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

Title: Quantitative Analysis of the Morphology of {101} and {001} Faceted Anatase TiO2 Nanocrystals and Its Implication on Photocatalytic Activity

Journal Article · · Chemistry of Materials

The atomistic structure and morphology (shape and size) of nanomaterials have strong influences on their physical and chemical properties. However, many characterization techniques focus exclusively on one length-scale regime or another when developing quantitative morphology/structural models. In this article, we demonstrate that powder X-ray diffraction and neutron pair distribution function (PDF) can be used to obtain accurate average morphology and atomistic structure of {001} and {101} faceted anatase TiO2 nanocrystals based on differential evolution refinements using Debye scattering equation calculations. It is also demonstrated that the morphology polydispersity of TiO2 nanocrystals can be effectively obtained from the diffraction data via a numerical refinement routine. The morphology refinement results are in good agreement with those from transmission electron microscopy and the modeling of small angle neutron scattering data. This method is successfully used to quantify the facet-specified photocatalytic hydrogen evolution activity of anatase TiO2 nanocrystals with different {001} to {101} ratios. It is found that the sample with an intermediate amount of both {001} and {101} facets shows the best photocatalytic hydrogen evolution reaction (HER) activity. As a result, it is expected that the simultaneous structure and morphology refinement technique can be generally used to study the relationship between morphology and functionality of nanomaterials.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1376372
Journal Information:
Chemistry of Materials, Vol. 29, Issue 13; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 58 works
Citation information provided by
Web of Science

References (80)

