聚苯胺改性Ti3C2(OH)2抗氧化性的第一性原理计算研究

doi:10.15541/jim20240143

无机材料学报 ›› 2024, Vol. 39 ›› Issue (10): 1151-1158.DOI: 10.15541/jim20240143 CSTR: 32189.14.10.15541/jim20240143

所属专题：【信息功能】MAX层状材料、MXene及其他二维材料(202409)

聚苯胺改性Ti₃C₂(OH)₂抗氧化性的第一性原理计算研究

周云凯¹^,²(), 刁亚琪¹^,³, 王明磊¹^,³, 张宴会¹^,³(), 王利民¹^,³

1.燕山大学亚稳材料制备科学与技术重点实验室先进结构材料中心, 秦皇岛 066004
2.河北科技师范学院研究生部, 秦皇岛 066004
3.燕山大学材料科学与工程学院, 秦皇岛 066004

收稿日期:2024-03-25 修回日期:2024-05-29 出版日期:2024-10-20 网络出版日期:2024-10-09
通讯作者: 张宴会, 讲师. E-mail: yhzhang@ysu.edu.cn
作者简介:周云凯(1986-), 男, 助理研究员. E-mail: zhouyunkai1986@hotmail.com
基金资助:
河北省高等学校科学技术研究项目(QN2023255);燕山大学校内培育项目(2022LGZD007);亚稳材料制备技术与科学国家重点实验室(燕山大学)开放课题(202413)

First-principles Calculation Study of the Oxidation Resistance of PANI Modified Ti₃C₂(OH)₂

ZHOU Yunkai¹^,²(), DIAO Yaqi¹^,³, WANG Minglei¹^,³, ZHANG Yanhui¹^,³(), WANG Limin¹^,³

1. Center for Advanced Structural Materials, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, China
2. Department of Graduates, Hebei Normal University of Science & Technology, Qinhuangdao 066004, China
3. School of Materials Science and Technology, Yanshan University, Qinhuangdao 066004, China

Received:2024-03-25 Revised:2024-05-29 Published:2024-10-20 Online:2024-10-09
Contact: ZHANG Yanhui, lecturer. E-mail: yhzhang@ysu.edu.cn
About author:ZHOU Yunkai (1986-), male, lecturer. E-mail: zhouyunkai1986@hotmail.com
Supported by:
Science and Technology Project of Hebei Education Department(QN2023255);Internal Funds of Yanshan University(2022LGZD007);Opening Project of State Key Laboratory of Metastable Materials Science and Technology (Yanshan University)(202413)

摘要/Abstract

摘要：

Ti₃C₂(OH)₂的抗氧化性和结构稳定性不佳极大地限制了其实际应用推广。本工作通过第一性原理计算方法, 对比研究了Ti₃C₂(OH)₂、聚苯胺(PANI)和PANI/Ti₃C₂(OH)₂复合材料的表面氧吸附行为。计算结果表明, Ti₃C₂基体上-OH官能团改变了活性吸附位点, 并一定程度上改善了Ti₃C₂基体的抗氧化性和结构稳定性。Ti₃C₂(OH)₂与PANI复合后, 表面PANI的氧吸附活性较高, 而Ti₃C₂(OH)₂的氧吸附能大幅度降低。经Bader电荷计算发现, 复合后从PANI端到Ti₃C₂(OH)₂发生了电子转移, 从而保护了后者。因此, PANI改性Ti₃C₂(OH)₂复合材料可以通过牺牲表面PANI来保护Ti₃C₂(OH)₂基体, 进而提高其结构稳定性和抗氧化性能。本工作对于提高MXene体系抗氧化性能、结构和电化学稳定性具有一定的理论指导意义。

关键词: MXene, 结构稳定性, 抗氧化性, PANI修饰, 第一性原理计算

Abstract:

The poor oxidation resistance and structural stability of Ti₃C₂(OH)₂ largely limit its wide applications. In this work, the surface adsorption behaviors of oxygen atoms on Ti₃C₂(OH)₂, polyaniline (PANI) and PANI/Ti₃C₂(OH)₂ composite were systematically studied and compared by first-principles calculation method. The simulation results suggest that the existence of -OH functional group can change the active sites on Ti₃C₂ matrix. Thereby the oxidation resistance and the structural stability of Ti₃C₂ matrix can be improved in some extent. Furthermore, after modifying Ti₃C₂(OH)₂ by PANI, the adsorption activity of PANI is much larger. Meanwhile, the adsorption energy of oxygen on the Ti₃C₂(OH)₂ end is significantly decreased, which is caused by the electron transfer from PANI to Ti₃C₂(OH)₂, as confirmed by the Bader charge calculation. Therefore, the oxidation resistance and the structural stability of the PANI modified Ti₃C₂(OH)₂ composite are improved by sacrificing PANI, since oxygen prefers to adsorb and attack PANI firstly. This work provides theoretical guidelines for the improvement of oxidation resistance, structural and chemical stability of MXene.

Key words: MXene, structural stability, oxidation resistance, PANI modification, first-principles calculation

中图分类号:

TB332
O242

周云凯, 刁亚琪, 王明磊, 张宴会, 王利民. 聚苯胺改性Ti₃C₂(OH)₂抗氧化性的第一性原理计算研究[J]. 无机材料学报, 2024, 39(10): 1151-1158.

ZHOU Yunkai, DIAO Yaqi, WANG Minglei, ZHANG Yanhui, WANG Limin. First-principles Calculation Study of the Oxidation Resistance of PANI Modified Ti₃C₂(OH)₂[J]. Journal of Inorganic Materials, 2024, 39(10): 1151-1158.

