Theoretical Calculation Studies on Interlayer Displacement Behavior and Photogenerated Carrier Dynamics of Covalent Triazine Frameworks

doi:10.6023/A24090266

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (2): 93-100.DOI: 10.6023/A24090266 Previous Articles Next Articles

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三嗪共价骨架材料的层间位错行为及其光生载流子动力学理论研究

陈铭晖^a, 张博心^a, 魏滔^a, 孙兆雪^a, 冯亚青^a, 张宝^a^,^b^,^*()

a 天津大学化工学院天津 300350
b 天津化工协同创新中心天津 300072

投稿日期:2024-09-09 发布日期:2024-10-22
作者简介:
^† 共同第一作者
基金资助:
国家自然科学基金(22478297); 国家自然科学基金(22078241); 中央高校基本科研业务费专项资金资助

Theoretical Calculation Studies on Interlayer Displacement Behavior and Photogenerated Carrier Dynamics of Covalent Triazine Frameworks

Minghui Chen^a, Boxin Zhang^a, Tao Wei^a, Zhaoxue Sun^a, Yaqing Feng^a, Bao Zhang^a^,^b()

a School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
b Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China

Received:2024-09-09 Published:2024-10-22
Contact: *E-mail: baozhang@tju.edu.cn
About author:
^† The authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22478297); National Natural Science Foundation of China(22078241); Fundamental Research Funds for the Central Universities

Covalent triazine frameworks (CTFs) represent a class of crystalline two-dimensional materials constructed by the interconnection of triazine rings. These materials are increasingly recognized for their potentials in photocatalysis due to their tunable functionality, adjustable bandgap, and structural stability. However, the inherent two-dimensional nature of these frameworks results in stacking through non-covalent interactions between layers, which means that the interlayer forces are relatively weak. This characteristic introduces the possibility of variations in stacking arrangements during both the framework formation process and its subsequent photocatalytic applications. Such variations in stacking can significantly impact the photocatalytic performance by altering its light absorption properties, exciton excitation, and migration characteristics, which, in turn, affect the photocatalytic dynamics of the material. Currently, the mechanisms underlying the formation of interlayer displacements in CTFs have not been extensively studied. Moreover, the influence of different displacement behaviors on the photocatalytic carrier dynamics within these frameworks remains underexplored and not well understood. To address this gap, this study employs density functional theory (DFT) to investigate the key factors influencing interlayer displacement behaviors in four types of CTFs: CTF-1, CTF-2, CTF-13, and CTF-133. The findings reveal that the process of interlayer displacement in these CTFs is a spontaneous process. Through analyses of electronic localization functions and charge density distributions, it was determined that the displacement is primarily caused by repulsive π-electron interactions on the nitrogen atoms within the triazine rings of adjacent layers. This repulsion creates a tendency for layer displacement, while the stacking of benzene ring units serves to stabilize the interlayer arrangement. Additionally, the study explores the photocatalytic carrier dynamics of CTF-1 frameworks with various stacking configurations. The results demonstrate that the CTF-1 frameworks with AA-stacking mode exhibits an optimal bandgap and carrier migration rate, positioning it as a promising candidate for use as a semiconductor photocatalyst. This study investigates the interlayer displacement behavior of triazine-based covalent organic framework materials from a microscopic perspective, and will provide theoretical insights and a basis for the design of novel catalysts based on CTFs.

Key words: covalent triazine framework, interlayer displacement, stacking mode, density functional theory method, semiconductor property

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Minghui Chen, Boxin Zhang, Tao Wei, Zhaoxue Sun, Yaqing Feng, Bao Zhang. Theoretical Calculation Studies on Interlayer Displacement Behavior and Photogenerated Carrier Dynamics of Covalent Triazine Frameworks[J]. Acta Chimica Sinica, 2025, 83(2): 93-100.

