Skip to main content Accessibility help

Stable Pt clusters anchored to monovacancies on graphene sheets

  • Bharat K. Medasani (a1), Jun Liu (a2) and Maria L. Sushko (a1)


First principles simulations and global optimization predict new mode of binding of Pt clusters with defects on graphene that significantly enhances their stability. Pt clusters were found to firmly bind to monovacancies in configuration transacting the vacancy site, while retaining the integrity of the cluster. Diffusion calculations support tight anchoring of Pt cluster to monovacancy. Pt cluster adsorbed on pristine graphene or other common defects exhibit a different mode of adsorption and only decorate one side of graphene. This study reveals strong influence of defect chemistry on the structure and mobility of Pt nanoclusters adsorbed on graphene and have important implications for catalytic and gas sensing applications.


Corresponding author

Address all correspondence to Maria L. Sushko at


Hide All
1. Georgakilas, V., Otyepka, M., Bourlinos, A.B., Chandra, V., Kim, N., Kemp, K.C., Hobza, P., Zboril, R., and Kim, K.S.: Functionalization of graphene: covalent and non-covalent approaches, derivatives and applications. Chem. Rev. 112, 6156 (2012).
2. Green, A., Isseroff, R., Lin, S., Wang, L., and Rafailovich, M.: Synthesis and characterization of iron nanoparticles on partially reduced graphene oxide as a cost-effective catalyst for polymer electrolyte membrane fuel cells. MRS Commun. 7, 166 (2017).
3. Cho, B., Yoon, J., Hahm, M.G., Kim, D.-H., Kim, A.R., Kahng, Y.H., Park, S.-W., Lee, Y.-J., Park, S.-G., Kwon, J.-D., Kim, C.S., Song, M., Jeong, Y., Nam, K.-S., and Ko, H.C.: Graphene-based gas sensor: metal decoration effect and application to a flexible device. J. Mater. Chem. C 2, 5280 (2014).
4. Ding, M., Sorescu, D.C., Kotchey, G.P., and Star, A.: Welding of gold nanoparticles on graphitic templates for chemical sensing. J. Am. Chem. Soc. 134, 3472 (2012).
5. Ding, M., Tang, Y., and Star, A.: Understanding interfaces in metal–graphitic hybrid nanostructures. J. Phys. Chem. Lett. 4, 147 (2013).
6. Wu, S.-Y. and Ho, J.-J.: Adsorption of a Pt13 cluster on graphene oxides at varied ratios of oxygen to carbon and its catalytic reactions for CO removal investigated with quantum-chemical calculations. J. Phys. Chem. C 118, 26764 (2014).
7. Fampiou, I. and Ramasubramaniam, A.: Binding of Pt Nanoclusters to point defects in graphene: adsorption, morphology, and electronic structure. J. Phys. Chem. C 116, 6543 (2012).
8. Padmanabhan, H. and Nanda, B.R.K.: Intertwined lattice deformation and magnetism in monovacancy graphene. Phys. Rev. B 93, 165403 (2016).
9. Zhang, C., Dabbs, D.M., Liu, L.M., Aksay, I.A., Car, R., and Selloni, A.: Combined effects of functional groups, lattice defects, and edges in the infrared spectra of graphene oxide. J. Phys. Chem. C 119, 18167 (2015).
10. Robertson, A.W., Lee, G.-D., He, K., Yoon, E., Kirkland, A.I., and Warner, J.H.: Stability and dynamics of the tetravacancy in graphene. Nano Lett. 14, 1634 (2014).
11. Kaloni, T.P., Singh, N., and Schwingenschlögl, U.: Prediction of a quantum anomalous Hall state in Co-decorated silicene. Phys. Rev. B 89, 035409 (2014).
12. Padilha, J.E. and Pontes, R.B.: Electronic and transport properties of structural defects in monolayer germanene: an ab initio investigation. Solid State Commun. 225, 38 (2016).
13. Singh, N., Kaloni, T.P., and Schwingenschlögl, U.: A first-principles investigation of the optical spectra of oxidized graphene. Appl. Phys. Lett. 102, 023101 (2013).
14. Piotrowski, M.J., Piquini, P., and Da Silva, J.L.F.: Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters. Phys. Rev. B 81, 155446 (2010).
15. Wales, D.J. and Doye, J.P.K.: Global optimization by basin-hopping and the lowest energy structures of lennard-jones clusters containing up to 110 atoms. J. Phys. Chem. A 101, 5111 (1997).
16. Fernando, A., Weerawardene, K.L.D.M., Karimova, N.V., and Aikens, C.M.: Quantum mechanical studies of large metal, metal oxide, and metal chalcogenide nanoparticles and clusters. Chem. Rev. 115, 6112 (2015).
17. Medasani, B., Park, Y.H., and Vasiliev, I.: Theoretical study of the surface energy, stress, and lattice contraction of silver nanoparticles. Phys. Rev. B 75, 235436 (2007).
18. Medasani, B. and Vasiliev, I.: Computational study of the surface properties of aluminum nanoparticles. Surf. Sci. 603, 2042 (2009).
19. Henkelman, G., Uberuaga, B.P., and Jónsson, H.: A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901 (2000).
20. Koh, Y.W. and Manzhos, S.: Curvature drastically changes diffusion properties of Li and Na on graphene. MRS Commun. 3, 171 (2013).
21. Kresse, G. and Hafner, J.: Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558 (1993).
22. Hutter, J., Iannuzzi, M., Schiffmann, F., and VandeVondele, J.: CP2K: atomistic simulations of condensed matter systems. Wiley Interdiscip. Rev. Comput. Mol. Sci. 4, 15 (2014).
23. Bahn, S.R. and Jacobsen, K.W.: An object-oriented scripting interface to a legacy electronic structure code. Comput. Sci. Eng. 4, 56 (2002).
24. Terrel, R., Chill, S., Xiao, P., Duncan, J., Stauffer, S., Bandy, R., and Henkelman, G.: TSASE: Transition State Library for ASE. Retreived Sept 18, 2017 from
25. Momma, K. and Izumi, F.: VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272 (2011).
Type Description Title
Supplementary materials

Medasani et al supplementary material
Medasani et al supplementary material 1

 PDF (431 KB)
431 KB

Stable Pt clusters anchored to monovacancies on graphene sheets

  • Bharat K. Medasani (a1), Jun Liu (a2) and Maria L. Sushko (a1)


Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed