Skip to main content
Fachgebiete
Automobil + Motoren Bauwesen + Immobilien Business IT + Informatik Elektrotechnik + Elektronik Energie + Nachhaltigkeit Finance + Banking Management + Führung Marketing + Vertrieb Maschinenbau + Werkstoffe Versicherung + Risiko
DE
EN
Themenseiten
Organisationspsychologie Projektmanagement Marketing Smart Manufacturing
Bücher
Zeitschriften
Weitere Formate
Podcasts Webinare Technik Webinare Wirtschaft Kongresse Veranstaltungskalender Awards
Jetzt Einzelzugang starten
Zugang für Unternehmen
Referenzkunden
ATZ-Fachkongress

Chassis.tech plus 2024


4 Kongresse in einer Veranstaltung

Treffen Sie in München die Fachleute von Chassis, Lenkung, Bremsen sowie Reifen/Räder.
Erweiterte Suche
Anmelden
nach oben
Topics in Catalysis
Erschienen in: Topics in Catalysis 10-11/2015

01.08.2015 | Original Paper

A Comparative Study of Methanol Adsorption and Dissociation over WO3(001) and ReO3(001)

verfasst von: Qingfeng Ge, Maciej Gutowski

Erschienen in: Topics in Catalysis | Ausgabe 10-11/2015

Einloggen

Aktivieren Sie unsere intelligente Suche, um passende Fachinhalte oder Patente zu finden.

search-config
loading …

Abstract

Tungsten (5d46s2) and rhenium (5d56s2) form MO3 oxides (M = W or Re) with similar structures. The adsorption and dissociation of methanol on these oxide surfaces, often used to probe the surface redox centers, have been analyzed using periodic density functional calculations. Molecular adsorption of methanol at the metal site on both surfaces with 0.5 ML oxygen coverage was found to be exothermic with adsorption energies of −74 and −106 kJ/mol on WO3(001) and ReO3(001), respectively. In contrast, heterolytic dissociation of methanol to adsorbed methoxide species at the metal site and H at the surface oxygen site is not energetically favored on WO3(001) but favored on ReO3(001). The dissociation energies to form coadsorbed methoxide and hydrogen adatom are 35 kJ/mol on WO3 and −112 kJ/mol on ReO3, respectively. The activation barrier for dissociating the molecularly adsorbed methanol on ReO3(001) was determined to be 19 kJ/mol. Dehydrogenation to form coadsorbed hydroxymethyl and hydrogen adatom is not energetically favorable on both surfaces with respect to the molecularly adsorbed methanol. However, the dehydrogenation path is exothermic on ReO3 with respect to the gas phase methanol, with the heats of reaction of −25 kJ/mol, but highly endothermic on WO3, with the heats of reaction of 114 kJ/mol.
Vorheriger Artikel Atomic Structure of Heterophase Junction from Theoretical Prediction
Nächster Artikel CO Dissociation at Vacancy Sites on Hägg Iron Carbide: Direct Versus Hydrogen-Assisted Routes Investigated with DFT

Sie haben noch keine Lizenz? Dann Informieren Sie sich jetzt über unsere Produkte:

Springer Professional "Wirtschaft+Technik"

Online-Abonnement

Mit Springer Professional "Wirtschaft+Technik" erhalten Sie Zugriff auf:

  • über 102.000 Bücher
  • über 537 Zeitschriften

aus folgenden Fachgebieten:

  • Automobil + Motoren
  • Bauwesen + Immobilien
  • Business IT + Informatik
  • Elektrotechnik + Elektronik
  • Energie + Nachhaltigkeit
  • Finance + Banking
  • Management + Führung
  • Marketing + Vertrieb
  • Maschinenbau + Werkstoffe
  • Versicherung + Risiko

Jetzt Wissensvorsprung sichern!

Jetzt informieren

Springer Professional "Technik"

Online-Abonnement

Mit Springer Professional "Technik" erhalten Sie Zugriff auf:

  • über 67.000 Bücher
  • über 390 Zeitschriften

aus folgenden Fachgebieten:

  • Automobil + Motoren
  • Bauwesen + Immobilien
  • Business IT + Informatik
  • Elektrotechnik + Elektronik
  • Energie + Nachhaltigkeit
  • Maschinenbau + Werkstoffe




 

Jetzt Wissensvorsprung sichern!

