Characterization of photocatalytic TiO2 powder under varied environments using near ambient pressure X-ray photoelectron spectroscopy

Krishnan, Padmaja; Liu, Minghui; Itty, Pierre A.; Liu, Zhi; Rheinheimer, Vanessa; Zhang, Min-Hong; Monteiro, Paulo J.  M.; Yu, Liya E.

doi:10.1038/srep43298

Title: Characterization of photocatalytic TiO₂ powder under varied environments using near ambient pressure X-ray photoelectron spectroscopy

Abstract

Consecutive eight study phases under the successive presence and absence of UV irradiation, water vapor, and oxygen were conducted to characterize surface changes in the photocatalytic TiO2 powder using near-ambient-pressure X-ray photoelectron spectroscopy (XPS). Both Ti 2p and O 1s spectra show hysteresis through the experimental course. Under all the study environments, the bridging hydroxyl (OH_br) and terminal hydroxyl (OH_t) are identified at 1.1–1.3 eV and 2.1–2.3 eV above lattice oxygen, respectively. This enables novel and complementary approach to characterize reactivity of TiO₂ powder. The dynamic behavior of surface-bound water molecules under each study environment is identified, while maintaining a constant distance of 1.3 eV from the position of water vapor. In the dark, the continual supply of both water vapor and oxygen is the key factor retaining the activated state of the TiO₂ powder for a time period. Two new surface peaks at 1.7–1.8 and 4.0–4.2 eV above lattice oxygen are designated as peroxides (OOH/H₂O₂) and H₂O₂ dissolved in water, respectively. The persistent peroxides on the powder further explain previously observed prolonged oxidation capability of TiO₂ powder without light irradiation.

Authors:

Krishnan, Padmaja ^[1]; Liu, Minghui ^[1]; Itty, Pierre A. ^[2]; Liu, Zhi ^[3]; Rheinheimer, Vanessa ^[1]; Zhang, Min-Hong ^[1]; Monteiro, Paulo J. M. ^[2]; Yu, Liya E. ^[1]

National Univ. of Singapore (Singapore). Dept. of Civil and Environmental Engineering
Univ. of California, Berkeley, CA (United States). Dept. of Civil and Environmental Engineering
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source

Publication Date:: 2017-02-27

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Research Foundation (NRF) (Singapore)

OSTI Identifier:: 1411654

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Scientific Reports

Additional Journal Information:: Journal Volume: 7; Journal ID: ISSN 2045-2322

Publisher:: Nature Publishing Group

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; photocatalysis; surface spectroscopy

Citation Formats


                    Krishnan, Padmaja, Liu, Minghui, Itty, Pierre A., Liu, Zhi, Rheinheimer, Vanessa, Zhang, Min-Hong, Monteiro, Paulo J.  M., and Yu, Liya E. Characterization of photocatalytic TiO2 powder under varied environments using near ambient pressure X-ray photoelectron spectroscopy.  United States: N. p., 2017. 
Web.  doi:10.1038/srep43298.

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                    Krishnan, Padmaja, Liu, Minghui, Itty, Pierre A., Liu, Zhi, Rheinheimer, Vanessa, Zhang, Min-Hong, Monteiro, Paulo J.  M., & Yu, Liya E. Characterization of photocatalytic TiO2 powder under varied environments using near ambient pressure X-ray photoelectron spectroscopy.  United States.  https://doi.org/10.1038/srep43298

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                    Krishnan, Padmaja, Liu, Minghui, Itty, Pierre A., Liu, Zhi, Rheinheimer, Vanessa, Zhang, Min-Hong, Monteiro, Paulo J.  M., and Yu, Liya E. Mon .  
"Characterization of photocatalytic TiO2 powder under varied environments using near ambient pressure X-ray photoelectron spectroscopy".  United States.  https://doi.org/10.1038/srep43298.  https://www.osti.gov/servlets/purl/1411654.

