Screening suitable metal ion bridges for the construction of unimpeded dual carrier-transfer channels in carbon nitride photocatalyst

doi:10.1016/j.cjche.2024.12.006

Chinese Journal of Chemical Engineering ›› 2025, Vol. 80 ›› Issue (4): 70-78.DOI: 10.1016/j.cjche.2024.12.006

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Screening suitable metal ion bridges for the construction of unimpeded dual carrier-transfer channels in carbon nitride photocatalyst

Meixian Liu^1,2,3, Shuyun Xue³, Yajun Zhang⁵, Linjuan Pei⁴, Zhanfeng Zheng²

1 School of Basic Medical Science, Shanxi Medical University, Taiyuan 030001, China;
2 State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China;
3 School and Hospital of Stomatology, Shanxi Medical University, Taiyuan 030001, China;
4 School of Chemistry and Material Science, Shanxi Normal University, Taiyuan 030032, China;
5 State Key Laboratory for Oxo Synthesis & Selective Oxidation, Lanzhou Institute of Chemical Physics, Lanzhou 730000, China

Received:2024-09-26 Revised:2024-12-18 Accepted:2024-12-19 Online:2025-02-26 Published:2025-04-28
Contact: Meixian Liu,E-mail:liumx@sxmu.edu.cn;Linjuan Pei,E-mail:20210124@sxnu.edu.cn;Zhanfeng Zheng,E-mail:zfzheng@sxicc.ac.cn
Supported by:
This work is supported by the National Natural Science Foundation of China (82301052), China Postdoctoral Science Foundation (2023M732151), Shanxi Provincial Science and Technology Department (202303021212131), Health Commission of Shanxi Province (2022XM14), Shanxi Provincial Education Department (2022L165), Shanxi Medical University (XD2232).

Screening suitable metal ion bridges for the construction of unimpeded dual carrier-transfer channels in carbon nitride photocatalyst

Meixian Liu^1,2,3, Shuyun Xue³, Yajun Zhang⁵, Linjuan Pei⁴, Zhanfeng Zheng²

1 School of Basic Medical Science, Shanxi Medical University, Taiyuan 030001, China;
2 State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China;
3 School and Hospital of Stomatology, Shanxi Medical University, Taiyuan 030001, China;
4 School of Chemistry and Material Science, Shanxi Normal University, Taiyuan 030032, China;
5 State Key Laboratory for Oxo Synthesis & Selective Oxidation, Lanzhou Institute of Chemical Physics, Lanzhou 730000, China

通讯作者: Meixian Liu,E-mail:liumx@sxmu.edu.cn;Linjuan Pei,E-mail:20210124@sxnu.edu.cn;Zhanfeng Zheng,E-mail:zfzheng@sxicc.ac.cn
基金资助:
This work is supported by the National Natural Science Foundation of China (82301052), China Postdoctoral Science Foundation (2023M732151), Shanxi Provincial Science and Technology Department (202303021212131), Health Commission of Shanxi Province (2022XM14), Shanxi Provincial Education Department (2022L165), Shanxi Medical University (XD2232).

Abstract

Abstract: The huge carrier transfer resistance caused by large-sized “nitrogen pot” severely limits the photocatalytic performance of carbon nitride (CN). This study aims to explore the selection principle of metal ion bridges for constructing dual carrier-transfer channels to delivery carriers to respectively active sites using photodegradation of phenol as the model reaction. Density functional theory (DFT) calculation was used to optimize the structure model of nitrogen vacancies (N_V, provide active sites for reduction of O₂ and oxidation of phenol) and metal ions (Fe³⁺, Co²⁺, Ni²⁺ or Cu²⁺) co-modified CN, and screen metal ion bridges based on the three parameters including bonding state of metal ion and “nitrogen pot”, electrostatic potential (ESP) distribution around the active sites, and three-electron bond length. Both calculation results and activity data show that Fe³⁺, Co²⁺ and Ni²⁺ can construct dual carrier-transfer channels to promote the degradation of phenol while Cu²⁺ cannot. N_V and Fe³⁺ co-modified CN (Fe/N_V-CN) showed the best catalytic performance among various catalysts and was used as the model catalyst for the detailed characterization to verify the calculation results. This work provides not only the novel strategy for constructing dual carrier-transfer channels in CN, but also the crucial basis for computer simulation as a prediction tool of catalyst structure design rationality.

