Multifunctionalized zirconium-based MOF as a novel support for dispersed copper : application in CO2 adsorption and catalytic conversion
Rosado, Albert (Institut de Ciència de Materials de Barcelona)
Popa, Ioana-Maria (RWTH Aachen University. Department of Chemistry)
Abo Markeb, Ahmad (Universitat Autònoma de Barcelona. Departament d'Enginyeria Química, Biològica i Ambiental)
Moral-Vico, Javier (Universitat Autònoma de Barcelona. Departament d'Enginyeria Química, Biològica i Ambiental)
Naughton, Eva Maria (University College Dublin)
Eckhardt, Hans-Georg (University College Dublin)
Ayllon, Jose Antonio (Universitat Autònoma de Barcelona. Departament de Química)
Lopez-Periago, Ana M. (Institut de Ciència de Materials de Barcelona)
Domingo, Concepción (Institut de Ciència de Materials de Barcelona)
Negahdar, Leila (University College Dublin)

Data:	2024
Resum:	CO2 conversion and utilization for global sustainability is an integral part of greenhouse gases management, typically for the production of fuels and specialty chemicals. Added value products, such as methanol, methane or formate, can be obtained by electrocatalysis and thermocatalysis, the two techniques addressed in this study. The main motivation of this study is to develop a copper based catalyst active in both processes, confronting the main concerns regarding typical metal catalysts related to nanoparticles aggregation and concomitant deactivation. For this, modified NU-1000, a water-stable mesoporous MOF, is used as a platform for the simultaneous coordination-stabilization of copper single atoms and CO2 adsorption. NU-1000 is synthetized with primary amino groups (-NH2 with affinity for CO2) by modifying the ligand prior to MOF synthesis, while post-synthetic solvent-assisted ligand incorporation is applied to insert thiol functionalities (-SH with affinity for copper) within the framework. To make the functionalized MOF catalytically active, a Cu2+ salt is impregnated into the MOF channels, which is further reduced with H2 to Cu+/Cu0 before performance assessment in CO2 conversion processes. The as-synthetized and spent catalysts were analysed regarding the structure (X-ray diffraction, infrared), bulk (mass spectrometry) and surface (X-ray photoelectron spectroscopy) composition, morphology (electronic microscopy and energy dispersive spectroscopy) and textural properties (N2 physisorption). The electrocatalytic reduction of CO2 was performed in the potential range of -0. 8 to -1. 8 V, indicating the formation of formic acid. Thermocatalytic experiments were carried out in an economically and energetically sustainable low-pressure (1 MPa) hydrogenation process. Methanol was obtained with 100% selectivity at temperatures up to 280 °C, and a space-time yield of ca. 100 mgMeOH gcat-1 h-1 which overcomes that of commercial CuZnO NPs designed for this purpose.
Ajuts:	Agencia Estatal de Investigación CEX2019-000917-S Agencia Estatal de Investigación TED2021-130407B-I00 Agencia Estatal de Investigación TED2021-1298378-C41 Agencia Estatal de Investigación PID2020-115631GB-I00
Nota:	Altres ajuts: María Zambrano ID 715364.
Drets:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original.
Llengua:	Anglès
Document:	Article ; recerca ; Versió publicada
Publicat a:	Journal of materials chemistry. A, Vol. 12, Issue 33 (July 2024) , p. 21758-21771, ISSN 2050-7496

DOI: 10.1039/d4ta03268c

15 p, 1.9 MB

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