Truxenone-based donor–acceptor covalent organic frameworks incorporated with metal sites for enhanced photocatalytic CO₂ reduction†

Yanyan Ren , Haiping Liu , Fang Duan *, Shuanglong Lu , Xin Chen and Mingliang Du *
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, P. R. China. E-mail: duanfang@jiangnan.edu.cn; du@jiangnan.edu.cn

First published on 25th June 2025

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1 Introduction

Photocatalytic CO₂ reduction is a potential approach to simultaneously alleviate the ever-growing energy demands and environmental pollution.^1–7 Extensive research has been conducted on photocatalytic CO₂ reduction using homogeneous and heterogeneous catalysts.^8–10 The initial photocatalytic activity and product selectivity of homogeneous catalysts are typically high but are often unstable during prolonged operations using noble metals and face difficulties in catalyst recovery and product separation. Heterogeneous catalysts can solve these issues, but they have low catalytic activity.^11,12 Anchoring a single catalytic metal center on a skeleton is one way to combine the benefits of homogeneous and heterogeneous catalytic processes. This requires single metal atoms or the mononuclear metal complexes to be atomically distributed and firmly bound to the carrier, exhibiting a synergistic effect between the catalytic sites and the skeleton.¹³ However, most photocatalysts also face problems such as low conversion efficiency, poor stability, uncontrollable selectivity, and the competitive hydrogen evolution reactions (HERs).^14,15 Therefore, there is an urgent need to immobilize the active species with high activity and selectivity in semi-conductors for the construction of photocatalytic CO₂ reduction reaction systems.

To date, many inorganic semiconductors, including metal oxides,^16–18 metal sulfides^19–22 and metal nitrides,²³ have been developed for use in photocatalytic CO₂ reduction. As a novel class of porous crystalline materials, COFs have been extensively applied in numerous frontier research areas, including molecular capture, gas adsorption and separation, electrocatalysis and photocatalysis.^24–27 COFs have numerous benefits as photocatalysts for CO₂ reduction: (1) similar to MOFs, the majority of COFs possess extensive surface areas and abundant nitrogen atoms in the skeletons, resulting in an enhanced CO₂ adsorption capacity; (2) owing to their strong covalent bonds, COFs exhibit superior thermal and chemical stabilities, and (3) they are easy to design and modify; for instance, the energy band structure can appropriately modified.^28–31 These advantages are very beneficial for improving photocatalytic CO₂ conversion. Nevertheless, their photocatalytic efficiencies are often constrained by a lack of effective active sites, low charge transfer and high charge recombination rates. To overcome these limitations, it is crucial to rationally design the structure of COFs. Incorporating metal sites into the COFs enables a high dispersion of catalytic sites.^32,33 Indeed, when CO₂ interacts with active sites in the frameworks of porous materials, the activation energy for CO₂ reduction will be decreased, making subsequent reactions more favorable.³⁴ The incorporation of metal active sites can systematically modify the photo-physical and electronic characteristics of the COFs, thus affecting the photocatalytic activity. Besides, the incorporation of donor–acceptor moieties into porous organic systems has been demonstrated to be an effective approach to accelerate photogenerated charge separation.^35–38 Donor–acceptor motifs within COFs have been demonstrated to effectively tune their electronic properties. Therefore, in recent years, numerous COFs featuring electron donors and acceptors or metal sites have been employed for photocatalytic CO₂ reduction. Their integration facilitates the activation of CO₂ molecules and promotes the transfer of photogenerated charges from the frameworks to metal sites.³⁹ The use of COFs with specialized coordination microenvironments as functional supporters for anchoring metal sites is anticipated to offer new prospects for constructing effective photocatalysts for the selective reduction of CO₂.

