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 TiO 2 Nanocrystals and Its Implication on Photocatalytic Activity

Abstract

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 TiO 2 nanocrystals based on differential evolution refinements using Debye scattering equation calculations. It is also demonstrated that the morphology polydispersity of TiO 2 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 TiO 2 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 relationshipmore » between morphology and functionality of nanomaterials.« less

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [1]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of Kentucky, Lexington, KY (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1376372
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 13; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Liu, Jue, Olds, Daniel, Peng, Rui, Yu, Lei, Foo, Guo Shiou, Qian, Shuo, Keum, Jong, Guiton, Beth S., Wu, Zili, and Page, Katharine. Quantitative Analysis of the Morphology of {101} and {001} Faceted Anatase TiO2 Nanocrystals and Its Implication on Photocatalytic Activity. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b01172.
Liu, Jue, Olds, Daniel, Peng, Rui, Yu, Lei, Foo, Guo Shiou, Qian, Shuo, Keum, Jong, Guiton, Beth S., Wu, Zili, & Page, Katharine. Quantitative Analysis of the Morphology of {101} and {001} Faceted Anatase TiO2 Nanocrystals and Its Implication on Photocatalytic Activity. United States. doi:10.1021/acs.chemmater.7b01172.
Liu, Jue, Olds, Daniel, Peng, Rui, Yu, Lei, Foo, Guo Shiou, Qian, Shuo, Keum, Jong, Guiton, Beth S., Wu, Zili, and Page, Katharine. 2017. "Quantitative Analysis of the Morphology of {101} and {001} Faceted Anatase TiO2 Nanocrystals and Its Implication on Photocatalytic Activity". United States. doi:10.1021/acs.chemmater.7b01172.
@article{osti_1376372,
title = {Quantitative Analysis of the Morphology of {101} and {001} Faceted Anatase TiO2 Nanocrystals and Its Implication on Photocatalytic Activity},
author = {Liu, Jue and Olds, Daniel and Peng, Rui and Yu, Lei and Foo, Guo Shiou and Qian, Shuo and Keum, Jong and Guiton, Beth S. and Wu, Zili and Page, Katharine},
abstractNote = {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.},
doi = {10.1021/acs.chemmater.7b01172},
journal = {Chemistry of Materials},
number = 13,
volume = 29,
place = {United States},
year = 2017,
month = 6
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on June 14, 2018
Publisher's Version of Record

Citation Metrics:
Cited by: 5works
Citation information provided by
Web of Science

Save / Share:
  • 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 TiO 2 nanocrystals based on differential evolution refinements using Debye scattering equation calculations. It is also demonstrated that the morphology polydispersity of TiO 2 nanocrystals can be effectively obtained from the diffractionmore » 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 TiO 2 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. 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.« less
  • the abstract for this product is not available at this time.
  • Inconsistencies in experimental thermochemical analysis of the anatase to rutile phase transition have led to various studies in order to elucidate the physical and chemical parameters affecting the stability of TiO2 at the nanoscale. Using a thermodynamic model, we present predictions of the transition enthalpy of nanocrystalline anatase and rutile as a function of shape, size, and degree of surface passivation, showing that thermochemical results can differ for various faceted or spherical nanoparticles.
  • Cited by 18
  • In this paper, a simple and efficient methodology for the low-temperature synthesis of phase-pure nanocrystalline rutile TiO{sub 2} with tuned morphology is reported. Control on morphology has been achieved by simple variation of the hydrothermal process, starting with titanium-tetrachloride without using mineralizers, additives or templating agents. The X-ray diffraction (XRD) and selected area electron diffraction (SAED) patterns showed no other phases of TiO{sub 2} establishing the formation of phase-pure rutile titania in the entire temperature range of synthesis (40-150 deg. C) and most noticeably even at a considerably low temperature (40 deg. C). Fourier transform infrared (FT-IR) spectra strongly indicatedmore » the presence of hydroxyl group or surface adsorbed water and the thermogravimetry and differential thermo-gravimetry (TG-DTG) showed no phase change up to 1000 deg. C. A combination of reaction parameters (temperature, time) with a thorough transmission electron microscopy (TEM) study demonstrated the formation of phase-pure rutile titania nanocrystals as nano-rods, bunched nano-spindles or spherical nanoparticles depending on the hydrothermal reaction conditions. The photocatalytic activity of the synthesized nanocrystals has been successfully evaluated on the photodegradation of methyl orange (MO), a well-known pollutant azo-dye, as a model reaction.« less