DFT方法研究一氧化氮在铬掺杂石墨烯上的吸附行为

doi:10.15541/jim20210078

无机材料学报 ›› 2021, Vol. 36 ›› Issue (10): 1047-1052.DOI: 10.15541/jim20210078 CSTR: 32189.14.10.15541/jim20210078

DFT方法研究一氧化氮在铬掺杂石墨烯上的吸附行为

何俊龙¹(), 宋二红²(), 王连军¹(), 江莞¹

1.东华大学材料科学与工程学院, 上海 201620
2.中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050

收稿日期:2021-02-05 修回日期:2021-03-02 出版日期:2021-10-20 网络出版日期:2021-03-15
通讯作者: 宋二红, 副研究员. E-mail: ehsong@mail.sic.ac.cn; 王连军, 教授. E-mail: wanglj@dhu.edu.cn
作者简介:何俊龙(1996-), 男, 硕士研究生. E-mail: woaichenzy@outlook.com
基金资助:
国家自然科学基金青年基金(51702345);上海市自然科学基金(21ZR1472900)

DFT Calculation of NO Adsorption on Cr Doped Graphene

HE Junlong¹(), SONG Erhong²(), WANG Lianjun¹(), JIANG Wan¹

1. College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
2. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2021-02-05 Revised:2021-03-02 Published:2021-10-20 Online:2021-03-15
Contact: SONG Erhong, associate professor. E-mail: ehsong@mail.sic.ac.cn; WANG Lianjun, professor. E-mail: wanglj@dhu.edu.cn
About author:HE Junlong(1996-), Master candidate. E-mail: woaichenzy@outlook.com
Supported by:
National Natural Science Foundation of China(51702345);Science and Technology Commission of Shanghai Municipality¬¬(21ZR1472900)

摘要/Abstract

摘要：

石墨烯具有较高的比表面积, 其电导率会因吸附微量气体分子而发生显著变化, 有望用作超高灵敏度的气体传感器。本研究基于密度泛函理论(DFT)的计算方法, 探讨了NO在石墨烯和Cr掺杂石墨烯上的吸附行为, 通过对比吸附前后的各自体系的电子结构变化, 发现Cr掺杂石墨烯有助于增强对NO气体分子的吸附能力, 吸附能增大到-1.58 eV, 基底转移到吸附物的电荷数增大了一个数量级, 达到0.143 e, 显著提升了气体探测灵敏度。本研究为工业、环境和军事监测领域中开发新型NO气体传感器提供了新的设计思路。

关键词: 密度泛函理论, 石墨烯传感器, NO吸附, 过渡金属, Cr掺杂石墨烯

Abstract:

Graphene has recently become one of the best candidates for ultrasensitive gas detector, due to its huge specific surface area and good conductivity of heat and electricity. In this study, a density functional theory (DFT) calculation is proposed to explore NO adsorption on graphene and Cr doped graphene. Compared with electronic structures of the two systems, it is found that the Cr substitution significantly enhances the adsorption behavior of NO molecules (adsorption energy being increased to -1.58 eV), while more electrons transfer from the substrate to the adsorbate (0.143 e). Therefore, this Cr doped graphene is expected to be an excellent candidate for sensing NO gas.

Key words: density functional theory, graphene gas sensor, NO adsorption, transition metal, Cr doped graphene

中图分类号:

TQ174

何俊龙, 宋二红, 王连军, 江莞. DFT方法研究一氧化氮在铬掺杂石墨烯上的吸附行为[J]. 无机材料学报, 2021, 36(10): 1047-1052.

HE Junlong, SONG Erhong, WANG Lianjun, JIANG Wan. DFT Calculation of NO Adsorption on Cr Doped Graphene[J]. Journal of Inorganic Materials, 2021, 36(10): 1047-1052.