Key words: Carbon nitride, Dual carrier-transfer channels, Metal ion bridges, Degradation, Computer simulation, Radical

摘要： The huge carrier transfer resistance caused by large-sized “nitrogen pot” severely limits the photocatalytic performance of carbon nitride (CN). This study aims to explore the selection principle of metal ion bridges for constructing dual carrier-transfer channels to delivery carriers to respectively active sites using photodegradation of phenol as the model reaction. Density functional theory (DFT) calculation was used to optimize the structure model of nitrogen vacancies (N_V, provide active sites for reduction of O₂ and oxidation of phenol) and metal ions (Fe³⁺, Co²⁺, Ni²⁺ or Cu²⁺) co-modified CN, and screen metal ion bridges based on the three parameters including bonding state of metal ion and “nitrogen pot”, electrostatic potential (ESP) distribution around the active sites, and three-electron bond length. Both calculation results and activity data show that Fe³⁺, Co²⁺ and Ni²⁺ can construct dual carrier-transfer channels to promote the degradation of phenol while Cu²⁺ cannot. N_V and Fe³⁺ co-modified CN (Fe/N_V-CN) showed the best catalytic performance among various catalysts and was used as the model catalyst for the detailed characterization to verify the calculation results. This work provides not only the novel strategy for constructing dual carrier-transfer channels in CN, but also the crucial basis for computer simulation as a prediction tool of catalyst structure design rationality.

关键词: Carbon nitride, Dual carrier-transfer channels, Metal ion bridges, Degradation, Computer simulation, Radical

Meixian Liu, Shuyun Xue, Yajun Zhang, Linjuan Pei, Zhanfeng Zheng. Screening suitable metal ion bridges for the construction of unimpeded dual carrier-transfer channels in carbon nitride photocatalyst[J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 70-78.

