Mechanistic exploration of furfural hydrogenation on copper surface in aqueous phase by DFT and AIMD simulations

Yao, Zhen; Xia, Guang-Jie; Cao, Wu; Zeng, Ke-Han; Wang, Yang‐Gang

doi:10.1016/j.jcat.2022.12.024

Cited by 16 publications

(10 citation statements)

References 52 publications

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“…As shown in Figure b, the first hydrogenation step toward the M-CHOH formation (pathway I) owns a reaction barrier of 0.57 eV and is endothermic by 0.33 eV, while the corresponding step toward the M-CH 2 O formation (pathway II) requires a barrier of 0.32 eV along with the release of the heat of 0.21 eV. Hence, the first hydrogenation has a kinetic and thermodynamic preference for the formation of the alkoxide intermediate, which is in perfect accordance with the observation reported from other studies focused on the selective conversion of furfural to furfuryl alcohol. , Nonetheless, the subsequent hydrogenation starting from M-CHOH toward M-CH 2 OH formation (pathway I) is more favorable than further hydrogenation of M-CH 2 O toward maltitol formation (pathway II) both kinetically (−0.05 vs 1.01 eV) and thermodynamically (−0.21 vs 0.33 eV). Eventually, the formed maltitol (M-CH 2 OH) was readily desorbed from the Ni(111) surface with an exothermic reaction energy of 0.43 eV.…”

Section: Resultssupporting

confidence: 88%

Continuous Hydrogenation of Maltose over Raney Ni in a Trickle-Bed Reactor

Fan,

Fang,

Zhao

et al. 2023

Ind. Eng. Chem. Res.

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Maltitol has been identified as an important value-added chemical with versatile applications and is typically manufactured via the catalytic hydrogenation of maltose, which is in urgent need of upgrading from batch to continuous operation to boost production efficiency. Here we propose a viable continuous approach for maltose hydrogenation in a trickle-bed reactor applying a millimeter-scale Raney Ni. The parametric study was performed at various temperatures, liquid flow rates, initial maltose concentrations, pressures, and hydrogen flow rates to maximize the catalytic performance and optimize the product distribution. Under the optimal reaction conditions, generally excellent conversion of maltose (91.0%) and a high yield of maltitol (87.9%) were obtained. Furthermore, a continuous hydrogenation of concentrated maltose proceeded properly, providing a slight reduction in maltose conversion but satisfactory space time yield of maltitol (0.150 gmaltitol gcat –1 h–1). Detailed kinetics and density functional theory calculations were combined to unravel the reaction mechanism of maltose hydrogenation. The continuous flow system based on a trickle-bed reactor proved to have high durability and remarkable substrate suitability, thus demonstrating a reliable scale-up capability for the industrial utilization of biomass-derived sugars.

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Section: Resultssupporting

confidence: 88%

Continuous Hydrogenation of Maltose over Raney Ni in a Trickle-Bed Reactor

Fan,

Fang,

Zhao

et al. 2023

Ind. Eng. Chem. Res.

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“…Therefore, we argue that the solvation energies of similar magnitude to FCHO* can be used for the reaction intermediates. However, we note that solvent-mediated mechanisms such as H-shuttling 25,75 and possible hydrogen bond stabilization for the other reaction intermediates have not considered in the model, which might affect the overall activity predictions.…”

Section: Endothermic Solvation Energies Activate Furfural Hydrogenati...mentioning

confidence: 99%

Solvation of furfural at metal|water interfaces: Implications for aqueous phase hydrogenation reactions

Liu

Vijay

et al. 2023

Preprint

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Metal|water interfaces are central to understanding aqueous phase heterogeneous catalytic processes. However, it is challenging to model the interactions between metal surfaces, adsorbates and the solvent water molecules at the interface. Herein, we use ab-initio molecular dynamics (AIMD) simulations to study the adsorption of furfural, a platform biomass chemical on several catalytically relevant metal|water interfaces (Pt, Rh, Pd, Cu and Au) at low coverages. We find that furfural adsorption is destabilized on all the metal|water interfaces compared to the metal|vacuum interfaces considered in this work. This destabilization is a result of the energetic penalty associated with the displacement of water molecules near the surface upon adsorption of furfural. This is evidenced by a linear correlation between solvation energy and the change in surface water coverage. To predict solvation energies without the need for computationally expensive AIMD simulations, we demonstrate OH binding energy in vacuum to be a good descriptor to estimate the solvation energies of furfural on different metal|water interfaces. Using microkinetic modeling, we further explain the origin of the activity for furfural hydrogenation on intrinsically strong-binding metals, such as Rh and Pt, under aqueous conditions, i.e., the endothermic solvation energies for furfural adsorption helps prevent surface poisoning. Our work sheds light on the development of active aqueous-phase catalytic systems via rationally tuning the solvation energies of reaction intermediates.

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“…Copper is also well recognized for activating terminal alkyne bonds. [75] Copper salts and complexes are utilized in several organic transformations like coupling reactions, [76] click reactions, [77] radical reactions, [78] hydrogenation reactions, [79] etc. Our research group demonstrated the synthesis of indenoisoquinolines 121 using a CuO@NiO nano-catalyst by reacting 2-iodobenzamides 119 and 1,3indanedione 120 as the starting materials (Scheme 44).…”

Section: Copper Catalysismentioning

confidence: 99%

Recent Advances in the 3 d‐Transition‐Metal‐Catalyzed Synthesis of Isoquinolines and its Derivatives

Maikhuri,

Rawat,

Rawat

2023

Adv Synth Catal

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The preservation of scarce rare earth metals, such as palladium, rhodium, iridium, and others, poses a significant challenge for humanity due to their limited availability. These rare earth metals might be replaced by earth‐abundant 3d‐transition metals such as cobalt, manganese, iron, nickel, copper, etc. Isoquinolines have acquired an important position in synthetic organic chemistry as well as medicinal chemistry. They manifest in a diverse range of natural and synthetic molecules, serving as pivotal synthons for the synthesis of numerous bioactive compounds with notable medicinal significance. Numerous reports on the synthesis of isoquinoline derivatives via transition metal catalysis have been published worldwide. In this review, we summarize recent approaches for synthesizing various isoquinoline derivatives using 3d‐transition‐metal catalysts since 2020. The review has been divided into different 3d‐transition‐metal‐based catalysis. We expect that this review will bring a better overview of the present status of the significant progress made in the 3d‐transition‐metal‐based synthesis of isoquinolines and persuade more advancements and research in this area in the near future.

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Mechanistic exploration of furfural hydrogenation on copper surface in aqueous phase by DFT and AIMD simulations

Cited by 16 publications

References 52 publications

Continuous Hydrogenation of Maltose over Raney Ni in a Trickle-Bed Reactor

Continuous Hydrogenation of Maltose over Raney Ni in a Trickle-Bed Reactor

Solvation of furfural at metal|water interfaces: Implications for aqueous phase hydrogenation reactions

Recent Advances in the 3 d‐Transition‐Metal‐Catalyzed Synthesis of Isoquinolines and its Derivatives

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