Support Effect in Liquid Phase Reactions

A special issue of Applied Sciences (ISSN 2076-3417). This special issue belongs to the section "Materials Science and Engineering".

Deadline for manuscript submissions: closed (30 November 2019) | Viewed by 12228

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Guest Editor
Dipartimento di Chimica, Università degli Studi di Milano, 20133 Milan, Italy
Interests: metal nanoparticles; heterogeneous catalysis; nanostructured metal oxides; functionalized carbons; metal carbides; biomass transformation
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Special Issue Information

Dear Colleagues,

This Special Issue will highlight the role of the support in metal catalyzed liquid phase reactions, including oxidation, hydrogenation and CC-coupling reactions. Supporting materials have been recognized as playing an important role in tuning the activity, selectivity and stability of supported metal nanoparticles. Indeed, the support properties can tune the interaction with the metallic particles dispersed on, or in it, thus modifying both the catalysts’ electronic and structural properties. In addition, the support can also provide different anchoring sites for the reactants, acting as an active and sometimes reactive surface.

Dr. Alberto Villa
Guest Editor

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Keywords

  • liquid phase reactions
  • support effect
  • metal nanoparticles
  • characterization
  • oxidation
  • hydrogenation
  • CC-coupling
  • esterification

Published Papers (4 papers)

