Abstracting photogenerated holes from covalent triazine frameworks through carbon dots for overall hydrogen peroxide photosynthesis

doi:10.1016/S1872-2067(24)60050-1

Abstract

Abstract:

Owing to the rapid recombination of photogenerated electron-hole pairs with strong Coulomb interactions, the photocatalytic activity of metal-free conjugated polymers is often unsatisfactory. This article reports a simple method for incorporating carbon dots (CDs) into highly crystalline covalent triazine frameworks (CTFs) by directly heating a pretreated mixture of 1,4-dicyanobenzene, CDs, and alkali metal salts in air. The resultant photocatalyst exhibits a H₂O₂ production rate, solar-to-chemical conversion efficiency, and apparent quantum yield of 2464 μmol h^-1 g^-1, 0.9% at full spectrum, and 13% at 500 nm, respectively, surpassing most reported photocatalysts. The results of this study reveal that CDs can serve as hole extractors to efficiently drive exciton dissociation and can offer active sites for water oxidation reactions. This study is also the first to observe that alkali metal ions can interact with the carboxylic acid groups on the surface of CDs during synthesis to enhance the hole-extraction ability of CTFs, thereby accelerating photocatalytic H₂O₂ production. This study provides insights into the rational design of highly efficient CDs-based photocatalysts.

Key words: Covalent triazine framework, Carbon dot, H₂O₂ photosynthesis, Photocatalytic process, Water oxidation reaction, Photocatalyst

Weijie Ren, Ning Li, Qing Chang, Jie Wu, Jinlong Yang, Shengliang Hu, Zhenhui Kang. Abstracting photogenerated holes from covalent triazine frameworks through carbon dots for overall hydrogen peroxide photosynthesis[J]. Chinese Journal of Catalysis, 2024, 62: 178-189.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60050-1

https://www.cjcatal.com/EN/Y2024/V62/I7/178

Figures/Tables 8

Fig. 1. Photocatalytic H2O2 production performance. (a,b) Time courses of H2O2 generation over CTFs and CDs@CTFs in different reaction solutions under simulated sunlight irradiation. (c) Comparison of the photocatalytic performances of CTFs and CDs@CTFs before and after introducing 0.1 μmol CsCl. (d) EPR spectra of CDs@CTFs and CDs@CTFs CsCl irradiated for 10 min for O2?? detection. (e) EPR spectra of CDs@CTFs and CDs@CTFs CsCl irradiated for 10 min for ·OH detection. (f) DRIFTS spectra of CDs@CTFs irradiated for various durations.

Fig. 2. Photocatalytic H2O2 production performance. (a) AQY of H2O2 generation over CDs@CTFs CsCl as a function of the incident light wavelength at different wavelengths. (b) Comparison of the H2O2 production performance of the proposed photocatalysts against previously reported photocatalysts. (c) Stability and durability of CDs@CTFs CsCl for H2O2 generation. (d) H2O2 evolution of CDs@CTFs CsCl during 10 h of outdoor sunlight irradiation with careful monitoring of the environmental temperature and solar intensity.

Fig. 3. Characterization of the CTFs and CDs@CTFs. (a) FTIR spectra of the CDs@CTFs, CTFs, and DCB. (b) Powder XRD patterns of the CTFs and CDs@CTFs. (c) HRTEM images and EDS maps of CDs@CTFs CsCl. (d) XPS C 1s spectra of the CTFs and CDs@CTFs. (e) Comparison of the photocatalytic activity of the CTFs against that of the calcined CTFs and CTFs/CDs. (f) UV-vis absorption of the CTFs, CDs@CTFs, and CDs@CTFs CsCl.

Fig. 4. Effect of metal ions on the CDs@CTFs. (a) Zeta potentials of CD solutions containing equal concentrations of different metal ions. (b) PL spectra of CD solutions before and after the addition of different metal ions. (c) Comparison of the photocatalytic activities of CDs@CTFs before and after the addition of different metal ions. (d) Comparison of the photocatalytic performance of CDs@CTFs containing different CsCl contents. (e) Zeta potentials of CD solutions containing different CsCl contents. (f) XRD spectra of CDs@CTFs containing different CsCl contents.

