Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy

Chen, Junchao; Wu, Xin-Ping; Hope, Michael A.; Qian, Kun; Halat, David M.; Liu, Tao; Li, Yuhong; Shen, Li; Ke, Xiaokang; Wen, Yujie; Du, Jia-Huan; Magusin, Pieter C.  M.  M.; Paul, Subhradip; Ding, Weiping; Gong, Xue-Qing; Grey, Clare P.; Peng, Luming

doi:10.1038/s41467-019-13424-7

Title: Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy

Abstract

Compared to nanomaterials exposing nonpolar facets, polar-faceted nanocrystals often exhibit unexpected and interesting properties. The electrostatic instability arising from the intrinsic dipole moments of polar facets, however, leads to different surface configurations in many cases, making it challenging to extract detailed structural information and develop structure-property relations. The widely used electron microscopy techniques are limited because the volumes sampled may not be representative, and they provide little chemical bonding information with low contrast of light elements. With ceria nanocubes exposing (100) facets as an example, here we show that the polar surface structure of oxide nanocrystals can be investigated by applying ¹⁷O and ¹H solid-state NMR spectroscopy and dynamic nuclear polarization, combined with DFT calculations. Both CeO₄-termination reconstructions and hydroxyls are present for surface polarity compensation and their concentrations can be quantified. These results open up new possibilities for investigating the structure and properties of oxide nanostructures with polar facets.

Authors:

^[1];

^[2];

^[3]; Qian, Kun ^[1];

^[3]; Liu, Tao ^[3]; Li, Yuhong ^[1]; Shen, Li ^[1]; Ke, Xiaokang ^[1];

^[1];

^[1]; Magusin, Pieter C. M. M. ^[3];

^[4]; Ding, Weiping ^[1]; Gong, Xue-Qing ^[5]; Grey, Clare P. ^[3];

^[1]

Nanjing Univ. (China)
East China Univ. of Science and Technology, Shanghai (China); Univ. of Minnesota, Minneapolis, MN (United States)
Univ. of Cambridge (United Kingdom)
Univ. of Nottingham (United Kingdom)
East China Univ. of Science and Technology, Shanghai (China)

Publication Date:: 2019-11-28

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1591836

Grant/Contract Number:: AC02-05CH11231; SC0012583

Resource Type:: Accepted Manuscript

Journal Name:: Nature Communications

Additional Journal Information:: Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723

Publisher:: Nature Publishing Group

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; characterization and analytical techniques; nanoparticles; solid-state NMR

Citation Formats


                    Chen, Junchao, Wu, Xin-Ping, Hope, Michael A., Qian, Kun, Halat, David M., Liu, Tao, Li, Yuhong, Shen, Li, Ke, Xiaokang, Wen, Yujie, Du, Jia-Huan, Magusin, Pieter C.  M.  M., Paul, Subhradip, Ding, Weiping, Gong, Xue-Qing, Grey, Clare P., and Peng, Luming. Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy.  United States: N. p., 2019. 
Web.  doi:10.1038/s41467-019-13424-7.

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                    Chen, Junchao, Wu, Xin-Ping, Hope, Michael A., Qian, Kun, Halat, David M., Liu, Tao, Li, Yuhong, Shen, Li, Ke, Xiaokang, Wen, Yujie, Du, Jia-Huan, Magusin, Pieter C.  M.  M., Paul, Subhradip, Ding, Weiping, Gong, Xue-Qing, Grey, Clare P., & Peng, Luming. Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy.  United States.  https://doi.org/10.1038/s41467-019-13424-7

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                    Chen, Junchao, Wu, Xin-Ping, Hope, Michael A., Qian, Kun, Halat, David M., Liu, Tao, Li, Yuhong, Shen, Li, Ke, Xiaokang, Wen, Yujie, Du, Jia-Huan, Magusin, Pieter C.  M.  M., Paul, Subhradip, Ding, Weiping, Gong, Xue-Qing, Grey, Clare P., and Peng, Luming. Thu .  
"Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy".  United States.  https://doi.org/10.1038/s41467-019-13424-7.  https://www.osti.gov/servlets/purl/1591836.