Truxenones, consisting of a central benzene ring fused with fluorenones, are capable of multiple reversible electron redox processes.^40–43 By creating 2D COFs with well-separated aryl-ketone units, the photostability can be further improved. Herein, D–A structured TRO-based COFs were constructed using truxenone units as electron-donors and biphenyl or bipyridine units as electron-acceptors. A series of non-noble metal ions were introduced by coordinating with bipyridine units on BPY-COF as catalytically active sites. Consequently, the optimal sample BPY-COF–Co exhibited the highest CO yield of 870 μmol g⁻¹ within 3 h with 100% selectivity. Under the synergistic effect between D–A structure and metal active sites, the photogenerated carrier separation and migration for BPY-COF–Co were accelerated, and the visible light absorption and CO₂ affinity were also enhanced. Moreover, density functional theory (DFT) results indicated that the Co sites provided active sites and reduced the energy barriers for the formation of *COOH intermediate. This study offers a significant insight into the design of COF photocatalysts for CO₂ photoreduction.

2 Results and discussion

2.1 Material synthesis and characterization

In this study, D–A structured TRO-based COFs are obtained via a facile Schiff-base reaction using 2,7,12-triamino-5H-diindeno[1,2-a:1′,2′-c]fluorene-5,10,15-trione (TRO–NH₂) as an electron-donor and 4,4′-biphenyldicarboxaldehyde (BPD) and 2,2′-bipyridyl-5,5′-dialdehyde (BPY) as electron-acceptors. Moreover, BPY-COF–Co was obtained by anchoring Co ions with bipyridine linker, as shown in Fig. 1a. More detailed synthesis steps and characterization methods are available in the ESI.†

The crystal structures of the obtained samples are determined by the powder X-ray diffraction (PXRD) in Fig. 1b–d. The simulated Pawley refinement patterns using the AA stacking mode match well with the experimental data (a = b = 43.101690 Å, c = 3.932416 Å for BPD-COF, a = b = 43.761841 Å, c = 3.775450 Å for BPY-COF, α = β = 90°, and γ = 120° for both COFs) in Fig. S2a and b.† There is a strong diffraction peak at 2.4° and several secondary weak peaks at 4.2°, 4.9° and 6.5° corresponding to the (100), (110), (200) and (210) facets, respectively for BPD-COF, BPY-COF and BPY-COF–Co samples, respectively. The identical location of diffraction peaks suggests that they all have similar crystal structures and the introduction of Co ions has negligible impact on the crystal structures of BPY-COF.⁴⁴ Moreover, no characteristic peaks of monomers or other impurities can be found in the PXRD patterns of BPD-COF and BPY-COF (Fig. S1a and b†), suggesting that the cobalt atom is linked to BPY-COF by a coordination bond rather than existing in the form of cobalt nanoparticles or cobalt salts.

The characteristic absorption peaks of BPD-COF and BPY-COF are presented in the Fourier transform infrared (FT-IR) spectra (Fig. S2a and b†). The intensities of amino groups (∼3349 cm⁻¹) in TRO–NH₂ monomer and aldehyde groups (∼1700 cm⁻¹) in BPD and BPY monomers exhibited dramatic decrease in BPD-COF and BPY-COF.⁴⁵ In Fig. 2a, the FT-IR spectra of BPY-COF–Co was similar to that of BPY-COF, demonstrating the retention of chemical structures even after Co ion loading.^46,47 The solid-state ¹³C nuclear magnetic resonance (¹³C NMR) spectra provided detailed information on the structure of COF skeletons, in which the peaks at 160 ppm could be attributed to the carbon atom of the CN bond (Fig. 2b). The distinct peaks at 120 and 150 ppm corresponding to the pyridine rings are clearly observable in the spectra, suggesting the successful synthesis of BPY-COF.⁴⁸ Results indicated that TRO-based COFs with different linkers were effectively synthesized via the Schiff-base reaction. The obtained COFs were characterized using X-ray photoelectron spectroscopy (XPS) to further determine the surface compositions and chemical states. XPS survey spectra indicated the presence of C, N, and O elements in BPD-COF and BPY-COF, and C, N, O, Co and Cl elements in BPY-COF–Co (Fig. 2c). The peak at 399.2 eV in the N 1s spectra of BPD-COF represented the N of imine bonds (Fig. S3a†). The N 1s spectrum of BPY-COF could be deconvoluted into two peaks: one at 399.2 eV for imine N and the other at 400.6 eV for pyridine N (Fig. S3c†). Three obvious peaks at 401.9, 400.6 and 399.2 eV in the N 1s spectrum of BPY-COF–Co was ascribed to Co–N, pyridine N and imine N, respectively (Fig. 2d). The O 1s spectra of BPD-COF, BPY-COF and BPY-COF–Co could be deconvolved into three peaks, which were assigned to the carbonyl groups of TRO at 531.6 eV, unreacted aldehyde group at 533.4 eV and surface absorbed oxygen at 535.8 eV, respectively (Fig. 2e, S3b and d†).⁴⁹ From the Co 2p spectrum in Fig. 2f, four peaks could be clearly found. The peak at 780.8 eV belonged to Co 2p_3/2, while the one at 796.8 eV belonged to Co 2p_1/2.⁵⁰ The Co 2p_1/2–2p_3/2 spin orbital level energy spacing was 16 eV for BPY-COF–Co,⁵¹ indicating that the Co species were in the +2 state.⁵² The above results indicated that Co ions were successfully introduced into the skeletons by coordinating with the pyridinic N of BPY-COF. Moreover, the oxidation state of Co species was unchanged after being integrated into BPY-COF–Co.

