氮掺杂Stone-Wales缺陷石墨烯吸附H2S的密度泛函理论研究

doi:10.11949/0438-1157.20210215

化工学报 ›› 2021, Vol. 72 ›› Issue (9): 4496-4503.DOI: 10.11949/0438-1157.20210215

氮掺杂Stone-Wales缺陷石墨烯吸附H₂S的密度泛函理论研究

马生贵^1,^2,³(),田博文¹,周雨薇¹,陈琳¹,江霞^1,^2,³(),高涛⁴

^1.四川大学建筑与环境学院，四川成都 610065
^2.国家烟气脱硫工程技术研究中心，四川成都 610065
^3.四川大学宜宾园区，四川宜宾 644000
^4.四川大学原子与分子物理研究所，四川成都 610065

收稿日期:2021-02-04 修回日期:2021-05-11 出版日期:2021-09-05 发布日期:2021-09-05
通讯作者: 江霞
作者简介:马生贵(1990—)，男，博士，助理研究员，masgui@scu.edu.cn
基金资助:
国家自然科学基金面上项目(51778383);四川大学-泸州市校市战略合作项目(2020CDLZ-15);大气污染源头控制与资源化四川省青年科技创新研究团队(2020JDTD0005)

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

Shenggui MA^1,^2,³(),Bowen TIAN¹,Yuwei ZHOU¹,Lin CHEN¹,Xia JIANG^1,^2,³(),Tao GAO⁴

^1.College of Architecture and Environment, Sichuan University, Chengdu 610065, Sichuan, China
^2.National Engineering Research Center for Flue Gas Desulfurization, Sichuan University, Chengdu 610065, Sichuan, China
^3.Sichuan University Yibin Park, Yibin 644000, Sichuan, China
^4.Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, Sichuan, China

Received:2021-02-04 Revised:2021-05-11 Online:2021-09-05 Published:2021-09-05
Contact: Xia JIANG

摘要/Abstract

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

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

中图分类号:

X 511

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.

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.

图/表 13

图1 能量收敛性测试：(a) k点；(b) 截断能

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

图2 SW缺陷石墨烯几何优化构型俯视图(Top、Bridge、Hollow-5和Hollow-7指H2S分子的吸附位点，数字1~5指氮原子的掺杂位点)

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)

表1 SW缺陷石墨烯吸附H2S分子的吸附能

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

图3 H2S分子在SW缺陷石墨烯的三种吸附位点上的最稳定构型：(a) Top位点上吸附构型的侧视图和俯视图；(b) Hollow-5位点上吸附构型的侧视图和俯视图；(c) Bridge位点上吸附构型的侧视图和俯视图

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

图4 S-Hollow-5吸附体系的电荷密度(a)和差分电荷密度图(b)(等值面值：0.0001)

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

表2 S-Hollow-5吸附体系的Bader电荷

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

图5 S-Hollow-5吸附体系的态密度、石墨烯表面的局域态密度和H2S分子的局域态密度

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

表3 氮掺杂SW缺陷石墨烯的形成能

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

图6 H2S分子在氮掺杂SW缺陷石墨烯上的三种吸附体系的稳定构型：(a) S-H体系吸附构型的侧视图和俯视图；(b) S-T体系吸附构型的侧视图和俯视图；(c) H-H体系吸附构型的侧视图和俯视图

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

表4 氮掺杂SW缺陷石墨烯吸附H2S分子的吸附能

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

图7 H-H吸附体系的电荷密度(a)和差分电荷密度图(b) (等值面值：0.0001)

