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

doi:10.6023/A24090266

摘要/Abstract

三嗪共价骨架(CTF)材料是一类由三嗪环连接构筑的结晶性二维骨架材料, 于光催化领域受到了越来越多的关注. 由于其特殊的二维结构, 各层之间通过非化学键的方式进行堆叠形成体相结构, 因此其各层之间的相互作用力较弱. 在形成骨架过程以及光催化过程中可能发生堆积方式的变化. 然而目前CTFs材料产生层间位错的机理尚未有所研究. 因此本工作采用密度泛函方法, 探究了四种三嗪骨架材料(CTF-1、CTF-2、CTF-13以及CTF-133)的层间位错行为的主要影响因素. 结果表明, 四种CTF发生层间位错行为的过程均为一自发行为, 是由于相邻两层之间三嗪环基团中氮原子上π电子斥力造成的, 而苯环单元的层间堆积能够稳定层间构型. 最后, 对不同堆积方式的CTF-1骨架的光生载流子动力学进行了研究, 发现AA堆积的CTF-1骨架材料具有合适的带隙以及光生载流子迁移速率, 是一种潜在的半导体光催化剂.

关键词: 三嗪基共价骨架材料, 层间位错行为, 堆积方式, 密度泛函理论, 半导体特性

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

引用此文

陈铭晖, 张博心, 魏滔, 孙兆雪, 冯亚青, 张宝. 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[J]. 化学学报, 2025, 83(2): 93-100.

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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图/表 11

图1. CTF-1、CTF-2、CTF-13以及CTF-133化学结构

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

图2. (a~d) CTF-1、CTF-2、CTF-13以及CTF-133优化后的晶体结构

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

图3. CTF-1、CTF-2、CTF-13以及CTF-133位错行为过程的总能量以及自由能变化

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

图4. (a~d)于Z=0.5c下的XY平面内的CTF-1、CTF-2、CTF-13以及CTF-133的π电子密度分布; (e~h)于Z=0.5c下的XY平面内的CTF-1、CTF-2、CTF-13以及CTF-133的π电子定域函数

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

图5. (a~d)于Z=c下XY平面内的CTF-1、CTF-2、CTF-13以及CTF-133的π电子定域函数; 层间位错分别为10% (e)以及30% (f)时CTF-1在Z=c下XY平面内的π电子定域函数

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

图6. (a) CTF-1、CTF-2、CTF-13以及CTF-133的各个原子的π布居数分布; (b) CBF的优化晶体结构; (c) CTF-1以及CBF位错行为过程的总能量以及自由能变化

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

图7. (a) CTF-1 AA堆积的结构图; (b, c) CTF-1 AA堆积在XY平面内Z=0及XY平面内Z=c时的π电子定域函数; (d) CTF-1 AB堆积的结构图; (e, f) CTF-1 AB堆积在XY平面内Z=0及XY平面内Z=c时的π电子定域函数

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

图8. (a)不同位错行为下的CTF-1的能级图; (b)沿堆积方向上的CTF-1的能级图

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

图9. 不同位错行为下的CTF-1的态密度

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

表1. 不同位错行为下层间CTF-1光生载流子的有效质量

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

表2. 不同位错行为下CTF-1层内光生载流子的有效质量以及光生载流子迁移率

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

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