The surface areas and porosities of the obtained COFs were determined using N₂ sorption isotherms at 77 K. The Brunauer–Emmett–Teller (BET) surface areas of BPD-COF, BPY-COF and BPY-COF–Co were determined to be 28.26 m² g⁻¹, 215.42 m² g⁻¹ and 56.05 m² g⁻¹, respectively (Fig. S4†). A greater number of exposed N atom active sites for BPY-COF suggest that CO₂ can be adsorbed onto the surface of the photocatalyst. Notably, BPY-COF exhibited a much higher BET surface area and thereby enabled more accessible active sites for photocatalytic CO₂ reduction. Besides, the pore size distributions were calculated to be 2.59 nm, 2.67 nm and 2.59 nm, respectively (Fig. S5a–c†). Compared with BPY-COF, BPY-COF–Co showed a considerably decreased BET surface area and a smaller pore size, possibly caused by the coordinated Co sites occupying part of the pore space of BPY-COF. Since CO₂ adsorption is the first process before the catalytic steps, the CO₂ sorption measurements on the BPD-COF, BPY-COF and BPY-COF–Co were conducted at 278 K. A large amount of CO₂ was adsorbed on the synthetic COFs, as observed in Fig. S6.† Compared with BPY-COF, the reduced CO₂ uptake capacity of BPY-COF–Co was attributed to the integration of Co ions, demonstrating that the incorporation of Co ions into BPY-COF occurred via the Co–N bond interaction. As shown in Fig. S7,† the chemical durability of BPY-COF–Co was evaluated by soaking it in different solvents, such as methanol, DMF, THF, 3 M HCl and 3 M NaOH for 24 h, respectively. The PXRD patterns of BPY-COF–Co after treatments still retained the previous crystallinity, indicating that it possessed good chemical stability. Moreover, the thermal stability of the obtained COFs was assessed using thermogravimetric analysis (TGA), and no apparent weight loss was observed below 500 °C (Fig. S8†), confirming the excellent thermal stability of the obtained COF samples.

Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results revealed the morphology of the obtained materials. SEM images revealed the irregular aggregate structures of the three COFs (Fig. 3a–c). Highly ordered porous networks with distinct honeycomb-like pores were observed in the TEM images (Fig. 3d–f). At the same time, SEM-EDX mappings of the BPY-COF–Co sample confirmed the presence of C, N, O and Co elements, which were homogeneously distributed in the covalent organic frameworks (Fig. S9a and b†).

