Zn-Promoted Selective Gas-Phase Hydrogenation of Tertiary and Secondary C4 Alkynols over Supported Pd
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Título: | Zn-Promoted Selective Gas-Phase Hydrogenation of Tertiary and Secondary C4 Alkynols over Supported Pd |
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Autor/es: | González-Fernández, Alberto | Berenguer-Murcia, Ángel | Cazorla-Amorós, Diego | Cárdenas-Lizana, Fernando |
Grupo/s de investigación o GITE: | Materiales Carbonosos y Medio Ambiente |
Centro, Departamento o Servicio: | Universidad de Alicante. Departamento de Química Inorgánica | Universidad de Alicante. Instituto Universitario de Materiales |
Palabras clave: | Selective gas phase hydrogenation | 2-methyl-3-butyn-2-ol | 3-butyn-2-ol | Hydrogen partial pressure | Support effects | PdZn alloy |
Área/s de conocimiento: | Química Inorgánica |
Fecha de publicación: | 1-jun-2020 |
Editor: | American Chemical Society |
Cita bibliográfica: | ACS Applied Materials & Interfaces. 2020, 12(25): 28158-28168. doi:10.1021/acsami.0c05285 |
Resumen: | We have investigated the gas-phase (P = 1 atm; T = 373 K) hydrogenation of (tertiary alkynol) 2-methyl-3-butyn-2-ol (MBY) and (secondary) 3-butyn-2-ol (BY) over a series of carbon (C), non-reducible (Al2O3 and MgO), and reducible (CeO2 and ZnO) supported monometallic [Pd (0.6–1.2% wt) and Zn (1% wt)] and bimetallic Pd–Zn (Pd:Zn mol ratio = 95:5, 70:30, and 30:70) catalysts synthesized by deposition–precipitation and colloidal deposition. The catalysts have been characterized by H2 chemisorption, hydrogen temperature-programmed desorption (H2-TPD), specific surface area (SSA), X-ray photoelectron spectroscopy (XPS), and transmission (TEM) and scanning transmission electron microscopy (STEM) analyses. Reaction over these catalysts generated the target alkenol [2-methyl-3-buten-2-ol (MBE) and 3-buten-2-ol (BE)] through partial hydrogenation and alkanol [2-methyl-butan-2-ol (MBA) and 2-butanol (BA)]/ketone [2-butanone (BONE)] as a result of full hydrogenation and double-bond migration. The catalysts exhibit a similar Pd nanoparticle size (2.7 ± 0.3 nm) but a modified electronic character (based on XPS). Hydrogenation activity is linked to surface hydrogen (from H2 chemisorption and H2-TPD). An increase in H2:alkynol (from 1 → 10) results in enhanced alkynol consumption with a greater rate in the transformation of MBY (vs BY); H2:alkynol had negligible effect on product distribution. Reaction selectivity is insensitive to the Pd site electron density with a similar response (SMBE = 65 ± 9% and SBE = 70 ± 8%) over Pdδ− (on Al2O3 and MgO) and Pdδ+ (on C and CeO2). A Pd/ZnO catalyst delivered enhanced alkenol selectivity (SMBE = 90% and SBE = 96%) attributed to PdZn alloy phase formation (proved by XRD and XPS) but low activity, ascribed to metal encapsulation. A two-fold increase in the consumption rate was recorded for Pd–Zn/Al2O3 (30:70) versus Pd/ZnO with a similar alloy content (32 ± 4% from XPS), ascribed to a contribution due to spillover hydrogen (from H2-TPD) where high alkenol selectivity was maintained. |
Patrocinador/es: | This research was funded by the Engineering and Physical Sciences Research Council (EPRSC; grant number EP/L016419/1; Ph.D. studentship to A.G.-F., CRITICAT program), the Spanish Ministerio de Ciencia Innovación y Universidades, Generalitat Valenciana and FEDER (RTI2018-095291-B-I00, MAT2017-87579-R MINECO/FEDER and PROMETEO/2018/076). |
URI: | http://hdl.handle.net/10045/108115 |
ISSN: | 1944-8244 (Print) | 1944-8252 (Online) |
DOI: | 10.1021/acsami.0c05285 |
Idioma: | eng |
Tipo: | info:eu-repo/semantics/article |
Derechos: | © 2020 American Chemical Society |
Revisión científica: | si |
Versión del editor: | https://doi.org/10.1021/acsami.0c05285 |
Aparece en las colecciones: | INV - MCMA - Artículos de Revistas |
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Archivo | Descripción | Tamaño | Formato | |
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Gonzalez-Fernandez_etal_2020_ACSApplMaterInterface_final.pdf | Versión final (acceso restringido) | 4,91 MB | Adobe PDF | Abrir Solicitar una copia |
Gonzalez-Fernandez_etal_2020_ACSApplMaterInterface_accepted.pdf | Accepted Manuscript (acceso abierto) | 58,09 MB | Adobe PDF | Abrir Vista previa |
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