Influence of residual chlorine on Ru/TiO2 active sites during CO2 methanation

Crawford, James M.; Petel, Brittney E.; Rasmussen, Mathew J.; Ludwig, Thomas; Miller, Elisa M.; Halingstad, Sawyer; Akhade, Sneha A.; Pang, Simon H.; Yung, Matthew M.

doi:10.1016/j.apcata.2023.119292

Influence of residual chlorine on Ru/TiO₂ active sites during CO₂ methanation

Journal Article · Mon Jun 05 00:00:00 EDT 2023 · Applied Catalysis. A, General

DOI:https://doi.org/10.1016/j.apcata.2023.119292· OSTI ID:1990040

Crawford, James M. ^[1]; Petel, Brittney E. ^[1]; Rasmussen, Mathew J. ^[1]; Ludwig, Thomas ^[2]; Miller, Elisa M. ^[1]; Halingstad, Sawyer ^[1]; Akhade, Sneha A. ^[2]; Pang, Simon H. ^[2]; ^[1]

National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Titania-supported ruthenium (Ru/TiO₂) is an established catalyst for the hydrogenation of carbon dioxide to methane (Sabatier reaction). Chlorine contamination, owed to the RuCl₃ precursor, is demonstrated to have a detrimental impact on methanation activity. After calcination and reduction the catalyst contains residual chlorine, shown by XPS. An aqueous ammonia wash removes Cl without leaching Ru. The washed catalysts exhibit improvements in CH₄ site-time yields. Low Ru loading catalysts encounter the greatest activity enhancements after washing (~4.5-fold). DFT calculations indicate that chlorine and CO₂ directly compete for adsorption on Ru step sites, with Cl impeding the adsorption of CO₂ at under-coordinated sites and at higher Cl coverages. H₂-chemisorption/TPR show that Cl removal lowers the onset of low temperature H₂ dissociation on Ru. Finally, DRIFTS provide evidence that the removal of Cl facilitates low temperature dissociative binding of CO₂, indicated by the formation of surface bound linear CO species.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE; USDOE Office of Fossil Energy (FE)

Grant/Contract Number:: AC36-08GO28308; AC52-07NA27344

OSTI ID:: 1990040

Alternate ID(s):: OSTI ID: 1999875

Report Number(s):: NREL/JA-5100-85305; MainId:86078; UUID:7e6355c3-554a-42b4-bde7-b15221912245; MainAdminID:69968

Journal Information:: Applied Catalysis. A, General, Journal Name: Applied Catalysis. A, General Vol. 663; ISSN 0926-860X

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Influence of residual chlorine on Ru/TiO2 active sites during CO2 methanation

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Influence of residual chlorine on Ru/TiO₂ active sites during CO₂ methanation