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Research

18 pages, 4049 KiB  
Article
Preformed Pd-Based Nanoparticles for the Liquid Phase Decomposition of Formic Acid: Effect of Stabiliser, Support and Au–Pd Ratio
by Felipe Sanchez, Ludovica Bocelli, Davide Motta, Alberto Villa, Stefania Albonetti and Nikolaos Dimitratos
Appl. Sci. 2020, 10(5), 1752; https://doi.org/10.3390/app10051752 - 04 Mar 2020
Cited by 10 | Viewed by 2146
Abstract
Hydrogen is one of the most promising energy carriers for the production of electricity based on fuel cell hydrogen technology. Recently, hydrogen storage chemicals, such as formic acid, have been proposed to be part of the long-term solution towards hydrogen economy for the [...] Read more.
Hydrogen is one of the most promising energy carriers for the production of electricity based on fuel cell hydrogen technology. Recently, hydrogen storage chemicals, such as formic acid, have been proposed to be part of the long-term solution towards hydrogen economy for the future of our planet. Herein we report the synthesis of preformed Pd nanoparticles using colloidal methodology varying a range of specific experimental parameters, such as the amount of the stabiliser and reducing agent, nature of support and Pd loading of the support. The aforementioned parameters have shown to affect mean Pd particle size, Pd oxidation, atomic content of Pd on the surface as well as on the catalytic performance towards formic acid decomposition. Reusability studies were carried out using the most active monometallic Pd material with a small loss of activity after five uses. The catalytic performance based on the Au–Pd atomic ratio was evaluated and the optimum catalytic performance was found to be with the Au/Pd atomic ratio of 1/3, indicating that the presence of a small amount of Pd is essential to promote significantly Au activity for the liquid phase decomposition of formic acid. Thorough characterisation has been carried out by means of XPS, SEM-EDX, TEM and BET. The observed catalytic performance is discussed in terms of the structure/morphology and composition of the supported Pd and Au–Pd nanoparticles. Full article
(This article belongs to the Special Issue Support Effect in Liquid Phase Reactions)
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14 pages, 2010 KiB  
Article
The Effect of Carbon Nanofibers Surface Properties in Hydrogenation and Dehydrogenation Reactions
by Stefano Cattaneo, Felipe J. Sanchez Trujillo, Nikolaos Dimitratos and Alberto Villa
Appl. Sci. 2019, 9(23), 5061; https://doi.org/10.3390/app9235061 - 23 Nov 2019
Cited by 6 | Viewed by 2102
Abstract
In this study, carbon nanofiber-supported Pd nanoparticles were used in the hydrogenation of cinnamaldehyde and in the dehydrogenation of cinnamyl alcohol. The different graphitisation of the surface of the nanofibers and the amount of oxygen functionalisation significantly affected both activity and selectivity to [...] Read more.
In this study, carbon nanofiber-supported Pd nanoparticles were used in the hydrogenation of cinnamaldehyde and in the dehydrogenation of cinnamyl alcohol. The different graphitisation of the surface of the nanofibers and the amount of oxygen functionalisation significantly affected both activity and selectivity to the various reaction products. In particular, a decrease in nanoparticle dimensions and oxygen content resulted in an increase in overall activity for both of the studied reactions. Moreover, the selectivity to hydrocinnamaldehyde enhanced with increasing surface oxygen content in the cinnamaldehyde hydrogenation, while the selectivity to cinnamaldehyde was higher with low-functionalised nanofibers in the cinnamyl alcohol dehydrogenation. Finally, the most active catalyst proved also to be stable in consecutive runs. Full article
(This article belongs to the Special Issue Support Effect in Liquid Phase Reactions)
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14 pages, 3520 KiB  
Article
Resonant-XRD Characterization of Nanoalloyed Au-Pd Catalysts for the Direct Synthesis of H2O2: Quantitative Analysis of Size Dependent Composition of the Nanoparticles
by Paolo Centomo, Patrizia Canton, Claudio Burato, Carlo Meneghini and Marco Zecca
Appl. Sci. 2019, 9(15), 2959; https://doi.org/10.3390/app9152959 - 24 Jul 2019
Cited by 4 | Viewed by 2700
Abstract
The focus of this work is on the relationship between the quantitative structural characterization of bimetallic Au-Pd nanoparticles dispersed in an amorphous polymer matrix and their catalytic activity in the direct synthesis of hydrogen peroxide (DS reaction). Resonant X-ray powder diffraction with synchrotron [...] Read more.
The focus of this work is on the relationship between the quantitative structural characterization of bimetallic Au-Pd nanoparticles dispersed in an amorphous polymer matrix and their catalytic activity in the direct synthesis of hydrogen peroxide (DS reaction). Resonant X-ray powder diffraction with synchrotron radiation was employed to probe selectively and to reveal fine details of the structure of bimetallic nanoparticles embedded in the support. The semi-quantitative analysis of the resonant X-ray powdered diffraction data, made on a large number of metal nanoparticles, shows that in one of the polymer-supported Au-Pd catalyst for the DS reaction (P75) featured by an overall molar Pd/Au of about 5.54, the smallest metal nanoparticles (MNPs), which account for more than 99.9% of the total MNPs number and for more than 95% of the metal surface, are formed by practically pure palladium. The relative number of bimetallic alloyed nanoparticles is very small (less than 4 × 102 ppm) and they contribute to only about 2% of the total metal surface. In a second gold-enriched catalyst (P50) with an overall molar Pd/Au of 1.84, the proportion of the bimetallic alloyed nanoparticles increased to about 97% and they account for about 99% of the metal surface. As a result of the metal intermixing, the catalytic productivity for the DS reaction increased from 97 to 109 mmolH2O2/molH2, owing to the gold-promotion of palladium. Full article
(This article belongs to the Special Issue Support Effect in Liquid Phase Reactions)
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14 pages, 3189 KiB  
Article
Furfural Hydrogenation on Modified Niobia
by Andrea Jouve, Stefano Cattaneo, Daniel Delgado, Nicola Scotti, Claudio Evangelisti, José M. López Nieto and Laura Prati
Appl. Sci. 2019, 9(11), 2287; https://doi.org/10.3390/app9112287 - 03 Jun 2019
Cited by 11 | Viewed by 4880
Abstract
In this study, niobia-based materials have been used as supports for Pt nanoparticles and used in the hydrogenation of furfural. The incorporation of dopants (W6+ and Ti4+) in the Nb2O5 structure induced modifications in the surface acidity [...] Read more.
In this study, niobia-based materials have been used as supports for Pt nanoparticles and used in the hydrogenation of furfural. The incorporation of dopants (W6+ and Ti4+) in the Nb2O5 structure induced modifications in the surface acidity of the support; in particular, the addition of W6+ increased the amount of Lewis acid sites, while the addition of Ti4+ decreased the number of Lewis acid sites. As a result, the catalytic activity towards the hydrogenation of furfural was affected; high surface acidity resulted in high catalytic activity. The selectivity of the reaction changed with the support acidity as well, with higher amount of furfuryl alcohol produced decreasing the Lewis acid sites. Full article
(This article belongs to the Special Issue Support Effect in Liquid Phase Reactions)
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