DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Energy level shifts at the silica/Ru(0001) heterojunction driven by surface and interface dipoles

Abstract

Charge redistribution at heterogeneous interfaces is a fundamental aspect of surface chemistry. Manipulating the amount of charges and the magnitude of dipole moments at the interface in a controlled way has attracted tremendous attention for its potential to modify the activity of heterogeneous catalysts in catalyst design. Two-dimensional ultrathin silica films with well-defined atomic structures have been recently synthesized and proposed as model systems for heterogeneous catalysts studies. R. Wlodarczyk et al. (Phys. Rev. B, 85, 085403 (2012)) have demonstrated that the electronic structure of silica/Ru(0001) can be reversibly tuned by changing the amount of interfacial chemisorbed oxygen. Here we carried out systematic investigations to understand the underlying mechanism through which the electronic structure at the silica/Ru(0001) interface can be tuned. As corroborated by both in situ X-ray photoelectron spectroscopy and density functional theory calculations, the observed interface energy level alignments strongly depend on the surface and interfacial charge transfer induced dipoles at the silica/Ru(0001) heterojunction. These observations may help to understand variations in catalytic performance of the model system from the viewpoint of the electronic properties at the confined space between the silica bilayer and the Ru(0001) surface. As a result, the same behavior is observed for the aluminosilicatemore » bilayer, which has been previously proposed as a model system for zeolites.« less

Authors:
 [1];  [2];  [2];  [2];  [2];  [2];  [2]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1328366
Report Number(s):
BNL-112657-2016-JA
Journal ID: ISSN 1022-5528; R&D Project: 16068; KC0403020
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Topics in Catalysis
Additional Journal Information:
Journal Name: Topics in Catalysis; Journal ID: ISSN 1022-5528
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 2D zeolites; charge transfer; surface and interface dipoles; energy level shift; density functional theory; in situ x-ray photoelectron spectroscopy

Citation Formats

Wang, Mengen, Zhong, Jian -Qiang, Kestell, John, Waluyo, Iradwikanari, Stacchiola, Dario J., Boscoboinik, J. Anibal, and Lu, Deyu. Energy level shifts at the silica/Ru(0001) heterojunction driven by surface and interface dipoles. United States: N. p., 2016. Web. doi:10.1007/s11244-016-0704-x.
Wang, Mengen, Zhong, Jian -Qiang, Kestell, John, Waluyo, Iradwikanari, Stacchiola, Dario J., Boscoboinik, J. Anibal, & Lu, Deyu. Energy level shifts at the silica/Ru(0001) heterojunction driven by surface and interface dipoles. United States. https://doi.org/10.1007/s11244-016-0704-x
Wang, Mengen, Zhong, Jian -Qiang, Kestell, John, Waluyo, Iradwikanari, Stacchiola, Dario J., Boscoboinik, J. Anibal, and Lu, Deyu. Mon . "Energy level shifts at the silica/Ru(0001) heterojunction driven by surface and interface dipoles". United States. https://doi.org/10.1007/s11244-016-0704-x. https://www.osti.gov/servlets/purl/1328366.
@article{osti_1328366,
title = {Energy level shifts at the silica/Ru(0001) heterojunction driven by surface and interface dipoles},
author = {Wang, Mengen and Zhong, Jian -Qiang and Kestell, John and Waluyo, Iradwikanari and Stacchiola, Dario J. and Boscoboinik, J. Anibal and Lu, Deyu},
abstractNote = {Charge redistribution at heterogeneous interfaces is a fundamental aspect of surface chemistry. Manipulating the amount of charges and the magnitude of dipole moments at the interface in a controlled way has attracted tremendous attention for its potential to modify the activity of heterogeneous catalysts in catalyst design. Two-dimensional ultrathin silica films with well-defined atomic structures have been recently synthesized and proposed as model systems for heterogeneous catalysts studies. R. Wlodarczyk et al. (Phys. Rev. B, 85, 085403 (2012)) have demonstrated that the electronic structure of silica/Ru(0001) can be reversibly tuned by changing the amount of interfacial chemisorbed oxygen. Here we carried out systematic investigations to understand the underlying mechanism through which the electronic structure at the silica/Ru(0001) interface can be tuned. As corroborated by both in situ X-ray photoelectron spectroscopy and density functional theory calculations, the observed interface energy level alignments strongly depend on the surface and interfacial charge transfer induced dipoles at the silica/Ru(0001) heterojunction. These observations may help to understand variations in catalytic performance of the model system from the viewpoint of the electronic properties at the confined space between the silica bilayer and the Ru(0001) surface. As a result, the same behavior is observed for the aluminosilicate bilayer, which has been previously proposed as a model system for zeolites.},
doi = {10.1007/s11244-016-0704-x},
journal = {Topics in Catalysis},
number = ,
volume = ,
place = {United States},
year = {2016},
month = {9}
}

