Kinetic Isotope Effect in the Hydrogenation and Deuteration of Graphene

被引：39

作者：

Paris, Alessio ^{[1
]}

Verbitskiy, Nikolay ^{[2
,3
]}

Nefedov, Alexei ^{[4
]}

Wang, Ying ^{[5
]}

Fedorov, Alexander ^{[6
,7
]}

Haberer, Danny ^{[6
]}

Oehzelt, Martin ^{[8
]}

Petaccia, Luca ^{[9
]}

Usachov, Dmitry ^{[7
]}

Vyalikh, Denis ^{[7
,10
]}

Sachdev, Hermann ^{[11
]}

Woell, Christoph ^{[4
]}

Knupfer, Martin ^{[6
]}

Buechner, Bernd ^{[6
]}

Calliari, Lucia ^{[1
]}

Yashina, Lada ^{[12
]}

Irle, Stephan ^{[5
]}

Grueneis, Alexander ^{[3
,6
]}

机构：

[1] FBK CMM, LISC, I-38123 Trento, Italy

[2] Moscow MV Lomonosov State Univ, Dept Mat Sci, Moscow 119992, Russia

[3] Univ Vienna, Fac Phys, A-1090 Vienna, Austria

[4] KIT, IFG, D-76344 Eggenstein Leopoldshafen, Germany

[5] Nagoya Univ, Grad Sch Sci, Dept Chem, Nagoya, Aichi 4648602, Japan

[6] IFW Dresden, D-01171 Dresden, Germany

[7] St Petersburg State Univ, St Petersburg 198504, Russia

[8] Elektronenspeicherring BESSY II, Helmholtz Zentrum Berlin Mat & Energie, D-12489 Berlin, Germany

[9] Elettra Sincrotrone Trieste, I-34149 Trieste, Italy

[10] Tech Univ Dresden, Inst Festkorperphys, D-01069 Dresden, Germany

[11] Max Planck Inst Polymer Res, D-55128 Mainz, Germany

[12] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119992, Russia

来源：

ADVANCED FUNCTIONAL MATERIALS | 2013年 / 23卷 / 13期

关键词：

functionalized graphene; isotope effect; deuterium; time-dependent spectroscopy; ATOMIC-HYDROGEN; BASAL-PLANE; DEUTERIUM; CHEMISORPTION; CLUSTER; OXYGEN; MODEL;

D O I：

10.1002/adfm.201202355

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Time-dependent photoemission spectroscopy is employed to study the kinetics of the hydro-genation/deuteration reaction of graphene. Resulting in an unusual kinetic isotope effect, the graphene deuteration reaction proceeds faster than hydrogenation and leads to substantially higher maximum coverages of deuterium (D/C approximate to 35% vs H/C approximate to 25%). These results can be explained by the fact that in the atomic state H and D have a lower energy barrier to overcome in order to react with graphene, while in the molecular form the bond between two atoms must be broken before the capture on the graphene layer. More importantly, D has a higher desorption barrier than H due to quantum mechanical zero-point energy effects related to the CD or CH stretch vibration. Molecular dynamics simulations based on a quantum mechanical electronic potential can reproduce the experimental trends and reveal the contribution of the constituent chemisorption, reflection, and associative desorption processes of H or D atoms onto graphene. Regarding the electronic structure changes, a tunable electron energy gap can be induced by both deuteration and hydrogenation.

引用

页码：1628 / 1635

页数：8

共 36 条

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