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

表5 H-H吸附体系的Bader电荷

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

图8 H-H吸附体系的态密度、石墨烯表面的局域态密度和H2S分子的局域态密度

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

参考文献 30

1	谢乐, 蒋崇文. 生物滴滤塔去除高浓度H₂S废气的模拟研究[J]. 化工学报, 2021, 72(8): 4346-4353.
	Xie L, Jiang C W. Simulation study on the removal of high concentration H₂S waste gas by biotrickling filter[J]. CIESC Journal, 2021, 72(8): 4346-4353.
2	张敏, 李涛, 陈曙旸, 等. 我国硫化氢中毒的特点与控制对策[J]. 工业卫生与职业病, 2005, 31(1): 12-14.
	Zhang M, Li T, Chen S Y, et al. Characteristics and control measures of hydrogen sulfide poisoning in China [J]. Industrial Health and Occupational Diseases, 2005, 31(1): 12-14.
3	杨嫱, 董小刚, 贺雪红, 等. 油田硫化氢腐蚀原因及防护措施[J]. 化工设计通讯, 2019, 45(8): 45-46.
	Yang Q, Dong X G, He X H, et al. Causes and protective measures of hydrogen sulfide in oil fields[J]. Chemical Engineering Design Communications, 2019, 45(8): 45-46.
4	杨振宇. 关于硫化氢废气处理新方法研究[J]. 节能与环保, 2019 (7): 75-77.
	Yang Z Y. Study on new treatment method of hydrogen sulfide waste gas[J]. Energy Conservation & Environmental Protection,2019 (7): 75-77.
5	Bagreev A, Bandosz T J. H₂S adsorption/oxidation on unmodified activated carbons: importance of prehumidification[J]. Carbon, 2001, 39(15): 2303-2311.
6	Adib F, Bagreev A, Bandosz T J. Adsorption/oxidation of hydrogen sulfide on nitrogen-containing activated carbons[J]. Langmuir, 2000, 16(4): 1980-1986.
7	Yang W J, Gao Z Y, Liu X S, et al. Single-atom iron catalyst with single-vacancy graphene-based substrate as a novel catalyst for NO oxidation: a theoretical study[J]. Catalysis Science & Technology, 2018, 8(16): 4159-4168.
8	Tetlow H, Posthuma de Boer J, Ford I J, et al. Growth of epitaxial graphene: theory and experiment[J]. Physics Reports, 2014, 542(3): 195-295.
9	张慧娟. SO₂和NO在石墨烯氧化物上吸附氧化的第一性原理研究[D]. 昆明: 昆明理工大学, 2015.
	Zhang H J. A first principles study of adsorption and oxidation of SO₂ and NO by graphene oxides[D]. Kunming: Kunming University of Science and Technology, 2015.
10	Zhou Q X, Fu Z B, Tang Y J, et al. First-principle study of the transition-metal adatoms on B-doped vacancy-defected graphene[J]. Physica E: Low-Dimensional Systems and Nanostructures, 2014, 60: 133-138.
11	Ye X, Ma S G, Jiang X, et al. The adsorption of acidic gaseous pollutants on metal and nonmetallic surface studied by first-principles calculation: a review[J]. Chinese Chemical Letters, 2019, 30(12): 2123-2131.
12	Gao Z Y, Yang W J, Ding X L, et al. Support effects on adsorption and catalytic activation of O₂ in single atom iron catalysts with graphene-based substrates[J]. Physical Chemistry Chemical Physics: PCCP, 2018, 20(10): 7333-7341.
13	Hohenberg P, Kohn W. Inhomogeneous electron gas[J]. Physical Review, 1964, 136(3B): b864.
14	Mineva T, Krishnamurty S, Salahub D R, et al. Temperature dependence of the molecular conformations of dilauroyl phosphatidylcholine: a density functional study[J]. International Journal of Quantum Chemistry, 2013, 113(5): 631-636.
15	Sham L J, Kohn W. One-particle properties of an inhomogeneous interacting electron gas[J]. Physical Review, 1966, 145(2): 561.
16	Leenaerts O, Partoens B, Peeters F M. Adsorption of H₂O, NH₃, CO, NO₂, and NO on graphene: a first-principles study[J]. Physical Review B, 2008, 77(12): 125416.
17	Lazar P, Karlický F, Jurečka P, et al. Adsorption of small organic molecules on graphene[J]. Journal of the American Chemical Society, 2013, 135(16): 6372-6377.
18	Ambrusi R E, Luna C R, Juan A, et al. DFT study of Rh-decorated pristine, B-doped and vacancy defected graphene for hydrogen adsorption[J]. RSC Advances, 2016, 6(87): 83926-83941.
19	Yang W J, Gao Z Y, Liu X S, et al. Directly catalytic reduction of NO without NH₃ by single atom iron catalyst: a DFT calculation[J]. Fuel, 2019, 243: 262-270.
20	Zhou Q X, Wang C Y, Fu Z B, et al. Adsorption of formaldehyde molecule on Stone-Wales defected graphene doped with Cr, Mn, and Co: a theoretical study[J]. Computational Materials Science, 2014, 83: 398-402.
21	刘笑涵. 石墨烯气体传感器吸附CO和CO₂性能研究[D]. 西安: 西安电子科技大学, 2019.
	Liu X H. Study for adsorption of CO and CO₂ on graphene gas sensor[D]. Xi'an: Xidian University, 2019.
22	Dai J Y, Yuan J M, Giannozzi P. Gas adsorption on graphene doped with B, N, Al, and S: a theoretical study[J]. Applied Physics Letters, 2009, 95(23): 232105.
23	Jia X T, Zhang H, Zhang Z M, et al. Effect of doping and vacancy defects on the adsorption of CO on graphene[J]. Materials Chemistry and Physics, 2020, 249: 123114.
24	Kresse G, Furthmüller J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set[J]. Computational Materials Science, 1996, 6(1): 15-50.
25	Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set[J]. Physical Review. B, Condensed Matter, 1996, 54(16): 11169-11186.
26	Kresse G, Hafner J. Ab initio molecular dynamics for open-shell transition metals[J]. Physical Review. B, Condensed Matter, 1993, 48(17): 13115-13118.
27	Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple[J]. Physical Review Letters, 1996, 77(18): 3865-3868.
28	Kresse G, Joubert D. From ultrasoft pseudopotentials to the projector augmented-wave method[J]. Physical Review B, 1999, 59(3): 1758.
29	Goerigk L, Grimme S. A thorough benchmark of density functional methods for general main group thermochemistry, kinetics, and noncovalent interactions[J]. Physical Chemistry Chemical Physics, 2011, 13(14): 6670-6688.
30	Zhang H P, Luo X G, Song H T, et al. DFT study of adsorption and dissociation behavior of H₂S on Fe-doped graphene[J]. Applied Surface Science, 2014, 317: 511-516.

