A combined experimental and DFT study of H2O effect on In2O3/ZrO2 catalyst for CO2 hydrogenation to methanol

Xiao Jiang; Xiaowa Nie; Yutao Gong; Colton M. Moran; Jianyang Wang; Jie Zhu; Huibin Chang; Xinwen Guo; Krista S. Walton; Chunshan Song

doi:10.1016/j.jcat.2020.01.014

A combined experimental and DFT study of H₂O effect on In₂O₃/ZrO₂ catalyst for CO₂ hydrogenation to methanol

Xiao Jiang, Xiaowa Nie, Yutao Gong, Colton M. Moran, Jianyang Wang, Jie Zhu, Huibin Chang, Xinwen Guo, Krista S. Walton, Chunshan Song

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

85 Scopus citations

Abstract

CO₂ hydrogenation with renewable energy is one of the promising approaches to mitigate CO₂ emissions and produce sustainable chemicals and fuels. The effect of adding H₂O in the feed gas on the activity and selectivity of In₂O₃/ZrO₂ catalysts for CO₂ hydrogenation to methanol was studied using combined experimentatal and computational efforts. Notably, adding an appropriate amount of H₂O (0.1 mol%) in the feed gas significantly enhanced the CH₃OH formation (ca. 20%) with improved selectivity. Characterization with STEM/EDS and CO₂-TPD confirmed the preservation of In-Zr strong interaction in the presence of additional H₂O and H₂O-induced oxygen vacancies, which significantly improved CO₂ adsorption capacity. XPS analysis revealed the formation of InOOH species due to H₂O addition, which appeared to correlate to H₂O-dependant enhancement of CH₃OH formation. Density functional theory calculations rationalized the effect of surface H₂O on InOOH formation and its correlation to CH₃OH synthesis activity. Adding H₂O was found to facilitate surface InOOH formation, suppress CO formation through COOH* intermediate, and promote CH₃OH formation via HCOO* intermediate. However, excess H₂O addition resulted in aggregation of In species and reduction of surface In⁰ for H₂ dissociation.

Original language	English (US)
Pages (from-to)	283-296
Number of pages	14
Journal	Journal of Catalysis
Volume	383
DOIs	https://doi.org/10.1016/j.jcat.2020.01.014
State	Published - Mar 2020

All Science Journal Classification (ASJC) codes

Catalysis
Physical and Theoretical Chemistry

UN SDGs

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

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10.1016/j.jcat.2020.01.014

Cite this

@article{5c8e280af968451f872caa56ecf59a73,

title = "A combined experimental and DFT study of H2O effect on In2O3/ZrO2 catalyst for CO2 hydrogenation to methanol",

abstract = "CO2 hydrogenation with renewable energy is one of the promising approaches to mitigate CO2 emissions and produce sustainable chemicals and fuels. The effect of adding H2O in the feed gas on the activity and selectivity of In2O3/ZrO2 catalysts for CO2 hydrogenation to methanol was studied using combined experimentatal and computational efforts. Notably, adding an appropriate amount of H2O (0.1 mol%) in the feed gas significantly enhanced the CH3OH formation (ca. 20%) with improved selectivity. Characterization with STEM/EDS and CO2-TPD confirmed the preservation of In-Zr strong interaction in the presence of additional H2O and H2O-induced oxygen vacancies, which significantly improved CO2 adsorption capacity. XPS analysis revealed the formation of InOOH species due to H2O addition, which appeared to correlate to H2O-dependant enhancement of CH3OH formation. Density functional theory calculations rationalized the effect of surface H2O on InOOH formation and its correlation to CH3OH synthesis activity. Adding H2O was found to facilitate surface InOOH formation, suppress CO formation through COOH* intermediate, and promote CH3OH formation via HCOO* intermediate. However, excess H2O addition resulted in aggregation of In species and reduction of surface In0 for H2 dissociation.",

author = "Xiao Jiang and Xiaowa Nie and Yutao Gong and Moran, {Colton M.} and Jianyang Wang and Jie Zhu and Huibin Chang and Xinwen Guo and Walton, {Krista S.} and Chunshan Song",

note = "Publisher Copyright: {\textcopyright} 2020",

year = "2020",

month = mar,

doi = "10.1016/j.jcat.2020.01.014",

language = "English (US)",

volume = "383",

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journal = "Journal of Catalysis",

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T1 - A combined experimental and DFT study of H2O effect on In2O3/ZrO2 catalyst for CO2 hydrogenation to methanol

AU - Jiang, Xiao

AU - Nie, Xiaowa

AU - Gong, Yutao

AU - Moran, Colton M.

AU - Wang, Jianyang

AU - Zhu, Jie

AU - Chang, Huibin

AU - Guo, Xinwen

AU - Walton, Krista S.

AU - Song, Chunshan

PY - 2020/3

Y1 - 2020/3

N2 - CO2 hydrogenation with renewable energy is one of the promising approaches to mitigate CO2 emissions and produce sustainable chemicals and fuels. The effect of adding H2O in the feed gas on the activity and selectivity of In2O3/ZrO2 catalysts for CO2 hydrogenation to methanol was studied using combined experimentatal and computational efforts. Notably, adding an appropriate amount of H2O (0.1 mol%) in the feed gas significantly enhanced the CH3OH formation (ca. 20%) with improved selectivity. Characterization with STEM/EDS and CO2-TPD confirmed the preservation of In-Zr strong interaction in the presence of additional H2O and H2O-induced oxygen vacancies, which significantly improved CO2 adsorption capacity. XPS analysis revealed the formation of InOOH species due to H2O addition, which appeared to correlate to H2O-dependant enhancement of CH3OH formation. Density functional theory calculations rationalized the effect of surface H2O on InOOH formation and its correlation to CH3OH synthesis activity. Adding H2O was found to facilitate surface InOOH formation, suppress CO formation through COOH* intermediate, and promote CH3OH formation via HCOO* intermediate. However, excess H2O addition resulted in aggregation of In species and reduction of surface In0 for H2 dissociation.

AB - CO2 hydrogenation with renewable energy is one of the promising approaches to mitigate CO2 emissions and produce sustainable chemicals and fuels. The effect of adding H2O in the feed gas on the activity and selectivity of In2O3/ZrO2 catalysts for CO2 hydrogenation to methanol was studied using combined experimentatal and computational efforts. Notably, adding an appropriate amount of H2O (0.1 mol%) in the feed gas significantly enhanced the CH3OH formation (ca. 20%) with improved selectivity. Characterization with STEM/EDS and CO2-TPD confirmed the preservation of In-Zr strong interaction in the presence of additional H2O and H2O-induced oxygen vacancies, which significantly improved CO2 adsorption capacity. XPS analysis revealed the formation of InOOH species due to H2O addition, which appeared to correlate to H2O-dependant enhancement of CH3OH formation. Density functional theory calculations rationalized the effect of surface H2O on InOOH formation and its correlation to CH3OH synthesis activity. Adding H2O was found to facilitate surface InOOH formation, suppress CO formation through COOH* intermediate, and promote CH3OH formation via HCOO* intermediate. However, excess H2O addition resulted in aggregation of In species and reduction of surface In0 for H2 dissociation.

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