References

[1] R.C. Shen, C.C. Qin, L. Hao, X.Z. Li, P. Zhang, X. Li, Realizing photocatalytic overall water splitting by modulating the thickness-induced reaction energy barrier of fluorenone-based covalent organic frameworks, Adv. Mater. 35 (39) (2023) e2305397.
[2] Z.W. Heng, W.C. Chong, Y.L. Pang, L.C. Sim, C.H. Koo, Photocatalytic degradation of organic pollutants using green oil palm frond-derived carbon quantum dots/titanium dioxide as multifunctional photocatalysts under visible light radiation, Chin. J. Chem. Eng. 51 (2022) 21-34.
[3] L.P. Xu, P.K. Wong, Z.F. Jiang, J.C. Yu, Iodide-mediated selective photocatalytic treatment of phenolic pollutants, Appl. Catal. B Environ. 338 (2023) 123080.
[4] X.Y. Sui, J.C. Wang, Z.Q. Zhao, B. Liu, M.M. Liu, M. Liu, C. Shi, X.J. Feng, Y.X. Fu, D.Y. Shi, S.Y. Li, Q.S. Qi, M. Xian, G. Zhao, Phenolic compounds induce ferroptosis-like death by promoting hydroxyl radical generation in the Fenton reaction, Commun. Biol. 7 (1) (2024) 199.
[5] J.H. Chaudhuri, D. Chatterjee, Modelling of chemical kinetics in the presence of hydrodynamic cavitation for wastewater treatment applications, Chem. Eng. Sci. 295 (2024) 120167.
[6] K.V. Divya Lakshmi, T. Siva Rao, J. Swathi Padmaja, I. Manga Raju, M. Ravi Kumar, Structure, photocatalytic and antibacterial activity study of Meso porous Ni and S Co-doped TiO₂ nano material under visible light irradiation, Chin. J. Chem. Eng. 27 (7) (2019) 1630-1641.
[7] Y.X. Deng, M.Y. Xing, J.L. Zhang, An advanced TiO₂/Fe₂TiO₅/Fe₂O₃ triple-heterojunction with enhanced and stable visible-light-driven Fenton reaction for the removal of organic pollutants, Appl. Catal. B Environ. 211 (2017) 157-166.
[8] H.C. Li, P.C. Ji, Y. Teng, H.L. Jia, M.Y. Guan, Preparation of carbon coated hyperdispersed Ru nanoparticles supported on TiO₂ HER electrocatalysts by dye-sensitization, New J. Chem. 47 (20) (2023) 9628-9634.
[9] H. Tan, X.M. Gu, P. Kong, Z. Lian, B. Li, Z.F. Zheng, Cyano group modified carbon nitride with enhanced photoactivity for selective oxidation of benzylamine, Appl. Catal. B Environ. 242 (2019) 67-75.
[10] J. Wang, R. Sheng, J.X. Xiao, L. Lu, Y.H. Peng, D. Gu, W. Xiao, Matched redox kinetics on triazine-based carbon nitride/Ni(OH)2 for stoichiometric overall photocatalytic CO₂ conversion, Small 20 (29) (2024) e2309707.
[11] T. Sun, C.X. Li, Y.P. Bao, J. Fan, E.Z. Liu, S-scheme MnCo₂S₄/g-C₃N₄ heterojunction photocatalyst for H₂ production, Acta Phys. Chim. Sin. (2023) 2212009.
[12] W. Liu, H.N. Che, B. Liu, Y.H. Ao, Unveiling the mechanism on photocatalytic singlet oxygen generation over rationally designed carbonylated carbon nitride, J. Mater. Chem. A 12 (22) (2024) 13427-13434.
[13] H.F. Liu, H.J. Li, J.M. Lu, S. Zeng, M. Wang, N.C. Luo, S.T. Xu, F. Wang, Photocatalytic cleavage of C-C bond in lignin models under visible light on mesoporous graphitic carbon nitride through π-π stacking interaction, ACS Catal. 8 (6) (2018) 4761-4771.
[14] G.L. Wang, Y. Zhao, H.R. Ma, C.J. Zhang, X.L. Dong, X.F. Zhang, Enhanced peroxymonosulfate activation on dual active sites of N vacancy modified g-C₃N₄ under visible-light assistance and its selective removal of organic pollutants, Sci. Total Environ. 756 (2021) 144139.
[15] X.S. Wang, C. Zhou, R. Shi, Q.Q. Liu, G.I.N. Waterhouse, L.Z. Wu, C.H. Tung, T.R. Zhang, Supramolecular precursor strategy for the synthesis of holey graphitic carbon nitride nanotubes with enhanced photocatalytic hydrogen evolution performance, Nano Res. 12 (9) (2019) 2385-2389.
[16] Q. Yang, W.B. Yang, F.F. He, K.W. Liu, H.M. Cao, H.J. Yan, One-step synthesis of nitrogen-defective graphitic carbon nitride for improving photocatalytic hydrogen evolution, J. Hazard. Mater. 410 (2021) 124594.
[17] Y.R. Zhao, M.Y. Sun, F. Zhou, G. Xu, Ultratrace aromatic anhydride dopant as intermediate island to promote charge transfer of graphitic carbon nitride for enhancing the photocatalytic degradation of rhodamine B, Langmuir 40 (3) (2024) 1858-1868.
[18] X. Rao, H.L. Dou, W.L. Chen, D. Long, S.H. Zheng, Z.Q. Chen, A. Abou Hassan, E.O.M. Ruiz, Y.P. Zhang, Embedding sodium ions in graphitic carbon nitride vacancies for visible light photocatalytic H₂ evolution, ACS Appl. Nano Mater. 3 (5) (2020) 4663-4669.
[19] K. Wada, N. Ohtani, Fabrication and characterization of carbon nitride fluorescent material using annealed melamine, Phys. Status Solidi B:. 256 (6) (2019) 256. https//doi.org/10.1002/pssb.201800521.
[20] X. Cao, M. Liao, X. Gu, L. Li, G. Wu, Studies on intermolecular electron transfer using electrostatic potential approach, Acta Chim. Sinica 50 (1992) 456-460.
[21] G.A. Meek, A.D. Baczewski, D.J. Little, B.G. Levine, Polaronic relaxation by three-electron bond formation in graphitic carbon nitrides, J. Phys. Chem. C 118 (8) (2014) 4023-4032.
[22] J.D. Xu, B. Lan, L.Y. Zhu, H. Xu, X.Y. Chen, W.J. Li, Y.F. Yuan, J.F. Yan, Y.M. Li, Synthesis and properties of ferrocene conjugated macrocycles with illusory topology of the Penrose stairs, Chem. Res. Chin. Univ. 40 (5) (2024) 881-886.
