Molecular-doped Precursor Derived Porous g-C₃N₄ for Photocatalytic H₂ Production

Abstract

Molecular design of novel precursors represents a strategic approach to mitigating severe charge recombination in g-C₃N₄. Distinct from conventional high-temperature thermal polymerization, this work develops novel precursors through low-temperature hydrothermal assembly of melamine-cyanuric acid supramolecule with hexamethylenetetramine doping. After the calcination of modified precursors, the obtained g-C₃N₄ has a porous structure and an ultra-high specific surface area. Advanced characterizations confirm the reduced layer stacking, the disrupted π-π conjugated structure, and critically, the accelerated charge transport efficiency. Remarkably, the modified g-C₃N₄ achieves a 22 times enhancement in visible-light-driven hydrogen evolution (λ>400 nm) compared to pristine g-C₃N₄, which is among the highest improvements reported for supramolecular modified g-C₃N₄ systems. This molecular engineering strategy for precursors establishes a new approach to designing high-performance photocatalysts.

Keywords

Graphite carbon nitride / Photocatalysis / Hydrogen / Supramolecule

References

[1] Gong B L, Ma X Q, Wang T G, Hou J L, Ji S X, Xu Q J, Cao H J. Adv. Colloid Interface Sci., 2024, 336: 103373

[2] Allakhverdiev S I. Int. J. Hydrogen Energy, 2024, 90: 199

[3] Huo R, Li M, Zheng W B, Ming P W, Li B, Zhang C M, Li Z L. Energ. Convers. Manage., 2024, 317: 118819

[4] Saini P, Kumar K, Saini S, Sethi M, Meena P, Gurjar A, Weigand W, Parewa V. Coord. Chem. Rev., 2024, 502: 215607

[5] Belousov A S, Shafiq I. J. Environ. Chem. Eng., 2023, 11: 110970

[6] Iervolino G, Zammit I, Vaiano V, Rizzo L. Top. Curr. Chem., 2020, 378: 225

[7] Fujishima A, Honda K. Nature, 1972, 238: 37

[8] Fu C H, Li D, Zhang J W, Guo W, Yang H, Zhao B, Chen Z M, Fu X, Liang Z Q, Jiang L. Chem. Res. Chinese Universities, 2023, 39: 891

[9] Li Z, Li R G, Jing H J, Xiao J P, Xie H C, Hong F, Ta N, Zhang X W, Zhu J, Li C. Nat. Catal., 2023, 6: 80

[10] Lin J K, Tian W J, Guan Z Y, Zhang H Y, Duan X G, Wang H, Sun H Q, Fang Y F, Huang Y P, Wang S B. Adv. Funct. Mater., 2022, 32: 2201743

[11] Ji H Q, Liu Y X, Du G Y, Huang T Y, Zhu Y, Sun Y Y, Pang H. Chem. Res. Chinese Universities, 2024, 40: 943

[12] Niu Q, Mi L H, Chen W, Li Q J, Zhong S H, Yu Y, Li L Y. Chin. J. Catal., 2023, 50: 45

[13] Qian Y T, Zhang F F, Kang D J, Pang H. Energy Environ. Mater., 2023, 6: e12414

[14] Li T, Tsubaki N, Jin Z L. J. Mater. Sci. Technol., 2024, 169: 82

[15] Meng C C, Huang M, Li Y C. Chem. Res. Chinese Universities, 2023, 39: 697

[16] Yu K, Zhang C, Chang Y, Feng Y, Yang Z, Yang T, Lou L-L, Liu S. Appl. Catal. B-Environ., 2017, 200: 514

[17] Ong W-J, Tan L-L, Ng Y H, Yong S-T, Chai S-P. Chem. Rev., 2016, 116: 7159

[18] Hayat A, Taha T, Alenad A M, Ullah I, Shah S J A, Uddin I, Ullah I, Hayat A, Khan W U. Surf. Interfaces, 2021, 25: 101166

[19] Jo W-K, Tonda S. J. Hazard. Mater., 2019, 368: 778

[20] Fei H, Shao J X, Li H, Li N J, Chen D Y, Xu Q F, He J H, Lu J M. Appl. Catal. B-Environ., 2021, 299: 120623

[21] Mao L H, Zhai B J, Wen L Y, Xiao W B, Shi J W, Kang X, Liu Y B, Cheng C, Jin H, Guo L J. Appl. Catal. B-Environ., 2025, 362: 124712

[22] Cheng C, Shi J W, Mao L H, Dong C-L, Huang Y-C, Zong S C, Liu J M, Shen S H, Guo L J. J. Colloid Interf. Sci., 2023, 637: 271