Fig. 5. Interaction of alkali metal ions with CDs. (a) Schematic illustration of the combination of CDs with alkali metal ions. (b) XPS Cs 3d spectra of CsCl and CDs@CTFs CsCl. (c) FTIR spectra of the CDs before and after the addition of CsCl. (d) TGA results of the CTFs, CDs@CTFs, and CDs@CTFs CsCl. (e) FTIR spectra of the CDs@CTFs with and without CsCl. (f) Photocatalytic performance of the CDs@CTFs in different alkali metal ion solutions. (g) Photocatalytic H2O2 production performance of NCDs@CTFs with different CsCl contents.

Fig. 6. Charge separation and transfer analysis. (a) Energy level structures of the CDs and CTFs. (b) PL spectra of the CTFs, CDs@CTFs, and CDs@CTFs CsCl. (c) Transient fluorescence spectroscopy (TFS) spectra of the CTFs, CDs@CTFs, and CDs@CTFs CsCl. (d) Electrochemical impedance spectroscopy (EIS) plots of the CTFs, CDs@CTFs, and CDs@CTFs CsCl. (e) Transient photocurrent response of the CTFs, CDs@CTFs, and CDs@CTFs CsCl.

Fig. 7. Role of CDs in charge transfer. (a,b) PL spectra of the CDs and CDs+CsCl before and after the addition of 2,4-dinitrotoluene and N,N-diethylaniline. (c,d) TFS spectra of the CDs and CDs+CsCl before and after the addition of 2,4-dinitrotoluene and N,N-diethylaniline. (e,f) Schematic illustration of the device structure used and the collected I-V curves of the CTFs and CDs@CTFs in darkness.

Fig. 8. Photogenerated charge separation and transfer mechanism. (a) Schematic diagram illustrating the carrier separation and transfer processes in the CTFs, CDs@CTFs, and CDs@CTFs CsCl. (b,c) Calculated mean charge density distributions of the CDs and CTFs in the z-direction before and after the introduction of Cs+ ions.