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@article{osti_1411654,

  title        = {Characterization of photocatalytic TiO2 powder under varied environments using near ambient pressure X-ray photoelectron spectroscopy},

  author       = {Krishnan, Padmaja and Liu, Minghui and Itty, Pierre A. and Liu, Zhi and Rheinheimer, Vanessa and Zhang, Min-Hong and Monteiro, Paulo J.  M. and Yu, Liya E.},

  abstractNote = {Consecutive eight study phases under the successive presence and absence of UV irradiation, water vapor, and oxygen were conducted to characterize surface changes in the photocatalytic TiO2 powder using near-ambient-pressure X-ray photoelectron spectroscopy (XPS). Both Ti 2p and O 1s spectra show hysteresis through the experimental course. Under all the study environments, the bridging hydroxyl (OHbr) and terminal hydroxyl (OHt) are identified at 1.1–1.3 eV and 2.1–2.3 eV above lattice oxygen, respectively. This enables novel and complementary approach to characterize reactivity of TiO2 powder. The dynamic behavior of surface-bound water molecules under each study environment is identified, while maintaining a constant distance of 1.3 eV from the position of water vapor. In the dark, the continual supply of both water vapor and oxygen is the key factor retaining the activated state of the TiO2 powder for a time period. Two new surface peaks at 1.7–1.8 and 4.0–4.2 eV above lattice oxygen are designated as peroxides (OOH/H2O2) and H2O2 dissolved in water, respectively. The persistent peroxides on the powder further explain previously observed prolonged oxidation capability of TiO2 powder without light irradiation.},

  doi          = {10.1038/srep43298},

  journal      = {Scientific Reports},

  number       = ,

  volume       = 7,

  place        = {United States},

  year         = {2017},

  month        = {2}

}

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Title: Characterization of photocatalytic TiO2 powder under varied environments using near ambient pressure X-ray photoelectron spectroscopy

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Electrochemical Synthesis of TiO 2 under Pulse Alternating Current: Effect of Thermal Treatment on the Photocatalytic Activity journal, February 2019

Early Transition Metal Doped Tungstite as an Effective Catalyst for Glucose Upgrading to 5-Hydroxymethylfurfural journal, August 2018

The surface science of nanoparticles for catalysis: electronic and steric effects of organic ligands journal, September 2018

Added value recyclability of glass fiber waste as photo-oxidation catalyst for toxic cytostatic micropollutants journal, January 2020

Facile synthesis of TiO 2 /rGO neatly electrodeposited on carbon fiber applied as ternary electrode for supercapacitor journal, March 2019

Band Gap Implications on Nano-TiO2 Surface Modification with Ascorbic Acid for Visible Light-Active Polypropylene Coated Photocatalyst journal, August 2018

Single-Step Reagentless Laser Scribing Fabrication of Electrochemical Paper-Based Analytical Devices journal, October 2017

Title: Characterization of photocatalytic TiO₂ powder under varied environments using near ambient pressure X-ray photoelectron spectroscopy

Chemistry of NO _x on TiO ₂ Surfaces Studied by Ambient Pressure XPS: Products, Effect of UV Irradiation, Water, and Coadsorbed K ⁺
journal, January 2013

Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn
journal, November 2010

Water as a Catalyst: Imaging Reactions of O ₂ with Partially and Fully Hydroxylated TiO ₂ (110) Surfaces
journal, January 2009

Photocatalytic Oxidation of Arsenic(III): Evidence of Hydroxyl Radicals
journal, March 2005

A surface science perspective on TiO2 photocatalysis
journal, June 2011

Experimental evidence for mixed dissociative and molecular adsorption of water on a rutile ${TiO}_{2} (110)$ surface without oxygen vacancies
journal, December 2009

A differentially pumped electrostatic lens system for photoemission studies in the millibar range
journal, November 2002

The Nature of Water Nucleation Sites on TiO ₂ (110) Surfaces Revealed by Ambient Pressure X-ray Photoelectron Spectroscopy
journal, June 2007

Near-ambient X-ray photoemission spectroscopy and kinetic approach to the mechanism of carbon monoxide oxidation over lanthanum substituted cobaltites
journal, August 2009

Photocatalytic degradation pathway of methylene blue in water
journal, May 2001

EPR Study of the Surface Characteristics of Nanostructured TiO ₂ under UV Irradiation
journal, August 2001

Photocatalytic Activity of Hydrogenated TiO ₂
journal, March 2013

The reaction of hydrogen atoms with hydrogen peroxide as a function of temperature
journal, May 2001

Methanol Oxidation on a Copper Catalyst Investigated Using in Situ X-ray Photoelectron Spectroscopy ^†
journal, September 2004

Ambient pressure photoelectron spectroscopy: A new tool for surface science and nanotechnology
journal, April 2008