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

Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Studying two-dimensional zeolites with the tools of surface science: MFI nanosheets on Au(111)
journal, February 2017


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Growth and Structure of Crystalline Silica Sheet on Ru(0001)
journal, September 2010


Preparation and characterization of atomically flat and ordered silica films on a Pd(100) surface
journal, April 2008


CO adsorption on a silica bilayer supported on Ru(0001)
journal, June 2016


Tuning the electronic structure of ultrathin crystalline silica films on Ru(0001)
journal, February 2012


Exchangelike Effects for Closed-Shell Adsorbates: Interface Dipole and Work Function
journal, August 2002


Van der Waals density functionals applied to solids
journal, May 2011


Observation of a novel high density 3O(2 × 2) structure on Ru(001)
journal, December 1997


Oxygen induced reconstruction of a close-packed surface: A LEED IV study on Ru(001)-p(2 × 1)O
journal, October 1989


Understanding silica-supported metal catalysts: Pd/silica as a case study
journal, October 2003


Growth of single-crystal SiO2 film on Ni(111) surface
journal, March 2002

  • Kundu, Manisha; Murata, Yoshitada
  • Applied Physics Letters, Vol. 80, Issue 11
  • DOI: 10.1063/1.1461052

Testing several recent van der Waals density functionals for layered structures
journal, August 2014

  • Björkman, Torbjörn
  • The Journal of Chemical Physics, Vol. 141, Issue 7
  • DOI: 10.1063/1.4893329

Proof that E n i = ε in density-functional theory
journal, December 1978


Numerical investigation of the validity of the Slater-Janak transition-state model in metallic systems
journal, October 2005


Reducing the Metal Work Function beyond Pauli Pushback: A Computational Investigation of Tetrathiafulvalene and Viologen on Coinage Metal Surfaces
journal, December 2008

  • Hofmann, Oliver T.; Rangger, Gerold M.; Zojer, Egbert
  • The Journal of Physical Chemistry C, Vol. 112, Issue 51
  • DOI: 10.1021/jp806834g

Adsorbate induced reconstruction by strong chemisorption: Ru(001)p(2×2)-O
journal, November 1989


Permeation of a Single-Layer SiO 2 Membrane and Chemistry in Confined Space
journal, June 2014

  • Emmez, Emre; Yang, Bing; Shaikhutdinov, Shamil
  • The Journal of Physical Chemistry C, Vol. 118, Issue 50
  • DOI: 10.1021/jp503253a

Thin silica films on Ru(0001): monolayer, bilayer and three-dimensional networks of [SiO4] tetrahedra
journal, January 2012

  • Yang, Bing; Kaden, William E.; Yu, Xin
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 32
  • DOI: 10.1039/c2cp41355h

Oxidation of the Ru(0001) surface covered by weakly bound, ultrathin silicate films
journal, April 2016


Exploring Zeolite Chemistry with the Tools of Surface Science: Challenges, Opportunities, and Limitations
journal, September 2014