Jetzt informieren
Literatur
1.
Henrich VE, Cox PA (1996) The surface science of metal oxides. Cambridge University Press, Cambridge
2.
Murrell LL, Grenoble DC, Kim CJ, Dispenziere NC (1987) Supported transition-metal oxides as acid cracking catalysts—periodic trends and their relationship to activity and selectivity. J Catal 107:463–470CrossRef
3.
Benitez VM, Querini CA, Figoli NS (2003) Characterization of WOx/Al2O3 and MoOx/Al2O3 catalysts and their activity and deactivation during skeletal isomerization of 1-butene. Appl Catal A 252:427–436CrossRef
4.
Mamede AS, Payen E, Grange P, Poncelet G, Ion A, Alifanti M, Parvulescu VI (2004) Characterization of WOx/CeO2 catalysts and their reactivity in the isomerization of hexane. J Catal 223:1–12CrossRef
5.
Di Gregorio F, Keller V (2004) Activation and isomerization of hydrocarbons over WO3/ZrO2 catalysts—I. Preparation, characterization, and X-ray photoelectron spectroscopy studies. J Catal 225:45–55CrossRef
6.
Benitez VM, Querini CA, Figoli NS, Comelli RA (1999) Skeletal isomerization of 1-butene on WOx/γ-Al2O3. Appl Catal A-Gen 178:205–218CrossRef
7.
Ji WJ, Chen Y, Kung HH (1997) Vapor phase aldol condensation of acetaldehyde on metal oxide catalysts. Appl Catal A 161:93–104CrossRef
8.
Hilbrig F, Schmelz H, Knozinger H, Sinev M, Bell AT, Schmal M, Forzatti P, Wachs IE, Uematsu T, Vedrine JC, Hums E (1993) Acidity of WOx/TiO2 catalysts for selective catalytic reduction (SCR). Stud Surf Sci Catal 75:1351–1362CrossRef
9.
Yuan YH, Iwasawa Y (2002) Performance and characterization of supported rhenium oxide catalysts for selective oxidation of methanol to methylal. J Phys Chem B 106:4441–4449CrossRef
10.
Viswanadham N, Shido T, Iwasawa Y (2001) Performances of rhenium oxide-encapsulated ZSM-5 catalysts in propene selective oxidation/ammoxidation. Appl Catal A 219:223–233CrossRef
11.
Barton Cole E, Lakkaraju PS, Rampulla DM, Morris AJ, Abelev E, Bocarsly AB (2010) Using a one-electron shuttle for the multielectron reduction of CO2 to methanol: kinetic, mechanistic, and structural insights. J Am Chem Soc 132:11539–11551CrossRef
12.
Ge Q (2013) Chapter 3—mechanistic understanding of catalytic CO2 activation from first principles theory. In: Suib SL (ed) New and future developments in catalysis. Elsevier, Amsterdam, pp 49–79CrossRef
13.
Wachs IE, Deo G, Juskelis MV, Weckhuysen BM (1997) Methanol oxidation over supported vanadium oxide catalysts: new fundamental insights about oxidation reactions over metal oxide catalysts from transient and steady state kinetics. In: Froment GF, Waugh KC (eds) Dynamics of surfaces and reaction kinetics in heterogeneous catalysis. Elsevier, Amsterdam, pp 305–314CrossRef
14.
Cheng W-H, Kung HH (1994) Methanol production and use. Marcel Dekker, New York
15.
Badlani M, Wachs IE (2001) Methanol: a “smart” chemical probe molecule. Catal Lett 75:137–149CrossRef
16.
Burcham LJ, Wachs IE (1999) The origin of the support effect in supported metal oxide catalysts: in situ infrared and kinetic studies during methanol oxidation. Catal Today 49:467–484CrossRef
17.
Wachs IE, Chen Y, Jehng JM, Briand LE, Tanaka T (2003) Molecular structure and reactivity of the group V metal oxides. Catal Today 78:13–24CrossRef
18.
Gao XT, Jehng JM, Wachs IE (2002) In situ UV-vis-NIR diffuse reflectance and Raman spectroscopic studies of propane oxidation over ZrO2-supported vanadium oxide catalysts. J Catal 209:43–50CrossRef
