Abstract
Keggin polyoxometalate structures are molecular clusters that, anchored to carbon matrices, have been used to form electrodes for energy storage devices, such as lithium batteries and supercapacitors. \([{\text{PMo}}_{12}{\text{O}}_{40}]^{3-}\) polyanions (PMo12) are examples of this kind of nanostructures that, grafted on amorphous carbon, have the capability to enhance the capacitive properties of these electrochemical ensembles. However, there is yet a poor understanding of the fundamental mechanisms for bond formation between them and carbon structures. It has been found experimentally that the presence of functional groups such as φ-NH2 and φ-OH assists on the chemical absorption of PMo12, but there is not enough information on the actual mechanism of the process. In order to gather further knowledge on these issues, we have performed quantum mechanical calculations, based on the density functional theory of atomic arrangements using graphene as carbon structure model, different functional groups, and PMo12. Our aim was to look for the nature of bonding among them, and to dig into the charge properties to relate them with the experimental observation. From the computations performed with PMo12 polyanion near to a graphene sheet, with and without the presence of functional groups, we conclude that there is a non-covalent/electrostatic bonding, made of weak \(\pi\)–\(\pi\) stacking interactions between PMo12 and graphene. Calculations show that φ-NH2 and φ-OH functional groups are able to form covalent bonds with PMo12 in top and side fashion arrangements, being the latter the most stable. This is a powerful argument to explain the empirical observation on these groups, enhancing the PMo12 adsorption over carbon structures. We also found that the presence of the functional groups together with PMo12 creates electronic states that may act as alternative pathways that ions can track within electrochemical cells. Our results offer first-principle information relevant to the understanding of these composite materials, and the methodology could be directly applied to other Keggin structures or different functional groups, attached to graphene, to find potential advantages for energy storage devices.
Similar content being viewed by others
References
Genovese M, Lian K (2015) Curr Opin Solid State Mater Sci 19:126
Ji Y, Huang L, Hu J, Streb C, Song YF (2015) Energy Environ Sci 8:776
Koper M (2013) Nat Chem 5:255
Subbaraman R, Tripkovic D, Strmcnik D, Chang KC, Uchimura M, Paulikas A, Stamenkovic V, Markovic N (2011) Science 334:1256
Wang X, Wang E, Lan Y, Hu C (2002) Electroanalysis 14:1116
Liu H, He P, Li Z, Sun C, Shi L, Liu Y, Zhu G, Li J (2005) Electrochem Commun 7:1357
Cuentas-Gallegos A, Miranda-Hernandez AVOM (2009) Electrochim Acta 54:4378
Bianchini C, Shen P (2009) Chem Rev 109:4183
Pan D, Chen J, Tao W, Nie L, Yao S (2006) Langmuir 22:5872
Kawasaki N, Wang H, Nakanishi R, Hamanaka S, Kitaura R, Shinohara H, Yokoyama T, Yoshikawa H, Awaga K (2011) Angew Chem Int Ed 50:3471
Azumi B, Ishihara T, Nishiguchi H, Takita Y (2002) Electrochemistry 70:869
Wang S, Li H, Li S, Liu F, Wu D, Feng X, Wu L (2013) Chem Eur J 19:10895
Cuentas-Gallegos A, Gonzales-Toledo M, Rincon M (2007) Rev Mex Fis S 53:91
Cuentas-Gallegos A, Martinez-Rosales R, Baibarac M, Gomez-Romero P, Rincon ME (2007) Electrochem Commun 9:2088