The Electronic Factor in Alkane Oxidation Catalysis
journal, January 2015

  • Eichelbaum, Maik; Hävecker, Michael; Heine, Christian
  • Angewandte Chemie International Edition, Vol. 54, Issue 10
  • DOI: 10.1002/anie.201410632

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Influence of electrostatic fields on molecular electronic structure: insights for interfacial charge transfer
journal, January 2010

  • Monti, Oliver L. A.; Steele, Mary P.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 39
  • DOI: 10.1039/c0cp01039a

Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

  • Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
  • Journal of Computational Chemistry, Vol. 32, Issue 7
  • DOI: 10.1002/jcc.21759

Reactivity of Oxide Precursor States on Ru(0001)
journal, July 2006

  • Blume, Raoul; Christen, Wolfgang; Niehus, Horst
  • The Journal of Physical Chemistry B, Vol. 110, Issue 28
  • DOI: 10.1021/jp061937a

Energy Level Realignment in Weakly Interacting Donor–Acceptor Binary Molecular Networks
journal, January 2014

  • Zhong, Jian-Qiang; Qin, Xinming; Zhang, Jia-Lin
  • ACS Nano, Vol. 8, Issue 2
  • DOI: 10.1021/nn406050e

Synthesis and Structure of Ultrathin Aluminosilicate Films
journal, November 2006

  • Stacchiola, Dario; Kaya, Sarp; Weissenrieder, Jonas
  • Angewandte Chemie International Edition, Vol. 45, Issue 45
  • DOI: 10.1002/anie.200602670

Preparation of silica films on Ru(0001): A LEEM/PEEM study
journal, January 2016


Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997


Universal energy-level alignment of molecules on metal oxides
journal, November 2011

  • Greiner, Mark T.; Helander, Michael G.; Tang, Wing-Man
  • Nature Materials, Vol. 11, Issue 1
  • DOI: 10.1038/nmat3159

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


Simultaneous Control of Surface Potential and Wetting of Solids with Chemisorbed Multifunctional Ligands
journal, June 1997

  • Bruening, Merlin; Cohen, Rami; Guillemoles, Jean François
  • Journal of the American Chemical Society, Vol. 119, Issue 24
  • DOI: 10.1021/ja964434z

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


Physisorption-Based Charge Transfer in Two-Dimensional SnS 2 for Selective and Reversible NO 2 Gas Sensing
journal, September 2015


Structure and Stability of a High-Coverage ( 1 × 1 ) Oxygen Phase on Ru(0001)
journal, October 1996


Exchange functional that tests the robustness of the plasmon description of the van der Waals density functional
journal, January 2014


Characterization of Various Oxygen Species on an Oxide Surface:  RuO 2 (110)
journal, May 2001

  • Kim, Y. D.; Seitsonen, A. P.; Wendt, S.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 18
  • DOI: 10.1021/jp003213j

Electronic and vibrational properties of ultrathin Si O 2 films grown on Mo(112)
journal, September 2005


First-principles study of the interaction and charge transfer between graphene and metals
journal, May 2009


Atomic Structure of a Thin Silica Film on a Mo(112) Substrate: A Two-Dimensional Network of SiO 4 Tetrahedra
journal, August 2005


Interaction of Probe Molecules with Bridging Hydroxyls of Two-Dimensional Zeolites: A Surface Science Approach
journal, June 2013

  • Boscoboinik, J. Anibal; Yu, Xin; Emmez, Emre
  • The Journal of Physical Chemistry C, Vol. 117, Issue 26
  • DOI: 10.1021/jp405533s

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

Ultrathin Silica Films on Metals: The Long and Winding Road to Understanding the Atomic Structure
journal, November 2012

  • Shaikhutdinov, Shamil; Freund, Hans-Joachim
  • Advanced Materials, Vol. 25, Issue 1
  • DOI: 10.1002/adma.201203426

Modeling Zeolites with Metal-Supported Two-Dimensional Aluminosilicate Films
journal, April 2012