19.
Schirber JE, Morosin B (1979) “Compressibility collapse” transition in ReO3. Phys Rev Lett 42:1485–1487CrossRef
20.
Woodward PM, Sleight AW, Vogt T (1997) Ferroelectric tungsten trioxide. J Solid State Chem 131:9–17CrossRef
21.
Butler MA, Nasby RD, Quinn RK (1976) Tungsten trioxide as an electrode for photoelectrolysis of water. Solid State Commun 19:1011–1014CrossRef
22.
Ferretti A, Rogers DB, Goodenough JB (1965) The relation of the electrical conductivity in single crystals of rhenium trioxide to the conductivities of Sr2MgReO6 and NaxWO3. J Phys Chem Solids 26:2007–2011CrossRef
23.
Gurlo A (2011) Nanosensors: towards morphological control of gas sensing activity. SnO2, In2O3, ZnO and WO3 case studies. Nanoscale 3:154–165CrossRef
24.
Mei D, Deskins NA, Dupuis M, Ge Q (2008) Density functional theory study of methanol decomposition on the CeO2(110) surface. J Phys Chem C 112:4257–4266CrossRef
25.
Mei D, Deskins NA, Dupuis M, Ge Q (2007) Methanol adsorption on the clean CeO2(111) surface: a density functional theory study. J Phys Chem C 111:10514–10522CrossRef
26.
Han Y, Liu C-J, Ge Q (2009) Effect of Pt clusters on methanol adsorption and dissociation over perfect and defective anatase TiO2(101) surface. J Phys Chem C 113:20674–20682CrossRef
27.
Ye J, Liu C, Ge Q (2012) A DFT study of methanol dehydrogenation on the PdIn(110) surface. Phys Chem Chem Phys 14:16660–16667CrossRef
28.
Kresse G, Furthmuller J (1996) Efficiency of ab initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput Mater Sci 6:15–50CrossRef
29.
Kresse G, Hafner J (1993) Ab initio molecular-dynamics for liquid-metals. Phys Rev B 47:558–561CrossRef
30.
Vanderbilt D (1990) Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Phys Rev B 41:7892–7895CrossRef
31.
Blochl PE (1994) Projector augmented-wave method. Phys Rev B 50:17953–17979CrossRef
32.
Hobbs D, Kresse G, Hafner J (2000) Fully unconstrained noncollinear magnetism within the projector augmented-wave method. Phys Rev B 62:11556–11570CrossRef
33.
Perdew JP, Chevary JA, Vosko SH, Jackson KA, Pederson MR, Singh DJ, Fiolhais C (1992) Atoms, molecules, solids, and surfaces—applications of the generalized gradient approximation for exchange and correlation. Phys Rev B 46:6671–6687CrossRef
34.
Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77:3865–3868CrossRef
35.
Monkhorst HJ, Pack JD (1976) Special points for Brillouin-zone integrations. Phys Rev B 13:5188–5192CrossRef
36.
Mills G, Jonsson H, Schenter GK (1995) Reversible work transition-state theory—application to dissociative adsorption of hydrogen. Surf Sci 324:305–337CrossRef
37.
Henkelman G, Jonsson H (2000) Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J Chem Phys 113:9978–9985CrossRef
38.
Henkelman G, Uberuaga BP, Jonsson H (2000) A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J Chem Phys 113:9901–9904CrossRef
39.
Pan Y-X, Liu C-J, Ge Q (2010) Effect of surface hydroxyls on selective CO2 hydrogenation over Ni4/γ-Al2O3: a density functional theory study. J Catal 272:227–234CrossRef
40.
Zhang Z, Tang M, Wang Z-T, Ke Z, Xia Y, Park K, Lyubinetsky I, Dohnálek Z, Ge Q (2015) Imaging of formaldehyde adsorption and diffusion on TiO2(110). Top Catal 58:103–113CrossRef
41.
Kresse G, Furthmuller J (2015) VASP, the Guide
42.
Yakovkin IN, Gutowski M (2007) Driving force for the WO3(001) surface relaxation. Surf Sci 601:1481–1488CrossRef
43.
