Effect of Surface Structure of TiO2 Nanoparticles on CO2 Adsorption and SO2 Resistance

Uma Tumuluri; Joshua D. Howe; William P. Mounfield; Meijun Li; Miaofang Chi; Zachary D. Hood; Krista S. Walton; David S. Sholl; Sheng Dai; Zili Wu

doi:10.1021/acssuschemeng.7b02295

Effect of Surface Structure of TiO₂ Nanoparticles on CO₂ Adsorption and SO₂ Resistance

Uma Tumuluri, Joshua D. Howe, William P. Mounfield, Meijun Li, Miaofang Chi, Zachary D. Hood, Krista S. Walton, David S. Sholl, Sheng Dai, Zili Wu

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

60 Scopus citations

Abstract

The effect of surface structure of TiO₂ nanocrystals on the structure, amount, and strength of adsorbed CO₂ and resistance to SO₂ was investigated using in situ IR spectroscopy and mass spectrometric techniques along with first-principles density functional theory (DFT) calculations. TiO₂ nanoshapes, including rods {(010) + (101) + (001)}, disks {(001) + (101)}, and truncated octahedra {(101) + (001)}, were used to represent different TiO₂ structures. Upon CO₂ adsorption, carboxylates and carbonates (bridged, monodentate) are formed on TiO₂ rods and disks, whereas only bidentate and monodentate carbonates are formed on TiO₂ truncated octahedra. In general, the order of thermal stability of the adsorbed CO₂ species is carboxylates ≈ monodentate carbonates > bridged carbonates > bidentate carbonates ≈ bicarbonates. TiO₂ rods and disks adsorb CO₂ more strongly than TiO₂ truncated octahedra, which is explained by the larger number of low coordinated surface oxygen and oxygen vacancies on the rods and disks than the truncated octahedra. Further IR studies showed that the structure and binding strength of the adsorbed CO₂ species are affected by the presence of SO₂. Among the three TiO₂ nanoshapes, CO₂ binding strength for truncated octahedra shows the most decrease due to accumulation of sulfates formed during the SO₂ adsorption cycle. The fundamental understanding obtained here on the effects of the surface structure, oxygen vacancies, and SO₂ on the interaction of CO₂ with TiO₂ may provide insights for the design of more efficient and sulfur-resistant TiO₂-based catalysts involved in CO₂ capture and conversion.

Original language	English
Pages (from-to)	9295-9306
Number of pages	12
Journal	ACS Sustainable Chemistry and Engineering
Volume	5
Issue number	10
DOIs	https://doi.org/10.1021/acssuschemeng.7b02295
State	Published - Oct 2 2017

Funding

This work was supported by the Center for Understanding and Control of Acid Gas-Induced Evolution of Materials for Energy (UNCAGE-ME), an Energy Frontier Research Center funded by U.S. Department of Energy. Part of the work including the IR, Raman and TEM was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. The DFT work was performed using EMSL, a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research. Z.D.H. gratefully acknowledges a Graduate Research Fellowship from the National Science Foundation (Grant DGE-1148903) and the Georgia Tech-ORNL Fellowship. Notice: This manuscript was authored by UT-Battelle, LLC under Contract DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy. gov/downloads/doe-public-access-plan).

Keywords

CO capture and conversion
IR spectroscopy
Oxygen vacancies
SO resistance
Surface structure
TiO nanoparticles

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1021/acssuschemeng.7b02295

Cite this

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title = "Effect of Surface Structure of TiO2 Nanoparticles on CO2 Adsorption and SO2 Resistance",

abstract = "The effect of surface structure of TiO2 nanocrystals on the structure, amount, and strength of adsorbed CO2 and resistance to SO2 was investigated using in situ IR spectroscopy and mass spectrometric techniques along with first-principles density functional theory (DFT) calculations. TiO2 nanoshapes, including rods {(010) + (101) + (001)}, disks {(001) + (101)}, and truncated octahedra {(101) + (001)}, were used to represent different TiO2 structures. Upon CO2 adsorption, carboxylates and carbonates (bridged, monodentate) are formed on TiO2 rods and disks, whereas only bidentate and monodentate carbonates are formed on TiO2 truncated octahedra. In general, the order of thermal stability of the adsorbed CO2 species is carboxylates ≈ monodentate carbonates > bridged carbonates > bidentate carbonates ≈ bicarbonates. TiO2 rods and disks adsorb CO2 more strongly than TiO2 truncated octahedra, which is explained by the larger number of low coordinated surface oxygen and oxygen vacancies on the rods and disks than the truncated octahedra. Further IR studies showed that the structure and binding strength of the adsorbed CO2 species are affected by the presence of SO2. Among the three TiO2 nanoshapes, CO2 binding strength for truncated octahedra shows the most decrease due to accumulation of sulfates formed during the SO2 adsorption cycle. The fundamental understanding obtained here on the effects of the surface structure, oxygen vacancies, and SO2 on the interaction of CO2 with TiO2 may provide insights for the design of more efficient and sulfur-resistant TiO2-based catalysts involved in CO2 capture and conversion.",