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@article{osti_1591836,

  title        = {Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy},

  author       = {Chen, Junchao and Wu, Xin-Ping and Hope, Michael A. and Qian, Kun and Halat, David M. and Liu, Tao and Li, Yuhong and Shen, Li and Ke, Xiaokang and Wen, Yujie and Du, Jia-Huan and Magusin, Pieter C.  M.  M. and Paul, Subhradip and Ding, Weiping and Gong, Xue-Qing and Grey, Clare P. and Peng, Luming},

  abstractNote = {Compared to nanomaterials exposing nonpolar facets, polar-faceted nanocrystals often exhibit unexpected and interesting properties. The electrostatic instability arising from the intrinsic dipole moments of polar facets, however, leads to different surface configurations in many cases, making it challenging to extract detailed structural information and develop structure-property relations. The widely used electron microscopy techniques are limited because the volumes sampled may not be representative, and they provide little chemical bonding information with low contrast of light elements. With ceria nanocubes exposing (100) facets as an example, here we show that the polar surface structure of oxide nanocrystals can be investigated by applying 17O and 1H solid-state NMR spectroscopy and dynamic nuclear polarization, combined with DFT calculations. Both CeO4-termination reconstructions and hydroxyls are present for surface polarity compensation and their concentrations can be quantified. These results open up new possibilities for investigating the structure and properties of oxide nanostructures with polar facets.},

  doi          = {10.1038/s41467-019-13424-7},

  journal      = {Nature Communications},

  number       = 1,

  volume       = 10,

  place        = {United States},

  year         = {2019},

  month        = {11}

}

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Title: Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy

Abstract

Citation Formats

Generalized Gradient Approximation Made Simple journal, October 1996

Extra-Low-Temperature Oxygen Storage Capacity of CeO 2 Nanocrystals with Cubic Facets journal, February 2011

Electron Microscopy of Solid Catalysts—Transforming from a Challenge to a Toolbox journal, March 2015

Projector augmented-wave method journal, December 1994

Isotropic High Field NMR Spectra of Li-Ion Battery Materials with Anisotropy >1 MHz journal, January 2012

Semiconducting and Piezoelectric Oxide Nanostructures Induced by Polar Surfaces journal, October 2004

NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries journal, October 2004

1H MAS NMR studies on the acidity of zeolites journal, July 1986

Image resolution and sensitivity in an environmental transmission electron microscope journal, November 2012

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

High Frequency Dynamic Nuclear Polarization journal, April 2013

Structure of the catalytically active copper–ceria interfacial perimeter journal, February 2019

Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR journal, February 2013

Identification of different oxygen species in oxide nanostructures with 17 O solid-state NMR spectroscopy journal, February 2015

A negative surface energy for alumina journal, April 2004

NMR chemical shifts of dilute 1H in inorganic solids journal, October 1985

Probing Oxide-Ion Mobility in the Mixed Ionic–Electronic Conductor La 2 NiO 4+δ by Solid-State 17 O MAS NMR Spectroscopy journal, September 2016

Single-atom electron energy loss spectroscopy of light elements journal, July 2015

Understanding the Conduction Mechanism of the Protonic Conductor CsH 2 PO 4 by Solid-State NMR Spectroscopy journal, March 2013

NMR spectroscopy: a potent tool for studying monolayer-protected metal nanoclusters journal, January 2018

Single-Crystal Nanorings Formed by Epitaxial Self-Coiling of Polar Nanobelts journal, February 2004

Surface-selective direct 17 O DNP NMR of CeO 2 nanoparticles journal, January 2017

Shape and Size Effects of ZnO Nanocrystals on Photocatalytic Activity journal, September 2009

Large Molecular Weight Nitroxide Biradicals Providing Efficient Dynamic Nuclear Polarization at Temperatures up to 200 K journal, August 2013

Finite element multiconfiguration Hartree-Fock calculations on carbon, oxygen, and neon: the nuclear quadrupole moments of carbon-11, oxygen-17, and neon-21 journal, January 1992

Advanced Solid State NMR Techniques for the Characterization of Sol–Gel-Derived Materials journal, September 2007

Rational strategy for shaped nanomaterial synthesis in reverse micelle reactors journal, May 2014

Powder Crystallography by Combined Crystal Structure Prediction and High-Resolution 1 H Solid-State NMR Spectroscopy journal, March 2010

Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics? journal, December 2008

Distinguishing faceted oxide nanocrystals with 17O solid-state NMR spectroscopy journal, September 2017

Entropic contributions enhance polarity compensation for CeO2(100) surfaces journal, November 2016

Interactions of Water with the (111) and (100) Surfaces of Ceria journal, September 2017

Taming multiple valency with density functionals: A case study of defective ceria journal, January 2005

Novel Stabilization Mechanism on Polar Surfaces: ZnO(0001)-Zn journal, January 2003

Characteristics of Pd deposition on the MgO(111) surface journal, December 1999

Mapping of Functional Groups in Metal-Organic Frameworks journal, July 2013

Theoretical insights into the hydrophobicity of low index CeO2 surfaces journal, June 2019