图/表 6

图1 Cr原子掺杂石墨烯扩散过程中优化的原子结构图

Fig. 1 Optimized structure of Cr-doped graphene (a) Initial state (IS); (b) Relaxed configuration of final state (FS); (c) Diffusion period of Cr atom on graphene; Gray and cyan spheres denote C and Cr atoms, respectively

图2 NO吸附在石墨烯和Cr掺杂石墨烯的原子结构示意图

Fig. 2 Atomic configuration of NO adsorption on graphene and Cr-doped graphene Graphene with N-end model (a) and O-end model (b), and Cr-doped graphene with N-end (c) and O-end model (d); Gray, cyan, blue, and red spheres denote C, Cr, N, and O atoms, respectively

图3 NO以N-end和O-end模式在3d过渡金属掺杂石墨烯上的吸附能

Fig. 3 Adsorption energy of NO adsorbed on 3d transition metal doped graphene via N-end and O-end model, respectively

表1 石墨烯和Cr掺杂石墨烯吸附NO分子后的电荷改变量∆Q

Table 1 Charge change (∆Q) of graphene and Cr doped graphene after NO adsorption

System	NO-O-end	NO-N-end
Graphene	-0.012 e	-0.009 e
Cr doped graphene	-0.119 e	-0.143 e

图4 NO吸附在石墨烯和Cr掺杂石墨烯前后的电子密度差示意图

Fig. 4 Charge density difference of graphene and Cr-doped graphene before and after NO adsorption (a) Graphene; NO adsorption on graphene via (b) N-end and (c) O-end model; (d) Cr-doped graphene; NO adsorption on Cr doped graphene via (e) N-end and (f) O-end model; Red and blue regions represent accumulation and loss of electrons, respectively

图5 石墨烯(a, b)与Cr掺杂石墨烯(c, d)吸附NO气体分子前(a, c)后(b, d)的态密度(DOS)图

Fig. 5 Density of states (DOS) of intrinsic graphene (a, b) and Cr-doped graphene (c, d) before (a, c) and after (b, d) NO adsorption

