Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOF

[EN] Recently, there has been a growing interest in using MOF templating to synthesize heterogeneous catalysts based on metal nanoparticles on carbonaceous supports. Unlike the common approach of direct pyrolysis of PdIn-MOFs at high temperatures, this work proposes a reductive chemical treatment un...

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Detalhes bibliográficos
Autores: Martínez, Jordan Santiago, Mazarío, Jaime, Wittee Lopes, Christian, Trasobares, Susana, Calvino Gamez, José Juan, Agostini, Giovanni, Oña-Burgos, Pascual|||0000-0002-2341-7867
Formato: artículo
Fecha de publicación:2024
País:España
Recursos:Universitat Politècnica de València (UPV)
Repositorio:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Idioma:inglés
OAI Identifier:oai:riunet.upv.es:10251/205661
Acesso em linha:https://riunet.upv.es/handle/10251/205661
Access Level:acceso abierto
Palavra-chave:MOF-mediated
Bimetallic nanoparticles
Heterogeneous catalysis
Alkyne semihydrogenation
Nanomaterials characterization
Descrição
Resumo:[EN] Recently, there has been a growing interest in using MOF templating to synthesize heterogeneous catalysts based on metal nanoparticles on carbonaceous supports. Unlike the common approach of direct pyrolysis of PdIn-MOFs at high temperatures, this work proposes a reductive chemical treatment under mild conditions before pyrolysis (resulting in PdIn-QT). The resulting material (PdIn-QT) underwent comprehensive characterization via state-of-the-art aberration-corrected electron microscopy, N2 physisorption, X-ray absorption spectroscopy, Raman, X-ray photoelectron spectroscopy, and X-ray diffraction. These analyses have proven the existence of PdIn bimetallic nanoparticles supported on N-doped carbon. In situ DRIFT spectroscopy reveals the advantageous role of indium (In) in regulating Pd activity in alkyne semihydrogenation. Notably, incorporating a soft nucleation step before pyrolysis enhances surface area, porosity, and nitrogen content compared to direct MOF pyrolysis. The optimized material exhibits outstanding catalytic performance with 96% phenylacetylene conversion and 96% selectivity to phenylethylene in the fifth cycle under mild conditions (5 mmol phenylacetylene, 7 mg cat, 5 mL EtOH, R.T., 1 H2 bar).