References

[1]	F.-K. Shang, Y.-H. Li, M.-Y. Qi, Z.-R. Tang, Y.-J. Xu, Catal. Today, 2023, 410, 85-101.
[2]	Y.-H. Li, Z.-R. Tang, Y.-J. Xu, Chin. J. Catal., 2022, 43, 708-730.
[3]	S.-H. Li, M.-Y. Qi, Z.-R. Tang, Y.-J. Xu, Chem. Soc. Rev., 2021, 50, 7539-7586.
[4]	M.-Y. Qi, M. Conte, M. Anpo, Z.-R. Tang, Y.-J. Xu, Chem. Rev., 2021, 121, 13051-13085.
[5]	H. Cai, F. Chen, C. Hu, W. Ge, T. Li, X. Zhang, H. Huang, Chin. J. Catal., 2024, 57, 123-132.
[6]	Y. Li, Y. Liu, Z. Wang, P. Wang, Z. Zheng, H. Cheng, Y. Dai, B. Huang, Chin. J. Catal., 2023, 45, 132-140.
[7]	Y. Zhang, J. Qiu, B. Zhu, G. Sun, B. Cheng, L. Wang, Chin. J. Catal., 2024, 57, 143-153.
[8]	Z. Zan, X. Li, X. Gao, J. Huang, Y. Luo, L. Han, Acta Phys.-Chim. Sin., 2023, 39, 2209016.
[9]	H. Zhang, J. Liu, Y. Zhang, B. Cheng, B. Zhu, L. Wang, J. Mater. Sci. Technol., 2023, 166, 241-249.
[10]	R. He, D. Xu, X. Li, J. Mater. Sci. Technol., 2023, 138, 256-258.
[11]	L. Wang, J. Sun, B. Cheng, R. H, J. Yu, J. Phys. Chem. Lett., 2023, 14, 4803-4814.
[12]	J. Wang, C. Guo, Y. Jiang, J. Wan, B. Zheng, Y. Li, B. Jiang, Sci. China Mater., 2023, 66, 1053-1061.
[13]	Y. Xu, W. Tai, Z. Wang, L. Zhang, D. Wang, J. Liao, Sci. China Mater., 2024, 67, 153-161.
[14]	H. S. Sasmal, A. Kumar Mahato, P. Majumder, R. Banerjee, J. Am. Chem. Soc., 2022, 144, 11482-11498.
[15]	M. Kou, Y. Wang, Y. Xu, L. Ye, Y. Huang, B. Jia, H. Li, J. Ren, Y. Deng, J. Chen, Y. Zhou, K. Lei, L. Wang, W. Liu, H. Huang, T. Ma, Angew. Chem. Int. Ed., 2022, 61, e202200413.
[16]	W. Zhang, L. Chen, S. Dai, C. Zhao, C. Ma, L. Wei, M. Zhu, S. Y. Chong, H. Yang, L. Liu, Y. Bai, M. Yu, Y. Xu, X. W. Zhu, Q. Zhu, S. An, R. S. Sprick, M. A. Little, X. Wu, S. Jiang, Y. Wu, Y. B. Zhang, H. Tian, W. H. Zhu, A. I. Cooper, Nature, 2022, 604, 72-79.
[17]	G. Huang, Q. Niu, Y. He, J. Tian, M. Gao, C. Li, N. An, J. Bi, J. Zhang, Nano Res., 2022, 15, 8001-8009.
[18]	K. Wang, L. M. Yang, X. Wang, L. Guo, G. Cheng, C. Zhang, S. Jin, B. Tan, A. Cooper, Angew. Chem. Int. Ed., 2017, 56, 14149-14153.
[19]	C. Zhu, Q. Fang, R. Liu, W. Dong, S. Song, Y. Shen, Environ. Sci. Technol., 2022, 56, 6699-6709.
[20]	C. Wang, H. Zhang, W. Luo, T. Sun, Y. Xu, Angew. Chem. Int. Ed., 2021, 60, 25381-25390.
[21]	L. Chen, L. Wang, Y. Wan, Y. Zhang, Z. Qi, X. Wu, H. Xu, Adv. Mater., 2020, 32, 1904433.
[22]	C. Wu, Z. Teng, C. Yang, F. Chen, H. B. Yang, L. Wang, H. Xu, B. Liu, G. Zheng, Q. Han, Adv. Mater., 2022, 34, 2110266.
[23]	C. Feng, Z.-P. Wu, K.-W. Huang, J. Ye, H. Zhang, Adv. Mater., 2022, 34, 2200180.