2.2 Optical and photoelectrochemical properties

Owing to the significance of optical properties for the photocatalytic performance, the light absorption of the synthesized COFs were recorded. According to Fig. 4a, the absorption intensity of BPY-COF–Co was higher than those of BPD-COF and BPY-COF, suggesting that the incorporation of metal ions enhanced the visible light absorption. Tauc plots in Fig. 4b revealed the optical band gaps (E_g) of BPD-COF, BPY-COF and BPY-COF–Co to be 1.42, 1.39 and 1.60 eV, respectively. In comparison with BPD-COF and BPY-COF, BPY-COF–Co exhibited a higher photocurrent response and smaller semicircle radius in the Nyquist plots, indicating its optimal effect on the separation of photogenerated electron–hole pairs (Fig. 4c and d). The positive slopes of Mott–Schottky plots demonstrated that all the obtained COFs were typical N-type semiconductors. For an N-type semiconductor, the CB position is close to its flat band potential. The flat band potentials (E_fb) of BPD-COF, BPY-COF and BPY-COF–Co were obtained as −2.05, −2.04 and −1.68 V, respectively (Fig. S10a–c†). The conduction band potentials (E_CB) of BPD-COF, BPY-COF and BPY-COF–Co were estimated to be −1.77, −1.76 and −1.40 V (vs. NHE), respectively, while their valence band potentials (E_VB) were calculated as −0.35, −0.37 and 1.27 V, respectively, using the equation E_VB = E_CB + E_g. As shown in Fig. S11,† the CB positions of the obtained samples were more negative than the reduction potential of CO₂/CO (−0.53 V vs. NHE), suggesting that these materials are theoretically capable of catalyzing CO₂ to CO. The intensity of the steady-state photoluminescence (PL) signals gradually decreased from BPD-COF to BPY-COF and BPY-COF–Co (Fig. 4e), suggesting that the introduction of Co ions significantly inhibited the recombination of photogenerated electrons and holes. Moreover, time-resolved fluorescence decay spectroscopy was used to determine the charge carrier lifetimes of BPD-COF, BPY-COF and BPY-COF–Co. The average fluorescence lifetimes were obtained as 0.62, 0.58 and 0.47 ns, respectively (Fig. 4f). Results revealed that the electrons in the BPY-COF–Co sample can be rapidly transferred and captured at the reactive sites, and the incorporation of Co ions can greatly inhibit the recombination of electrons and holes.⁵³

2.3 Photocatalytic performance of CO₂RR

To evaluate the photocatalytic CO₂ reduction performance of different COF samples, the experiments are conducted using [Ru(bpy)₃]Cl₂·6H₂O (bpy = 2,2′-bipyridine) as a photosensitizer and triethanolamine (TEOA) as a sacrificial agent in acetonitrile solution under visible light irradiation (Fig. S12†). BPD-COF and pristine BPY-COF can only yield 39 and 96 μmol g⁻¹ of CO, respectively after photocatalytic CO₂RR for 3 h (Fig. 5a). However, the BPY-COF–Co sample can produce 870 μmol g⁻¹ of CO after a 3 h reaction, which is about 9 times that of BPY-COF, indicating that the incorporation of Co active sites into the framework of BPY-COF can significantly promote the photocatalytic performance. Fig. S13† shows that the CO production continuously increases with the extension of reaction time using BPD-COF, BPY-COF and BPY-COF–Co. Moreover, the photocatalytic performance of BPY-COF coordinated with various metal ions, including Ni²⁺, Zn²⁺, Fe³⁺ and Cu²⁺, shows that BPY-COF–Co has the highest performance, as shown in Fig. 5b. Among the different anionic cobalt salts, BPY-COF–CoCl₂ using CoCl₂ as the cobalt source shows the optimal performance (Fig. 5c). These results reveal that the photocatalytic performance of CO₂RR is affected by the types of metal ions and corresponding anions, which may be related to the electronic properties of different metal ions and sizes of different anions. The results demonstrate that the Co sites in BPY-COF facilitate the transfer of electrons from nitrogen atoms to metal ions and serve as a bridge to inject the accumulated electrons into CO₂ molecules. To investigate the optimal photocatalytic conditions, a serious of controlled experiments with different solvent systems or sacrificial agents were performed using BPY-COF–Co as the photocatalyst. From Fig. S14a and b,† it is observed that acetonitrile is the most suitable solvent system and TEOA is the optimal electron donor for this system. According to Fig. 5d, the key factors for CO₂-to-CO conversion were studied. No CO can be detected in the absence of a photocatalyst and photosensitizer, revealing the photocatalytic nature of the reaction. However, the photocatalytic performance of BPY-COF–Co for the CO₂RR is greatly restricted without adding TEOA, suggesting that TEOA serves as a critical sacrificial agent. When the CO₂RR is conducted in the dark, no products can be detected, further revealing that illumination is essential for the CO₂ conversion. Besides, no carbonaceous products can be produced under the Ar atmosphere, confirming that the CO is produced from CO₂ rather than the organic solvent used in the reaction. As shown in Fig. 5e, the CO generation rate by BPY-COF–Co shows negligible change, demonstrating its cycling stability and reusability for photocatalytic CO₂RR. Furthermore, no obvious changes are observed in the XRD patterns (Fig. S15a†), FT-IR spectra (Fig. S15b†) and XPS spectra (Fig. S16a–d†) of BPY-COF–Co after four cycles photocatalysis, demonstrating the good stability of BPY-COF–Co during the cyclic reaction.