编辑推荐 0

Metrics

阅读次数

全文

1008

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
1	0	28	20	0	959

来源	本网站	其他网站

次数	230	778
比例	23%	77%

摘要

589

最新录用	在线预览	正式出版

23	0	566

来源	本网站	其他网站

次数	415	174
比例	70%	30%

[1]	葛加丽, 管图祥, 邱新民, 吴健, 沈丽明, 暴宁钟. 垂直多孔碳包覆的FeF₃正极的构筑及储锂性能研究[J]. 化工学报, 2023, 74(7): 3058-3067.
[2]	顾浩, 张福建, 刘珍, 周文轩, 张鹏, 张忠强. 力电耦合作用下多孔石墨烯膜时间维度的脱盐性能及机理研究[J]. 化工学报, 2023, 74(5): 2067-2074.
[3]	党迎喜, 谈朋, 刘晓勤, 孙林兵. 辐射冷却和太阳能加热驱动的CO₂变温捕获[J]. 化工学报, 2023, 74(1): 469-478.
[4]	余后川, 任腾, 张宁, 姜晓滨, 代岩, 张晓鹏, 鲍军江, 贺高红. 二维氧化石墨烯膜离子选择性传递调控的研究进展[J]. 化工学报, 2023, 74(1): 303-312.
[5]	杜峰, 尹思琦, 罗辉, 邓文安, 李传, 黄振薇, 王文静. H₂在Mo _x S _y 团簇上吸附解离的尺寸效应研究[J]. 化工学报, 2022, 73(9): 3895-3903.
[6]	俞夏琪, 冯格, 赵金燕, 李嘉远, 邓声威, 郑靖楠, 李雯雯, 王亚秋, 沈榄, 刘旭, 徐威威, 王建国, 王式彬, 姚子豪, 毛成立. 基体（TDI-TMP-T313）与氧化剂（AP）相互作用的第一性原理研究[J]. 化工学报, 2022, 73(8): 3511-3517.
[7]	黄凯, 王思洁, 苏海萍, 练成, 刘洪来. 石墨烯层间距调控抑制锂枝晶生长的第一性原理研究[J]. 化工学报, 2022, 73(8): 3501-3510.
[8]	韩双, 张楠, 王慧, 张璇, 杨金栾, 张蔓琳, 张志超. 金霉素分子印迹电化学传感器的制备与应用[J]. 化工学报, 2022, 73(8): 3758-3767.
[9]	赵继昊, 唐伟强, 徐小飞, 赵双良, 贺炅皓. 高分子复合材料中键合剂在不同纳米填料表面的吸附能计算[J]. 化工学报, 2022, 73(7): 3174-3181.
[10]	刘洪超, 陈苏航, 段先力, 吴凡, 徐小飞, 宋先雨, 赵双良, 刘洪来. Janus石墨烯量子点在生物膜中的输运行为：分子动力学模拟[J]. 化工学报, 2022, 73(7): 2835-2843.
[11]	李智超, 郑瑜, 张润楠, 姜忠义. 高通量抗污染氧化石墨烯膜研究进展[J]. 化工学报, 2022, 73(6): 2370-2380.
[12]	张苗, 杨洪海, 尹勇, 徐悦, 沈俊杰, 卢心诚, 施伟刚, 王军. 氧化石墨烯/水脉动热管的启动及传热特性[J]. 化工学报, 2022, 73(3): 1136-1146.
[13]	陈雪梅, 王彤, 高玉箔, 彭鼎程, 罗雨婷. 利用激光诱导石墨烯实现高效太阳能界面蒸发[J]. 化工学报, 2022, 73(12): 5648-5659.
[14]	罗小松, 黄金保, 周梅, 牟鑫, 徐伟伟, 吴雷. 对苯二甲酸丁二醇酯二聚体水/醇/氨解机理的理论研究[J]. 化工学报, 2022, 73(11): 4859-4871.
[15]	徐欢, 柯律, 张生辉, 张子林, 韩广东, 崔金声, 唐道远, 黄东辉, 高杰峰, 何新建. GO表面原位生长CNTs改善聚丙烯导热复合材料分散与界面形态[J]. 化工学报, 2022, 73(11): 5150-5157.

氮掺杂Stone-Wales缺陷石墨烯吸附H₂S的密度泛函理论研究

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 30

相关文章 15

编辑推荐 0

Metrics

本文评价