图/表 11

表1 Ti3C2、Ti3C2(OH)2和Ti3C2O2单胞晶胞参数和Ti-C键长

Table 1 Lattice parameters and Ti-C bond lengths in Ti3C2, Ti3C2(OH)2 and Ti3C2O2

System	a/Å	d_Ti1-C/Å	d_Ti2-C/Å
Ti₃C₂	3.10^[TW], 3.06^[30], 3.10^[31]	2.14^[TW], 2.22^[30], 2.22^[31]	2.09^[TW], 2.05^[30], 2.05^[31]
Ti₃C₂(OH)₂	3.08^[TW], 3.09^[31], 3.09^[31], 3.11^[31]	2.18^[TW], 2.21^[31], 2.19^[31], 2.22^[31]	2.08^[TW], 2.08^[31], 2.06^[31], 2.07^[31]
Ti₃C₂O₂	3.04^[TW], 3.09^[31], 3.08^[31], 3.10^[31]	2.23^[TW], 2.20^[31], 2.22^[31]	2.16^[TW], 2.14^[31], 2.05^[31], 2.11^[31]

图1 MXene纳米片层表面构型的原子结构正视和俯视示意图

Fig. 1 Front and top views of the atomic structures of nano-slabs of MXene (a1, a2) Ti3C2; (b1, b2) Ti3C2(OH)2; (c1, c2) Ti3C2O2

图2 全还原式red-PANI(C6H5N1)原子结构的正视图(a)和俯视图(b)

Fig. 2 Front (a) and top (b) views of the atomic structures of red-PANI (C6H5N1)

图3 red-PANI/Ti3C2(OH)2复合材料原子结构的正视图(a)和俯视图(b)

Fig. 3 Front (a) and top (b) views of the atomic structures of red-PANI/Ti3C2(OH)2 composite

图4 纯Ti3C2纳米片层表面的氧吸附位点正视图和俯视图及其吸附能(eV/O)

Fig. 4 Front and top views of the oxygen adsorption sites on Ti3C2 surface and their adsorption energies (a1, a2) TiA, the atop site, (b1, b2) TiB, the bridge site and (c1, c2) TiC, the hollow site of Ti atoms located on the Ti3C2 surface

图5 Ti3C2(OH)2纳米片层表面的氧吸附位点正视图和俯视图及其吸附能(eV/O)

Fig. 5 Front and top views of the oxygen adsorption sites on Ti3C2(OH)2 surface and their adsorption energies (a1, a2) HA, the atop site, (b1, b2) HB, the bridge site and (c1, c2) HC, the hollow site of H atoms located on the Ti3C2(OH)2 surface

图6 Ti3C2O2纳米片层表面的氧吸附位点正视图和俯视图及其吸附能(eV/O)

Fig. 6 Front and top views of the oxygen adsorption sites on Ti3C2O2 surface and their adsorption energies (a1, a2) OA, the atop of -O functional group, (b1, b2) TiA, (c1, c2) TiB, and (d1, d2) TiC, are respectively the atop, the bridge and the hollow of Ti atoms located on the Ti3C2O2 surface

图7 全还原式red-PANI纳米片层表面的氧吸附位点正视图和俯视图及其吸附能(eV/O)

Fig. 7 Front and top views of the oxygen adsorption sites on red-PANI surface and their adsorption energies (a1, a2) NHA, the atop site of -NH, (b1, b2) HA, the atop site of -CH, and (c1, c2) CB, the bridge site of C atoms located on the red-PANI surface

图8 Red-PANI/Ti3C2(OH)2复合材料表面的氧吸附位点正视图和俯视图及其吸附能(eV/O)

Fig. 8 Front and top views of the oxygen adsorption sites on red-PANI/Ti3C2(OH)2 surface and their adsorption energies (a1, a2) HA, the atop site of H atoms, (b1, b2) CB, the bridge site of C atoms located on the red-PANI end surface, and (c1, c2) HC, the hollow site of H atoms located on the Ti3C2(OH)2 end

表2 Ti3C2、Ti3C2(OH)2和Ti3C2O2表面三类氧吸附位点的晶胞参数a(Å)

Table 2 Lattice parameters a (Å) for three kinds of adsorption sites on surfaces of Ti3C2, Ti3C2(OH)2 and Ti3C2O2

Position	Ti_A/H_A/O_A	Ti_B/H_B/O_B	Ti_C/H_C/O_C
@Ti₃C₂	3.10	3.08	3.09
@Ti₃C₂(OH)₂	3.10	3.07	3.11
@Ti₃C₂O₂	3.04	3.04	3.04

表3 Ti3C2(OH)2与PANI复合前后的Bader电荷及复合造成的电荷转移

Table 3 Bader charge of Ti3C2(OH)2 and PANI before and after their combination, together with the electron transfer information

System	Atom label	Before	After	Transfer
PANI	C1	-0.01	-0.02	-0.01
	C2-N	+0.45	+0.44	-0.01
	N	-1.22	-1.23	-0.01
	H1-N	+0.42	+0.42	0
	H2	+0.04	+0.04	0
Ti₃C₂(OH)₂	Ti1(End)	+1.57	+1.50	-0.07
	Ti2(Middle)	+1.44	+1.19	-0.25
	H	+0.55	+0.48	-0.07
	O	-1.23	-1.15	+0.08
	C	-1.62	-1.42	+0.20

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聚苯胺改性Ti₃C₂(OH)₂抗氧化性的第一性原理计算研究

First-principles Calculation Study of the Oxidation Resistance of PANI Modified Ti₃C₂(OH)₂

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