[23] Mao L H, Zhai B J, Shi J W, Kang X, Lu B R, Liu Y B, Cheng C, Jin H, Lichtfouse E, Guo L J. ACS Nano, 2024, 18: 13939

[24] Kang X, Jiang Y Z, Shi J W, Mao L H, Liu Y B, Zhai B J, Jin H, Guo L J. J. Colloid Interf. Sci., 2025, 685: 716

[25] Abou Saoud W, Belkessa N, Azzaz A A, Rochas V, Mezino V, Presset M-A, Lechevin S, Genouel A, Rouxel S, Monsimert D. Chem. Eng. J., 2023, 468: 143710

[26] Acar E G, Koç B K, Israr M, Aslan E, Altan O, Patir İ H H, Metin Ö. J. Environ. Chem. Eng., 2025, 13: 115343

[27] Lv X T, Jin X L, Meng J W, Yang K T, Lin S L, Hao W X, Zhao M Y, Wang H Q, Zhang X H, Lv C D, Xie H Q. J. Colloid Interf. Sci., 2025, 686: 1009

[28] Ke Y L, You Q L, Ai J, Yang X F, Shang Q G, Liu Y Y, Wang D S, Liao G Y. J. Mater. Sci. Technol., 2023, 152: 37

[29] Yin F X, Qin P Q, Xu J S, Cao S W. Acta Phys. -Chimi. Sin., 2023, 39: 2212062

[30] Chen G Q, Zheng Z X, Zhong W, Wang G H, Wu X H. Acta Phys.-Chimi. Sin., 2024, 40: 2406021

[31] Liu X L, Zhang Q Q, Cui Z H, Ma F H, Guo Y H, Wang Z Y, Liu Y Y, Zheng Z K, Cheng H F, Dai Y, Huang B B, Wang P. Int. J. Hydrogen Energy, 2022, 47: 18738

[32] Chen S, Wen X Y, Chen Y L, Xia Z Y, Chen Q R, Huang L L, Huang H N, Pan H W, Fu Y L, He J R, Li W S. Chem. Engin. J., 2024, 479: 147813

[33] Jiang Z C, Long Q, Cheng B, He R A, Wang L X. J. Mater. Sci. Technol., 2023, 162: 1

[34] Zhong R Y, Liang Y J, Huang F, Liang S N, Liu S W. Chin. J. Catal., 2023, 53: 109

[35] Chen Y L, Liu X Q, Hou L, Guo X R, Fu R W, Sun J M. Chem. Eng. J., 2020, 383: 123132

[36] Li Y-Y, Zhou B-X, Zhang H-W, Ma S-F, Huang W-Q, Peng W, Hu W, Huang G-F. Nanoscale, 2019, 11: 6876

[37] Mao L H, Chen K L, Jiang Y Z, Kang X, Zhang Y Z, Cheng C, Chen Y, Shi J W. Sustainable Energy Fuels, 2025, 9: 1498

[38] Liu Q, Wang X L, Yang Q, Zhang Z G, Fang X M. Appl. Surf. Sci., 2018, 450: 46

[39] Du J G, Xu Z, Li H, Yang H J, Xu S J, Wang J, Jia Y N, Ma S L, Zhan S H. Appl. Surf. Sci., 2021, 541: 148487

[40] Zou J, Liao G D, Jiang J Z, Xiong Z G, Bai S S, Wang H T, Wu P X, Zhang P, Li X. Chin. J. Struct., 2022, 41: 2201025

[41] Zhong L, Ying M F, Mou Z G, Luo R, Sun J H, Liu D, Lei W W. J. Colloid Interf. Sci., 2022, 612: 479

[42] Li Y H, He Z J, Liu L, Jiang Y, Ong W J, Duan Y Y, Ho W K, Dong F. Nano Energy, 2023, 105: 108032

[43] Zhai B J, Li Y, Jiang Y Z, Mao L H, Shi J W, Zhao Q Q, Bin Z D, Wang F Y, Du Y P, Jin H. J. Colloid Interf. Sci., 2025, 685: 1099

[44] Yang Y, Liu J J, Gu M L, Cheng B, Wang L X, Yu J G. Appl. Catal. B-Environ., 2023, 333: 122780

[45] Xue Y J, Zhao G Y, Zhang W Q, Zhao J S, Meng F P, Zhao F. ACS Appl. Polym. Mater., 2024, 6: 11444

[46] Mao L H, Lu B R, Shi J W, Zhang Y Z, Kang X, Chen Y B, Jin H, Guo L J. Catalysis Today, 2023, 409: 94

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Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH