF-Co | TEOA | 426000 (CO) | – | [ |
| EPCo-COF-AT | MeCN | 17700 (CO) | 97.8 | [ |
Fig 37
(a) Schematic diagram of Co-2, 3-DHTA-COF. (b) Photocatalytic CO and H2 release rates. (c) Effect of the acetonitrile/H2O volume ratio on the photocatalytic CO2RR. Reprinted with permission from Ref. [269], Copyright 2023, Springer. (d) Schematic diagram of TTCOF-Zn. (e) Photocatalytic CO release performance. (f) CO production performance over time. Reprinted with permission from Ref. [267], Copyright 2019, Wiley-VCH GmbH."
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