Amorphous Molybdenum Phosphide Nanoparticles for Electrocatalytic Hydrogen Evolution journal August 2014
Synthesis of Highly Monodisperse Citrate-Stabilized Silver Nanoparticles of up to 200 nm: Kinetic Control and Catalytic Properties journal April 2014
Graphene-Wrapped Fe3O4 Anode Material with Improved Reversible Capacity and Cyclic Stability for Lithium Ion Batteries journal September 2010
Nanomaterials for Rechargeable Lithium Batteries journal April 2008
Titanium Dioxide Nanomaterials:  Synthesis, Properties, Modifications, and Applications journal July 2007
Seed-Mediated Growth of Anatase TiO 2 Nanocrystals with Core–Antenna Structures for Enhanced Photocatalytic Activity journal August 2015
Anatase TiO2 single crystals with a large percentage of reactive facets journal May 2008
Shaped Pd–Ni–Pt Core-Sandwich-Shell Nanoparticles: Influence of Ni Sandwich Layers on Catalytic Electrooxidations journal June 2014
Ligand-Mediated Synthesis of Shape-Controlled Cesium Lead Halide Perovskite Nanocrystals via Reprecipitation Process at Room Temperature journal February 2016
Construction of Evolutionary Tree for Morphological Engineering of Nanoparticles journal July 2009
Direct Electrodeposition of Tetrahexahedral Pd Nanocrystals with High-Index Facets and High Catalytic Activity for Ethanol Electrooxidation journal June 2010
Synthesis of Tetrahexahedral Platinum Nanocrystals with High-Index Facets and High Electro-Oxidation Activity journal May 2007
Shape Control of Semiconductor and Metal Oxide Nanocrystals through Nonhydrolytic Colloidal Routes journal May 2006
Colloidal nanocrystal synthesis and the organic–inorganic interface journal September 2005
The Morphology of TiO 2 (B) Nanoparticles journal October 2015
The Shape of TiO 2 -B Nanoparticles journal April 2014
Particle size distributions from small-angle scattering using global scattering functions journal July 2004
Experimental evidence for quasimelting in small particles journal July 1989
GaN:ZnO Solid Solution as a Photocatalyst for Visible-Light-Driven Overall Water Splitting journal June 2005
Ferroelectric order in individual nanometre-scale crystals journal July 2012
A profile refinement method for nuclear and magnetic structures journal June 1969
Rietveld refinement of Debye–Scherrer synchrotron X-ray data from Al 2 O 3 journal April 1987
Rietveld refinement with spallation neutron powder diffraction data journal December 1982
Eine quantitative Prüfung der Theorie für die Interferenzerscheinungen bei Röntgenstrahlen journal January 1913
Scherrer after sixty years: A survey and some new results in the determination of crystallite size journal April 1978
The Effect of Cold‐Work Distortion on X‐Ray Patterns journal June 1950
Whole powder pattern modelling journal February 2002
Debye function analysis of structure in diffraction from nanometer-sized particles journal February 2000
Zerstreuung von Röntgenstrahlen journal January 1915
Nonaqueous Synthesis of TiO 2 Nanocrystals Using TiF 4 to Engineer Morphology, Oxygen Vacancy Concentration, and Photocatalytic Activity journal April 2012
Crystal symmetry breaking and vacancies in colloidal lead chalcogenide quantum dots journal June 2016
Unraveling Atomic Positions in an Oxide Spinel with Two Jahn−Teller Ions: Local Structure Investigation of CuMn 2 O 4 journal August 2009
Local Atomic Ordering in BaTaO 2 N Studied by Neutron Pair Distribution Function Analysis and Density Functional Theory journal August 2007
Building and refining complete nanoparticle structures with total scattering data journal February 2011
Nanoscale Ni/Mn Ordering in the High Voltage Spinel Cathode LiNi 0.5 Mn 1.5 O 4 journal September 2016
Relationship between the atomic pair distribution function and small-angle scattering: implications for modeling of nanoparticles journal April 2009
Influence of neglected small-angle scattering in radial distribution function analysis journal August 1971
DShaper : an approach for handling missing low- Q data in pair distribution function analysis of nanostructured systems journal October 2015
Electrochemical Photolysis of Water at a Semiconductor Electrode journal July 1972
Reactivity of Anatase TiO 2 Nanoparticles:  The Role of the Minority (001) Surface journal October 2005
Structure and energetics of stoichiometric TiO 2 anatase surfaces journal March 2001
Anatase shows its reactive side journal August 2008
The surface science of titanium dioxide journal January 2003
Anatase TiO 2 with Dominant High-Energy {001} Facets: Synthesis, Properties, and Applications journal September 2011
Synthesis of Titania Nanosheets with a High Percentage of Exposed (001) Facets and Related Photocatalytic Properties journal March 2009
Constructing Hierarchical Spheres from Large Ultrathin Anatase TiO 2 Nanosheets with Nearly 100% Exposed (001) Facets for Fast Reversible Lithium Storage journal May 2010
On the True Photoreactivity Order of {001}, {010}, and {101} Facets of Anatase TiO2 Crystals journal January 2011
Titanium Dioxide Crystals with Tailored Facets journal May 2014
