Abstract
At the density functional theory level, the electronic reactivity of oxidized and doped (with N, B, and P) graphene (G) has been analyzed. Molecular hardness and electrophilicity were used as global reactivity descriptors, while those at the local level, Fukui functions, Mulliken charges and molecular electrostatic potential were used in the order to characterize the intramolecular and intermolecular reactivity. These descriptors show that in GO, the global and local reactivity of the basal plane is improved mainly by hydroxyl groups, which improve besides the physisorption of small molecules, while, the active carbon atoms around the functional group would allow enhancement of the consecutively chemisorption. Furthermore, epoxide, carbonyl and carboxyl groups allow mainly enhancement of intermolecular non-covalent interactions. On the other hand, doping with N and B atoms increases the electrophilic character and the reactivity in the bulk. Specifically, in N-doped G, N and around carbon atoms would be able to serve as active sites of detection by frontier-controlled processes, explaining the improvement in electrochemical sensing; in addition, electron-deficient carbon atoms around N enhance the physisorption. Respecting the B-doped G, dopant and carbon atoms adjacent to B act as donor sites, suggesting that adsorption of cations on B-doped G is a frontier-controlled process; moreover, positively-charged B atoms enhance charge-controlled interactions with polarized molecules, and consecutively, in a frontier-controlled step, chemisorption is possible. Finally, P-doping increases the electrophilic reactivity in the bulk; also, P atoms enhance the physisorption of chemical species with negatively-charged centers or lone-pair electrons, and consecutively, chemisorption on P is possible.
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Bolotin KI, Sikes KJ, Jiang Z, Klima M, Fudenberg G, Hone J, Kim P, Stormer HL (2008) Ultrahigh electron mobility in suspended graphene. Solid State Commun 146(9–10):351–355
Geim AK, Novoselov KS (2007) The rise of graphene. Nat Mater 6(3):183–191
Chen S, Wu Q, Mishra C, Kang J, Zhang H, Cho K, Cai W, Balandin AA, Ruoff RS (2012) Thermal conductivity of isotopically modified graphene. Nat Mater 11:203–217
Lee C, Wei X, Kysar JW, Hone J (2008) Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321(5887):385–388
Sharma R, Baik JH, Perera CJ, Strano MS (2010) Anomalously large reactivity of single graphene layers and edges toward electron transfer chemistries. Nano Letters 10(2):398–405
Lerf A, He H, Forster M, Klinowski J (1998) Structure of graphite oxide revisited. J Phys Chem B 102(23):4477–4482
Cai W, Piner RD, Stadermann FJ, Park S, Shaibat MA, Ishii Y, Yang D, Velamakanni A, An SJ, Stoller M, An J, Chen D, Ruoff RS (2008) Synthesis and solid-state NMR structural characterization of 13C-labeled graphite oxide. Science 321(5897):1815–1817
Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80(6):1339–1339
Chunder A, Pal T, Khondaker SI, Zhai L (2010) Reduced graphene oxide/copper phthalocyanine composite and its optoelectrical properties. J Phys Chem C 114(35):15129–15135
Zhu J, Li Y, Chen Y, Wang J, Zhang B, Zhang J, Blau WJ (2011) Graphene oxide covalently functionalized with zinc phthalocyanine for broadband optical limiting. Carbon 49(6):1900–1905
Pyun J (2011) Graphene oxide as catalyst: application of carbon materials beyond nanotechnology. Angew Chem Int Ed 50(1):46–48
Ji Z, Shen X, Zhu G, Zhou H, Yuan A (2012) Reduced graphene oxide/nickel nanocomposites: facile synthesis, magnetic and catalytic properties. J Mater Chem 22(8):3471–3477
Zhang N, Qiu H, Liu Y, Wang W, Li Y, Wang X, Gao J (2011) Fabrication of gold nanoparticle/graphene oxide nanocomposites and their excellent catalytic performance. J Mater Chem 21(30):11080–11083
Wei Y, Gao C, Meng F-L, Li H-H, Wang L, Liu J-H, Huang X-J (2011) SnO2/Reduced graphene oxide nanocomposite for the simultaneous electrochemical detection of cadmium(II), lead(II), copper(II), and Mercury(II): an interesting favorable mutual interference. J Phys Chem C 116(1):1034–1041
