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

Jue Liu; Daniel Olds; Rui Peng; Lei Yu; Guo Shiou Foo; Shuo Qian; Jong Keum; Beth S. Guiton; Zili Wu; Katharine Page

doi:10.1021/acs.chemmater.7b01172

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

Jue Liu, Daniel Olds, Rui Peng, Lei Yu, Guo Shiou Foo, Shuo Qian, Jong Keum, Beth S. Guiton, Zili Wu, Katharine Page

Research output: Contribution to journal › Article › peer-review

62 Scopus citations

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 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. 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.

Original language	English
Pages (from-to)	5591-5604
Number of pages	14
Journal	Chemistry of Materials
Volume	29
Issue number	13
DOIs	https://doi.org/10.1021/acs.chemmater.7b01172
State	Published - Jul 11 2017

Funding

This work was principally supported through the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Early Career Research Program, Award No. KC040602, under Contract No. DE-AC05-00OR22725. Research conducted at the NOMAD beamline at ORNL's Spallation Neutron Source and High Flux Isotope Reactor was sponsored by the Scientific User Facilities Division, Office of Basic Sciences, U.S. Department of Energy. Bio-SANS is operated by Center for Structural Molecular Biology (FWP-ERKP291), sponsored by DOE Office of Biological and Environmental Research. Research at the 11-ID-B beamline used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Photocatalysis work was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility.

Funders	Funder number
Office of Basic Sciences	FWP-ERKP291
Scientific User Facilities Division
National Science Foundation	1355438
U.S. Department of Energy
Office of Science
Basic Energy Sciences	DE-AC05-00OR22725, KC040602
Biological and Environmental Research
Argonne National Laboratory	DE-AC02-06CH11357

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10.1021/acs.chemmater.7b01172

Cite this

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title = "Quantitative Analysis of the Morphology of {101} and {001} Faceted Anatase TiO2 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 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. 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.",

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