Tanner RE, Altman EI (2001) Effect of surface treatment on the γ-WO3(001) surface: a comprehensive study of oxidation and reduction by scanning tunneling microscopy and low-energy electron diffraction. J Vac Sci Technol A 19:1502–1509CrossRef
44.
Li M, Posadas A, Ahn CH, Altman EI (2005) Scanning tunneling microscopy study of terminal oxygen structures on WO3(100) thin films. Surf Sci 579:175–187CrossRef
45.
Huang X, Zhai HJ, Li J, Wang LS (2006) On the structure and chemical bonding of tri-tungsten oxide clusters W3O n − and W3On (n = 7 − 10): W3O8 as a potential molecular model for O-deficient defect sites in tungsten oxides. J Phys Chem A 110:85–92CrossRef
46.
Ling S, Mei D, Gutowski M (2011) Reactivity of hydrogen and methanol on (001) surfaces of WO3, ReO3, WO3/ReO3 and ReO3/WO3. Catal Today 165:41–48CrossRef
47.
Wachs IE (1996) Raman and IR studies of surface metal oxide species on oxide supports: supported metal oxide catalysts. Catal Today 27:437–455CrossRef
48.
Macht J, Baertsch CD, May-Lozano M, Soled SL, Wang Y, Iglesia E (2004) Support effects on Bronsted acid site densities and alcohol dehydration turnover rates on tungsten oxide domains. J Catal 227:479–491CrossRef
49.
Onfroy T, Clet G, Houalla M (2005) Acidity, surface structure, and catalytic performance of WOx supported on monoclinic zirconia. J Phys Chem B 109:3345–3354CrossRef
50.
Pan Y, Liu C-J, Ge Q (2008) Adsorption and protonation of CO2 on partially hydroxylated γ-Al2O3 surfaces: a density functional theory study. Langmuir 24:12410–12419CrossRef
51.
Pan Y-X, Kuai P, Liu Y, Ge Q, Liu C-J (2010) Promotion effects of Ga2O3 on CO2 adsorption and conversion over a SiO2-supported Ni catalyst. Energy Environ Sci 3:1322–1325CrossRef
52.
Pan Y-X, Liu C-J, Mei D, Ge Q (2010) Effects of hydration and oxygen vacancy on CO2 adsorption and activation on β-Ga2O3(100). Langmuir 26:5551–5558CrossRef
53.
Yin S, Swift T, Ge Q (2011) Adsorption and activation of CO2 over the Cu-Co catalyst supported on partially hydroxylated γ-Al2O3. Catal Today 165:10–18CrossRef
Metadaten
Titel
A Comparative Study of Methanol Adsorption and Dissociation over WO3(001) and ReO3(001)
verfasst von
Qingfeng Ge
Maciej Gutowski
Publikationsdatum
01.08.2015
Verlag
Springer US
Erschienen in
Topics in Catalysis / Ausgabe 10-11/2015
Print ISSN: 1022-5528
Elektronische ISSN: 1572-9028
DOI
https://doi.org/10.1007/s11244-015-0402-0

Weitere Artikel der Ausgabe 10-11/2015

Topics in Catalysis 10-11/2015 Zur Ausgabe

Original Paper

The Catalyst Selectivity Index (CSI): A Framework and Metric to Assess the Impact of Catalyst Efficiency Enhancements upon Energy and CO2 Footprints

Original Paper

Sticking Probability and Reactivity of Hyperthermal O2 Molecules Impinging on CO Pre-covered Pd(100): Effect of Rotational States with K > 1

OriginalPaper

Prediction of Ir0.5M0.5O2 (M = Cr, Ru or Pb) Mixed Oxides as Active Catalysts for Oxygen Evolution Reaction from First-Principles Calculations

Original Paper

Adsorption and Reaction of SO2 on Graphene-Supported Pt Nanoclusters

Preface

Preface

Original Paper

Efficient Hydrolytic Hydrogenation of Cellulose on Mesoporous HZSM-5 Supported Ru Catalysts

Premium Partner

    Marktübersichten

    Die im Laufe eines Jahres in der „adhäsion“ veröffentlichten Marktübersichten helfen Anwendern verschiedenster Branchen, sich einen gezielten Überblick über Lieferantenangebote zu verschaffen. 

    Zur Marktübersicht
    Bildnachweise