Effect of Fluorination on the Surface Properties of Titania P25 Powder: An FTIR Study journal October 2009
Hydrothermal Stability of {001} Faceted Anatase TiO 2 journal August 2011
DISCUS : a program for diffuse scattering and defect-structure simulation journal April 1997
The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
  • Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287 https://doi.org/10.1016/j.nimb.2012.05.037
journal September 2012
Fast synthesis and refinement of the atomic pair distribution function journal May 2015
The Bio-SANS instrument at the High Flux Isotope Reactor of Oak Ridge National Laboratory journal June 2014
Mantid—Data analysis and visualization package for neutron scattering and μ SR experiments
  • Arnold, O.; Bilheux, J. C.; Borreguero, J. M.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 764 https://doi.org/10.1016/j.nima.2014.07.029
journal November 2014
Irena : tool suite for modeling and analysis of small-angle scattering journal February 2009
Small-angle scattering. Information content and error analysis journal April 1980
Efficient algorithms for calculating small-angle scattering from large model structures journal May 2014
NIH Image to ImageJ: 25 years of image analysis journal June 2012
Prediction of TiO 2 Nanoparticle Phase and Shape Transitions Controlled by Surface Chemistry journal July 2005
X-ray line broadening from filed aluminium and wolfram journal January 1953
A fundamental parameters approach to X-ray line-profile fitting journal April 1992
Size, Shape, and Internal Atomic Ordering of Nanocrystals by Atomic Pair Distribution Functions: A Comparative Study of γ-Fe 2 O 3 Nanosized Spheres and Tetrapods journal October 2009
Differential Evolution – A Simple and Efficient Heuristic for global Optimization over Continuous Spaces journal January 1997
Estimating grain-size distributions in nanocrystalline materials from X-ray diffraction profile analysis journal March 1998
A total scattering Debye function analysis study of faulted Pt nanocrystals embedded in a porous matrix journal October 2016
Crossing the boundary between face-centred cubic and hexagonal close packed: the structure of nanosized cobalt is unraveled by a model accounting for shape, size distribution and stacking faults, allowing simulation of XRD, XANES and EXAFS journal September 2014
DEBUSSY 2.0 : the new release of a Debye user system for nanocrystalline and/or disordered materials journal November 2015
DEBUSSY : a Debye user system for nanocrystalline materials journal November 2010
Magnetite–Maghemite Nanoparticles in the 5–15 nm Range: Correlating the Core–Shell Composition and the Surface Structure to the Magnetic Properties. A Total Scattering Study. journal November 2013
Structure of Flame-Made Silica Nanoparticles by Ultra-Small-Angle X-ray Scattering journal March 2004
The real origin of lognormal size distributions of nanoparticles in vapor growth processes journal January 1999
Evidence for Crystal-Face-Dependent TiO 2 Photocatalysis from Single-Molecule Imaging and Kinetic Analysis journal May 2011
Enhanced Photocatalytic CO 2 -Reduction Activity of Anatase TiO 2 by Coexposed {001} and {101} Facets journal June 2014
Direct Observation of Charge Separation on Anatase TiO 2 Crystals with Selectively Etched {001} Facets journal February 2016
Engineering Coexposed {001} and {101} Facets in Oxygen-Deficient TiO 2 Nanocrystals for Enhanced CO 2 Photoreduction under Visible Light journal January 2016
Synthesis, characterization and enhanced photocatalytic CO 2 reduction activity of graphene supported TiO 2 nanocrystals with coexposed {001} and {101} facets journal January 2016
Methods, Mechanism, and Applications of Photodeposition in Photocatalysis: A Review journal December 2016
Modulating the photocatalytic redox preferences between anatase TiO 2 {001} and {101} surfaces journal January 2017
A selectively exposed crystal facet-engineered TiO 2 thin film photoanode for the higher performance of the photoelectrochemical water splitting reaction journal January 2015

Cited By (7)

Interaction mechanism between TiO 2 nanostructures and bovine leukemia virus proteins in photoluminescence-based immunosensors journal January 2018
Engineering the Surface/Interface Structures of Titanium Dioxide Micro and Nano Architectures towards Environmental and Electrochemical Applications journal November 2017
The Role of Surface Texture on the Photocatalytic H2 Production on TiO2 journal January 2019
Insight into Different Mechanisms for Oxidation of Liquid and Gaseous Pollutants by Bi−NaBiO 3 with or without Visible Light Illumination journal March 2019
TiO 2 nanocrystals with the {001} and {101} facets co-exposed with MIL-100(Fe): an egg-like composite nanomaterial for efficient visible light-driven photocatalysis journal January 2019
Understanding structure of small $${\hbox {TiO}}_2$$ nanoparticles and adsorption mechanisms of PbS quantum dots for solid-state applications: a combined theoretical and experimental study journal June 2019
A suite-level review of the neutron powder diffraction instruments at Oak Ridge National Laboratory journal September 2018