[24]	W. Zhao, P. Yan, B. Li, M. Bahri, L. Liu, X. Zhou, R. Clowes, N. D. Browning, Y. Wu, J. W. Ward, A. I. Cooper, J. Am. Chem. Soc., 2022, 144, 9902-9909.
[25]	S. Zhang, G. Cheng, L. Guo, N. Wang, B. Tan, S. Jin, Angew. Chem. Int. Ed., 2020, 59, 6007-6014.
[26]	Z. Zhang, X. Chen, H. Zhang, W. Liu, W. Zhu, Y. Zhu, Adv. Mater., 2020, 32, e1907746.
[27]	J. Yang, F. Kang, X. Wang, Q. Zhang, Mater. Horizons, 2022, 9, 121-146.
[28]	C. Krishnaraj, H. Sekhar Jena, L. Bourda, A. Laemont, P. Pachfule, J. Roeser, C. V. Chandran, S. Borgmans, S. M. J. Rogge, K. Leus, C. V. Stevens, J. A. Martens, V. Van Speybroeck, E. Breynaert, A. Thomas, P. Van Der Voort, J. Am. Chem. Soc., 2020, 142, 20107-20116.
[29]	H. Wang, C. Yang, F. Chen, G. Zheng, Q. Han, Angew. Chem. Int. Ed., 2022, 61, e202202328.
[30]	L. Dordevic, F. Arcudi, M. Cacioppo, M. Prato, Nat. Nanotechnol., 2022, 17, 112-130.
[31]	Y. Zhai, B. Zhang, R. Shi, S. Zhang, Y. Liu, B. Wang, K. Zhang, G. I. N. Waterhouse, T. Zhang, S. Lu, Adv. Energy Mater., 2022, 12, 2103426.
[32]	L. Shi, B. Wang, S. Lu, Matter, 2023, 6, 728-760.
[33]	M. L. Liu, B. B. Chen, C. M. Li, C. Z. Huang, Green Chem., 2019, 21, 449-471.
[34]	B. Jana, Y. Reva, T. Scharl, V. Strauss, A. Cadranel, D. M. Guldi, J. Am. Chem. Soc., 2021, 143, 20122-20132.
[35]	Y. Wang, X. Liu, J. Liu, B. Han, X. Hu, F. Yang, Z. Xu, Y. Li, S. Jia, Z. Li, Y. Zhao, Angew. Chem. Int. Ed., 2018, 57, 5765-5771.
[36]	Y. Li, Y. Zhao, J. Wu, Y. Han, H. Huang, Y. Liu, Z. Kang, J. Mater. Chem. A, 2021, 9, 25453-25462.
[37]	Y. Zhao, L. Xu, X. Wang, Z. Wang, Y. Liu, Y. Wang, Q. Wang, Z. Wang, H. Huang, Y. Liu, W.-Y. Wong, and Z. Kang, Nano Today, 2022, 43, 101428.
[38]	P. Ma, X. Zhang, C. Wang, Z. Wang, K. Wang, Y. Feng, J. Wang, Y. Zhai, J. Deng, L. Wang, K. Zheng, Appl. Catal. B, 2022, 300, 120736.
[39]	P. Wei, Y. Chen, T. Zhou, Z. Wang, Y. Zhang, H. Wang, H. Yu, J. Jia, K. Zhang, C. Peng, ACS Catal., 2023, 13, 587-600.
[40]	X. Meng, Q. Chang, C. Xue, J. Yang, S. Hu, Chem. Comm., 2017, 53, 3074-3077.
[41]	V. C. Hoang, M. Hassan, V. G. Gomes, Appl. Mater. Today, 2018, 12, 342-358.
[42]	W. Ren, Q. Chang, N. Li, J. Yang, S. Hu, Chem. Eng. J., 2023, 451, 139035.
[43]	L. Liang, Q. Chang, T. Cai, N. Li, C. Xue, J. Yang, S. Hu, Chem. Eng. J., 2022, 428, 131139.
[44]	C.-F. Cheng, H.-Y. Hsueh, C.-H. Lai, C.-J. Pan, B.-J. Hwang, C.-C. Hu, R.-M. Ho, NPG Asia Mater., 2015, 7, e170.
[45]	B.-H. Lee, H. Shin, A. S. Rasouli, H. Choubisa, P. Ou, R. Dorakhan, I. Grigioni, G. Lee, E. Shirzadi, R. K. Miao, J. Wicks, S. Park, H. S. Lee, J. Zhang, Y. Chen, Z. Chen, D. Sinton, T. Hyeon, Y.-E. Sung, E. H. Sargent, Nat. Catal., 2023, 6, 234-243.
