[en] The adsorption and desorption kinetics of molecules is of significant fundamental and applied interest. In this paper, we present a new method to quantify the energy barriers for the adsorption and desorption of gas molecules on few-atom clusters, by exploiting reaction induced changes of the doping level of a graphene substrate. The method is illustrated for oxygen adsorption on Au3 clusters. The gold clusters were deposited on a graphene field effect transistor and exposed to O2. From the change in graphene's electronic properties during adsorption, the energy barrier for the adsorption of O2 on Au3 is estimated to be 0.45 eV. Electric current pulses increase the temperature of the graphene strip in a controlled way and provide the required thermal energy for oxygen desorption. The oxygen binding energy on Au3/graphene is found to be 1.03 eV and the activation entropy is 1.4 meV K-1. The experimental values are compared and interpreted on the basis of density functional theory calculations of the adsorption barrier, the binding energy and the activation entropy. The large value of the activation entropy is explained by the hindering effect that the adsorbed O2 has on the fluxional motion of the Au3 cluster.
Disciplines :
Physics
Author, co-author :
Libeert, Guillaume ; Quantum Solid-State Physics, Department of Physics and Astronomy, KU Leuven, Leuven, Belgium. ewald.janssens@kuleuven.be
Murugesan, Ramasamy ; Semiconductor Physics Laboratory, Department of Physics and Astronomy, KU Leuven, Leuven, Belgium
Guba, Márton; Budapest University of Technology and Economics, Department of Inorganic and Analytical Chemistry and MTA-BME Computation driven research group, Budapest, Hungary
Keijers, Wout; Quantum Solid-State Physics, Department of Physics and Astronomy, KU Leuven, Leuven, Belgium. ewald.janssens@kuleuven.be
Collienne, Simon ; Université de Liège - ULiège > Complex and Entangled Systems from Atoms to Materials (CESAM)
Raes, Bart; Quantum Solid-State Physics, Department of Physics and Astronomy, KU Leuven, Leuven, Belgium. ewald.janssens@kuleuven.be
Brems, Steven; Imec, Leuven, Belgium
De Gendt, Stefan; Imec, Leuven, Belgium ; Division of Molecular Design and Synthesis, Department of Chemistry, KU Leuven, Leuven, Belgium
Höltzl, Tibor ; Budapest University of Technology and Economics, Department of Inorganic and Analytical Chemistry and MTA-BME Computation driven research group, Budapest, Hungary ; Furukawa Electric Institute of Technology Ltd., Budapest, Hungary
Houssa, Michel ; Semiconductor Physics Laboratory, Department of Physics and Astronomy, KU Leuven, Leuven, Belgium ; Imec, Leuven, Belgium
Van de Vondel, Joris ; Quantum Solid-State Physics, Department of Physics and Astronomy, KU Leuven, Leuven, Belgium. ewald.janssens@kuleuven.be
Janssens, Ewald ; Quantum Solid-State Physics, Department of Physics and Astronomy, KU Leuven, Leuven, Belgium. ewald.janssens@kuleuven.be
BUTE - Budapesti Műszaki és Gazdaságtudományi Egyetem MTA - Magyar Tudományos Akadémia FWO - Fonds Wetenschappelijk Onderzoek Vlaanderen KU Leuven - Katholieke Universiteit Leuven EU - European Union F.R.S.-FNRS - Fonds de la Recherche Scientifique
Montemore M. M. van Spronsen M. A. Madix R. J. Friend C. M. Chem. Rev. 2017 118 2816 2862
Brown W. A. Kose R. King D. A. Chem. Rev. 1998 98 797 832
Rakić V. and Damjanović L., Temperature-programmed desorption (TPD) methods, in Calorimetry and thermal methods in catalysis, ed. A. Auroux, Springer, Berlin, Heidelberg, first edition, 2013, pp. 131-174
Campbell C. T. Sellers J. R. J. Am. Chem. Soc. 2012 134 18109 18115
Luo Z. Castleman Jr. A. W. Khanna S. N. Chem. Rev. 2016 116 14456 14492
Reber A. C. Khanna S. N. Acc. Chem. Res. 2017 50 255 263
Lei Y. Mehmood F. Lee S. Greeley J. Lee B. Seifert S. et al. Science 2010 328 224 228
Corma A. Concepción P. Boronat M. Sabater M. J. Navas J. Yacaman M. J. et al. Nat. Chem. 2013 5 775 781