参考文献 56

[1]	JOHNSON C, HENSHAW J, MCLNNES G. Impact of aircraft and surface emissions of nitrogen oxides ontropospheric ozone and global warming. Nature, 1992, 355(6355):69-71. DOI URL
[2]	LELIEVELD J, KLING MÜ, LLER K, et al. Effects of fossil fuel and total anthropogenic emission removal on public health and climate. Proceedings of the National Academy of Sciences, 2019, 116(15):7192-7197. DOI URL
[3]	POTYRAILO R A, GO S, SEXTON D, et al. Extraordinary performance of semiconducting metal oxide gas sensors using dielectric excitation. Nature Electronics, 2020, 3(5):280-289. DOI URL
[4]	TSAI Y T, CHANG S J, JI L W, et al. High sensitivity of NO gas sensors based on novel Ag-doped ZnO nanoflowers enhanced with a UV light-emitting diode. ACS Omega, 2018, 3(10):13798-13807. DOI URL
[5]	LI QIANG, SHI WANYAN, ZHANG CHEN, et al. SO₂ non- equilibrium gas sensor based on Na₃Zr₂Si₂PO₁₂ solid electrolyte. Journal of Inorganic Materials, 2018, 33(2):229-236 DOI URL
[6]	JIN W, HO H L, CAO Y C, et al. Gas detection with micro- and nano-engineered optical fibers. Optical Fiber Technology, 2013, 19(6 Part B):741-759. DOI URL
[7]	LI J, YAN H, DANG H, et al. Structure design and application of hollow core microstructured optical fiber gas sensor: a review. Optics & Laser Technology, 2021, 135:106658.
[8]	AKSHYA S, JULIET A V. A computational study of a chemical gas sensor utilizing Pd-rGO composite on SnO₂ thin film for the detection of NO_x. Scientific Reports, 2021, 11(1):970. DOI URL
[9]	HANG T, WU J, XIAO S, et al. Anti-biofouling NH₃ gas sensor based on reentrant thorny ZnO/graphene hybrid nanowalls. Microsystems & Nanoengineering, 2020, 6:41.
[10]	CHU Y X, LIU H R, YAN S. Preparation and gas sensing properties of SnO₂/NiO composite semiconductor nanofibers. Journal of Inorganic Materials, 2021, 36(9):950-958. DOI URL
[11]	KRENO L E, LEONG K, FARHA O K, et al. Metal-organic framework materials as chemical sensors. Chemical Reviews, 2012, 112(2):1105-1125. DOI URL
[12]	LEE J S, KWON O S, PARK S J, et al. Fabrication of ultrafine metal-oxide-decorated carbon nanofibers for DMMP sensor application. ACS Nano, 2011, 5(10):7992-8001. DOI URL
[13]	GUO X, WANG X, YANG R, et al. EDTA assistant preparation and gas sensing properties of Co₃O₄ nanomaterials. Journal of Inorganic Materials, 2020, 35:1215-1221.
[14]	LIANG JIRAN, ZHANG YE, YANG RAN,et al Room- temperature NH₃ gas sensing property of VO₂(B)/ZnO hierarchical heterogeneous composite with nanorod structure. Journal of Inorganic Materials, 2018, 33(12):1323-1329. DOI URL
[15]	XU SHUANG, YANG YING, WU HONGYUAN, et al. Preparation of one-dimensional Pt/SnO₂ nanofibers and NO_x gas-sensing properties. Journal of Inorganic Materials, 2013, 28(6):584-588. DOI URL
[16]	HAN SHUANGSHUANG, LIU LIYUE, SHAN YONGKUI, et al. Research of graphene/antireflection nanostructure composite transparent conducting films. Journal of Inorganic Materials, 2017, 32(2):197-202. DOI URL
[17]	NAN HUI, WANG WENLI, HAN JIANHUA, et al. Low-cost preparation of graphene papers from chemical reduction with FeI₂/Ni²+ for conductivity and catalytic propert. Journal of Inorganic Materials, 2017, 32(9):997-1003. DOI URL
[18]	YANG G, LEE C, KIM J, et al. Flexible graphene-based chemical sensors on paper substrates. Physical Chemistry Chemical Physics, 2013, 15(6):1798-1801. DOI URL
[19]	CHOI J H, LEE J, BYEON M, et al. Graphene-based gas sensors with high sensitivity and minimal sensor-to-sensor variation. ACS Applied Nano Materials, 2020, 3(3):2257-2265. DOI URL
[20]	YUAN W, SHI G. Graphene-based gas sensors. Journal of Materials Chemistry A, 2013, 1(35):10078-10091.
[21]	XING WEIWEI, ZHANG CHENXIAO, FAN SHANGCHUN, et al. Research progress on resonant characteristics of graphene. Journal of Inorganic Materials, 2016, 31(7):673-680. DOI URL
[22]	PUMERA M, AMBROSI A, BONANNI A, et al. Graphene for electrochemical sensing and biosensing. TrAC Trends in Analytical Chemistry, 2010, 29(9):954-965. DOI URL
[23]	GOMEZ DE ARCO L, ZHANG Y, SCHLENKER C W, et al. Continuous, highly flexible, and transparent graphene films by chemical vapor deposition for organic photovoltaics. ACS Nano, 2010, 4(5):2865-2873. DOI URL
[24]	CASTRO NETO A H, GUINEA F, PERES N M R, et al. The electronic properties of graphene. Reviews of Modern Physics, 2009, 81(1):109-162. DOI URL
[25]	RATINAC K R, YANG W, RINGER S P, et al. Toward ubiquitous environmental gas sensors-capitalizing on the promise of graphene. Environmental Science & Technology, 2010, 44(4):1167-1176. DOI URL
[26]	NOVOSELOV K S, GEIM A K, MOROZOV S V, et al. Electric field effect in atomically thin carbon films. Science, 2004, 306(5696):666-669. DOI URL
[27]	MEYER J C, GEIM A K, KATSNELSON M I, et al. The structure of suspended graphene sheets. Nature, 2007, 446(7131):60-63. DOI URL