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium journal, May 1994

The Structures of C–Ce2O3+δ, Ce7O12, and Ce11O20 journal, November 1999

Clustering of Oxygen Vacancies at CeO 2 ( 111 ) : Critical Role of Hydroxyls journal, February 2016

Acidic Properties and Structure–Activity Correlations of Solid Acid Catalysts Revealed by Solid-State NMR Spectroscopy journal, March 2016

Understanding Surface and Interfacial Chemistry in Functional Nanomaterials via Solid-State NMR journal, March 2017

Measuring the surface stress polar dependence journal, February 2005

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

Opposite Face Sensitivity of CeO 2 in Hydrogenation and Oxidation Catalysis journal, August 2014

Morphology-dependent interplay of reduction behaviors, oxygen vacancies and hydroxyl reactivity of CeO 2 nanocrystals journal, January 2015

Trimethylphosphine-Assisted Surface Fingerprinting of Metal Oxide Nanoparticle by 31 P Solid-State NMR: A Zinc Oxide Case Study journal, February 2016

Ceria Nanocrystals Exposing Wide (100) Facets: Structure and Polarity Compensation journal, November 2014

A polarity-induced defect mechanism for conductivity and magnetism at polar–nonpolar oxide interfaces journal, October 2014

Fundamentals and Catalytic Applications of CeO 2 -Based Materials journal, April 2016

Surface hydroxyl concentration on Zr(OH)4 quantified by 1H MAS NMR journal, August 2011

Multiple-Quantum Magic-Angle Spinning NMR: A New Method for the Study of Quadrupolar Nuclei in Solids journal, December 1995

Unique Electronic and Structural Effects in Vanadia/Ceria-Catalyzed Reactions journal, October 2015

Fast MAS 1 H NMR Study of Water Adsorption and Dissociation on the (100) Surface of Ceria Nanocubes: A Fully Hydroxylated, Hydrophobic Ceria Surface journal, March 2017

Opposite Face Sensitivity of CeO 2 in Hydrogenation and Oxidation Catalysis journal, August 2014

NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries journal, December 2004

Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction journal, April 2020

Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect journal, February 2020

Probing Oxide-Ion Mobility in the Mixed Ionic-Electronic Conductor La$_2$NiO$_{4+δ}$ by Solid-State $^{17}$O MAS NMR Spectroscopy. text, January 2016

Advanced Solid State NMR Techniques for the Characterization of Sol—Gel-Derived Materials journal, December 2007

Measuring the surface stress polar dependence text, January 2007

A polarity-induced defect mechanism for conductivity and magnetism at polar-nonpolar oxide interfaces text, January 2014

Probing Interactions of γ‐Alumina with Water via Multinuclear Solid‐State NMR Spectroscopy journal, March 2020

Generalized Gradient Approximation Made Simple
journal, October 1996

Extra-Low-Temperature Oxygen Storage Capacity of CeO ₂ Nanocrystals with Cubic Facets
journal, February 2011

Electron Microscopy of Solid Catalysts—Transforming from a Challenge to a Toolbox
journal, March 2015

Projector augmented-wave method
journal, December 1994

Isotropic High Field NMR Spectra of Li-Ion Battery Materials with Anisotropy >1 MHz
journal, January 2012

Semiconducting and Piezoelectric Oxide Nanostructures Induced by Polar Surfaces
journal, October 2004

NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries
journal, October 2004

1H MAS NMR studies on the acidity of zeolites
journal, July 1986

Image resolution and sensitivity in an environmental transmission electron microscope
journal, November 2012

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

High Frequency Dynamic Nuclear Polarization
journal, April 2013

Structure of the catalytically active copper–ceria interfacial perimeter
journal, February 2019

Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR
journal, February 2013

Identification of different oxygen species in oxide nanostructures with ¹⁷ O solid-state NMR spectroscopy
journal, February 2015

A negative surface energy for alumina
journal, April 2004

NMR chemical shifts of dilute 1H in inorganic solids
journal, October 1985

Probing Oxide-Ion Mobility in the Mixed Ionic–Electronic Conductor La ₂ NiO _4+δ by Solid-State ¹⁷ O MAS NMR Spectroscopy
journal, September 2016

Single-atom electron energy loss spectroscopy of light elements
journal, July 2015

Understanding the Conduction Mechanism of the Protonic Conductor CsH ₂ PO ₄ by Solid-State NMR Spectroscopy
journal, March 2013

NMR spectroscopy: a potent tool for studying monolayer-protected metal nanoclusters
journal, January 2018

