CO2 methanation reaction pathways over unpromoted and NaNO3-promoted Ru/Al2O3 catalysts

Sang Jae Park; Xiang Wang; Madelyn R. Ball; Laura Proano; Zili Wu; Christopher W. Jones

doi:10.1039/d2cy00515h

CO₂ methanation reaction pathways over unpromoted and NaNO₃-promoted Ru/Al₂O₃ catalysts

Sang Jae Park
, Xiang Wang
, Madelyn R. Ball
, Laura Proano
, Zili Wu
, Christopher W. Jones

Surface Chemistry & Catalysis Group

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

19 Scopus citations

Abstract

Catalytic CO₂ sorbents, materials that adsorb and pre-concentrate CO₂ on the catalyst surface prior to subsequent conversion, are becoming important materials in CO₂ capture and utilization. In this work, a prototypical CO₂ methanation catalyst - Ru/Al₂O₃ - and a related catalytic sorbent - NaNO₃/Ru/Al₂O₃ - are used for CO₂ methanation in flowing hydrogen in a fixed bed reactor at temperatures ranging from 220 to 280 °C. Activation energies for the NaNO₃/Ru/Al₂O₃ material are slightly higher than unpromoted Ru/Al₂O₃ catalysts, and the reaction orders vary more significantly. In situ IR spectroscopy and steady-state isotopic kinetic analysis (SSITKA) using in situ IR/MS spectroscopy show that bicarbonate and linear carbonyl species are the likely reaction intermediates over unpromoted Ru/Al₂O₃, while bidentate carbonate, formate and linear carbonyl species are among likely reaction intermediates over NaNO₃/Ru/Al₂O₃. Rate laws consistent with the obtained experimental data are proposed after kinetic modeling of multiple plausible reaction pathways. Results suggest that the pathway over the NaNO₃/Ru/Al₂O₃ catalyst likely has an additional kinetically relevant irreversible step in the CO₂ methanation reaction pathway.

Original language	English
Pages (from-to)	4637-4652
Number of pages	16
Journal	Catalysis Science and Technology
Volume	12
Issue number	14
DOIs	https://doi.org/10.1039/d2cy00515h
State	Published - Jun 9 2022

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 (US DoE), Office of Science, Basic Energy Sciences (BES) under Award DE-SC0012577. Fundamental structural characterization was performed at the Georgia Tech Institute for Electronics and Nanotechnology, a member of the National Nanotechnology Coordinated Infrastructure (NNCI), which is supported by the National Science Foundation (ECCS-1542174). X. W. (SSITKA-IR effort) was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science program.

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title = "CO2 methanation reaction pathways over unpromoted and NaNO3-promoted Ru/Al2O3 catalysts",

abstract = "Catalytic CO2 sorbents, materials that adsorb and pre-concentrate CO2 on the catalyst surface prior to subsequent conversion, are becoming important materials in CO2 capture and utilization. In this work, a prototypical CO2 methanation catalyst - Ru/Al2O3 - and a related catalytic sorbent - NaNO3/Ru/Al2O3 - are used for CO2 methanation in flowing hydrogen in a fixed bed reactor at temperatures ranging from 220 to 280 °C. Activation energies for the NaNO3/Ru/Al2O3 material are slightly higher than unpromoted Ru/Al2O3 catalysts, and the reaction orders vary more significantly. In situ IR spectroscopy and steady-state isotopic kinetic analysis (SSITKA) using in situ IR/MS spectroscopy show that bicarbonate and linear carbonyl species are the likely reaction intermediates over unpromoted Ru/Al2O3, while bidentate carbonate, formate and linear carbonyl species are among likely reaction intermediates over NaNO3/Ru/Al2O3. Rate laws consistent with the obtained experimental data are proposed after kinetic modeling of multiple plausible reaction pathways. Results suggest that the pathway over the NaNO3/Ru/Al2O3 catalyst likely has an additional kinetically relevant irreversible step in the CO2 methanation reaction pathway.",

author = "Park, \{Sang Jae\} and Xiang Wang and Ball, \{Madelyn R.\} and Laura Proano and Zili Wu and Jones, \{Christopher W.\}",

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year = "2022",

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doi = "10.1039/d2cy00515h",

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T1 - CO2 methanation reaction pathways over unpromoted and NaNO3-promoted Ru/Al2O3 catalysts

AU - Park, Sang Jae

AU - Wang, Xiang

AU - Ball, Madelyn R.

AU - Proano, Laura

AU - Wu, Zili

AU - Jones, Christopher W.

PY - 2022/6/9

Y1 - 2022/6/9

N2 - Catalytic CO2 sorbents, materials that adsorb and pre-concentrate CO2 on the catalyst surface prior to subsequent conversion, are becoming important materials in CO2 capture and utilization. In this work, a prototypical CO2 methanation catalyst - Ru/Al2O3 - and a related catalytic sorbent - NaNO3/Ru/Al2O3 - are used for CO2 methanation in flowing hydrogen in a fixed bed reactor at temperatures ranging from 220 to 280 °C. Activation energies for the NaNO3/Ru/Al2O3 material are slightly higher than unpromoted Ru/Al2O3 catalysts, and the reaction orders vary more significantly. In situ IR spectroscopy and steady-state isotopic kinetic analysis (SSITKA) using in situ IR/MS spectroscopy show that bicarbonate and linear carbonyl species are the likely reaction intermediates over unpromoted Ru/Al2O3, while bidentate carbonate, formate and linear carbonyl species are among likely reaction intermediates over NaNO3/Ru/Al2O3. Rate laws consistent with the obtained experimental data are proposed after kinetic modeling of multiple plausible reaction pathways. Results suggest that the pathway over the NaNO3/Ru/Al2O3 catalyst likely has an additional kinetically relevant irreversible step in the CO2 methanation reaction pathway.

AB - Catalytic CO2 sorbents, materials that adsorb and pre-concentrate CO2 on the catalyst surface prior to subsequent conversion, are becoming important materials in CO2 capture and utilization. In this work, a prototypical CO2 methanation catalyst - Ru/Al2O3 - and a related catalytic sorbent - NaNO3/Ru/Al2O3 - are used for CO2 methanation in flowing hydrogen in a fixed bed reactor at temperatures ranging from 220 to 280 °C. Activation energies for the NaNO3/Ru/Al2O3 material are slightly higher than unpromoted Ru/Al2O3 catalysts, and the reaction orders vary more significantly. In situ IR spectroscopy and steady-state isotopic kinetic analysis (SSITKA) using in situ IR/MS spectroscopy show that bicarbonate and linear carbonyl species are the likely reaction intermediates over unpromoted Ru/Al2O3, while bidentate carbonate, formate and linear carbonyl species are among likely reaction intermediates over NaNO3/Ru/Al2O3. Rate laws consistent with the obtained experimental data are proposed after kinetic modeling of multiple plausible reaction pathways. Results suggest that the pathway over the NaNO3/Ru/Al2O3 catalyst likely has an additional kinetically relevant irreversible step in the CO2 methanation reaction pathway.

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DO - 10.1039/d2cy00515h

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JO - Catalysis Science and Technology

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IS - 14

ER -

CO₂ methanation reaction pathways over unpromoted and NaNO₃-promoted Ru/Al₂O₃ catalysts

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