Baeza-Rostro D, Cuentas-Gallegos A (2013) J New Mater Electr Syst 13:203
Ruiz V, Suarez-Guevara J, Gomez-Romero P (2012) Electrochem Commun 24:35
Suarez-Guevara J, Ruiz V, Gomez-Romero P (2014) J Mater Chem A 2:1014
Suarez-Guevara J, Ruiz V, Gomez-Romero P (2014) PCCP 16:20411
Chen HY, Wee G, Al-Oweini R, Friedl J, Tan K, Wang Y, Wong C, Kortz U, Stimming U, Srinivasan M (2014) ChemPhysChem 15:2162
Alcaniz-Monge J, Trautwein G, Parres-Esclapez S, Macia-Agullo J (2008) Microporous Mesoporous Mater 115:440
Song Y, Wang E, Kang Z, Lan Y, Tian C (2007) Mater Res Bull 42:1485
Fei B, Lu H, Hu Z, Xin J (2006) Nanotechnology 17:1589
Kang Z, Wang Y, Wang E, Lian S, Gao L, You W, Hu C, Xu L (2004) Solid State Commun 129:559
Cuentas-Gallegos A, Jimenez-Penaloza S, Baeza-Rostro D, German-Garcia A (2010) J New Mater Electr Syst 13:369
Cuentas-Gallegos A, Martinez-Rosales R, Rincon M, Hirata G, Orozco G (2006) Opt Mater 29:126
Cuentas-Gallegos A, Zamudio-Flores A, Casas-Cabanas M (2011) J Nano Res 14:11
Tessonnier J, Goubert-Renaudin S, Alia S, Yan Y, Barteau M (2013) Langmuir 29:393
Petit C, Bandosz T (2009) J Phys Chem C 113:3800
Over H (2012) Chem Rev 112:3356
Toma FM, Sartorel A, Iurlo M, Carraro M, Parisse P, Maccato C, Rapino S, Gonzalez BR, Amenitsch H, Ros TD, Casalis L, Goldoni A, Marcaccio M, Scorrano G, Scoles G, Paolucci F, Prato M, Bonchio M (2010) Nat Chem 2:826
Li S, Yu X, Zhang G, Ma Y, Yao J, de Oliveira P (2011) Carbon 49:1906
Wen S, Guan W, Kan Y, Yang G, Ma N, Yan L, Su Z, Chen G (2013) Phys Chem Chem Phys 15:9177
Wen S, Guan W, Wang J, Lang Z, Yan L, Su Z (2012) Dalton Trans 41:4602
Yang M, Gill-Choi B, Chul-Jung YKHS, Suk-Huh Y, Bok-Lee S (2014) Adv Funct Mater 24:7301
Rozanska X, Sautet P, Delbecq F, Lefebvre F, Borshch S, Chermette H, Basset JM, Grinenval E (2011) Phys Chem Chem Phys 13:15955
Aparicio-Angles X, Clotet A, Bo C, Poblet JM (2011) Phys Chem Chem Phys 13:15143
Aparicio-Angles X, Miro P, Clotet A, Bo C, Poblet JM (2012) Chem Sci 3:2020
Garrigue P, Delville M, Labrugere C, Cloutet E, Kulesza P, Morand J, Kuhn A (2004) Chem Mater 16:2984
Cuentas-Gallegos A, Lopez-Cortina S, Brousse T, Pacheco-Catalan D, Fuentes-Quezada E, Mosqueda H, Orozco-Gamboa G (2016) J Solid State Electrochem 20:67
Bulat F, Burgess J, Matis B, Baldwin J, Macaveiu L, Murray J, Politzer P (2012) J Phys Chem A 116:8644
Darvish-Ganji M, Hosseini-khahb S, Amini-tabar Z (2015) Phys Chem Chem Phys 17:2504
Liu W, Tkatchenko A, Scheffler M (2014) Acc Chem Res 47:3369
Tkatchenko A, Scheffler M (2009) Phys Rev Lett 102:073005
Carrasco J, Liu W, Michaelides A, Tkatchenko A (2014) J Chem Phys 140:084704
Blum V, Gehrke R, Hanke F, Havu P, Havu V, Ren X, Reuter K, Scheffler M (2009) Comput Phys Commun 180:2175
Havu V, Havu P, Blum V, Scheffler M (2009) J Comput Phys 228:8367
van Lenthe E, Ehlers A, Baerends E (1999) J Chem Phys 110:8943
Lopez X, Carbo J, Bo C, Poblet JM (2012) Chem Soc Rev 41:7537
Monkhorst H, Pack J (1976) Phys Rev B 13:5188
Kostyrko T, Lambert CJ, Bulka BR (2010) Phys Rev B Condens Matter Mater Phys 81:085308
Ordejon P, Artacho E, Soler J (1996) Phys Rev B Condens Matter Mater Phys 53:R10441
Sanchez-Portal D, Ordejon P, Artacho E, Soler JM (1997) Int J Quantum Chem 65:453
Soler JM, Artacho E, Gale JD, Garcia A, Junquera J, Ordejon P, Sanchez-Portal D (2002) J Phys Condens Matter 14:2745
Junquera J, Paz O, Sanchez-Portal D, Artacho E (2001) Phys Rev B Condens Matter Mater Phys 64:235111
