Related Experiment Video
Updated: Aug 17, 2025
Synthesis and Testing of Supported Pt-Cu Solid Solution Nanoparticle Catalysts for Propane Dehydrogenation
Published on: July 18, 2017
In Situ Generated Boron Peroxo as Mild Oxidant in Propane Oxidative Dehydrogenation Revealed by Density Functional
Yuchen Liu1, Ziyi Liu1, Wen-Duo Lu1
1State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory for Catalytic Conversion of Carbon Resources, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China.
Abstract:
Boron-based materials catalyzing oxidative dehydrogenation is emerging as a promising protocol for efficient conversion of light alkanes to olefins, while the origin of its remarkable selectivity remains unclear. By means of density functional theory calculations, this work addresses the crucial role of boron peroxo as the mild oxidant in propane ODH: (1) Surface boron peroxo species can be generated in situ in the presence of peroxo species, preferably at the >B-O-B< sites of the zigzag edge, and show high activity to dehydrogenate propane (ΔG⧧ = 13.5 kcal/mol, ΔG = 8.9 kcal/mol). (2) The >B-O-O· site shows high discriminability of secondary H over primary H of the propane molecule, leading to significantly higher yield of iso-propyl (CH3ĊHCH3) than n-propyl (CH3CH2ĊH2); thus, propene formation is favored over deep oxidation. This provides physical insights into the origin of the remarkable olefin selectivity in the boron-containing ODH catalytic systems.
Related Concept Videos
03:08Hydroboration-Oxidation of Alkenes
02:36Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
02:21Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate
02:44Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
02:35Regioselectivity of Electrophilic Additions-Peroxide Effect