[46]	Z. Zhang, J. T. Yates, Jr., Chem. Rev., 2012, 112, 5520-5551.
[47]	S. Lin, Q. Wang, H. Huang, Y. Zhang, Small, 2022, 18, 2200914.
[48]	J.-P. Liao, M. Zhang, P. Huang, L.-Z. Dong, T.-T. Ma, G.-Z. Huang, Y.-F. Liu, M. Lu, S.-L. Li, Y.-Q. Lan, ACS Catal., 2024, 14, 3778-3787.
[49]	X. Wang, Y. Jin, N. Li, H. Zhang, X. Liu, X. Yang, H. Pan, T. Wang, K. Wang, D. Qi, J. Jiang, Angew. Chem. Int. Ed., 2024, 63, e202401014.
[50]	Y. Zhao, P. Zhang, Z. Yang, L. Li, J. Gao, S. Chen, T. Xie, C. Diao, S. Xi, B. Xiao, C. Hu, W. Choi, Nat. Commun., 2021, 12, 3701.
[51]	Y. Zheng, S. Xia, F. Dong, H. Sun, Y. Pang, J. Yang, Y. Huang, S. Zheng, Adv. Funct. Mater., 2020, 31, 2006159.
[52]	J. Liu, P. Lyu, Y. Zhang, P. Nachtigall, Y. Xu, Adv. Mater., 2018, 30, 1705401.
[53]	Z. Yang, H. Chen, S. Wang, W. Guo, T. Wang, X. Suo, D.-E. Jiang, X. Zhu, I. Popovs, S. Dai, J. Am. Chem. Soc., 2020, 142, 6856-6860.
[54]	W. Ren, H. Wang, Q. Chang, N. Li, J. Yang, S. Hu, Carbon, 2021, 184, 102-108.
[55]	Q. Zhang, R. Wang, B. Feng, X. Zhong, K. Ostrikov, Nat. Commun., 2021, 12, 6856.
[56]	C. Rosso, G. Filippini, M. Prato, ACS Catal., 2020, 10, 8090-8105.
[57]	Q. Chang, W. Xu, N. Li, C. Xue, Y. Wang, Y. Li, H. Wang, J. Yang, S. Hu, Appl. Catal. B, 2020, 263, 118299.
[58]	B. Wang, S. Lu, Matter, 2022, 5, 110-149.
[59]	Y.-Q. Zhang, D.-K. Ma, Y.-G. Zhang, W. Chen, S.-M. Huang, Nano Energy, 2013, 2, 545-552.
[60]	Q. Chen, C. Lu, B. Ping, G. Li, J. Chen, Z. Sun, Y. Zhang, Q. Ruan, L. Tao, Appl. Catal. B, 2023, 324, 122216.
[61]	Y. Liu, J. Wang, J. Wu, Y. Zhao, H. Huang, Y. Liu, Z. Kang, Appl. Catal. B, 2022, 319, 121944.
[62]	Y. Wang, X. Liu, X. Han, R. Godin, J. Chen, W. Zhou, C. Jiang, J. F. Thompson, K. B. Mustafa, S. A. Shevlin, J. R. Durrant, Z. Guo, J. Tang, Nat. Commun., 2020, 11, 2531.
[63]	X. Wang, L. Cao, F. Lu, M. J. Meziani, H. Li, G. Qi, B. Zhou, B. A. Harruff, F. Kermarrec, Y. P. Sun, ChemComm, 2009, 3774-3776.
[64]	H. Huang, P. Cui, Y. Chen, L. Yan, X. Yue, S. Qu, X. Wang, S. Du, B. Liu, Q. Zhang, Z. Lan, Y. Yang, J. Ji, X. Zhao, Y. Li, X. Wang, X. Ding, M. Li, Joule, 2022, 6, 2186-2202.
[65]	D. Shi, V. Adinolfi, R. Comin, M. Yuan, E. Alarousu, A. Buin, Y. Chen, S. Hoogland, A. Rothenberger, K. Katsiev, Y. Losovyj, X. Zhang, P. A. Dowben, O. F. Mohammed, E. H. Sargent, O. M. Bakr, Science, 2015, 347, 519-522.
[66]	Y. Lin, C. Yang, S. Wu, X. Li, Y. Chen, W. L. Yang, Adv. Funct. Mater., 2020, 30, 2002918.
[67]	A. Deng, Y. Sun, Z. Gao, S. Yang, Y. Liu, H. He, J. Zhang, S. Liu, H. Sun, S. Wang, Nano Energy, 2023, 108, 108228.