Ethanol decomposition on a Pd(110) surface: a density functional theory investigation.

Area of Science:

• Surface science
• Catalysis
• Computational chemistry

Background:

• Ethanol decomposition is crucial for catalysis.
• Understanding reaction mechanisms on metal surfaces is key.
• Palladium surfaces are widely studied for catalytic applications.

Purpose of the Study:

• To comprehensively investigate ethanol decomposition on Palladium(110) using density functional theory.
• To map out the reaction mechanism and identify key intermediates.
• To compare the reactivity and selectivity of Pd(110) with Pd(111).

Main Methods:

• Self-consistent periodic density functional theory (DFT) calculations.
• Analysis of geometries and energies of reaction intermediates.
• Mapping of the ethanol decomposition network on Pd(110).

Main Results:

• The most stable adsorption follows gas-phase bond order rules.
• The primary decomposition pathway is CH(3)CH(2)OH → ... → C + CO + H + CH(4).
• Initial dehydrogenation is the rate-limiting step; no C-O scission observed.

Conclusions:

• Pd(110) shows higher activity and different selectivity than Pd(111) for ethanol decomposition.
• Local electronic and geometrical effects of the metal surface influence reactivity.
• Four distinct Brønsted-Evans-Polanyi relations were identified for C-H, C-O, and C-C bond scissions across Pd(111) and Pd(110).