Unlocking mixed oxides with unprecedented stoichiometries from heterometallic metal-organic frameworks for the catalytic hydrogenation of CO2

Javier Castells-Gil; Samy Ould-Chikh; Adrian Ramírez; Rafia Ahmad; Gonzalo Prieto; Alberto Rodríguez Gómez; Luis Carlos Garzon Tovar; Selvedin Telalovic; Lingmei Liu; Alessandro Genovese; Natalia M. Padial; Antonio Aguilar-Tapia; Pierre Bordet; Luigi Cavallo; Carlos Martí-Gastaldo; Jorge Gascon

doi:10.1016/j.checat.2021.03.010

Unlocking mixed oxides with unprecedented stoichiometries from heterometallic metal-organic frameworks for the catalytic hydrogenation of CO2

Javier Castells-Gil, Samy Ould-Chikh, Adrian Ramírez, Rafia Ahmad, Gonzalo Prieto, Alberto Rodríguez Gómez, Luis Carlos Garzon Tovar, Selvedin Telalovic, Lingmei Liu, Alessandro Genovese, Natalia M. Padial, Antonio Aguilar-Tapia, Pierre Bordet, Luigi Cavallo, Carlos Martí-Gastaldo, Jorge Gascon

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20 Scopus citations

Abstract

Their complex surface chemistry and high oxygen lattice mobilities place mixed-metal oxides among the most important families of materials. Modulation of stoichiometry in mixed-metal oxides has been shown to be a very powerful tool for tuning optical and catalytic properties. However, accessing different stoichiometries is not always synthetically possible. Here, we show that the thermal decomposition of the recently reported metal-organic framework MUV-101(Fe, Ti) results in the formation of carbon-supported titanomaghemite nanoparticles with an unprecedented Fe/Ti ratio close to 2, not achievable by soft-chemistry routes. The resulting titanomaghemite phase displays outstanding catalytic activity for the production of CO from CO2 via the reverse water-gas shift (RWGS) reaction with CO selectivity values of ca. 100% and no signs of deactivation after several days on stream. Theoretical calculations suggest that the reaction proceeds through the formation of COOH* species, favoring in this way CO over other byproducts.

Original language	English (US)
Journal	Chem Catalysis
DOIs	https://doi.org/10.1016/j.checat.2021.03.010
State	Published - Apr 26 2021

Bibliographical note

KAUST Repository Item: Exported on 2021-05-04
Acknowledgements: Daliang Zhang is acknowledged for his help with Digital Micrograph scripts used to acquire image stacks during our in situ TEM experiments. This work was supported by the European Union (ERC Stg Chem-fs-MOF 714122) and the Spanish government (CTQ2017-83486-P and CEX2019-000919-M). N.M.P. thanks the European Union for a Marie Skłodowska-Curie Global Fellowship (H2020-MSCA-IF-2016-GF-749359-EnanSET).

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10.1016/j.checat.2021.03.010

https://repository.kaust.edu.sa/bitstream/10754/669061/1/Castells-Gil%20et%20al_final.pdf

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Castells-Gil, J., Ould-Chikh, S., Ramírez, A., Ahmad, R., Prieto, G., Gómez, A. R., Garzon Tovar, L. C., Telalovic, S., Liu, L., Genovese, A., Padial, N. M., Aguilar-Tapia, A., Bordet, P., Cavallo, L., Martí-Gastaldo, C., & Gascon, J. (2021). Unlocking mixed oxides with unprecedented stoichiometries from heterometallic metal-organic frameworks for the catalytic hydrogenation of CO2. Chem Catalysis. https://doi.org/10.1016/j.checat.2021.03.010

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title = "Unlocking mixed oxides with unprecedented stoichiometries from heterometallic metal-organic frameworks for the catalytic hydrogenation of CO2",

abstract = "Their complex surface chemistry and high oxygen lattice mobilities place mixed-metal oxides among the most important families of materials. Modulation of stoichiometry in mixed-metal oxides has been shown to be a very powerful tool for tuning optical and catalytic properties. However, accessing different stoichiometries is not always synthetically possible. Here, we show that the thermal decomposition of the recently reported metal-organic framework MUV-101(Fe, Ti) results in the formation of carbon-supported titanomaghemite nanoparticles with an unprecedented Fe/Ti ratio close to 2, not achievable by soft-chemistry routes. The resulting titanomaghemite phase displays outstanding catalytic activity for the production of CO from CO2 via the reverse water-gas shift (RWGS) reaction with CO selectivity values of ca. 100% and no signs of deactivation after several days on stream. Theoretical calculations suggest that the reaction proceeds through the formation of COOH* species, favoring in this way CO over other byproducts.",

author = "Javier Castells-Gil and Samy Ould-Chikh and Adrian Ram{\'i}rez and Rafia Ahmad and Gonzalo Prieto and G{\'o}mez, {Alberto Rodr{\'i}guez} and {Garzon Tovar}, {Luis Carlos} and Selvedin Telalovic and Lingmei Liu and Alessandro Genovese and Padial, {Natalia M.} and Antonio Aguilar-Tapia and Pierre Bordet and Luigi Cavallo and Carlos Mart{\'i}-Gastaldo and Jorge Gascon",