Moreover, isotope labeling experiments of ¹³CO₂ were performed to further verify the source of the product. The peak at m/z = 29 indicates that the generated ¹³CO is from gaseous ¹³CO₂ species rather than the decomposition of other organic compounds such as TEOA, [Ru(bpy)₃]Cl₂·6H₂O and photocatalyst in Fig. 5f. This observation confirms the excellent long-term stability of BPY-COF–Co for CO₂ reduction. Moreover, no other liquid byproducts can be detected from ¹H NMR analysis such as CH₃OH, C₂H₅OH and HCOOH (Fig. S17†), suggesting its high CO selectivity.

2.4 Photocatalytic mechanism

To detect the reaction intermediates, in situ diffuse reflection infrared Fourier transform spectroscopy (DRIFTS) measurements were conducted to trace the evolution of species by BPY-COF–Co (Fig. 6a). Absorption peaks at 1189 and 1341 cm⁻¹ were attributed to *COOH species, which is commonly recognized as the crucial intermediate in the CO₂ reduction to CO.^54,55 The characteristic vibration peaks at 1241 cm⁻¹ belonged to the carboxylate (*CO₂⁻) vibration. Moreover, the emergence of absorption peaks at 1402 and 1466 cm⁻¹ was indicative of the symmetric stretching of *HCO₃⁻, suggesting that CO₂ molecules were adsorbed and captured onto the photocatalysts. This analysis indicated that *HCO₃⁻ is the adsorption form of CO₂ and *COOH is the main intermediate in the photocatalytic CO₂RR process.

In the photocatalytic CO₂RR process, the photocatalysts constructed using the D–A junctions were excited under visible light, causing the electrons to migrate from the donor to the acceptor and enhance the intermolecular charge transfer. Apparently, the high energy level difference between the electron donor and acceptor improved the photocatalytic performance. Therefore, we calculated the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of all the monomers using DFT calculations to verify the intramolecular electron-transfer ability. The LUMO and HOMO of D–A structured COFs were mostly derived from the acceptor and the donor, respectively. Compared with truxenone units, the LUMO orbitals of biphenyl and bipyridine units exhibited lower energy levels and easily accepted electrons. Similarly, the HOMO orbital energy level of truxenone units was higher, and it was easier to lose electrons compared to biphenyl and bipyridine units. As shown in Fig. 6b, the D–A LUMO energy level difference (ΔE_LUMO) of BPY-COF (0.38 eV) was larger than that of BPD-COF (0.02 eV), making the photogenerated electrons more inclined to move from the truxenone units to bipyridine units.

