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Title: Understanding the Photocatalytic Properties of Pt/CeOx /TiO2 : Structural Effects on Electronic and Optical Properties

Abstract

Ceria-titania interfaces play a crucial role in different chemical processes but are especially promising for the photocatalytic splitting of water using light in the visible wavelength region when Pt is added to the system. Yet, the complexity of this hierarchical structure hampers the study of the origin of its outstanding properties. In this article, the structural, electronic and optoelectronic properties of CeO2/TiO2 systems containing 1D, 2D, and 3D particles of ceria are analyzed by means of density functional calculations. Adsorption sites and vacancy effects have been studied to model Pt adsorption. Density of states calculations and absorption spectra simulations explain the behavior of these systems. Conclusively, these models are used for the screening of other metals that can be combined with this heterostructure to possibly find more efficient water splitting photocatalysts.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Seville (Spain)
  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); Ministerio de Economía y Competitividad
OSTI Identifier:
1550795
Alternate Identifier(s):
OSTI ID: 1525539
Report Number(s):
BNL-211932-2019-JAAM
Journal ID: ISSN 1439-4235
Grant/Contract Number:  
SC0012704; CTQ2015-64669-P
Resource Type:
Accepted Manuscript
Journal Name:
ChemPhysChem
Additional Journal Information:
Journal Volume: 20; Journal Issue: 12; Journal ID: ISSN 1439-4235
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CeO2; interface; Pt; TiO2; water splitting

Citation Formats

Plata, J. J., Remesal, E. R., Graciani, Jesús, Márquez, A. M., Rodríguez, J. A., and Sanz, Javier Fernández. Understanding the Photocatalytic Properties of Pt/CeOx /TiO2 : Structural Effects on Electronic and Optical Properties. United States: N. p., 2019. Web. doi:10.1002/cphc.201900141.
Plata, J. J., Remesal, E. R., Graciani, Jesús, Márquez, A. M., Rodríguez, J. A., & Sanz, Javier Fernández. Understanding the Photocatalytic Properties of Pt/CeOx /TiO2 : Structural Effects on Electronic and Optical Properties. United States. doi:10.1002/cphc.201900141.
Plata, J. J., Remesal, E. R., Graciani, Jesús, Márquez, A. M., Rodríguez, J. A., and Sanz, Javier Fernández. Thu . "Understanding the Photocatalytic Properties of Pt/CeOx /TiO2 : Structural Effects on Electronic and Optical Properties". United States. doi:10.1002/cphc.201900141. https://www.osti.gov/servlets/purl/1550795.
@article{osti_1550795,
title = {Understanding the Photocatalytic Properties of Pt/CeOx /TiO2 : Structural Effects on Electronic and Optical Properties},
author = {Plata, J. J. and Remesal, E. R. and Graciani, Jesús and Márquez, A. M. and Rodríguez, J. A. and Sanz, Javier Fernández},
abstractNote = {Ceria-titania interfaces play a crucial role in different chemical processes but are especially promising for the photocatalytic splitting of water using light in the visible wavelength region when Pt is added to the system. Yet, the complexity of this hierarchical structure hampers the study of the origin of its outstanding properties. In this article, the structural, electronic and optoelectronic properties of CeO2/TiO2 systems containing 1D, 2D, and 3D particles of ceria are analyzed by means of density functional calculations. Adsorption sites and vacancy effects have been studied to model Pt adsorption. Density of states calculations and absorption spectra simulations explain the behavior of these systems. Conclusively, these models are used for the screening of other metals that can be combined with this heterostructure to possibly find more efficient water splitting photocatalysts.},
doi = {10.1002/cphc.201900141},
journal = {ChemPhysChem},
number = 12,
volume = 20,
place = {United States},
year = {2019},
month = {5}
}

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Works referenced in this record:

The Role of Interstitial Sites in the Ti3d Defect State in the Band Gap of Titania
journal, June 2008


Dopant Incorporation in Ceria for Enhanced Water-Splitting Activity during Solar Thermochemical Hydrogen Generation
journal, June 2012

  • Le Gal, Alex; Abanades, Stéphane
  • The Journal of Physical Chemistry C, Vol. 116, Issue 25
  • DOI: 10.1021/jp302146c

Sonochemical Deposition of Au Nanoparticles on Different Facets-Dominated Anatase TiO 2 Single Crystals and Resulting Photocatalytic Performance
journal, July 2013

  • Cheng, Kun; Sun, Wenbin; Jiang, Hai-Ying
  • The Journal of Physical Chemistry C, Vol. 117, Issue 28
  • DOI: 10.1021/jp403489r

Efficient Visible-Light Photocatalytic Water Splitting by Minute Amounts of Gold Supported on Nanoparticulate CeO 2 Obtained by a Biopolymer Templating Method
journal, May 2011

  • Primo, Ana; Marino, Tiziana; Corma, Avelino
  • Journal of the American Chemical Society, Vol. 133, Issue 18
  • DOI: 10.1021/ja2011498

F and Fe co-doped TiO2 with enhanced visible light photocatalytic activity
journal, March 2011

  • Zhang, Yihe; Lv, Fengzhu; Wu, Tao
  • Journal of Sol-Gel Science and Technology, Vol. 59, Issue 2
  • DOI: 10.1007/s10971-011-2449-0

Promoted Ceria: A Structural, Catalytic, and Computational Study
journal, September 2013

  • Farra, Ramzi; García-Melchor, Max; Eichelbaum, Maik
  • ACS Catalysis, Vol. 3, Issue 10
  • DOI: 10.1021/cs4005002

Cu Deposited on CeOx-Modified TiO 2 (110): Synergistic Effects at the Metal–Oxide Interface and the Mechanism of the WGS Reaction
journal, June 2016


Preparation, formation mechanism and photocatalysis of ultrathin mesoporous single-crystal-like CeO2 nanosheets
journal, January 2013

  • Yu, Yifu; Zhu, Yingming; Meng, Ming
  • Dalton Transactions, Vol. 42, Issue 34
  • DOI: 10.1039/c3dt51247a

Characterization of Structural and Surface Properties of Nanocrystalline TiO 2 −CeO 2 Mixed Oxides by XRD, XPS, TPR, and TPD
journal, July 2009

  • Watanabe, Shingo; Ma, Xiaoliang; Song, Chunshan
  • The Journal of Physical Chemistry C, Vol. 113, Issue 32
  • DOI: 10.1021/jp8110309

Mapping Central α-Helix Linker Mediated Conformational Transition Pathway of Calmodulin via Simple Computational Approach
journal, August 2014

  • Wang, Jinan; Peng, Shaoliang; Cossins, Benjamin P.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 32
  • DOI: 10.1021/jp507186h

Gold, Copper, and Platinum Nanoparticles Dispersed on CeO x /TiO 2 (110) Surfaces: High Water-Gas Shift Activity and the Nature of the Mixed-Metal Oxide at the Nanometer Level
journal, January 2010

  • Park, Joon B.; Graciani, Jesus; Evans, Jaime
  • Journal of the American Chemical Society, Vol. 132, Issue 1
  • DOI: 10.1021/ja9087677

A New Type of Strong Metal–Support Interaction and the Production of H 2 through the Transformation of Water on Pt/CeO 2 (111) and Pt/CeO x /TiO 2 (110) Catalysts
journal, May 2012

  • Bruix, Albert; Rodriguez, José A.; Ramírez, Pedro J.
  • Journal of the American Chemical Society, Vol. 134, Issue 21
  • DOI: 10.1021/ja302070k

Density Functional Theory Study on the Role of Ceria Addition in Ti x Ce 1– x O 2 Adsorbents for Thiophene Adsorption
journal, January 2012

  • Guo, Jiahua; Janik, Michael J.; Song, Chunshan
  • The Journal of Physical Chemistry C, Vol. 116, Issue 5
  • DOI: 10.1021/jp2063996

Modifying ceria (111) with a TiO 2 nanocluster for enhanced reactivity
journal, November 2013

  • Nolan, Michael
  • The Journal of Chemical Physics, Vol. 139, Issue 18
  • DOI: 10.1063/1.4829758

Exploring the Structural and Electronic Properties of Pt/Ceria-Modified TiO 2 and Its Photocatalytic Activity for Water Splitting under Visible Light
journal, June 2012

  • Kundu, Shankhamala; Ciston, Jim; Senanayake, Sanjaya D.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 26
  • DOI: 10.1021/jp304475x

Nature of the Mixed-Oxide Interface in Ceria–Titania Catalysts: Clusters, Chains, and Nanoparticles
journal, July 2013

  • Johnston-Peck, Aaron C.; Senanayake, Sanjaya D.; Plata, José J.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 28
  • DOI: 10.1021/jp3125268

High catalytic activity of Au/CeOx/TiO2(110) controlled by the nature of the mixed-metal oxide at the nanometer level
journal, March 2009

  • Park, J. B.; Graciani, J.; Evans, J.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 13
  • DOI: 10.1073/pnas.0812604106

Structure and special chemical reactivity of interface-stabilized cerium oxide nanolayers on TiO 2 (110)
journal, January 2014

  • Agnoli, Stefano; Reeder, Askia E.; Senanayake, Sanjaya D.
  • Nanoscale, Vol. 6, Issue 2
  • DOI: 10.1039/C3NR04623K

New Insight into SO 2 Poisoning and Regeneration of CeO 2 –WO 3 /TiO 2 and V 2 O 5 –WO 3 /TiO 2 Catalysts for Low-Temperature NH 3 –SCR
journal, May 2018

  • Xu, Liwen; Wang, Chizhong; Chang, Huazhen
  • Environmental Science & Technology, Vol. 52, Issue 12
  • DOI: 10.1021/acs.est.8b01990

CeO2-TiO2 as a visible light active catalyst for the photoreduction of CO2 to methanol
journal, November 2015


CO2 photoreduction with H2O vapor on highly dispersed CeO2/TiO2 catalysts: Surface species and their reactivity
journal, May 2016


Sol–gel synthesized TiO2–CeO2 nanocomposite: an efficient photocatalyst for degradation of methyl orange under sunlight
journal, October 2015

  • Wandre, T. M.; Gaikwad, P. N.; Tapase, A. S.
  • Journal of Materials Science: Materials in Electronics, Vol. 27, Issue 1
  • DOI: 10.1007/s10854-015-3823-4

Synthesis of CeO2/TiO2 nanotubes and heterogeneous photocatalytic degradation of methylene blue
journal, October 2018

  • Tuyen, Le Thi Thanh; Quang, Dao Anh; Tam Toan, Tran Thanh
  • Journal of Environmental Chemical Engineering, Vol. 6, Issue 5
  • DOI: 10.1016/j.jece.2018.09.022

Role of Interface Contact in CeO 2 –TiO 2 Photocatalytic Composite Materials
journal, December 2013

  • Muñoz-Batista, Mario J.; Gómez-Cerezo, María Natividad; Kubacka, Anna
  • ACS Catalysis, Vol. 4, Issue 1
  • DOI: 10.1021/cs400878b

TiO 2 /CeO 2 Hybrid Photocatalyst with Enhanced Photocatalytic Activity: Optimization of Synthesis Variables
journal, April 2014

  • Eskandarloo, Hamed; Badiei, Alireza; Behnajady, Mohammad A.
  • Industrial & Engineering Chemistry Research, Vol. 53, Issue 19
  • DOI: 10.1021/ie403460d

Rendering Photoreactivity to Ceria: The Role of Defects
journal, October 2017

  • Yang, Chengwu; Yu, Xiaojuan; Pleßow, Philipp N.
  • Angewandte Chemie International Edition, Vol. 56, Issue 45
  • DOI: 10.1002/anie.201707965

Photoaktivierung von Cerdioxid: die Rolle von Defekten
journal, October 2017

  • Yang, Chengwu; Yu, Xiaojuan; Pleßow, Philipp N.
  • Angewandte Chemie, Vol. 129, Issue 45
  • DOI: 10.1002/ange.201707965

A comparison between photocatalytic and catalytic oxidation of 2-Propanol over Au/TiO 2 –CeO 2 catalysts
journal, May 2016

  • Fiorenza, Roberto; Bellardita, Marianna; Palmisano, Leonardo
  • Journal of Molecular Catalysis A: Chemical, Vol. 415
  • DOI: 10.1016/j.molcata.2016.01.025

TiO2@Pt@CeO2 nanocomposite as a bifunctional catalyst for enhancing photo-reduction of Cr (VI) and photo-oxidation of benzyl alcohol
journal, March 2018


First-principles study of the Pt Ce O 2 ( 111 ) interface
journal, August 2007


Adsorption, Oxidation State, and Diffusion of Pt Atoms on the CeO 2 (111) Surface
journal, July 2010

  • Bruix, Albert; Neyman, Konstantin M.; Illas, Francesc
  • The Journal of Physical Chemistry C, Vol. 114, Issue 33
  • DOI: 10.1021/jp104490k

Density Functional Modeling of the Interactions of Platinum Clusters with CeO 2 Nanoparticles of Different Size
journal, July 2011

  • Vayssilov, Georgi N.; Migani, Annapaola; Neyman, Konstantin
  • The Journal of Physical Chemistry C, Vol. 115, Issue 32
  • DOI: 10.1021/jp204222k

Platinum adsorption on ceria: A comparative theoretical study of different surfaces
journal, February 2017


Creating single-atom Pt-ceria catalysts by surface step decoration
journal, February 2016

  • Dvořák, Filip; Farnesi Camellone, Matteo; Tovt, Andrii
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms10801

Support nanostructure boosts oxygen transfer to catalytically active platinum nanoparticles
journal, March 2011

  • Vayssilov, Georgi N.; Lykhach, Yaroslava; Migani, Annapaola
  • Nature Materials, Vol. 10, Issue 4
  • DOI: 10.1038/nmat2976

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


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


Projector augmented-wave method
journal, December 1994


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


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


Ab initiomolecular dynamics for liquid metals
journal, January 1993


Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

Reply to “Comment on ‘Taming multiple valency with density functionals: A case study of defective ceria' ”
journal, December 2005


Linear response approach to the calculation of the effective interaction parameters in the LDA + U method
journal, January 2005


Tuning LDA+U for electron localization and structure at oxygen vacancies in ceria
journal, December 2007

  • Castleton, C. W. M.; Kullgren, J.; Hermansson, K.
  • The Journal of Chemical Physics, Vol. 127, Issue 24
  • DOI: 10.1063/1.2800015

Modeling of Ce O 2 , Ce 2 O 3 , and Ce O 2 x in the LDA + U formalism
journal, January 2007


The electronic structure of oxygen vacancy defects at the low index surfaces of ceria
journal, December 2005


Communication: Improving the density functional theory+ U description of CeO 2 by including the contribution of the O 2 p electrons
journal, January 2012

  • Plata, José J.; Márquez, Antonio M.; Sanz, Javier Fdez.
  • The Journal of Chemical Physics, Vol. 136, Issue 4
  • DOI: 10.1063/1.3678309

A theoretical insight into the catalytic effect of a mixed-metal oxide at the nanometer level: The case of the highly active metal/CeOx/TiO2(110) catalysts
journal, March 2010

  • Graciani, Jesús; Plata, José J.; Sanz, Javier Fdez.
  • The Journal of Chemical Physics, Vol. 132, Issue 10
  • DOI: 10.1063/1.3337918

Linear optical properties in the projector-augmented wave methodology
journal, January 2006


The stability of ionic crystal surfaces
journal, November 1979


Periodic boundary conditions in ab initio calculations
journal, February 1995


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