CO2 hydrogenation: Selectivity control of CO versus CH4 achieved using Na doping over Ru/m-ZrO2 at low pressure

Rabelo-Neto, Raimundo C.; Almeida, Mayra P.; Silveira, Erika B.; Ayala, Martin; Watson, Caleb D.; Villarreal, Jesus; Cronauer, Donald C.; Kropf, A. Jeremy; Martinelli, Michela; Noronha, Fabio B.; Jacobs, Gary

doi:10.1016/j.apcatb.2022.121533

Title: CO₂ hydrogenation: Selectivity control of CO versus CH₄ achieved using Na doping over Ru/m-ZrO₂ at low pressure

Journal Article · 21 May 2022 · Applied Catalysis. B, Environmental

DOI: https://doi.org/10.1016/j.apcatb.2022.121533 · OSTI ID:2203864

Rabelo-Neto, Raimundo C. ^[1]; Almeida, Mayra P. ^[2]; Silveira, Erika B. ^[1]; Ayala, Martin ^[3]; Watson, Caleb D. ^[3]; Villarreal, Jesus ^[3]; Cronauer, Donald C. ^[4]; Kropf, A. Jeremy ^[4]; Martinelli, Michela ^[5]; Noronha, Fabio B. ^[6]; Jacobs, Gary ^[3]

Instituto Nacional de Tecnologia, Rio de Janeiro (Brazil)
Instituto Nacional de Tecnologia, Rio de Janeiro (Brazil); Instituto Militar de Engenharia, Rio de Janeiro (Brazil)
University of Texas, San Antonio, TX (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
University of Kentucky Center for Applied Energy Research, Lexington, KY (United States)
Instituto Nacional de Tecnologia, Rio de Janeiro (Brazil); Instituto Militar de Engenharia, Rio de Janeiro (Brazil); University of Lille (France); Centre National de la Recherche Scientifique (CNRS) (France); École Nationale Supérieure de Chimie de Lille (ENSCL); University of Artois (France)

By doping 1%Ru/m-ZrO₂ with sodium, selectivity tuning between CO and CH₄ during CO₂ hydrogenation was achieved by controlling the relative rates of reverse water-gas shift and CO methanation. By increasing basicity through Na loading: (1) the formate C-H bond is weakened in DRIFTS of adsorbed CO, accelerating C-H bond formation of formate and promoting CO formation at the Ru/m-ZrO₂ interface; and (2) the coverage of Na increases on ensembles of Ru atoms responsible for methanation. Increasing Na content shifts selectivity from CH₄ (useful for synthetic natural gas) to CO, which can be used for Fischer-Tropsch synthesis or methanol-to-gasoline. Electronic modification of formate is likely due to enhanced basicity (strengthening bonding between catalyst and the-CO₂ function of formate and weakening C-H). In conclusion, no electron transfer from Na to Ru was detected in XANES. DRIFTS as a function of time and XPS results showed that Na exacerbates site blocking and deactivation.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy and Carbon Management (FECM); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2203864

Journal Information:: Applied Catalysis. B, Environmental, Journal Name: Applied Catalysis. B, Environmental Vol. 315; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: CO2 hydrogenation: Selectivity control of CO versus CH4 achieved using Na doping over Ru/m-ZrO2 at low pressure

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Title: CO₂ hydrogenation: Selectivity control of CO versus CH₄ achieved using Na doping over Ru/m-ZrO₂ at low pressure