Wen SZ, Yang GC, Yan LK, Lii HB, Su ZM (2012) ChemPhysChem 14:610
te Velde G, Bickelhaupt F, Baerends E, Fonseca-Guerra C, van Gisbergen S, Snijders J, Ziegler T (2001) J Comput Chem 22:931
Ziegler T, Rauk A (1977) Theor Chim Acta 46:1
Ziegler T, Rauk A, Baerends EJ (1977) Theor Chim Acta 43:261
Baerends EJ, Autschbach J, Bérces A, Bo C, Boerrigter PM, Cavallo L, Chong DP, Deng L, Dickson RM, Ellis DE, Fan L, Fischer TH, Fonseca-Guerra C, van Gisbergen SJA, Groeneveld JA, Gritsenko OV, Grüning M, Harris FE, van den Hoek P, Jacobsen H, van Kessel G, Kootstra F, van Lenthe E, Osinga VP, Patchkovskii S, Philipsen PHT, Post D, Pye CC, Ravenek W, Ros P, Schipper PRT, Schreckenbach G, Snijders JG, Sola M, Swart M, Swerhone D, te Velde G, Vernooijs P, Versluis L, Visser O, van Wezenbeek E, Wiesenekker G, Wolff SK, Woo TK, Ziegler T. Amsterdam density functional (adf) (2014) Theoretical Chemistry. Vrije Universiteit, Amsterdam. http://www.scm.com
Schleyer PvR, Maerker C, Dransfeld A, Jiao H, Hommes NJvE (1996) J Am Chem Soc 118:6317
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels Farkas AD, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 1:1
Ditchfield R, Hehre W, Pople J (1971) J Chem Phys 54:724
Rassolov V, Ratner M, Pople J, Redfern P, Curtiss L (2001) J Comp Chem 22:976
Hay P, Wadt W (1985) J Chem Phys 82:299
Mulliken R (1955) J Chem Phys 23:1833
Arellano J, Molina L, Rubio A, Alonso J (2000) J Chem Phys 112:8114
Nalewajski R, Mrozek J, Michalak A (1997) Int J Quantum Chem 61:589
Nalewajski R, Mrozek J (1994) Int J Quantum Chem 51:187
Poater J, Solà M (2011) Chem Commun 47:11647
Karadakov P (2008) J Phys Chem A 112:7303
Gogonea V, Schleyer P, Schreiner P (1998) Angew Chem Int Ed 37:1945
Wolinski K, Hilton J, Pulay P (1990) J Am Chem Soc 112:8251
Pyykko P, Atsumi M (2009) Chem Eur J 15:12770
Keïta B, Chauveau F, Théobald F, Bélanger D, Nadjo L (1992) Surf Sci 264:2761
Watson BA, Barteau MA, Haggerty L, Lenhoff AM, Weber RS (1992) Langmuir 8:1145
Kaba MS, Song IK, Barteau MA (1996) J Phys Chem 100:19577
Song IK, Kaba M, Coulston G, Kourtakis K, Barteau MA (1996) Chem Mater 8:2352
Kaba MS, Song IK, Barteau MA (1997) J Vac Sci Technol A 15:1299
Song IK, Kaba M, Barteau MA, Lee WY (1998) Catal Today 44:285
Liu S, Wang C, Zhai H, Li D (2003) J Mol Struct 654:215
Ma D, Liang L, Chen W, Liu H, Song YF (2013) Adv Funct Mater 23:6100
Acknowledgments
The authors want to acknowledge the support given by Cátedras-CONACYT (Consejo Nacional de Ciencia y Tecnología) under Project No. 1191; DGTIC (Dirección General de Cómputo y de Tecnologías de Información y Comunicación) and the Supercomputing Department of Universidad Nacional Autónoma de México for the computing resources under Project No. SC15-1-IR-88. The authors would like to acknowledge the financial support given by DGAPA (Dirección General de Asuntos del Personal Académico) under Project No. IN112414. We also thank Dr. Gabriel Merino for helpful discussions and Dr. Shizheng Wen for technical support.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Muñiz, J., Cuentas-Gallegos, A.K., Robles, M. et al. Bond formation, electronic structure, and energy storage properties on polyoxometalate–carbon nanocomposites. Theor Chem Acc 135, 92 (2016). https://doi.org/10.1007/s00214-016-1855-3
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00214-016-1855-3