note = "KAUST Repository Item: Exported on 2021-05-04 Acknowledgements: Daliang Zhang is acknowledged for his help with Digital Micrograph scripts used to acquire image stacks during our in situ TEM experiments. This work was supported by the European Union (ERC Stg Chem-fs-MOF 714122) and the Spanish government (CTQ2017-83486-P and CEX2019-000919-M). N.M.P. thanks the European Union for a Marie Sk{\l}odowska-Curie Global Fellowship (H2020-MSCA-IF-2016-GF-749359-EnanSET).",

year = "2021",

month = apr,

day = "26",

doi = "10.1016/j.checat.2021.03.010",

language = "English (US)",

journal = "Chem Catalysis",

issn = "2667-1093",

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Castells-Gil, J, Ould-Chikh, S, Ramírez, A, Ahmad, R, Prieto, G, Gómez, AR, Garzon Tovar, LC , Telalovic, S, Liu, L, Genovese, A, Padial, NM, Aguilar-Tapia, A, Bordet, P, Cavallo, L, Martí-Gastaldo, C & Gascon, J 2021, 'Unlocking mixed oxides with unprecedented stoichiometries from heterometallic metal-organic frameworks for the catalytic hydrogenation of CO2', Chem Catalysis. https://doi.org/10.1016/j.checat.2021.03.010

TY - JOUR

T1 - Unlocking mixed oxides with unprecedented stoichiometries from heterometallic metal-organic frameworks for the catalytic hydrogenation of CO2

AU - Castells-Gil, Javier

AU - Ould-Chikh, Samy

AU - Ramírez, Adrian

AU - Ahmad, Rafia

AU - Prieto, Gonzalo

AU - Gómez, Alberto Rodríguez

AU - Garzon Tovar, Luis Carlos

AU - Telalovic, Selvedin

AU - Liu, Lingmei

AU - Genovese, Alessandro

AU - Padial, Natalia M.

AU - Aguilar-Tapia, Antonio

AU - Bordet, Pierre

AU - Cavallo, Luigi

AU - Martí-Gastaldo, Carlos

AU - Gascon, Jorge

N1 - KAUST Repository Item: Exported on 2021-05-04 Acknowledgements: Daliang Zhang is acknowledged for his help with Digital Micrograph scripts used to acquire image stacks during our in situ TEM experiments. This work was supported by the European Union (ERC Stg Chem-fs-MOF 714122) and the Spanish government (CTQ2017-83486-P and CEX2019-000919-M). N.M.P. thanks the European Union for a Marie Skłodowska-Curie Global Fellowship (H2020-MSCA-IF-2016-GF-749359-EnanSET).

PY - 2021/4/26

Y1 - 2021/4/26

N2 - Their complex surface chemistry and high oxygen lattice mobilities place mixed-metal oxides among the most important families of materials. Modulation of stoichiometry in mixed-metal oxides has been shown to be a very powerful tool for tuning optical and catalytic properties. However, accessing different stoichiometries is not always synthetically possible. Here, we show that the thermal decomposition of the recently reported metal-organic framework MUV-101(Fe, Ti) results in the formation of carbon-supported titanomaghemite nanoparticles with an unprecedented Fe/Ti ratio close to 2, not achievable by soft-chemistry routes. The resulting titanomaghemite phase displays outstanding catalytic activity for the production of CO from CO2 via the reverse water-gas shift (RWGS) reaction with CO selectivity values of ca. 100% and no signs of deactivation after several days on stream. Theoretical calculations suggest that the reaction proceeds through the formation of COOH* species, favoring in this way CO over other byproducts.

AB - Their complex surface chemistry and high oxygen lattice mobilities place mixed-metal oxides among the most important families of materials. Modulation of stoichiometry in mixed-metal oxides has been shown to be a very powerful tool for tuning optical and catalytic properties. However, accessing different stoichiometries is not always synthetically possible. Here, we show that the thermal decomposition of the recently reported metal-organic framework MUV-101(Fe, Ti) results in the formation of carbon-supported titanomaghemite nanoparticles with an unprecedented Fe/Ti ratio close to 2, not achievable by soft-chemistry routes. The resulting titanomaghemite phase displays outstanding catalytic activity for the production of CO from CO2 via the reverse water-gas shift (RWGS) reaction with CO selectivity values of ca. 100% and no signs of deactivation after several days on stream. Theoretical calculations suggest that the reaction proceeds through the formation of COOH* species, favoring in this way CO over other byproducts.

UR - http://hdl.handle.net/10754/669061

UR - https://linkinghub.elsevier.com/retrieve/pii/S2667109321000178

U2 - 10.1016/j.checat.2021.03.010

DO - 10.1016/j.checat.2021.03.010

M3 - Article

SN - 2667-1093

JO - Chem Catalysis

JF - Chem Catalysis

ER -

Unlocking mixed oxides with unprecedented stoichiometries from heterometallic metal-organic frameworks for the catalytic hydrogenation of CO2

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