Catalytic Mechanisms in Rhenium-Based Systems

Rhenium occupies a unique position among transition metals owing to its rich redox chemistry, variable oxidation states and strong affinity for oxygen ligands. In heterogeneous catalysis, rhenium often manifests as supported oxo-species or forms alloys with noble metals, enabling a spectrum of reactions from hydrogenation and dehydrogenation to the water–gas shift and selective oxidations. Mechanistically, many Re catalysts operate via a Mars–van Krevelen cycle, in which lattice oxygen participates directly in substrate oxidation and is subsequently replenished by gas-phase O2. In hydrogenation processes, Re centres can activate dihydrogen via heterolytic splitting, generating hydride species that furnish hydrogen atoms to unsaturated substrates. The electronic interplay between Re and supports or secondary metals modulates adsorption energies and transition-state barriers, thus steering selectivity and activity. Promoter elements such as potassium or cobalt tune the acid–base properties of oxide supports and stabilise specific Re oxidation states under reaction conditions. Bimetallic Pd–Re systems exemplify synergistic behaviour in biomass-derived transformations, where Re modifies hydrogen dosing and Pd provides facile adsorption sites. Across industrially relevant applications, from syngas conversion to fine-chemical synthesis, understanding the interplay of Re oxidation state dynamics, support interactions and alloying effects is central to optimising catalyst performance and longevity.

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Catalytic Mechanisms in Rhenium-Based Systems publication trend

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Technical terms

Perrhenate: the perrhenate anion [ReO4]− commonly used as a soluble precursor for rhenium oxide catalysts.

Temperature-programmed reduction (TPR): an analytical method in which a catalyst is heated under a reducing gas flow while monitoring gas consumption or evolved species to assess reducibility.

Turnover frequency (TOF): the number of substrate molecules converted per catalytic active site per unit time, indicating intrinsic activity.

References

1. Catalytic Ability of K- and Co-Promoted Oxo-Re and Oxo-ReMo Nanosized Compositions for Water–Gas Shift Reaction. Catalysts (2023).
2. Alloying and Segregation in PdRe/Al2O3 Bimetallic Catalysts for Selective Hydrogenation of Furfural. Catalysts (2024).
3. Palladium-Rhenium Catalysts for Selective Hydrogenation of Furfural: Influence of Catalyst Preparation on Structure and Performance. Catalysts (2023).