skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Influence of cluster–support interactions on reactivity of size-selected NbxOy clusters

Abstract

Size-selected niobium oxide nanoclusters (Nb3O5, Nb3O7, Nb4O7, and Nb4O10) were deposited at room temperature onto a Cu(111) surface and a thin film of Cu2O on Cu(111), and their interfacial electronic interactions and reactivity toward water dissociation were examined. These clusters were specifically chosen to elucidate the effects of the oxidation state of the metal centers; Nb3O5 and Nb4O7 are the reduced counterparts of Nb3O7 and Nb4O10, respectively. From two-photon photoemission spectroscopy (2PPE) measurements, we found that the work function increases upon cluster adsorption in all cases, indicating a negative interfacial dipole moment with the positive end pointing into the surface. The amount of increase was greater for the clusters with more metal centers and higher oxidation state. Additional analysis with DFT calculations of the clusters on Cu(111) indicated that the reduced clusters donate electrons to the substrate, indicating that the intrinsic cluster dipole moment makes a larger contribution to the overall interfacial dipole moment than charge transfer. X-ray photoelectron spectroscopy (XPS) measurements showed that the Nb atoms of Nb3O7 and Nb4O10 are primarily Nb5+ on Cu(111), while for the reduced Nb3O5 and Nb4O7 clusters, a mixture of oxidation states was observed on Cu(111). Temperature-programmed desorption (TPD) experiments with D2O showedmore » that water dissociation occurred on all systems except for the oxidized Nb3O7 and Nb4O10 clusters on the Cu2O film. A comparison of our XPS and TPD results suggests that Nb5+ cations associated with Nb=O terminal groups act as Lewis acid sites which are key for water binding and subsequent dissociation. TPD measurements of 2-propanol dehydration also show that the clusters active toward water dissociation are indeed acidic. DFT calculations of water dissociation on Nb3O7 support our TPD results, but the use of bulk Cu2O(111) as a model for the Cu2O film merits future scrutiny in terms of interfacial charge transfer. The combination of our experimental and theoretical results suggests that both Lewis acidity and metal reducibility are important for water dissociation.« less

Authors:
 [1];  [2];  [1];  [1];  [3]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Stony Brook Univ., Stony Brook, NY (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1224194
Report Number(s):
BNL-108466-2015-JA
Journal ID: ISSN 1932-7447; R&D Project: CO007; KC0301020
Grant/Contract Number:  
SC00112704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 119; Journal Issue: 26; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Nakayama, Miki, Xue, Meng, An, Wei, Liu, Ping, and White, Michael G. Influence of cluster–support interactions on reactivity of size-selected NbxOy clusters. United States: N. p., 2015. Web. doi:10.1021/acs.jpcc.5b00691.
Nakayama, Miki, Xue, Meng, An, Wei, Liu, Ping, & White, Michael G. Influence of cluster–support interactions on reactivity of size-selected NbxOy clusters. United States. https://doi.org/10.1021/acs.jpcc.5b00691
Nakayama, Miki, Xue, Meng, An, Wei, Liu, Ping, and White, Michael G. 2015. "Influence of cluster–support interactions on reactivity of size-selected NbxOy clusters". United States. https://doi.org/10.1021/acs.jpcc.5b00691. https://www.osti.gov/servlets/purl/1224194.
@article{osti_1224194,
title = {Influence of cluster–support interactions on reactivity of size-selected NbxOy clusters},
author = {Nakayama, Miki and Xue, Meng and An, Wei and Liu, Ping and White, Michael G.},
abstractNote = {Size-selected niobium oxide nanoclusters (Nb3O5, Nb3O7, Nb4O7, and Nb4O10) were deposited at room temperature onto a Cu(111) surface and a thin film of Cu2O on Cu(111), and their interfacial electronic interactions and reactivity toward water dissociation were examined. These clusters were specifically chosen to elucidate the effects of the oxidation state of the metal centers; Nb3O5 and Nb4O7 are the reduced counterparts of Nb3O7 and Nb4O10, respectively. From two-photon photoemission spectroscopy (2PPE) measurements, we found that the work function increases upon cluster adsorption in all cases, indicating a negative interfacial dipole moment with the positive end pointing into the surface. The amount of increase was greater for the clusters with more metal centers and higher oxidation state. Additional analysis with DFT calculations of the clusters on Cu(111) indicated that the reduced clusters donate electrons to the substrate, indicating that the intrinsic cluster dipole moment makes a larger contribution to the overall interfacial dipole moment than charge transfer. X-ray photoelectron spectroscopy (XPS) measurements showed that the Nb atoms of Nb3O7 and Nb4O10 are primarily Nb5+ on Cu(111), while for the reduced Nb3O5 and Nb4O7 clusters, a mixture of oxidation states was observed on Cu(111). Temperature-programmed desorption (TPD) experiments with D2O showed that water dissociation occurred on all systems except for the oxidized Nb3O7 and Nb4O10 clusters on the Cu2O film. A comparison of our XPS and TPD results suggests that Nb5+ cations associated with Nb=O terminal groups act as Lewis acid sites which are key for water binding and subsequent dissociation. TPD measurements of 2-propanol dehydration also show that the clusters active toward water dissociation are indeed acidic. DFT calculations of water dissociation on Nb3O7 support our TPD results, but the use of bulk Cu2O(111) as a model for the Cu2O film merits future scrutiny in terms of interfacial charge transfer. The combination of our experimental and theoretical results suggests that both Lewis acidity and metal reducibility are important for water dissociation.},
doi = {10.1021/acs.jpcc.5b00691},
url = {https://www.osti.gov/biblio/1224194}, journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 26,
volume = 119,
place = {United States},
year = {Fri Apr 17 00:00:00 EDT 2015},
month = {Fri Apr 17 00:00:00 EDT 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 24 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

