Discovering the role of substrate in aldehyde hydrogenation

Cattaneo, Stefano; Capelli, Sofia; Bossola, Filippo; Santo, Vladimiro Dal; Araujo-López, Eduard; Sharapa, Dmitry I.; Studt, Felix; Villa, Alberto; Chieregato, Alessandro; Vandegehuchte, Bart D.; Prati, Laura

doi:10.1016/j.jcat.2021.05.012

Cited by 10 publications

(12 citation statements)

References 33 publications

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“…This result well accords with the obtained TOF ranging from 0.72 to 1.07 s −1 in the experiment of biomass hydrogenation at the mild conditions. 91 We can also observe this trend from the coverage consumed by OH* (θ OH* ) in Figure 7b under different reaction conditions. The Pt/TiO 2 is almost poisoned by OH*, and the empty sites (θ*) can be as low as 10 −2 even at the relative high temperature of 373 K. On Pt/TiO 2−x , θ OH* decreases a lot and the θ* increases to around 0.61.…”

Section: Aldehyde Hydrogenation In Aqueous Phasesupporting

confidence: 56%

“…When the temperature is elevated to 373 K, the TOF on Pt/TiO 2– x can reach the order of several s –1 . This result well accords with the obtained TOF ranging from 0.72 to 1.07 s –1 in the experiment of biomass hydrogenation at the mild conditions . We can also observe this trend from the coverage consumed by OH* (θ OH* ) in Figure b under different reaction conditions.…”

Section: Resultsmentioning

confidence: 93%

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Aldehyde Hydrogenation by Pt/TiO₂ Catalyst in Aqueous Phase: Synergistic Effect of Oxygen Vacancy and Solvent Water

Cao

Xia

Yao

et al. 2022

JACS Au

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The aldehyde hydrogenation for stabilizing and upgrading biomass is typically performed in aqueous phase with supported metal catalysts. By combining density functional theory calculations and ab initio molecular dynamics simulations, the model reaction of formaldehyde hydrogenation with a Pt/TiO 2 catalyst is investigated with explicit solvent water molecules. In aqueous phase, both the O vacancy (Ov) on support and solvent molecules could donate charges to a Pt cluster, where the Ov could dominantly reduce the Pt cluster from positive to negative. During the formaldehyde hydrogenation, the water molecules could spontaneously protonate the O in the aldehyde group by acid/base exchange, generating the OH* at the metal−support interface by long-range proton transfer. By comparing the stoichiometric and reduced TiO 2 support, it is found that the further hydrogenation of OH* is hard on the positively charged Pt cluster over stoichiometric TiO 2 . However, with the presence of Ov on reduced support, the OH* hydrogenation could become not only exergonic but also kinetically more facile, which prohibits the catalyst from poisoning. This mechanism suggests that both the proton transfer from solvent water molecules and the easier OH* hydrogenation from Ov could synergistically promote aldehyde hydrogenation. That means, even for such simple hydrogenation in water, the catalytic mechanism could explicitly relate to all of the metal cluster, oxide support, and solvent waters. Considering the ubiquitous Ov defects in reducible oxide supports and the common aqueous environment, this synergistic effect may not be exclusive to Pt/TiO 2 , which can be crucial for supported metal catalysts in biomass conversion.

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Section: Aldehyde Hydrogenation In Aqueous Phasesupporting

confidence: 56%

Section: Resultsmentioning

confidence: 93%

Aldehyde Hydrogenation by Pt/TiO₂ Catalyst in Aqueous Phase: Synergistic Effect of Oxygen Vacancy and Solvent Water

Cao

Xia

Yao

et al. 2022

JACS Au

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“…Moreover, looking at the T1 values of the individual carbon atoms on Pd/GNP, we were able to identify the specific adsorption mode of benzaldehyde. The aldehydic carbon (C 1 , Table 4 ) showed a stronger adsorption on the Pd/GNP surface (T1 ads /T1 bulk = 0.65) compared to the others; thus, we hypothesized that benzaldehyde approaches the surface of Pd/GNP with an orthogonal configuration, and not with a flat configuration ( Figure 6 ) as depicted by DFT calculation [ 20 ] on different type of carbon support [ 20 ].…”