Single-Crystal Nanorings Formed by Epitaxial Self-Coiling of Polar Nanobelts
journal, February 2004

Surface-selective direct ¹⁷ O DNP NMR of CeO ₂ nanoparticles
journal, January 2017

Shape and Size Effects of ZnO Nanocrystals on Photocatalytic Activity
journal, September 2009

Large Molecular Weight Nitroxide Biradicals Providing Efficient Dynamic Nuclear Polarization at Temperatures up to 200 K
journal, August 2013

Finite element multiconfiguration Hartree-Fock calculations on carbon, oxygen, and neon: the nuclear quadrupole moments of carbon-11, oxygen-17, and neon-21
journal, January 1992

Advanced Solid State NMR Techniques for the Characterization of Sol–Gel-Derived Materials
journal, September 2007

Rational strategy for shaped nanomaterial synthesis in reverse micelle reactors
journal, May 2014

Powder Crystallography by Combined Crystal Structure Prediction and High-Resolution ¹ H Solid-State NMR Spectroscopy
journal, March 2010

Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?
journal, December 2008

Distinguishing faceted oxide nanocrystals with 17O solid-state NMR spectroscopy
journal, September 2017

Entropic contributions enhance polarity compensation for CeO2(100) surfaces
journal, November 2016

Interactions of Water with the (111) and (100) Surfaces of Ceria
journal, September 2017

Taming multiple valency with density functionals: A case study of defective ceria
journal, January 2005

Novel Stabilization Mechanism on Polar Surfaces: ZnO(0001)-Zn
journal, January 2003

Characteristics of Pd deposition on the MgO(111) surface
journal, December 1999

Mapping of Functional Groups in Metal-Organic Frameworks
journal, July 2013

Theoretical insights into the hydrophobicity of low index CeO2 surfaces
journal, June 2019

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994

The Structures of C–Ce2O3+δ, Ce7O12, and Ce11O20
journal, November 1999

Clustering of Oxygen Vacancies at ${CeO}_{2} (111)$ : Critical Role of Hydroxyls
journal, February 2016

Acidic Properties and Structure–Activity Correlations of Solid Acid Catalysts Revealed by Solid-State NMR Spectroscopy
journal, March 2016

Understanding Surface and Interfacial Chemistry in Functional Nanomaterials via Solid-State NMR
journal, March 2017

Measuring the surface stress polar dependence
journal, February 2005

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

Opposite Face Sensitivity of CeO ₂ in Hydrogenation and Oxidation Catalysis
journal, August 2014

Morphology-dependent interplay of reduction behaviors, oxygen vacancies and hydroxyl reactivity of CeO ₂ nanocrystals
journal, January 2015

Trimethylphosphine-Assisted Surface Fingerprinting of Metal Oxide Nanoparticle by ³¹ P Solid-State NMR: A Zinc Oxide Case Study
journal, February 2016

Ceria Nanocrystals Exposing Wide (100) Facets: Structure and Polarity Compensation
journal, November 2014

A polarity-induced defect mechanism for conductivity and magnetism at polar–nonpolar oxide interfaces
journal, October 2014

Fundamentals and Catalytic Applications of CeO ₂ -Based Materials
journal, April 2016

Surface hydroxyl concentration on Zr(OH)4 quantified by 1H MAS NMR
journal, August 2011

Multiple-Quantum Magic-Angle Spinning NMR: A New Method for the Study of Quadrupolar Nuclei in Solids
journal, December 1995

Unique Electronic and Structural Effects in Vanadia/Ceria-Catalyzed Reactions
journal, October 2015

Fast MAS ¹ H NMR Study of Water Adsorption and Dissociation on the (100) Surface of Ceria Nanocubes: A Fully Hydroxylated, Hydrophobic Ceria Surface
journal, March 2017

Opposite Face Sensitivity of CeO ₂ in Hydrogenation and Oxidation Catalysis
journal, August 2014

NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries
journal, December 2004

Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction
journal, April 2020

Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020

Probing Oxide-Ion Mobility in the Mixed Ionic-Electronic Conductor La$_2$NiO$_{4+δ}$ by Solid-State $^{17}$O MAS NMR Spectroscopy.
text, January 2016

Advanced Solid State NMR Techniques for the Characterization of Sol—Gel-Derived Materials
journal, December 2007

Measuring the surface stress polar dependence
text, January 2007

A polarity-induced defect mechanism for conductivity and magnetism at polar-nonpolar oxide interfaces
text, January 2014

Probing Interactions of γ‐Alumina with Water via Multinuclear Solid‐State NMR Spectroscopy
journal, March 2020