An IRAS study of hydroxyl species (OD(a)) on oxygen-modified Cu(110) surface
journal, September 1993


Oxide ultra-thin films on metals: new materials for the design of supported metal catalysts
journal, January 2008


Infrared Spectroscopy of Niobium Oxide Cluster Cations in a Molecular Beam:  Identifying the Cluster Structures
journal, March 2003


Stoichiometric and Oxygen-Rich M 2 O n and M 2 O n (M = Nb, Ta; n = 5−7) Clusters: Molecular Models for Oxygen Radicals, Diradicals, and Superoxides
journal, March 2011


Oxidation of Cu(111): two new oxygen induced reconstructions
journal, December 1991


Nanostructured Oxides in Chemistry:  Characterization and Properties
journal, September 2004


Oxidation, Reduction, and Condensation of Alcohols over (MO 3 ) 3 (M = Mo, W) Nanoclusters
journal, September 2014


Water-Gas Shift Reaction on a Highly Active Inverse CeO x /Cu(111) Catalyst: Unique Role of Ceria Nanoparticles
journal, October 2009


Niobium Compounds:  Preparation, Characterization, and Application in Heterogeneous Catalysis
journal, December 1999


Gas-Phase Reactivity of the Ti 8 C 12 + Met-car with Triatomic Sulfur-Containing Molecules:  CS 2 , SCO, and SO 2
journal, March 2006


Scanning tunneling microscopy studies of oxygen adsorption on Cu(111)
journal, January 2001


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Two new oxygen induced reconstructions on Cu(111)
journal, May 1992


Formation and distribution of neutral vanadium, niobium, and tantalum oxide clusters: Single photon ionization at 26.5eV
journal, October 2006


Virial Field Relationship for Molecular Charge Distributions and the Spatial Partitioning of Molecular Properties
journal, April 1972


Reactions of Niobium and Tantalum Oxide Cluster Cations and Anions with n -Butane
journal, April 2001


A new generation of water gas shift catalysts for fuel cell applications
journal, May 2003


A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006


The molecular structures and reactivity of supported niobium oxide catalysts
journal, October 1990


The interaction of water with solid surfaces: fundamental aspects revisited
journal, May 2002


Niobium-containing catalysts—the state of the art
journal, February 2003


Work function changes induced by deposition of ultrathin dielectric films on metals: A theoretical analysis
journal, December 2008


Raman studies of the structure of niobium oxide/titanium oxide (Nb2O5.TiO2)
journal, November 1993


Water-gas shift reaction: finding the mechanistic boundary
journal, January 1995


Ab initiomolecular dynamics for liquid metals
journal, January 1993


A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000


Density functional study of water-gas shift reaction on M3O3x/Cu(111)
journal, January 2012


Inverse oxide/metal catalysts: A versatile approach for activity tests and mechanistic studies
journal, February 2010


Electronic charging of non-metallic clusters: size-selected MoxSy clusters supported on an ultrathin alumina film on NiAl(110)
journal, January 2012


Autocatalytic Water Dissociation on Cu(110) at Near Ambient Conditions
journal, March 2008


Studies of Metal Oxide Clusters:  Elucidating Reactive Sites Responsible for the Activity of Transition Metal Oxide Catalysts
journal, June 2002


Autocatalytic Reduction of a Cu 2 O/Cu(111) Surface by CO: STM, XPS, and DFT Studies
journal, July 2010


Oxygen adsorption and stability of surface oxides on Cu ( 111 ) : A first-principles investigation
journal, April 2006


Molecular structures of supported niobium oxide catalysts under in situ conditions
journal, September 1991


Photoelectron spectroscopy and diffraction of NbO x /Nb(110) surface
journal, July 2008


Control of the Charge State of Metal Atoms on Thin MgO Films
journal, March 2007


Exfoliated HNb 3 O 8 Nanosheets as a Strong Protonic Solid Acid
journal, May 2005