keywords = "CO capture and conversion, IR spectroscopy, Oxygen vacancies, SO resistance, Surface structure, TiO nanoparticles",

author = "Uma Tumuluri and Howe, {Joshua D.} and Mounfield, {William P.} and Meijun Li and Miaofang Chi and Hood, {Zachary D.} and Walton, {Krista S.} and Sholl, {David S.} and Sheng Dai and Zili Wu",

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T1 - Effect of Surface Structure of TiO2 Nanoparticles on CO2 Adsorption and SO2 Resistance

AU - Tumuluri, Uma

AU - Howe, Joshua D.

AU - Mounfield, William P.

AU - Li, Meijun

AU - Chi, Miaofang

AU - Hood, Zachary D.

AU - Walton, Krista S.

AU - Sholl, David S.

AU - Dai, Sheng

AU - Wu, Zili

PY - 2017/10/2

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N2 - The effect of surface structure of TiO2 nanocrystals on the structure, amount, and strength of adsorbed CO2 and resistance to SO2 was investigated using in situ IR spectroscopy and mass spectrometric techniques along with first-principles density functional theory (DFT) calculations. TiO2 nanoshapes, including rods {(010) + (101) + (001)}, disks {(001) + (101)}, and truncated octahedra {(101) + (001)}, were used to represent different TiO2 structures. Upon CO2 adsorption, carboxylates and carbonates (bridged, monodentate) are formed on TiO2 rods and disks, whereas only bidentate and monodentate carbonates are formed on TiO2 truncated octahedra. In general, the order of thermal stability of the adsorbed CO2 species is carboxylates ≈ monodentate carbonates > bridged carbonates > bidentate carbonates ≈ bicarbonates. TiO2 rods and disks adsorb CO2 more strongly than TiO2 truncated octahedra, which is explained by the larger number of low coordinated surface oxygen and oxygen vacancies on the rods and disks than the truncated octahedra. Further IR studies showed that the structure and binding strength of the adsorbed CO2 species are affected by the presence of SO2. Among the three TiO2 nanoshapes, CO2 binding strength for truncated octahedra shows the most decrease due to accumulation of sulfates formed during the SO2 adsorption cycle. The fundamental understanding obtained here on the effects of the surface structure, oxygen vacancies, and SO2 on the interaction of CO2 with TiO2 may provide insights for the design of more efficient and sulfur-resistant TiO2-based catalysts involved in CO2 capture and conversion.

AB - The effect of surface structure of TiO2 nanocrystals on the structure, amount, and strength of adsorbed CO2 and resistance to SO2 was investigated using in situ IR spectroscopy and mass spectrometric techniques along with first-principles density functional theory (DFT) calculations. TiO2 nanoshapes, including rods {(010) + (101) + (001)}, disks {(001) + (101)}, and truncated octahedra {(101) + (001)}, were used to represent different TiO2 structures. Upon CO2 adsorption, carboxylates and carbonates (bridged, monodentate) are formed on TiO2 rods and disks, whereas only bidentate and monodentate carbonates are formed on TiO2 truncated octahedra. In general, the order of thermal stability of the adsorbed CO2 species is carboxylates ≈ monodentate carbonates > bridged carbonates > bidentate carbonates ≈ bicarbonates. TiO2 rods and disks adsorb CO2 more strongly than TiO2 truncated octahedra, which is explained by the larger number of low coordinated surface oxygen and oxygen vacancies on the rods and disks than the truncated octahedra. Further IR studies showed that the structure and binding strength of the adsorbed CO2 species are affected by the presence of SO2. Among the three TiO2 nanoshapes, CO2 binding strength for truncated octahedra shows the most decrease due to accumulation of sulfates formed during the SO2 adsorption cycle. The fundamental understanding obtained here on the effects of the surface structure, oxygen vacancies, and SO2 on the interaction of CO2 with TiO2 may provide insights for the design of more efficient and sulfur-resistant TiO2-based catalysts involved in CO2 capture and conversion.

KW - CO capture and conversion

KW - IR spectroscopy

KW - Oxygen vacancies

KW - SO resistance

KW - Surface structure

KW - TiO nanoparticles

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