Section: Resultsmentioning

confidence: 99%

An Insight into the Role of Reactant Structure Effect in Pd/C Catalysed Aldehyde Hydrogenation

et al. 2022

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The different activity of a 1% Pd/carbon catalyst towards aromatic and aliphatic aldehydes hydrogenation has been explored by 13C NMR relaxation. The ratio between T1 relaxation times of adsorbed (ads) and free diffusing (bulk) molecules (T1ads/T1bulk) can be used as an indicator of the relative strength of interaction between the reactant and the catalytic surface, where the lower the T1ads/T1bulk, the higher the adsorption strength. It can be seen that 1% Pd/carbon showed a reverse catalytic behaviour towards benzaldehyde and octanal hydrogenation, which can be explained by analysing the T1 relaxation times related to each substrate in the presence of the catalyst. Comparing and correlating the different T1ads/T1bulk values, we were able to prove that the different catalytic results mainly depend on the contrasting adsorption behaviour of substrates on the catalyst. Moreover, the role of the solvent has been disclosed, as NMR results revealed that the adsorption of the reactants was strongly affected by the choice of solvent, which is revealed to be critical in modulating catalytic activity. As a consequence, T1ads/T1bulk measurements can provide a guide to the selection of appropriate reaction conditions for improving catalytic activity.

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“…Aldehydes, in fact, can be found in several biomass-derived feedstock . First, Laura investigated one of the critical parameters that govern the reactivity of the carbonylic group toward hydrogenation and hydrodeoxygenation, that is the effect of the side chains of aldehydes . In this work, she demonstrated that the presence of a p-electron conjugation on the side chains strongly affects the conversion of aldehydes to alcohols and hydrocarbons.…”

Section: Liquid-phase Hydrogenation Reactionsmentioning

confidence: 99%

A Career in Catalysis: Laura Prati

2023

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This account celebrates the long and successful scientific career of Laura Prati, recalling her most important scientific achievements since the beginning of her work as a researcher in inorganic chemistry. Laura went through many aspects of liquid-phase heterogeneous catalysis, taking her first steps in the field of catalysts synthesis, where she pursued the development of innovative strategies for preparing catalysts until laying the foundations of the colloidal synthesis of metal nanoparticles, with particular interest in gold. Her investigations in colloids for catalysis had a natural outcome on catalysts synthesis and optimization. In her career, she dealt with liquidphase oxidation reactions, with particular attention to biomass valorization processes. According to this, she could not help to deal also with hydrogenation and hydrogenolysis reactions, to which she dedicated herself, especially in the more recent years. Her discoveries have influenced many researchers in the area of heterogeneous catalysis and design of materials.

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Discovering the role of substrate in aldehyde hydrogenation

Cited by 10 publications

References 33 publications

Aldehyde Hydrogenation by Pt/TiO₂ Catalyst in Aqueous Phase: Synergistic Effect of Oxygen Vacancy and Solvent Water

Aldehyde Hydrogenation by Pt/TiO₂ Catalyst in Aqueous Phase: Synergistic Effect of Oxygen Vacancy and Solvent Water

An Insight into the Role of Reactant Structure Effect in Pd/C Catalysed Aldehyde Hydrogenation

A Career in Catalysis: Laura Prati

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Discovering the role of substrate in aldehyde hydrogenation

Cited by 10 publications

References 33 publications

Aldehyde Hydrogenation by Pt/TiO2 Catalyst in Aqueous Phase: Synergistic Effect of Oxygen Vacancy and Solvent Water

Aldehyde Hydrogenation by Pt/TiO2 Catalyst in Aqueous Phase: Synergistic Effect of Oxygen Vacancy and Solvent Water

An Insight into the Role of Reactant Structure Effect in Pd/C Catalysed Aldehyde Hydrogenation

A Career in Catalysis: Laura Prati

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Product

Resources

About

Aldehyde Hydrogenation by Pt/TiO₂ Catalyst in Aqueous Phase: Synergistic Effect of Oxygen Vacancy and Solvent Water

Aldehyde Hydrogenation by Pt/TiO₂ Catalyst in Aqueous Phase: Synergistic Effect of Oxygen Vacancy and Solvent Water