[28]	LEE C, WEI X, KYSAR J W, et al. Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science, 2008, 321(5887):385-388. DOI URL
[29]	WANG LIN, TIAN LINHAI, WEI GUODONG, et al. Epitaxial growth of graphene and their applications in devices. Journal of Inorganic Materials, 2011, 26(10):1009-1019. DOI URL
[30]	WANG X, BAI H, SHI G. Size fractionation of graphene oxide sheets by pH-assisted selective sedimentation. Journal of the American Chemical Society, 2011, 133(16):6338-6342. DOI URL
[31]	XU Y, SHI G. Assembly of chemically modified graphene: methods and applications. Journal of Materials Chemistry, 2011, 21(10):3311-3323. DOI URL
[32]	WANG GUIXIN, PEI ZHIBIN, YE CHANGHUI. Inkjet- printing and performance investigation of self-powered flexible graphene oxide humidity sensors. Journal of Inorganic Materials, 2019, 34(1):114-120. DOI URL
[33]	SCHEDIN F, GEIM A K, MOROZOV S V, et al. Detection of individual gas molecules adsorbed on graphene. Nature Materials, 2007, 6(9):652-655. DOI URL
[34]	HWANG E H, ADAM S, DAS SARMA S. Transport in chemically doped graphene in the presence of adsorbed molecules. Physical Review B, 2007, 76(19):195421.
[35]	ROMERO H E, JOSHI P, GUPTA A K, et al. Adsorption of ammonia on graphene. Nanotechnology, 2009, 20(24):245501.
[36]	CHEN C W, HUNG S C, YANG M D, et al. Oxygen sensors made by monolayer graphene under room temperature. Applied Physics Letters, 2011, 99(24):243502.
[37]	YU K, WANG P, LU G, et al. Patterning vertically oriented graphene sheets for nanodevice applications. The Journal of Physical Chemistry Letters, 2011, 2(6):537-542. DOI URL
[38]	RUMYANTSEV S, LIU G, SHUR M S, et al. Selective gas sensing with a single pristine graphene transistor. Nano Letters, 2012, 12(5):2294-2298. DOI URL
[39]	AO Z M, YANG J, LI S, et al. Enhancement of CO detection in Al doped graphene. Chemical Physics Letters, 2008, 461(4):276-279. DOI URL
[40]	ZHENG Z, WANG H. Different elements doped graphene sensor for CO₂ greenhouse gases detection: the DFT study. Chemical Physics Letters, 2019, 721:33-37. DOI URL
[41]	KAUSHAL S, KAUR M, KAUR N, et al. Heteroatom-doped graphene as sensing materials: a mini review. RSC Advances, 2020, 10(48):28608-28629.
[42]	SRIVASTAVA S, JAIN S K, GUPTA G, et al. Boron-doped few- layer graphene nanosheet gas sensor for enhanced ammonia sensing at room temperature. RSC Advances, 2020, 10(2):1007-1014. DOI URL
[43]	ZHANG X, LU Z, TANG Y, et al. A density function theory study on the NO reduction on nitrogen doped graphene. Phys.Chem.Chem.Phys., 2014, 16(38): 20561-1-9.
[44]	PRAMANIK A, KANG H S. Density functional theory study of O₂ and NO adsorption on heteroatom-doped graphenes including the van der Waals interaction. The Journal of Physical Chemistry C, 2011, 115(22):10971-10978.
[45]	LIAO Y, PENG R, PENG S, et al. The adsorption of H₂ and C₂H₂ on Ge-doped and Cr-doped graphene structures: a DFT study. Nanomaterials, 2021, 11(1):231. DOI URL
[46]	DELLEY B. An all-electron numerical method for solving the local density functional for polyatomic molecules. The Journal of Chemical Physics, 1990, 92(1):508-517. DOI URL
[47]	DELLEY B. From molecules to solids with the DMol³ approach. The Journal of Chemical Physics, 2000, 113(18):7756-7764. DOI URL
[48]	PERDEW J P, BURKE K, ERNZERHOF M. Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18):3865-3868. DOI URL
[49]	DELLEY B. Hardness conserving semilocal pseudopotentials. Physical Review B, 2002, 66(15):155125.
[50]	HIRSHFELD F L. Bonded-atom fragments for describing molecular charge densities. Theoretica Chimica Acta, 1977, 44(2):129-138. DOI URL
[51]	HENKELMAN G, JÓNSSON H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. The Journal of Chemical Physics, 2000, 113(22):9978-9985. DOI URL
[52]	GEIM A K, NOVOSELOV K S. The rise of graphene. Nature Materials, 2007, 6(3):183-191. DOI URL
[53]	SONG E H, WEN Z, JIANG Q. CO catalytic oxidation on copper-embedded graphene. The Journal of Physical Chemistry C, 2011, 115(9):3678-3683. DOI URL
[54]	SONG E H, YAN J M, LIAN J S, et al. External electric field catalyzed N₂O decomposition on Mn-embedded graphene. The Journal of Physical Chemistry C, 2012, 116(38):20342-20348.
[55]	MAITARAD P, JUNKAEW A, PROMARAK V, et al. Complete catalytic cycle of NO decomposition on a silicon-doped nitrogen- coordinated graphene: mechanistic insight from a DFT study. Applied Surface Science, 2020, 508:145255.
[56]	LÜ Y A, ZHUANG G L, WANG J G, et al. Enhanced role of Al or Ga-doped graphene on the adsorption and dissociation of N₂O under electric field. Phys. Chem. Chem. Phys., 2011, 13(27):12472-12477.

DFT方法研究一氧化氮在铬掺杂石墨烯上的吸附行为

DFT Calculation of NO Adsorption on Cr Doped Graphene

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