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Fig. & Tab. 11

Figure 1. The chemical structures of CTF-1, CTF-2, CTF-13 and CTF-133

Figure 2. (a~d) The optimized crystalline structures of CTF-1, CTF-2, CTF-13 and CTF-133

Figure 3. The energy and free energy differences of CTF-1, CTF-2, CTF-13 and CTF-133 in the layer-displacement processing

Figure 4. (a~d) The π electron density distribution of CTF-1, CTF-2, CTF-13 and CTF-133 in the XY plane of Z=0.5c; (e~h) the π ELF distribution of CTF-1, CTF-2, CTF-13 and CTF-133 in the XY plane of Z=0.5c

Figure 5. (a~d) The π ELF distribution of CTF-1, CTF-2, CTF-13 and CTF-133 in the XY plane of Z=c; (e, f) the π ELF distribution of CTF-1 in the XY plane of Z=c when the layer-displacement was 10% and 30% respectively

Figure 6. (a) The population distribution of π election density on each atom of CTF-1, CTF-2, CTF-13 and CTF-133; (b) the optimized crystalline structure of CBF; (c) the energy and free energy differences of CTF-1 and CBF in the layer-displacement processing

Figure 7. (a) The AA stacking of CTF-1; (b, c) the π ELF distribution of AA stacking of CTF-1 in the XY planes of Z=0 and Z=c; (d) the AB stacking of CTF-1; (e, f) the π ELF distribution of AB stacking of CTF-1 in the XY planes of Z=0 and Z=c

Figure 8. (a) The energy level spectra of CTF-1 in the layer-dislocation processing; (b) the energy level spectra of CTF-1 through stacking directions

Figure 9. The DOS of CTF-1 in the layer-displacement processing

不同层间位错的CTF-1	有效质量
不同层间位错的CTF-1	m_e^*/m₀	－m_h^*/m₀
AA Stacking	1.161	1.832
1	1.657	2.101
3	1.823	2.415
5	1.925	2.596
7	2.531	3.005
AB Stacking	2.716	3.204

Table 1. The effective mass of electrons and holes of CTF-1 with the layer-displacement

不同层间位错的CTF-1	沿层内方向有效质量				E_d/eV	C^2D/(N•m⁻¹)	μ_2D/(cm²•V⁻¹•s⁻¹)
不同层间位错的CTF-1	Direction	Carriers	m_e^*/m₀	m_d^*/m₀	E_d/eV	C^2D/(N•m⁻¹)	μ_2D/(cm²•V⁻¹•s⁻¹)
AA Stacking	x	Electron	2.091	2.161	4.53	87.35	139.23
	x	Hole	3.832	3.778	2.37	87.35	41.67
	y	Electron	2.234	2.161	4.83	95.32	162.00
	y	Hole	3.724	3.778	2.63	95.32	50.15
1	x	Electron	4.432	4.778	3.78	67.23	40.44
	x	Hole	5.652	6.058	1.95	67.23	16.45
	y	Electron	5.152	4.778	3.67	71.32	41.65
	y	Hole	6.493	6.058	2.03	71.32	18.17
3	x	Electron	5.814	5.769	3.51	56.13	25.97
	x	Hole	6.516	6.547	2.39	56.13	15.58
	y	Electron	5.724	5.769	2.57	61.74	20.91
	y	Hole	6.579	6.547	3.73	61.74	26.75
5	x	Electron	5.897	5.855	2.91	47.15	17.82
	x	Hole	6.516	6.867	2.35	47.15	12.27
	y	Electron	5.814	5.855	1.89	69.21	17.00
	y	Hole	7.236	6.867	2.73	69.21	18.01
7	x	Electron	5.931	5.935	3.23	37.78	15.64
	x	Hole	7.005	7.079	1.37	37.78	5.56
	y	Electron	5.939	5.935	4.23	54.19	29.37
	y	Hole	7.154	7.079	3.23	54.19	18.80
AB Stacking	x	Electron	6.016	6.214	3.78	31.73	14.68
	x	Hole	6.704	6.964	3.25	31.73	11.26
	y	Electron	6.418	6.214	2.67	59.25	19.36
	y	Hole	7.234	6.964	1.93	59.25	12.49

Table 2. The effective mass of electrons and holes of in-plane CTF-1 with the layer-displacement

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三嗪共价骨架材料的层间位错行为及其光生载流子动力学理论研究

Theoretical Calculation Studies on Interlayer Displacement Behavior and Photogenerated Carrier Dynamics of Covalent Triazine Frameworks

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