First-principles study on structural stability of graphene oxide and catalytic activity of nitric acid

Lin Qi-Min; Zhang Xia; Lu Qi-Chao; Luo Yan-Bin; Cui Jian-Gong; Yan Xin; Ren Xiao-Min; Huang Xue

doi:10.7498/aps.68.20191304

Abstract

The stability and electronic structure properties of graphene fumigated by nitric acid are systematically studied by the first-principles method based on ultrasoft pseudopotentials. The model of graphene oxide fumigated by nitric acid is built based on the 2 × 2 supercell model with orthogonal graphene unit cells, which contains 15 carbon and 2 oxygen atoms. The results show that the fumigated graphene containing a carbon atom bonded to an oxygen atom is a stable structure with lower energy, which is consistent with the experimental result. In addition, the mechanical stability analysis shows ${ {C_{66}} > 0,\;{C_{11}} > 0,\;{C_{11}}{C_{22}} > C_{12}^2} $, which satisfies the mechanical stability condition. By analyzing the reactant and product, it can be concluded that the nitric acid acts as catalyst. Moreover, the process of graphene oxidation catalyzed by nitric acid is endothermic and the reaction needs heating. By analyzing the electronic properties of the structure, the graphene oxide is determined to be an intrinsic semiconductor with a direct band gap of 1.12 eV and work function of 5.28 eV. These results provide theoretical basis for preparing the graphene oxide and its applications in the field of optoelectronic devices.

Keywords:

Authors and contacts

1.
State Key Laboratory of Information Photonics and Optical Communications, Beijing University of Posts and Telecommunications, Beijing 100876, China
2.
State Key Laboratory of Dynamic Testing Technology, North University of China, Taiyuan 030051, China
3.
Beijing Computing Center, Beijing 100094, China

Corresponding author: Zhang Xia, xzhang@bupt.edu.cn ; Cui Jian-Gong, jgcui@nuc.edu.cn ;

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 61774021, 61911530133, 61935003), the Fundamental Research Business Expenses of Central Universities, China (Grant No. 2018XKJC05), the Natural Science Foundation of Shanxi Province, China (Grant No. 201801D221198), and the Fund of State Key Laboratory of Information Photonics and Optical Communications (Beijing University of Posts and Telecommunications), China (Grant No. IPOC2019ZT07)

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References

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图 1 替位与吸附位组成的石墨烯结构　(a)石墨烯结构; (b)吸附位结构; (c), (d)在同一模型中一个氧原子替换和一个氧原子吸附近邻碳原子结构; (e), (f)在同一结构中一个氧原子替换和一个氧原子吸附不相邻碳原子结构

Figure 1. Graphene structures with substitutional and adsorbed oxygen: (a) Pure graphene; (b) adsorbed oxygen; (c), (d) substitutional and adsorbed oxygen between adjacent carbon; (e), (f) substitutional and adsorbed oxygen between nonadjacent carbon.

DownLoad: Full-Size Img PowerPoint

图 2 电荷密度图　(a)结构c及其电荷密度的俯视图; (b)结构c绕y轴转角50°的电荷密度图(黄色是电荷分布, 蓝色是其周期边界剖面)

Figure 2. Charge density of structure c: (a) Top view; (b) rotation 50 degrees around the y axis (yellow represents the charge distribution and blue represents the periodic boundary profile).

DownLoad: Full-Size Img PowerPoint

图 3 包含碳氧双键的氧化石墨烯能带结构图(图中红色虚线代表费米能级)

Figure 3. Band structures of the graphene oxide with carbon oxygen double bond (red dashed line represents the Fermi level).

DownLoad: Full-Size Img PowerPoint

图 4 石墨烯氧化前后沿z轴方向的势能分布图　(a)石墨烯势能分布图; (b)氧化石墨烯势能分布图

Figure 4. Potential energy along the z-axis: (a) Graphene; (b) gra-phene oxide.

DownLoad: Full-Size Img PowerPoint

表 1 结构总能和碳氧原子键长

Table 1. Total energy of structures and the bond length of carbon and oxygen.

	结构c		结构d		结构e		结构f
总能/eV	–0.58		–0.65		2.30		3.09
	替位	吸附位	替位	吸附位	替位	吸附位	替位	吸附位
碳氧键长/Å	1.38	1.24	1.38	1.24	1.46	1.38	1.46	1.38
碳氧键数量	2	1	2	1	3	1	3	1
注: 以纯净石墨烯结构的总能作为能量零点.

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表 2 结构a, c, d的弹性常数

Table 2. The elastic constants of structures a, c and d.