Concepción P. Boronat M. García-García S. Fernández E. Corma A. ACS Catal. 2017 7 3560 3568
Yin C. Negreiros F. R. Barcaro G. Beniya A. Sementa L. Tyo E. C. et al. J. Mater. Chem. A 2017 5 4923 4931
Beniya A. Higashi S. Ohba N. Jinnouchi R. Hirata H. Watanabe Y. Nat. Commun. 2020 11 1 10
Lee S. Fan C. Wu T. Anderson S. L. J. Am. Chem. Soc. 2004 126 5682 5683
Sangnier A. Matrat M. Nicolle A. Dujardin C. Chizallet C. J. Phys. Chem. C 2018 122 26974 26986
Bower J. E. Jarrold M. F. J. Chem. Phys. 1992 97 11 8312 8321
Schedin F. Geim A. K. Morozov S. V. Hill E. W. Blake P. Katsnelson M. I. et al. Nat. Mater. 2007 6 652 655
Baachaoui S. Aldulaijan S. Sementa L. Fortunelli A. Dhouib A. Raouafi N. J. Phys. Chem. C 2021 125 26418 26428
Ricciardella F. Vollebregt S. Polichetti T. Miscuglio M. Alfano B. Miglietta M. L. et al. Nanoscale 2017 9 6085 6093
Berdiyorov G. R. Abdullah H. Al Ezzi M. Rakhmatullaeva G. V. Bahlouli H. Tit N. AIP Adv. 2016 6 125102
Cortés-Arriagada D. Villegas-Escobar N. Ortega D. E. Appl. Surf. Sci. 2018 427 227 236
Tian W. Liu X. Yu W. Appl. Sci. 2018 8 1118
Rumyantsev S. Liu G. Shur M. S. Potyrailo R. A. Balandin A. A. Nano Lett. 2012 12 2294 2298
Seol J. H. Jo I. Moore A. L. Lindsay L. Aitken Z. H. Pettes M. T. et al. Science 2010 328 213 216
Moser J. Barreiro A. Bachtold A. Appl. Phys. Lett. 2007 91 163513
Bae M. H. Ong Z. Y. Estrada D. Pop E. Nano Lett. 2010 10 4787 4793
Freitag M. Chiu H. Y. Steiner M. Perebeinos V. Avouris P. Nat. Nanotechnol. 2010 5 497 501
Scheerder J. E. Picot T. Reckinger N. Sneyder T. Zharinov V. S. Colomer J. F. et al. Nanoscale 2017 9 10494 10501
Scheerder J. E. Liu S. Zharinov V. S. Reckinger N. Colomer J. F. Cheng H. P. et al. Adv. Mater. Interfaces 2018 5 1801274
Di Vece M. Palomba S. Palmer R. E. Phys. Rev. B: Condens. Matter Mater. Phys. 2005 72 073407
Adam S. Hwang E. H. Galitski V. M. Sarma S. D. Proc. Natl. Acad. Sci. U. S. A. 2007 104 18392 18397
Dorgan V. E. Bae M. H. Pop E. Appl. Phys. Lett. 2010 97 082112
Kresse G. Hafner J. Phys. Rev. B: Condens. Matter Mater. Phys. 1993 47 558
Kresse G. Furthmüller J. Comput. Mater. Sci. 1996 6 15 50
Kresse G. Joubert D. Phys. Rev. B: Condens. Matter Mater. Phys. 1999 59 1758
Blöchl P. E. Phys. Rev. B: Condens. Matter Mater. Phys. 1994 50 17953
Perdew J. P. Burke K. Ernzerhof M. Phys. Rev. Lett. 1996 77 3865
Grimme S. J. Comput. Chem. 2006 27 1787 1799
Sławińska J. Dabrowski P. Zasada I. Phys. Rev. B: Condens. Matter Mater. Phys. 2011 83 245429
Mortensen J. J. Hansen L. B. Jacobsen K. W. Phys. Rev. B: Condens. Matter Mater. Phys. 2005 71 035109
Enkovaara J. Rostgaard C. Mortensen J. J. Chen J. Dułak M. Ferrighi L. et al. J. Phys.: Condens. Matter 2010 22 253202
Larsen A. H. Mortensen J. J. Blomqvist J. Castelli I. E. Christensen R. Dułak M. et al. J. Phys.: Condens. Matter 2017 29 273002
Grimme S. Antony J. Ehrlich S. Krieg H. J. Chem. Phys. 2010 132 154104
Larsen A. H. Vanin M. Mortensen J. J. Thygesen K. S. Jacobsen K. W. Phys. Rev. B: Condens. Matter Mater. Phys. 2009 80 195112
Collinge G. Yuk S. F. Nguyen M. T. Lee M. S. Glezakou V. A. Rousseau R. ACS Catal. 2020 10 9236 9260
Mehmood F. Pachter R. Lu W. Boeckl J. J. J. Phys. Chem. C 2013 117 10366 10374
Upadhyay S. K., Chemical kinetics and reaction dynamics, Springer, Dordrecht, 2007
Yang L. M. Dornfeld M. Frauenheim T. Ganz E. Phys. Chem. Chem. Phys. 2015 17 26036 26042
Wang H. Wu Y. Cong C. Shang J. Yu T. ACS Nano 2010 4 7221 7228
Jia M. Vanbuel J. Ferrari P. Schöllkopf W. Fielicke A. Nguyen M. T. et al. J. Phys. Chem. C 2020 124 7624 7633
Sun J. J. Cheng J. Nat. Commun. 2019 10 1 7
Zarshenas M. Gervilla V. Sangiovanni D. G. Sarakinos K. Phys. Chem. Chem. Phys. 2021 23 13087 13094
Ishigami M. Chen J. H. Cullen W. G. Fuhrer M. S. Williams E. D. Nano Lett. 2007 7 1643 1648
Lado-Touriño I. Páez-Pavón A. Nanomaterials 2021 11 1378
Plant S. R. Cao L. Yin F. Wang Z. W. Palmer R. E. Nanoscale 2014 6 1258 1263