  • Boscoboinik, Jorge Anibal; Yu, Xin; Yang, Bing
  • Angewandte Chemie International Edition, Vol. 51, Issue 24
  • DOI: 10.1002/anie.201201319

Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111)
journal, December 1992


Adsorption of Au and Pd on Ruthenium-Supported Bilayer Silica
journal, August 2014

  • Büchner, Christin; Lichtenstein, Leonid; Stuckenholz, Stefanie
  • The Journal of Physical Chemistry C, Vol. 118, Issue 36
  • DOI: 10.1021/jp5055342

Oxidation and Reduction under Cover: Chemistry at the Confined Space between Ultrathin Nanoporous Silicates and Ru(0001)
journal, April 2016

  • Zhong, Jian-Qiang; Kestell, John; Waluyo, Iradwikanari
  • The Journal of Physical Chemistry C, Vol. 120, Issue 15
  • DOI: 10.1021/acs.jpcc.6b02851

Distance Dependence of Electron Tunneling through Self-Assembled Monolayers Measured by Conducting Probe Atomic Force Microscopy:  Unsaturated versus Saturated Molecular Junctions
journal, March 2002

  • Wold, David J.; Haag, Rainer; Rampi, Maria Anita
  • The Journal of Physical Chemistry B, Vol. 106, Issue 11
  • DOI: 10.1021/jp013476t

Unexpected interplay of bonding height and energy level alignment at heteromolecular hybrid interfaces
journal, April 2014

  • Stadtmüller, Benjamin; Lüftner, Daniel; Willenbockel, Martin
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4685

Understanding Silica-Supported Metal Catalysts: Pd/Silica as a Case Study.
journal, February 2004


Synthesis and Structure of Ultrathin Aluminosilicate Films.
journal, January 2007

  • Stacchiola, Dario; Kaya, Sarp; Weissenrieder, Jonas
  • ChemInform, Vol. 38, Issue 5
  • DOI: 10.1002/chin.200705206

High-resolution X-ray luminescence extension imaging
journal, February 2021


Oxygen induced reconstruction of a close-packed surface: A LEED IV study on Ru(001)-p(2 × 1)O
journal, October 1989


Works referencing / citing this record:

Ionization‐Facilitated Formation of 2D (Alumino)Silicate–Noble Gas Clathrate Compounds
journal, March 2019

  • Zhong, Jian‐Qiang; Wang, Mengen; Akter, Nusnin
  • Advanced Functional Materials, Vol. 29, Issue 20
  • DOI: 10.1002/adfm.201806583

Wasserbildung unter dünnen Silika-Filmen: Echtzeitbeobachtung einer chemischen Reaktion in einem physikalisch eingegrenzten Raum
journal, June 2018

  • Prieto, Mauricio J.; Klemm, Hagen W.; Xiong, Feng
  • Angewandte Chemie, Vol. 130, Issue 28
  • DOI: 10.1002/ange.201802000

Water Formation under Silica Thin Films: Real-Time Observation of a Chemical Reaction in a Physically Confined Space
journal, June 2018

  • Prieto, Mauricio J.; Klemm, Hagen W.; Xiong, Feng
  • Angewandte Chemie International Edition, Vol. 57, Issue 28
  • DOI: 10.1002/anie.201802000

Extent of Fock-exchange mixing for a hybrid van der Waals density functional?
journal, May 2018

  • Jiao, Yang; Schröder, Elsebeth; Hyldgaard, Per
  • The Journal of Chemical Physics, Vol. 148, Issue 19
  • DOI: 10.1063/1.5012870

Chemistry in confined space through the eyes of surface science—2D porous materials
journal, December 2018


Selective Catalytic Transfer Hydrogenolysis of Glycerol to 2-Isopropoxy-Propan-1-Ol over Noble Metal Ion-Exchanged Mordenite Zeolite
journal, October 2019

  • Singh, Bhupendra Kumar; Kim, Yongseok; Kwon, Seungdon
  • Catalysts, Vol. 9, Issue 11
  • DOI: 10.3390/catal9110885