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

doi:10.15541/jim20240143

Abstract

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

CLC Number:

TB332
O242

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.

Figures/Tables 11

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]

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

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

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

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

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

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

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

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

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

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

References 31

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

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