Effect of surface structure on photocatalytic activity of TiO2 thin films prepared by sol-gel method
journal, December 2000

Structure of Clean and Adsorbate-Covered Single-Crystal Rutile TiO ₂ Surfaces
journal, December 2012

Ultraviolet Irradiation Suppresses Adhesion on TiO ₂
journal, April 2009

Mechanism of Photocatalytic Water Splitting in TiO ₂ . Reaction of Water with Photoholes, Importance of Charge Carrier Dynamics, and Evidence for Four-Hole Chemistry
journal, October 2008

Photoelectron Spectroscopy Study of Stoichiometric and Reduced Anatase TiO ₂ (101) Surfaces: The Effect of Subsurface Defects on Water Adsorption at Near-Ambient Pressures
journal, June 2015

Exploring the Environmental Photochemistry on the TiO ₂ (110) Surface in Situ by Near Ambient Pressure X-ray Photoelectron Spectroscopy
journal, March 2015

Characteristics of Water Adsorbed on TiO ₂ Photocatalytic Systems with Increasing Temperature as Studied by Solid-State ¹ H NMR Spectroscopy
journal, July 2004

Influence of the OH groups on the photocatalytic activity and photoinduced hydrophilicity of microwave assisted sol–gel TiO2 film
journal, June 2009

Highly enhanced photocatalytic oxidation of CO on titania deposited with Pt nanoparticles: kinetics and mechanism
journal, October 2003

Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O ⁻ in Aqueous Solution
journal, April 1988

Investigation of solid/vapor interfaces using ambient pressure X-ray photoelectron spectroscopy
journal, January 2013

Environmental Applications of Semiconductor Photocatalysis
journal, January 1995

Surface electronic and structural properties of nanostructured titanium oxide grown by pulsed laser deposition
journal, February 2011

Role of point defects on the reactivity of reconstructed anatase titanium dioxide (001) surface
journal, July 2013

Combined investigation of water sorption on TiO2 rutile (110) single crystal face: XPS vs. periodic DFT
journal, January 2007

Electron traps and their effect on the surface chemistry of TiO2(110)
journal, January 2010

Eu(III) Sorption to TiO ₂ (Anatase and Rutile): Batch, XPS, and EXAFS Studies
journal, May 2009

Characterization of ultra-thin TiO2 films grown on Mo(112)
journal, December 2006

TiO2 photocatalysis and related surface phenomena
journal, December 2008

Characterization of the Active Surface Species Responsible for UV-Induced Desorption of O ₂ from the Rutile TiO ₂ (110) Surface
journal, March 2013

Titania Nanoparticles Prepared with Pulsed Laser Ablation of Rutile Single Crystals in Water
journal, July 2004

Biomimetic synthesis of inorganic nanocomposites by a de novo designed peptide
journal, January 2014

New ambient pressure photoemission endstation at Advanced Light Source beamline 9.3.2
journal, May 2010

Photocatalytic degradation of organic water contaminants: Mechanisms involving hydroxyl radical attack
journal, March 1990

Experimental Investigation of the Interaction of Water and Methanol with Anatase−TiO ₂ (101)
journal, March 2003

Bactericidal Activity of Photocatalytic TiO2 Reaction: toward an Understanding of Its Killing Mechanism
journal, September 1999

Single-Step Reagentless Laser Scribing Fabrication of Electrochemical Paper-Based Analytical Devices
journal, October 2017

Electrochemical Synthesis of TiO ₂ under Pulse Alternating Current: Effect of Thermal Treatment on the Photocatalytic Activity
journal, February 2019

Early Transition Metal Doped Tungstite as an Effective Catalyst for Glucose Upgrading to 5-Hydroxymethylfurfural
journal, August 2018

The surface science of nanoparticles for catalysis: electronic and steric effects of organic ligands
journal, September 2018

Added value recyclability of glass fiber waste as photo-oxidation catalyst for toxic cytostatic micropollutants
journal, January 2020

Facile synthesis of TiO ₂ /rGO neatly electrodeposited on carbon fiber applied as ternary electrode for supercapacitor
journal, March 2019

Band Gap Implications on Nano-TiO2 Surface Modification with Ascorbic Acid for Visible Light-Active Polypropylene Coated Photocatalyst
journal, August 2018

Single-Step Reagentless Laser Scribing Fabrication of Electrochemical Paper-Based Analytical Devices
journal, October 2017