Critical role of solvent-modulated hydrogen-binding strength in the catalytic hydrogenation of benzaldehyde on palladium

Cheng, Guanhua; Jentys, Andreas; Gutiérrez, Oliver Y.; Liu, Yue; Chin, Ya-Huei Cathy; Lercher, Johannes A.

doi:10.1038/s41929-021-00701-2

Cited by 71 publications

(53 citation statements)

References 46 publications

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“…Density functional theory (DFT) calculation demonstrates that the sequential hydrogenation of the O atom followed by C atom in carbonyl group has much lower free energy barrier than the opposite sequence (Fig. 4b , 0.198 eV vs. 0.631 eV), consistent with the kinetic results 41 and the recently reported DFT calculation 42 . Therefore, the RDS for Pd/Py-COF and Pd/Be-COF is the same and involves the O hydrogenation step.…”

Section: Resultssupporting

confidence: 88%

The promotion effect of π-π interactions in Pd NPs catalysed selective hydrogenation

et al. 2022

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The utilization of weak interactions to improve the catalytic performance of supported metal catalysts is an important strategy for catalysts design, but still remains a big challenge. In this work, the weak interactions nearby the Pd nanoparticles (NPs) are finely tuned by using a series of imine-linked covalent organic frameworks (COFs) with different conjugation skeletons. The Pd NPs embedded in pyrene-COF are ca. 3 to 10-fold more active than those in COFs without pyrene in the hydrogenation of aromatic ketones/aldehydes, quinolines and nitrobenzene, though Pd have similar size and surface structure. With acetophenone (AP) hydrogenation as a model reaction, systematic studies imply that the π-π interaction of AP and pyrene rings in the vicinity of Pd NPs could significantly reduce the activation barrier in the rate-determining step. This work highlights the important role of non-covalent interactions beyond the active sites in modulating the catalytic performance of supported metal NPs.

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Section: Resultssupporting

confidence: 88%

The promotion effect of π-π interactions in Pd NPs catalysed selective hydrogenation

et al. 2022

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“…We observed that the rates of hydrogenation and hydrogenolysis decreased with the addition of a base, with a net effect of increasing the selectivity to hydrogenolysis (Table S4–S8). This suggest that alkaline conditions increase the hydrogen binding strength, which in turn decreases the rate constant of hydrogen addition [25, 26] . As more hydrogen atoms are involved in hydrogenation than in hydrogenolysis this effect is stronger for the former and favors so hydrogenolysis.…”

Section: Methodsmentioning

confidence: 99%

“…This suggest that alkaline conditions increase the hydrogen binding strength, which in turn decreases the rate constant of hydrogen addition. [25,26] As more hydrogen atoms are involved in hydrogenation than in hydrogenolysis this effect is stronger for the former and favors so hydrogenolysis.…”

Section: Angewandte Chemiementioning

confidence: 99%

Controlling Reaction Routes in Noble‐Metal‐Catalyzed Conversion of Aryl Ethers

et al. 2022

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Hydrogenolysis and hydrolysis of aryl ethers in the liquid phase are important reactions for accessing functionalized cyclic compounds from renewable feedstocks. On supported noble metals, hydrogenolysis is initiated by a hydrogen addition to the aromatic ring followed by CÀ O bond cleavage. In water, hydrolysis and hydrogenolysis proceed by partial hydrogenation of the aromatic ring prior to water or hydrogen insertion. The mechanisms are common for the studied metals, but the selectivity to hydrogenolysis increases in the order Pd < Rh < Ir < Ru � Pt in decalin and water; the inverse was observed for the selectivity to hydrolysis in water. Hydrogenolysis selectivity correlates with the Gibbs free energy of hydrogen adsorption. Hydrogenolysis has the highest standard free energy of activation and a weak dependence on H 2 pressure, thus, the selectivity to hydrogenolysis is maximized by increasing temperature and decreasing H 2 pressure. Selectivity to CÀ O bond cleavage reaches > 95 % in water and alkaline conditions.

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“…For example, molecular water is an excellent solvent for liquid bio-based ketone reduction to alcohols because it affects the activation barriers of such a reaction. 11,36,37 Secondly, the dissociated protons in the solvents could add to the reactant in the solution, which is called transfer hydrogenation. 38,39 For these hydrogen transfer-enabled systems, it is expected to observe kinetic isotope effects within the solvents such as alcohols, thiols, water, and amines, where X–H/X–D or H 2 O/D 2 O are present.…”

Section: Types Of Kinetic Isotope Effectsmentioning

confidence: 99%

“…Based on the theory of atomic isotopes, researchers have widely utilized isotope effects in various scientific areas, e.g., enzyme chemistry, 7,8 homogeneous catalysis, 9,10 and heterogeneous catalysis. [11][12][13] Essentially, the study of isotope effects could reveal the fundamental knowledge of a reaction or process and further draw a clear understanding of the reaction mechanism and rate-limiting steps. In previous reports, the most commonly tested isotopic atoms are C ( 12 C and 13 C), 14,15 H (H and D), 10,16 and O ( 16 O and 18 O).…”

Section: Introductionmentioning

confidence: 99%

Perceptions on the treatment of apparent isotope effects during the analyses of reaction rate and mechanism

Gao

Chang

2022

Phys. Chem. Chem. Phys.

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Critical role of solvent-modulated hydrogen-binding strength in the catalytic hydrogenation of benzaldehyde on palladium

Cited by 71 publications

References 46 publications

The promotion effect of π-π interactions in Pd NPs catalysed selective hydrogenation

The promotion effect of π-π interactions in Pd NPs catalysed selective hydrogenation

Controlling Reaction Routes in Noble‐Metal‐Catalyzed Conversion of Aryl Ethers

Perceptions on the treatment of apparent isotope effects during the analyses of reaction rate and mechanism

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