[23] Q.C. Li, Y. Zhang, Y.B. Zeng, M.Y. Ding, Ordered porous nitrogen-vacancy carbon nitride for efficient visible-light hydrogen evolution, J. Colloid Interface Sci. 642 (2023) 53-60.
[24] M.E. Wang, C.Z. Fan, S.J. Yang, M.L. Liu, J. Luo, Y.N. Liu, L. Tang, Z.X. Gong, S.W. Leng, Nitrogen deficient carbon nitride for efficient visible light driven tetracycline degradation: A combination of experimental and DFT studies, Catal. Sci. Technol. 10 (20) (2020) 6800-6808.
[25] C. Cometto, R. Kuriki, L.J. Chen, K. Maeda, T.C. Lau, O. Ishitani, M. Robert, A carbon nitride/Fe quaterpyridine catalytic system for photostimulated CO₂-to-CO conversion with visible light, J. Am. Chem. Soc. 140 (24) (2018) 7437-7440.
[26] G.M. Ba, T.T. Huo, Q.H. Deng, H.P. Li, W.G. Hou, Mechanochemical synthesis of nitrogen-deficient mesopore-rich polymeric carbon nitride with highly enhanced photocatalytic performance, ACS Sustainable Chem. Eng. 8 (50) (2020) 18606-18615.
[27] Y.P. Wang, Q.L. Li, L.C. Zhang, Y.K. Wu, H. Chen, T.H. Li, M.W. Xu, S.J. Bao, A gel-limiting strategy for large-scale fabrication of Fe-N-C single-atom ORR catalysts, J. Mater. Chem. A 9 (11) (2021) 7137-7142.
[28] W.D. Oh, C.Z. Ng, S.L. Ng, J.W. Lim, K.H. Leong, Rapid degradation of organics by peroxymonosulfate activated with ferric ions embedded in graphitic carbon nitride, Sep. Purif. Technol. 230 (2020) 115852.
[29] I. Khan, N. Baig, A. Qurashi, Graphitic carbon nitride impregnated niobium oxide (g-C₃N₄/Nb₂O₅) type (II) heterojunctions and its synergetic solar-driven hydrogen generation, ACS Appl. Energy Mater. 2 (1) (2019) 607-615.
[30] Z.Y. Gu, Z.T. Cui, Z.J. Wang, K.S. Qin, Y. Asakura, T. Hasegawa, S. Tsukuda, K. Hongo, R. Maezono, S. Yin, Carbon vacancies and hydroxyls in graphitic carbon nitride: Promoted photocatalytic NO removal activity and mechanism, Appl. Catal. B Environ. 279 (2020) 119376.
[31] C. Lu, X. Chen, Nanostructure engineering of graphitic carbon nitride for electrochemical applications, ACS Nano 15 (12) (2021) 18777-18793.
[32] J.T. Gao, Y. Wang, D. Shijian Zhou, D. Wei Lin, P. Yan Kong, A facile one-step synthesis of Fe-doped g-C₃N₄ nanosheets and their improved visible-light photocatalytic performance, ChemCatChem 9 (9) (2017) 1708-1715.
[33] Q.Z. Gao, J. Xu, Z.P. Wang, Y.F. Zhu, Enhanced visible photocatalytic oxidation activity of perylene diimide/g-C₃N₄ n-n heterojunction via π-π interaction and interfacial charge separation, Appl. Catal. B Environ. 271 (2020) 118933.
[34] Z.H. Han, G. Chen, C.M. Li, Y.S. Zhou, Y.D. Hu, W.N. Xing, Biocoordination polymer cross-linking structure to a 3D star topology inorganic photocatalyst nanocrystal with improved hydrogen evolution performance, Inorg. Chem. 57 (21) (2018) 13067-13070.
[35] M.X. Liu, J.L. Liu, Z.Q. Zeng, X. Wang, J.F. Jia, X.M. Gu, Z.F. Zheng, Steric hindrance effect induced photopurification of styrene oxide over surface modified polymeric carbon nitride, Sep. Purif. Technol. 300 (2022) 121929.
[36] Y. Nosaka, A.Y. Nosaka, Generation and detection of reactive oxygen species in photocatalysis, Chem. Rev. 117 (17) (2017) 11302-11336.
[37] H. Tan, P. Kong, R.G. Zhang, M.T. Gao, M.X. Liu, X.M. Gu, W.F. Liu, Z.F. Zheng, Controllable generation of reactive oxygen species on cyano-group-modified carbon nitride for selective epoxidation of styrene, Innovation 2 (1) (2021) 100089.
[38] M. Zhang, M. de Respinis, H. Frei, Time-resolved observations of water oxidation intermediates on a cobalt oxide nanoparticle catalyst, Nat. Chem. 6 (4) (2014) 362-367.
[39] X. Zhang, P.J. Ma, C. Wang, L.Y. Gan, X.J. Chen, P. Zhang, Y. Wang, H. Li, L.H. Wang, X.Y. Zhou, K. Zheng, Unraveling the dual defect sites in graphite carbon nitride for ultra-high photocatalytic H₂O₂ evolution, Energy Environ. Sci. 15 (2) (2022) 830-842.
[40] M.X. Liu, M.T. Gao, L.J. Pei, Y.L. Ji, X.M. Gu, H. Wang, H. Tan, J. Zhao, J.F. Jia, Z.F. Zheng, Tailoring phenol photomineralization pathway over polymeric carbon nitride with cyano group multifunctional active sites, Appl. Catal. B Environ. 284 (2021) 119710.
[41] T. Holopainen, L. Alvila, J. Rainio, T.T. Pakkanen, IR spectroscopy as a quantitative and predictive analysis method of phenol-formaldehyde resol resins, J. Appl. Polym. Sci. 69 (11) (1998) 2175-2185.
[42] L.L. Wang, W.Y. Cheng, J.X. Wang, J. Yang, Q.Q. Liu, Construction of intramolecular and interfacial built-in electric field in a donor-acceptor conjugated polymers-based S-scheme heterojunction for high photocatalytic H₂ generation, Chin. J. Catal. 58 (2024) 194-205.

Screening suitable metal ion bridges for the construction of unimpeded dual carrier-transfer channels in carbon nitride photocatalyst

Screening suitable metal ion bridges for the construction of unimpeded dual carrier-transfer channels in carbon nitride photocatalyst

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