In addition, the Gibbs free energy diagrams of the CO₂RR using BPY-COF and BPY-COF–Co, including CO₂ adsorption, *COOH formation, *CO formation and CO desorption, were obtained using DFT calculations based on the optimized structure (Fig. 6c, S18 and S19a–d†). The adsorbed *CO₂ molecules were formed after CO₂ adsorption. It can be found that BPY-COF–Co exhibited a lower calculated adsorption energy for CO₂ (−0.50 eV) than BPY-COF (−0.28 eV), indicating that BPY-COF–Co was capable of easily adsorbing CO₂. The gradual production of *COOH intermediate resulted from the protonation of *CO₂ molecules at the first hydrogenation step. The formation of *COOH showed the highest free energy barriers of 2.31 eV for BPY-COF–Co and 3.01 eV for BPY-COF, indicating that it was the rate-determining step for the photocatalytic CO₂RR. The reduced generation energy barrier of BPY-COF–Co suggested that the introduction of Co ions enhanced the charge transfer dynamic between BPY-COF and Co sites. Consequently, *COOH could be effectively immobilized by the Co centers in BPY-COF–Co, thereby improving the photocatalytic CO₂RR performance. In addition, the charge density difference distribution presented in Fig. 6d further indicates the photoelectron transfer process. BPY-COF–Co showed a new electronic depletion region next to the yellow isosurfaces (Co sites) and a stronger electron accumulation region around cyan isosurfaces (BPY-COF), demonstrating an effective carrier transfer progress from Co sites to COF, thus improving the photocatalytic activity. The *COOH intermediate was further protonated to form *CO products, followed by CO desorption. Because of the interaction between the Co center and the generated CO molecules, the desorption of CO from BPY-COF–Co was an endothermic process, while it was an exothermic process on BPY-COF. Based on the above analysis, a rational CO₂ photoreduction mechanism is proposed in Fig. 7. Under visible light illumination, the electrons were transferred from the excited photosensitizer to BPY-COF–Co, as shown in Fig. S20.† CO₂ molecules were easily captured by the metal active sites in the BPY-COF–Co photocatalyst. Subsequently, the absorbed CO₂ molecules received photogenerated electrons and interacted with protons to form the *COOH intermediate. Afterwards, deprotonation of the *COOH intermediate gave CO as the final product.

3 Conclusion

In summary, highly crystalline TRO-based COFs, composed of truxenone units as the electron-donors and biphenyl or bipyridine units as electron-acceptors, were synthesized via the Schiff-base condensation to accelerate photogenerated carrier separation and migration. In addition, a series of non-noble metal ions were introduced as active centers for photocatalytic CO₂RR by coordinating with bipyridine units on BPY-COF. The optimal sample BPY-COF–Co exhibited a high CO yield of 870 μmol g⁻¹ in a 3 h reaction with 100% selectivity and a preeminent cycling durability. The photoelectrochemical measurement results indicated that the electrons can be quickly transferred and trapped at the reactive sites for the BPY-COF–Co sample, and the incorporation of Co ions can greatly hinder the recombination of electrons and holes. DFT calculations revealed that the synergetic effect of the introduction of Co ions and the D–A structure greatly promoted CO₂ adsorption and activation and reduced energy barriers for the *COOH intermediate generation. This work highlights the importance of the structural design of COF photocatalysts and provides new insights into the electron transfer pathway for future photocatalytic CO₂RR studies.

Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

Author contributions

Yanyan Ren: designed and performed the experiments and wrote the manuscript. Fang Duan: supervised the project and revised the manuscript. All authors: analyzed and discussed the experimental results.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work was financially supported by the National Key Research and Development Program of China (No. 2022YFA1203600) and the National Natural Science Foundation of China (No. 52173201). Many thanks to the Central Laboratory, School of Chemical and Material Engineering, Jiangnan University, for their help in the characterization and analysis of the as-obtained samples.

Notes and references

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Footnote

† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d5ta02995c

This journal is © The Royal Society of Chemistry 2025