Qian Z, Shaojun Y, Jing Z, Ling Z, Pingli K, Jinghong L, Jingwei X, Hua Z, Xi-Ming S (2011) Fabrication of an electrochemical platform based on the self-assembly of graphene oxide–multiwall carbon nanotube nanocomposite and horseradish peroxidase: direct electrochemistry and electrocatalysis. Nanotechnology 22(49):494010
Geng D, Yang S, Zhang Y, Yang J, Liu J, Li R, Sham T-K, Sun X, Ye S, Knights S (2011) Nitrogen doping effects on the structure of graphene. Appl Surf Sci 257(21):9193–9198
Denis PA (2011) Chemical reactivity of lithium doped monolayer and bilayer graphene. J Phys Chem C 115(27):13392–13398
Dai J, Yuan J, Giannozzi P (2009) Gas adsorption on graphene doped with B, N, Al, and S: a theoretical study. Appl Phys Lett 95(23):232105
Cazorla C (2010) Ab initio study of the binding of collagen amino acids to graphene and A-doped (A=H, Ca) graphene. Thin Solid Films 518(23):6951–6961
Mousavi H, Moradian R (2011) Nitrogen and boron doping effects on the electrical conductivity of graphene and nanotube. Solid State Sci 13(8):1459–1464
Gao S, Ren Z, Wan L, Zheng J, Guo P, Zhou Y (2011) Density functional theory prediction for diffusion of lithium on boron-doped graphene surface. Appl Surf Sci 257(17):7443–7446
Wu Z-S, Ren W, Xu L, Li F, Cheng H-M (2011) Doped graphene sheets as anode materials with superhigh rate and large capacity for lithium ion batteries. ACS Nano 5(7):5463–5471
Zhou YG, Zu XT, Gao F, Nie JL, Xiao HY (2009) Adsorption of hydrogen on boron-doped graphene: a first-principles prediction. J Appl Phys 105(1):014309
Hernández Rosas J, Ramírez Gutiérrez R, Escobedo-Morales A, Chigo Anota E (2011) First principles calculations of the electronic and chemical properties of graphene, graphane, and graphene oxide. J Mol Model 17(5):1133–1139
Peralta-Inga Z, Murray JS, Edward Grice M, Boyd S, O’Connor CJ, Politzer P (2001) Computational characterization of surfaces of model graphene systems. J Mol Struct (THEOCHEM) 549(1–2):147–158
Radovic LR (2009) Active sites in graphene and the mechanism of CO2 formation in carbon oxidation. J Am Chem Soc 131(47):17166–17175
Acharya CK, Sullivan DI, Turner CH (2008) Characterizing the interaction of Pt and PtRu clusters with boron-doped, nitrogen-doped, and activated carbon: density functional theory calculations and parameterization. J Phys Chem C 112(35):13607–13622
Berashevich J, Chakraborty T (2010) Doping graphene by adsorption of polar molecules at the oxidized zigzag edges. Phys Rev B 81(20):205431
Gong K, Du F, Xia Z, Durstock M, Dai L (2009) Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323(5915):760–764
Wang X, Zeng Z, Ahn H, Wang G (2009) First-principles study on the enhancement of lithium storage capacity in boron doped graphene. Appl Phys Lett 95(18):183103
Panchakarla LS, Subrahmanyam KS, Saha SK, Govindaraj A, Krishnamurthy HR, Waghmare UV, Rao CNR (2009) Synthesis, structure, and properties of boron- and nitrogen-doped graphene. Adv Mater 21(46):4726–4730
Beheshti E, Nojeh A, Servati P (2011) A first-principles study of calcium-decorated, boron-doped graphene for high capacity hydrogen storage. Carbon 49(5):1561–1567
Baltazar SE, García ALE, Pérez-Robles JF, Romero AH, Rubio Secades Á (2008) Influence of S and P doping in a graphene sheet. J Comput Theor Nanosci 5:1–9
Geerlings P, De Proft F, Langenaeker W (2003) Conceptual density functional theory. Chem Rev 103(5):1793–1874
Parr RG, Pearson RG (1983) Absolute hardness: companion parameter to absolute electronegativity. J Am Chem Soc 105(26):7512–7516
Parr RG, Lv S, Liu S (1999) Electrophilicity index. J Am Chem Soc 121(9):1922–1924
Chattaraj PK, Sarkar U, Roy DR (2006) Electrophilicity Index. Chem Rev 106(6):2065–2091
Parr RG, Yang W (1984) Density functional approach to the frontier-electron theory of chemical reactivity. J Am Chem Soc 106(14):4049–4050
Pérez P, Toro-Labbé A, Aizman A, Contreras R (2002) Comparison between experimental and theoretical scales of electrophilicity in benzhydryl cations. J Org Chem 67(14):4747–4752
Chattaraj PK, Maiti B, Sarkar U (2003) Philicity: a unified treatment of chemical reactivity and selectivity. J Phys Chem A 107(25):4973–4975
Chattaraj PK (2000) Chemical reactivity and selectivity: local HSAB principle versus frontier orbital theory. J Phys Chem A 105(2):511–513
