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Thermal stability of copper-based MOF under different atmospheres

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Abstract

MIL-53(Cu), belonging to the group of metal–organic frameworks (MOFs) with terephthalate as a ligand, was prepared. The success of the synthesis was confirmed by XRD, FTIR, SEM and chemical analysis. The MOF thermal behavior was studied by thermogravimetry, in situ and ex situ XRD and mass spectrometry, using different atmospheres (inert, oxidizing and reducing). This MOF had a higher stability when the inert atmosphere was used (622 K), and this was lower (559 K) under an oxidizing atmosphere. The integrated intensities of the main peak of each phase in the X-ray diffractograms showed that under inert or reducing atmospheres (CO or H2) the decomposition generated metallic copper. Under oxidizing atmosphere, a mixture of copper oxides (Cu2O and CuO) was obtained, in which Cu2O was an intermediate, with only traces observed at 773 K. The FWHM calculation at the main peak of each phase indicated the formation of larger crystallites under hydrogen atmosphere and smaller ones under CO. There was a tendency of the formed copper oxides to sinter in the presence of air. The main volatile compounds formed during the thermal treatment of the MOF (decomposition of terephthalate) were CO2 and benzene. Thus, this study contributes to the development of new copper-based catalysts by the thermal treatment of MOF, which allows greater control of the phases formed (metallic Cu or CuO).

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Acknowledgements

This research used facilities of the Brazilian Synchrotron Light Laboratory (LNLS), part of the Brazilian Center for Research in Energy and Materials (CNPEM), a private non-profit organization under the supervision of the Brazilian Ministry for Science, Technology, and Innovations (MCTI). The XPD beamline staff is acknowledged for the assistance during the experiments (Proposal Number 20190118). We thank FAPERJ [Grant Number E-26/010.101231/2018 (ref. 210.359/2018)] for financial support. This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior—Brasil (CAPES)—Finance Code 001. We thank the Laboratory of Macromolecules and Colloids Applied to the Petroleum Industry (LMCP) of IMA/UFRJ for the CHN analysis. F. M. Z. Zotin thanks CNPq for a productivity research scholarship.

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  1. Instituto de Química, Universidade do Estado do Rio de Janeiro, Rua São Francisco Xavier, 524, Pavilhão Haroldo Lisboa da Cunha, Rio de Janeiro, 20550-900, RJ, Brasil

    Samara da Silva Montani, Juliana Fonseca de Lima, Fatima Maria Zanon Zotin & Luz Amparo Palacio

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  1. Samara da Silva Montani
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All authors contributed to the study, conception and design. Material preparation, data collection and analysis were performed by SSM. The first draft of the manuscript was written by LAP, and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Luz Amparo Palacio.

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da Silva Montani, S., de Lima, J.F., Zanon Zotin, F.M. et al. Thermal stability of copper-based MOF under different atmospheres. J Therm Anal Calorim 148, 119–131 (2023). https://doi.org/10.1007/s10973-022-11769-8

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