DFT study of adsorption of H2S on N-doped Stone-Wales defected graphene

doi:10.11949/0438-1157.20210215

Abstract

Abstract:

Density functional theory is used to study the adsorption behavior of H₂S molecules on nitrogen-doped Stone-Wales (SW) defected graphene. The adsorption differences of H₂S molecules on SW defect graphene and nitrogen-doped SW defected graphene were analyzed by adsorption energy, differential charge density, Bader charge and electronic density of states. Computation results showed that doping of N atom can improve the interaction between H₂S molecule and graphene sheet effectively, and it can increase the charge transfer between them. The nitrogen atom is mainly used as the bridge for electron transfer between H₂S and graphene surface. H₂S molecules were adsorbed selectively on the hollow of pentatomic carbon of SW defected graphene and nitrogen-doped SW defected graphene, which indicated that the charge distribution of the pentatomic carbon could promote the occurrence of adsorption.

Key words: density functional theory (DFT), N-doped, Stone-Wales defect, graphene, H₂S adsorption

摘要：

利用密度泛函理论研究H₂S分子在氮掺杂Stone-Wales（SW）缺陷石墨烯上的吸附行为，通过吸附能、差分电荷密度、Bader电荷和电子态密度等分析了H₂S分子在SW缺陷石墨烯及氮掺杂SW缺陷石墨烯上的吸附差异。计算结果表明氮原子掺杂可以有效提升H₂S分子与石墨烯表面的相互作用，并加强二者之间的电荷转移。其中，氮原子主要作为电子传递的桥梁参与H₂S与石墨烯表面之间的电荷转移。H₂S分子被选择性吸附在SW缺陷及氮掺杂SW缺陷石墨烯的五元碳环中心处，这说明五元碳环的电荷分布促进H₂S分子的吸附行为。

关键词: 密度泛函理论, 氮掺杂, Stone-Wales缺陷, 石墨烯, H₂S吸附

CLC Number:

X 511

Shenggui MA, Bowen TIAN, Yuwei ZHOU, Lin CHEN, Xia JIANG, Tao GAO. DFT study of adsorption of H₂S on N-doped Stone-Wales defected graphene[J]. CIESC Journal, 2021, 72(9): 4496-4503.

马生贵, 田博文, 周雨薇, 陈琳, 江霞, 高涛. 氮掺杂Stone-Wales缺陷石墨烯吸附H₂S的密度泛函理论研究[J]. 化工学报, 2021, 72(9): 4496-4503.

Figures/Tables 13

Fig.1 The energy convergence test: (a) k-points; (b) kinetic energy cutoff

Fig.2 The top view optimized geometric structures of SW defected graphene (Top, Bridge, Hollow-5 and Hollow-7 are the adsorption sites of H2S, number 1—5 are the doping sites of N atom)

Table 1 Adsorption energies of H2S molecules adsorbed on the SW defected graphene

H₂S分子初始构型的几何方向	吸附位点	吸附能/eV
H-S键平行于石墨烯表面	Top	-0.40
	Hollow-5	-0.15
	Hollow-7	-0.14
	Bridge	-0.17
硫原子朝向石墨烯	Top	-0.35
	Hollow-5	-0.51
	Hollow-7	-0.13
	Bridge	-0.35
氢原子朝向石墨烯	Top	-0.15
	Hollow-5	-0.16
	Hollow-7	-0.15
	Bridge	-0.14

Fig.3 The most stable structures of H2S molecules adsorbed on the SW defected graphene at three adsorption sites: (a) side and top view of the adsorption structure at Top site; (b) side and top view of the adsorption structure at Hollow-5 site; (c) side and top view of the adsorption structure at Bridge site

Fig.4 Charge density (a) and deformation charge density (b) of the S-Hollow-5 adsorption system (values of absolute isosurface:0.0001)

Table 2 Bader atomic charges of the S-Hollow-5 adsorption system

原子	序号	吸附前电荷量/e	吸附后电荷量/e	转移电荷量/e
C	1	+0.005	+0.022	+0.017
	2	-0.079	-0.012	+0.067
	3	-0.038	-0.040	-0.002
	4	+0.180	+0.046	-0.134
	5	+0.042	-0.071	-0.113
S	—	—	+0.049	+0.049
H	1	—	-0.010	-0.010
	2	—	-0.021	-0.021

Fig.5 The DOS of S-Hollow-5 adsorption system, the LDOS of graphene sheet and the LDOS of H2S molecule

Table 3 Formation energies of N doped SW defected graphene

氮掺杂位点	E_f /eV
1	2.94
2	3.14
3	3.93
4	3.75
5	2.72

Fig.6 The stable structures of three adsorption systems of H2S molecules adsorbed on the N doped SW defected graphene: (a) side and top view of the adsorption structure of S-H system; (b) side and top view of the adsorption structure of S-T system; (c) side and top view of the adsorption structure of H-H system

Table 4 Adsorption energies of H2S molecules adsorbed on the N doped SW defected graphene

吸附构型	E_ads/eV
S-T	-0.60
S-H	-0.56
H-H	-0.65

Fig.7 Charge density (a) and deformation charge density (b) of the H-H adsorption system (values of absolute isosurface:0.0001)

Table 5 Bader atomic charges of the H-H adsorption system

原子	序号	吸附前电荷量/e	吸附后电荷量/e	转移电荷量/e
C	1	+0.512	+0.512	0
	2	+0.339	+0.339	0
	3	-0.101	-0.105	-0.004
	4	+0.015	+0.006	-0.009
N	—	-1.283	-1.283	0
S	—	—	-0.076	-0.076
H	1	—	+0.053	+0.053
H	2	—	+0.051	+0.051

Fig.8 The DOS of H-H adsorption system, the LDOS of graphene sheet and the LDOS of H2S molecule

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DFT study of adsorption of H₂S on N-doped Stone-Wales defected graphene

氮掺杂Stone-Wales缺陷石墨烯吸附H₂S的密度泛函理论研究

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