Mimicking Real Catalysts: Model Stepped Nickel Surfaces in Furfural Catalysis─Insights into Adsorption, Reactivity, and Defect-Driven Conversion Pathways DOI Creative Commons
Sotirios Tsatsos, Georgios Kyriakou

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 3022 - 3033

Published: March 17, 2025

The catalytic conversion of furanic compounds into renewable chemicals is essential for sustainable manufacturing. Here, we report a unique self-hydrogenation pathway furfural to 2-methylfuran on Ni(119) surface, showing how steps and nickel carbides govern reaction selectivity. Thermal desorption spectroscopic measurements reveal that undergoes decarbonylation furan terraces, while step sites act as "hydrogen transfer pumps", abstracting hydrogen from facilitating its diffusion terrace-bound molecules, thereby promoting selective hydrogenation 2-methylfuran. Moreover, the surface-bound enhances hydrogenolysis, with product selectivity closely connected concentration. DFT calculations show preference top edges, where strong bonding electron redistribution stabilize intermediates promote transformations. We further demonstrate these insights provide framework designing advanced catalysts through surface structure optimization. By linking model real-world applications, this approach enables development efficient tailored biomass conversion.

Language: Английский

Pseudo-catalytic kinetics induced by electron withdrawal of Na ions for cellulose activation: A theoretical multiscale study DOI
Young-Oh Kim, Joonmyung Choi

Fuel, Journal Year: 2024, Volume and Issue: 364, P. 131097 - 131097

Published: Jan. 30, 2024

Language: Английский

Citations

4
Understanding the Electronic Effects of Lewis Acid Catalysts in Accelerating Polar Diels–Alder Reactions DOI
Luís R. Domingo, Mar Ríos‐Gutiérrez, Patricia Pérez

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12349 - 12359

Published: Aug. 19, 2024

The electronic effects of Lewis acid (LA) catalysts in reducing the activation energies polar Diels–Alder (P-DA) reactions have been studied within Molecular Electron Density Theory. To this end, a quantum topological energy partitioning scheme, namely, Relative Interacting Atomic Energy (RIAE) analysis, is applied to transition state structures (TSs) and ground reagents two different LA-catalyzed P-DA reactions. Analyses ξEtotalX total interacting frameworks f(X) show that stabilization electrophilic frameworks, resulting from global electron density transfer (GEDT), cause an effective decrease energies. On other hand, in-depth analysis ξEintraA intra-atomic atoms belonging ethylenic framework cyclopentadiene with acrolein indicates strong carbonyl carbon, GEDT taking place at TSs, main factor responsible for these Finally, increase TSs causes larger C–C distance, framework, thereby decreasing suggested Pauli repulsion.

Language: Английский

Citations

4
Influence of the Nature of Group 15 Element on [AuI]–C≡E/Azide 1,3-Dipolar Cycloaddition Reaction DOI
Daniel González‐Pinardo, Israel Fernández

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

The impact of the nature Group 15 element on both bonding situation and reactivity gold(I)-C ≡ E (E = N to Bi) complexes has been studied quantum chemically within density theory functional framework. For this purpose, 1,3-dipolar cycloaddition reaction involving tBuN3 as dipole selected its main features, including regioselectivity transformation in-plane aromaticity corresponding transition structures, have investigated. It is found that increased one moves down (N ≪ P < As Sb Bi). This trend rationalized by using combined activation strain model energy decomposition analysis methods, which indicate process mainly dominated required reactants reach state geometries.

Language: Английский

Citations

0
Computational study of silver-catalyzed stereoselective hydroalkylation of alkynes: Pauli repulsion controlled Z/E selectivity DOI

Lingfei Hu,

Han Gao, Yanlei Hu

et al.

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(52), P. 6412 - 6415

Published: Jan. 1, 2021

The σ)(π Pauli repulsion is revealed as the dominant factor affecting stereoselectivity of 1,2-alkyl migration alkynyl boronate complexes. This due to cationic silver induced unequal redistribution alkyne π electron density.

Language: Английский

Citations

24
Mimicking Real Catalysts: Model Stepped Nickel Surfaces in Furfural Catalysis─Insights into Adsorption, Reactivity, and Defect-Driven Conversion Pathways DOI Creative Commons
Sotirios Tsatsos, Georgios Kyriakou

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 3022 - 3033

Published: March 17, 2025

The catalytic conversion of furanic compounds into renewable chemicals is essential for sustainable manufacturing. Here, we report a unique self-hydrogenation pathway furfural to 2-methylfuran on Ni(119) surface, showing how steps and nickel carbides govern reaction selectivity. Thermal desorption spectroscopic measurements reveal that undergoes decarbonylation furan terraces, while step sites act as "hydrogen transfer pumps", abstracting hydrogen from facilitating its diffusion terrace-bound molecules, thereby promoting selective hydrogenation 2-methylfuran. Moreover, the surface-bound enhances hydrogenolysis, with product selectivity closely connected concentration. DFT calculations show preference top edges, where strong bonding electron redistribution stabilize intermediates promote transformations. We further demonstrate these insights provide framework designing advanced catalysts through surface structure optimization. By linking model real-world applications, this approach enables development efficient tailored biomass conversion.

Language: Английский

Citations

0