Fievez T, Weckhuysen BM, Geerlings P, Proft FD (2009) Chemical reactivity indices as a tool for understanding the support-effect in supported metal oxide catalysts. J Phys Chem C 113(46):19905–19912
Cote LJ, Kim F, Huang J (2008) Langmuir−Blodgett assembly of graphite oxide single layers. J Am Chem Soc 131(3):1043–1049
Schniepp HC, Li J-L, McAllister MJ, Sai H, Herrera-Alonso M, Adamson DH, Prud’homme RK, Car R, Saville DA, Aksay IA (2006) Functionalized single graphene sheets derived from splitting graphite oxide. J Phys Chem B 110(17):8535–8539
Pandey D, Reifenberger R, Piner R (2008) Scanning probe microscopy study of exfoliated oxidized graphene sheets. Surf Sci 602(9):1607–1613
Stewart JP (2007) Optimization of parameters for semiempirical methods V: modification of NDDO approximations and application to 70 elements. J Mol Model 13(12):1173–1213
MOPAC2009, James J. P. Stewart, Stewart Computational Chemistry, Version 11.038W web: http://OpenMOPAC.net
Perdew JP, Burke K, Ernzerhof M (1997) Generalized gradient approximation made simple [Phys Rev Lett 77, 3865 (1996)]. Phys Rev Lett 78(7):1396–1396
Neese F (2004) ORCA—an ab initio, Density Functional and Semiempirical program package, Version 2.8. Max-Planck-Insitut für Bioanorganische Chemie, Mülheim and der Ruhr
Allouche A-R (2011) Gabedit—a graphical user interface for computational chemistry softwares. J Comput Chem 32(1):174–182
Tang S, Cao Z (2011) Adsorption of nitrogen oxides on graphene and graphene oxides: insights from density functional calculations. J Chem Phys 134(4):044710
Al-Aqtash N, Vasiliev I (2011) Ab initio study of boron- and nitrogen-doped graphene and carbon nanotubes functionalized with carboxyl groups. J Phys Chem C 115(38):18500–18510
Wang D-W, Gentle IR, Lu GQ (2010) Enhanced electrochemical sensitivity of PtRh electrodes coated with nitrogen-doped graphene. Electrochem Commun 12(10):1423–1427
Fan H, Li Y, Wu D, Ma H, Mao K, Fan D, Du B, Li H, Wei Q (2012) Electrochemical bisphenol A sensor based on N-doped graphene sheets. Anal Chim Acta 711:24–28
Wang Y, Shao Y, Matson DW, Li J, Lin Y (2010) Nitrogen-doped graphene and its application in electrochemical biosensing. ACS Nano 4(4):1790–1798
Sheng Z-H, Zheng X-Q, Xu J-Y, Bao W-J, Wang F-B, Xia X-H (2012) Electrochemical sensor based on nitrogen doped graphene: simultaneous determination of ascorbic acid, dopamine and uric acid. Biosens Bioelectron 34(1):125–131
Okamoto Y (2009) First-principles molecular dynamics simulation of O2 reduction on nitrogen-doped carbon. Appl Surf Sci 256(1):335–341
Qu L, Liu Y, Baek J-B, Dai L (2010) Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano 4(3):1321–1326
Yu L, Pan X, Cao X, Hu P, Bao X (2011) Oxygen reduction reaction mechanism on nitrogen-doped graphene: a density functional theory study. J Catal 282(1):183–190
Zhang L, Xia Z (2011) Mechanisms of oxygen reduction reaction on nitrogen-doped graphene for fuel cells. J Phys Chem C 115(22):11170–11176
Zhang L, Niu J, Dai L, Xia Z (2012) Effect of microstructure of nitrogen-doped graphene on oxygen reduction activity in fuel cells. Langmuir 28(19):7542–7550
Li Y, Wang J, Li X, Geng D, Banis MN, Li R, Sun X (2012) Nitrogen-doped graphene nanosheets as cathode materials with excellent electrocatalytic activity for high capacity lithium-oxygen batteries. Electrochem Commun 18:12–15
Zhang YH, Chen YB, Zhou KG, Liu CH, Zeng J, Zhang HL, Peng Y (2009) Improving gas sensing properties of graphene by introducing dopants and defects: a first-principles study. Nanotechnology 20(18):185504
Dai J, Yuan J (2010) Adsorption of molecular oxygen on doped graphene: atomic, electronic, and magnetic properties. Phys Rev B 81(16):165414
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The author thanks Juan M. Perez for the provided help in the last stage of the article, and to reviewers for comments and suggestions.
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Cortés Arriagada, D. Global and local reactivity indexes applied to understand the chemistry of graphene oxide and doped graphene. J Mol Model 19, 919–930 (2013). https://doi.org/10.1007/s00894-012-1642-6
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DOI: https://doi.org/10.1007/s00894-012-1642-6