Simulating Temperature Programmed Desorption of Oxygen on Pt(111) Using DFT Derived Coverage Dependent Desorption Barriers

被引:18
作者
Miller, Spencer D. [1 ]
Pushkarev, Vladimir V. [1 ]
Gellman, Andrew J. [1 ]
Kitchin, John R. [1 ]
机构
[1] Carnegie Mellon Univ, Dept Chem Engn, Pittsburgh, PA 15213 USA
关键词
Coverage dependence; Temperature programmed desorption; Density functional theory; Late transition metals; ATOMIC OXYGEN; ADSORPTION; NO; OXIDATION; CO; O-2; CHEMISORPTION; CALORIMETER; ENVIRONMENT; OXIDE;
D O I
10.1007/s11244-013-0166-3
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
The dissociative adsorption energy of oxygen on Pt(111) is known to be coverage dependent. Simple Redhead analysis of temperature programmed desorption (TPD) experiments that assumes a coverage independent desorption barrier can lead to errors in estimated properties such as desorption barriers and adsorption energies. A simple correction is to assume a linear coverage dependence of the desorption barrier, but there is usually no formal justification given for that functional form. More advanced TPD analysis methods that are suitable for determining coverage dependent adsorption parameters are limited by their need for large amounts of high quality, low noise data. We present a method to estimate the functional form of the coverage dependent desorption barrier from density functional theory calculations for use in analysis of TPD spectra. Density functional theory was employed to calculate the coverage dependence of the adsorption energy. Simulated TPD spectra were then produced by empirically scaling the DFT based adsorption energies utilizing the Bronstead-Evans-Polyani relationship between adsorption energies and desorption barriers. The resulting simulated spectra show better agreement with the experimental spectra than spectra predicted using barriers that are either coverage-independent or simply linearly dependent on coverage. The empirically derived scaling of the desorption barriers for Pt(111) is shown to be useful in predicting the low coverage desorption barriers for oxygen desorption from other metal surfaces, which showed reasonable agreement with the reported experimental values for those other metals.
引用
收藏
页码:106 / 117
页数:12
相关论文
共 50 条
[1]   Calorimeter for adsorption energies of larger molecules on single crystal surfaces [J].
Ajo, HM ;
Ihm, H ;
Moilanen, DE ;
Campbell, CT .
REVIEW OF SCIENTIFIC INSTRUMENTS, 2004, 75 (11) :4471-4480
[2]   Angle and energy distributions of thermally desorbing oxygen from Pt(111): The influences of a dynamically variable activation barrier [J].
Allers, KH ;
Pfnur, H ;
Feulner, P ;
Menzel, D .
ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS, 1996, 197 :253-268
[3]   GENERATION OF ATOMIC OXYGEN ON AG(111) AND AG(110) USING NO2 - A TPD, LEED, HREELS, XPS AND NRA STUDY [J].
BARE, SR ;
GRIFFITHS, K ;
LENNARD, WN ;
TANG, HT .
SURFACE SCIENCE, 1995, 342 (1-3) :185-198
[4]   LINEAR FREE-ENERGY RELATIONSHIPS FOR C1-OXYGENATE DECOMPOSITION ON TRANSITION-METAL SURFACES [J].
BARTEAU, MA .
CATALYSIS LETTERS, 1991, 8 (2-4) :175-184
[5]   The Bronsted-Evans-Polanyi relation and the volcano curve in heterogeneous catalysis [J].
Bligaard, T ;
Norskov, JK ;
Dahl, S ;
Matthiesen, J ;
Christensen, CH ;
Sehested, J .
JOURNAL OF CATALYSIS, 2004, 224 (01) :206-217
[6]   ATOMIC AND MOLECULAR-OXYGEN ADSORPTION ON AG(111) [J].
CAMPBELL, CT .
SURFACE SCIENCE, 1985, 157 (01) :43-60
[7]   THE ADSORPTION OF OXYGEN ON GOLD [J].
CANNING, NDS ;
OUTKA, D ;
MADIX, RJ .
SURFACE SCIENCE, 1984, 141 (01) :240-254
[8]   INTERACTION OF NO AND O-2 WITH PD(111) SURFACES .1. [J].
CONRAD, H ;
ERTL, G ;
KUPPERS, J ;
LATTA, EE .
SURFACE SCIENCE, 1977, 65 (01) :235-244
[9]   ADSORPTION OF HYDROGEN ON PALLADIUM SINGLE-CRYSTAL SURFACES [J].
CONRAD, H ;
ERTL, G ;
LATTA, EE .
SURFACE SCIENCE, 1974, 41 (02) :435-446
[10]   ADSORPTION OF CO ON PD SINGLE-CRYSTAL SURFACES [J].
CONRAD, H ;
ERTL, G ;
KOCH, J ;
LATTA, EE .
SURFACE SCIENCE, 1974, 43 (02) :462-480