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)

FullText HTML : translate this paragraph

References

[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

Cited By

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.

DownLoad: CSV

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

[1]	Lei Xue-Ling, Zhu Ju-Yong, Ke Qiang, Ouyang Chu-Ying. First-principles study of catalytic mechanism of boron-doped graphene oxide on oxygen evolution reaction of lithium peroxide. Acta Physica Sinica, 2024, 73(9): 098804. doi: 10.7498/aps.73.20240197
[2]	Li Xing-Long, Zhao Hao-Yu, Wu Wen-Jie, Jiang Wei-Feng, Zheng Jia-Jin, Zhang Zu-Xing, Yu Ke-Han, Wei Wei. Graphene oxide modified tilted fiber Bragg grating for 10^–12 level heavy metal ion sensing. Acta Physica Sinica, 2022, 71(5): 050702. doi: 10.7498/aps.71.20211315
[3]	Li Fa-Yun, Yang Zhi-Xiong, Cheng Xue, Zeng Li-Ying, Ouyang Fang-Ping. First-principles study of electronic structure and optical properties of monolayer defective tellurene. Acta Physica Sinica, 2021, 70(16): 166301. doi: 10.7498/aps.70.20210271
[4]	Zhao Wen-Qi, Zhang Dai, Cui Ming-Hui, Du Ying, Zhang Shu-Yu, Ou Qiong-Rong. Graphene modification based on plasma technologies. Acta Physica Sinica, 2021, 70(9): 095208. doi: 10.7498/aps.70.20202078
[5]	Chen Chao, Duan Fang-Li. Effect of functional groups on crumpling behavior and structure of graphene oxide. Acta Physica Sinica, 2020, 69(19): 193102. doi: 10.7498/aps.69.20200651
[6]	Mo Jia-Wei, Qiu Yin-Wei, Yi Ruo-Bing, Wu Jun, Wang Zhi-Kun, Zhao Li-Hua. Temperature-dependent properties of metastable graphene oxide. Acta Physica Sinica, 2019, 68(15): 156501. doi: 10.7498/aps.68.20190670
[7]	Sun Rui, Chen Chen, Ling Wei-Jun, Zhang Ya-Ni, Kang Cui-Ping, Xu Qiang. Watt-level passively Q-switched mode-locked Tm: LuAG laser with graphene oxide saturable absorber. Acta Physica Sinica, 2019, 68(10): 104207. doi: 10.7498/aps.68.20182224
[8]	Hu Jun, Gao Yi. Interfacial water and catalysis. Acta Physica Sinica, 2019, 68(1): 016803. doi: 10.7498/aps.68.20182180
[9]	Sheng Zhe, Dai Xian-Ying, Miao Dong-Ming, Wu Shu-Jing, Zhao Tian-Long, Hao Yue. First-principles study of hydrogen storage properties of silicene under different Li adsorption components. Acta Physica Sinica, 2018, 67(10): 107103. doi: 10.7498/aps.67.20172720
[10]	Qiao Zhi-Xing, Qin Cheng-Bing, He Wen-Jun, Gong Ya-Ni, Xiao Lian-Tuan, Zhang Guo-Feng, Chen Rui-Yun, Gao Yan, Jia Suo-Tang. Lifetime modulation of graphene oxide film by laser direct writing for the fabrication of micropatterns. Acta Physica Sinica, 2018, 67(6): 066802. doi: 10.7498/aps.67.20172331
[11]	Chen Hao, Peng Tong-Jiang, Liu Bo, Sun Hong-Juan, Lei De-Hui. Effect of reduction temperature on structure and hydrogen sensitivity of graphene oxides at room temperature. Acta Physica Sinica, 2017, 66(8): 080701. doi: 10.7498/aps.66.080701
[12]	Yang Guang-Min, Liang Zhi-Cong, Huang Hai-Hua. The first-principle calculation on the Li cluster adsorbed on graphene. Acta Physica Sinica, 2017, 66(5): 057301. doi: 10.7498/aps.66.057301
[13]	Lin Wen-Qiang, Xu Bin, Chen Liang, Zhou Feng, Chen Jun-Lang. Molecular dynamics simulations of the adsorption of bisphenol A on graphene oxide. Acta Physica Sinica, 2016, 65(13): 133102. doi: 10.7498/aps.65.133102
[14]	Cao Hai-Yan, Bi Heng-Chang, Xie Xiao, Su Shi, Sun Li-Tao. Functional tissues based on graphene oxide: facile preparation and dye adsorption properties. Acta Physica Sinica, 2016, 65(14): 146802. doi: 10.7498/aps.65.146802
[15]	Huang Yan-Ping, Yuan Jian-Mei, Guo Gang, Mao Yu-Liang. First-principles study on saturated adsorption of alkali metal atoms on silicene. Acta Physica Sinica, 2015, 64(1): 013101. doi: 10.7498/aps.64.013101
[16]	Xue Bin, Wang Hong-Yang, Qin Meng, Cao Yi, Wang Wei. A photocatalysis system based on composite nanostructures of controlable peptide nanotubes and graphene. Acta Physica Sinica, 2015, 64(9): 098702. doi: 10.7498/aps.64.098702
[17]	Huang Shi-Sheng, Wang Yong-Gang, Li Hui-Quan, Lin Rong-Yong, Yan Pei-Guang. Experimental studies of multiple pulses in a passively ytterbium-doped fiber laser based on graphene-oxide saturable absorber. Acta Physica Sinica, 2014, 63(8): 084202. doi: 10.7498/aps.63.084202
[18]	Lu Jing-Jing, Feng Miao, Zhan Hong-Bing. Preparation of graghene oxide/chitosan composite films and investigations on their nonlinear optical limiting effect. Acta Physica Sinica, 2013, 62(1): 014204. doi: 10.7498/aps.62.014204
[19]	Liu Yuan, Yao Jie, Chen Chi, Miao Ling, Jiang Jian-Jun. First-principles study on the piezoelectric properties of hydrogen modified graphene nanoribbons. Acta Physica Sinica, 2013, 62(6): 063601. doi: 10.7498/aps.62.063601
[20]	Gao Yan, Chen Rui-Yun, Wu Rui-Xiang, Zhang Guo-Feng, Xiao Lian-Tuan, Jia Suo-Tang. Electric field induced polarization dynamics of graphene oxide. Acta Physica Sinica, 2013, 62(23): 233601. doi: 10.7498/aps.62.233601

Catalog

Vol. 68, Issue 24 - 2019-12-20

Metrics

Abstract views: 10385
PDF Downloads: 118
Cited By: 0

姓名
邮箱
手机号码
标题
留言内容
验证码

Search

Article

留言板