On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper
journal, January 2008


Catalytic Dehydration of 2-Propanol on (WO 3 ) 3 Clusters on TiO 2 (110)
journal, April 2008


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Water gas shift reaction kinetics and reactor modeling for fuel cell grade hydrogen
journal, November 2003


On the Mutual Potential Energy of a Plane Network of Doublets
journal, February 1927


Special points for Brillouin-zone integrations
journal, June 1976


Adsorption of molecular nitrogen by the W(110) plane
journal, January 1976


XPS analysis of the surface composition of niobium for superconducting RF cavities
journal, April 1998


Structure and Bonding of Tungsten Oxide Clusters on Nanostructured Cu-O Surfaces
journal, November 2011


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


In Situ Spectroscopic Investigation of the Molecular and Electronic Structures of SiO 2 Supported Surface Metal Oxides
journal, October 2007


Photodecomposition of water and hydrogen evolution from aqueous methanol solution over novel niobate photocatalysts
journal, January 1986


X-ray Photoemission Study of the Charge State of Au Nanoparticles on Thin MgO/Fe(001) Films
journal, October 2009


Recent Advances in Catalysts for Methanol Synthesis via Hydrogenation of CO and CO 2
journal, December 2003


The preparation of and water adsorption on thin films of niobium oxide on Pt(111)
journal, January 1994


Catalytic application of niobium compounds
journal, February 2003


Formation, Structures, and Reactivities of Niobium Oxide Cluster Ions
journal, January 1996


Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992


Electronic structure of supported small metal clusters
journal, January 1983


Nb 3d and O 1s core levels and chemical bonding in niobates
journal, February 2005


Niobium Oxide Nanoscrolls as Building Blocks for Dye-Sensitized Hydrogen Production from Water under Visible Light Irradiation
journal, October 2008


Dehydration of methanol to dimethyl ether over Nb2O5 and NbOPO4 catalysts: Microcalorimetric and FT-IR studies
journal, September 2007


Reversible work transition state theory: application to dissociative adsorption of hydrogen
journal, February 1995


The Oxidation Activity and Acid-base Properties of V 2 O 5 -based Binary Catalysts
journal, October 1977


Electronic Structure of the Thiophene/Au(111) Interface Probed by Two-Photon Photoemission
journal, July 2010


Surface distribution of Cu adatoms deduced from work function measurements
journal, January 2002


Oxygen Atoms on Cu(100) Formed at 100 K, Active for CO Oxidation and Water−Hydrogen Abstraction, Characterized by HREELS and TPD
journal, June 1997


Hydroxyl Chain Formation on the Cu(110) Surface: Watching Water Dissociation
journal, October 2008


Tuning the Charge State of (WO 3 ) 3 Nanoclusters Deposited on MgO/Ag(001) Films
journal, August 2012


Surface Dipoles and Electron Transfer at the Metal Oxide–Metal Interface: A 2PPE Study of Size-Selected Metal Oxide Clusters Supported on Cu(111)
journal, June 2014


Two-photon photoemission spectroscopy: atomic oxygen on Cu(111) and styrene on oxygen covered Cu(111)
conference, October 2004


Water-gas shift activity of Cu surfaces and Cu nanoparticles supported on metal oxides
journal, May 2009


Electronic structure of Cu 2 O and CuO
journal, December 1988


WGS and reforming properties of NbMCM-41 materials
journal, May 2006


Probing the Electronic Structure of Early Transition-Metal Oxide Clusters:  Polyhedral Cages of (V 2 O 5 ) n - ( n = 2−4) and (M 2 O 5 ) 2 - (M = Nb, Ta)
journal, October 2007


Water Resistant, Catalytically Active Nb and Ta Isolated Lewis Acid Sites, Homogeneously Distributed by Direct Synthesis in a Beta Zeolite
journal, July 2009

  • Corma, Avelino; Llabrés i Xamena, Francesc X.; Prestipino, Carmelo
  • The Journal of Physical Chemistry C, Vol. 113, Issue 26, p. 11306-11315
  • https://doi.org/10.1021/jp902375n

The surface chemistry of H2O on clean and oxygen-covered Cu(110)
journal, February 1984


Reversible switching of tetra-tert-butyl-azobenzene on a Au(111) surface induced by light and thermal activation
journal, August 2007


Electronic Structure at Organic/Metal Interfaces:  Naphthalene/Cu(111)
journal, November 2000


Works referencing / citing this record:

Survey of short and long cuprophilic d 10 –d 10 contacts for tetranuclear copper clusters. Understanding of bonding and ligand role from a planar superatom perspective
journal, January 2018


Self-organizing layers from complex molecular anions
journal, May 2018


Investigation of Layer Structured NbSe 2 as an Intercalation Anode Material for Sodium-Ion Hybrid Capacitors
journal, January 2019


Self-organizing layers from complex molecular anions
journal, May 2018


Morphology and reactivity of size-selected titanium oxide nanoclusters on Au(111)
journal, February 2020