	C₁₁/N·m^–1	C₂₂/N·m^–1	C₁₂/N·m^–1	C₆₆/N·m^–1
结构a	2445.1	2438.7	441.9	0.939
结构c	1607.5	958.7	163.9	0.986
结构d	975.8	1295.3	463.5	–266.9

DownLoad: CSV

map

[1]	Novoselov K S, Geim A K, Morozov S V, Jiang D, Zhang Y, Dubonos S V, Grigorieva I V, Firsov A A 2004 Science 306 666 Google Scholar
[2]	池明赫, 赵磊 2018 67 217101 Google Scholar Chi M H, Zhao L 2018 Acta Phys. Sin. 67 217101 Google Scholar
[3]	刘贵立, 杨忠华 2018 67 076301 Google Scholar Liu G L, Yang Z H 2018 Acta Phys. Sin. 67 076301 Google Scholar
[4]	刘乐, 汤建, 王琴琴, 时东霞, 张广宇 2018 67 226501 Google Scholar Liu L, Tang J, Wang Q Q, Shi D X, Zhang G Y 2018 Acta Phys. Sin. 67 226501 Google Scholar
[5]	蒲晓庆, 吴静, 郭强, 蔡建臻 2018 67 217301 Google Scholar Pu X Q, Wu J, Guo Q, Cai J Z 2018 Acta Phys. Sin. 67 217301 Google Scholar
[6]	王建军, 王飞, 原鹏飞, 孙强, 贾瑜 2012 61 106801 Google Scholar Wang J J, Wang F, Yuan P F, Sun Q, Jia Y 2012 Acta Phys. Sin. 61 106801 Google Scholar
[7]	王逸飞, 李晓薇 2018 67 116301 Google Scholar Wang Y F, Li X W 2018 Acta Phys. Sin. 67 116301 Google Scholar
[8]	张晓波, 青芳竹, 李雪松 2019 68 096801 Google Scholar Zhang X B, Qing F Z, Li X S 2019 Acta Phys. Sin. 68 096801 Google Scholar
[9]	Hsieh Y P, Hofmann M, Chang K W, Jhu J G, Li Y Y, Chen K Y, Yang C C, Chang W S, Chen L C 2014 ACS Nano 8 443 Google Scholar
[10]	Bae S, Kim H, Lee Y, Xu X, Park J S, Zheng Y, Balakrishnan J, Lei T, Kim H R, Song Y I, Kim Y J, Kim K S, Ozyilmaz B, Ahn J H, Hong B H, Iijima S 2010 Nat. Nanotechnol. 5 574 Google Scholar
[11]	Yang H, Wu X, Ma Q, Yilihamu A, Yang S N, Zhang Q Q, Feng S C, Yang S 2019 Chemosphere 216 9 Google Scholar
[12]	Luo D, Zhang F H, Ren Z S, Ren W Y, Yu L, Jiang L L, Ren B S, Wang L, Wang Z M, Yu Y, Zhang Q Y, Ren Z F 2019 Mater. Today Phys. 9 100097 Google Scholar
[13]	莫佳伟, 裘银伟, 伊若冰, 吴俊, 王志坤, 赵丽华 2019 68 156501 Google Scholar Mo J W, Qiu Y W, Yi R B, Wu J, Wang Z K, Zhao L H 2019 Acta Phys. Sin. 68 156501 Google Scholar
[14]	李闯, 蔡理, 李伟伟, 谢丹, 刘保军, 向兰, 杨晓阔, 董丹娜, 刘嘉豪, 李成, 危波 2019 68 118102 Google Scholar Li C, Cai L, Li W W, Xie D, Liu B J, Xiang L, Yang X K, Dong D N, Liu J H, Li C, Wei B 2019 Acta Phys. Sin. 68 118102 Google Scholar
[15]	Yan J A, Xian L, Chou M Y 2009 Phys. Rev. Lett. 103 086802 Google Scholar
[16]	Cai W W, Piner R D, Stadermann F J, Park S, Shaibat M A, Ishii Y, Yang D X, Velamakanni A, An S J, Stoller M, An J, Chen D M, Ruoff R S 2008 Science 321 1815 Google Scholar
[17]	张勇, 施毅敏, 包优赈, 喻霞, 谢忠祥, 宁锋 2017 66 197302 Google Scholar Zhang Y, Shi Y M, Bao Y Z, Yu X, Xie Z X, Ning F 2017 Acta Phys. Sin. 66 197302 Google Scholar
[18]	Yi W C, Hu T, Su T, Islam R, Miao M S, Liu J Y 2017 J. Mater. Chem. C 5 8498 Google Scholar
[19]	张梅玲, 陈玉红, 张材荣, 李公平 2019 68 087101 Google Scholar Zhang M L, Chen Y H, Zhang C R, Li G P 2019 Acta Phys. Sin. 68 087101 Google Scholar
[20]	房彩红, 尚家香, 刘增辉 2012 61 047101 Google Scholar Fang C H, Shang J X, Liu Z H 2012 Acta Phys. Sin. 61 047101 Google Scholar
[21]	杜玉杰, 常本康, 张俊举, 李飙, 王晓晖 2012 61 067101 Google Scholar Du Y J, Chang B K, Zhang J J, Li B, Wang X H 2012 Acta Phys. Sin. 61 067101 Google Scholar

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