Ruthenium-based MOF catalysts for methanation of CO2derivatives

Mitigating climate change is one of the biggest challenges of today's society. The most direct way to achieve this goal is to capture and use CO2as a source of energy and chemicals. This work, inspired by previous publications focused on homogeneous catalysis, proposes the transformation of the...

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Detalles Bibliográficos
Autores: Arnaiz, I., Márquez-Álvarez, C., Zubimendi, M., Molina, M.A., Beale, A.M., Sánchez-Sánchez, M., Pérez-Pariente, J.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/425173
Acceso en línea:http://hdl.handle.net/10261/425173
https://www.scopus.com/inward/record.uri?eid=2-s2.0-105008492938&doi=10.1016%2Fj.jcou.2025.103127&partnerID=40&md5=21e48b4e36d1e037ebbb268009856a6d
Access Level:acceso abierto
Palabra clave:Alternative route
CO<sub>2</sub>methanation
Dialkylureas
Ru-BTC
Ru-HKUST-1
XANES-EXAFS
Descripción
Sumario:Mitigating climate change is one of the biggest challenges of today's society. The most direct way to achieve this goal is to capture and use CO2as a source of energy and chemicals. This work, inspired by previous publications focused on homogeneous catalysis, proposes the transformation of the easy-to-prepare CO2derivatives dialkylureas into C1 chemicals using Ru-MOFs as heterogeneous catalysts. This choice is due to (i) the well-known ability of Ru to catalyze hydrogenation reactions and (ii) that Ru-complexes were the pioneer homogenous catalyst in converting CO2into an added-value C1 chemical, methanol. Apart from the already reported MOF Ru-HKUST-1, we have prepared a new Ru-MOF material, denoted Ru-BTC, analogous to the semiamorphous Fe-BTC. It has been found by XAS that Ru-BTC and Ru-HKUST-1 have different metal environment and oxidation states: only 3+ in Ru-BTC, a 50:50 mixture of 2+ and 3+ in Ru-HKUST-1. Both Ru-MOFs catalyzed the hydrogenation of N,N'-dimethylurea under relatively mild conditions, giving methane as the main product. Ru-BTC was particularly efficient: 67 % conversion and 96 % selectivity to CH4at 150 ºC and 30 bars of H2using a Ru/dimethylurea weight ratio of 1 %. Ru-MOFs were also able to transform CO2into CH4, again being Ru-BTC the most effective catalyst, but giving much poorer selectivity to CH4. Ru-MOFs, particularly Ru-BTC, were damaged under reaction conditions, but no significant Ru leaching was observed. © 2025 Elsevier Ltd. All rights reserved.