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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:
- first-principles calculation /
- graphene oxide /
- catalytic
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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.
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).
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).
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.
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
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[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 物理学报 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 物理学报 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 物理学报 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 物理学报 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 物理学报 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 物理学报 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 物理学报 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 物理学报 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 物理学报 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 物理学报 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 物理学报 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 物理学报 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 物理学报 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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