Boron-based catalysts show excellent performance in oxidative dehydrogenation (ODH) of light alkanes to alkenes with high selectivity and extremely good antioxidation properties. However, the anti-deep-oxidation mechanism remains unclear. Herein, we chose -BN and BO as representative boron-based catalysts to investigate their reactions with two important intermediates in the light alkane ODH, Et· (evolving to ethene) and EtO· (evolving to ethene or CO), to elucidate the origin of the antioxidation of alkanes. The density functional theory calculations reveal that surface boron sites could eliminate alkoxy in their vicinity, resulting in exceptional inhibition of alkane deep-oxidation. The analysis of the electronic and geometric structures of key stationary points showed that the oxophilicity of B determined the low deep-oxidation of alkanes, and the homoleptic coordination of B with all three ligating atoms being O moderately enhanced its oxophilicity. This work represents a novel conceptual advance in the mechanistic understanding of alkane ODH.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.jpclett.1c02709 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Electrogenerated Lewis Acid-Catalyzed Claisen Rearrangement of Allyl Aryl Ethers.
Org Lett
December 2024
Division of Applied Chemistry, Graduate School of Environmental, Life, Natural Science and Technology, Okayama University, 3-1-1 Tsushima-naka, Kita-ku, Okayama 700-8530, Japan.
Catalysts for Claisen rearrangement have been intensively studied to overcome the need for high temperature. However, previous studies have encountered challenges, such as the need for heating, a long reaction time, and/or the need for equivalent amounts of catalyst. In this study, we introduce an effective electrogenerated boron-based Lewis acid catalyst for the aromatic Claisen rearrangement, which proceeds in a few minutes at ambient temperature.
View Article and Find Full Text PDFDual Catalytic Activity of Pd-Dispersed MOF for Ammonia-Free Hydrogen Generation from Ammonia Borane and Sodium Borohydride in Aqueous and Methanol Solvents.
Langmuir
December 2024
Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India.
The development of effective catalysts for hydrogen (H) generation from chemical hydrides is essential for advancing hydrogen-based energy technologies. Herein, we synthesized a Pd-dispersed CPO-27 catalyst exhibiting exceptional performance for hydrolysis of two boron-based chemical hydrides, i.e.
View Article and Find Full Text PDFAluminium porphyrins catalyse the hydrogenation of CO with H.
Chem Sci
December 2024
Department of Inorganic Chemistry, Faculty of Science, Charles University Albertov 6, 128 00 Praha 2 Czech Republic
Boron-based frustrated Lewis pairs (FLPs) have become well-established catalysts for the hydrogenation of a wide range of functional groups. Conversely, aluminium-based FLP hydrogenation catalysts are less common, especially for CO reduction. They are mostly confined to the hydrogenation of imines, alkenes, and alkynes even though aluminium is much more abundant than boron and forms structurally related compounds.
View Article and Find Full Text PDFPerformance Descriptor of Subsurface Metal-Promoted Boron Catalysts for Low-Temperature Propane Oxidative Dehydrogenation to Propylene.
J Am Chem Soc
December 2024
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China.
Boron-based catalysts have exhibited excellent olefin selectivity in the oxidative dehydrogenation of propane (ODHP) reaction. The substrate material should be a potential platform for performance modulation of boron catalysts in this reaction since the introduction of subsurface Ni promoters significantly improves the activity. In this study, we deciphered the substrate effect and identified a performance descriptor to comprehend the roles of subsurface materials in BO/metal/BN ODHP catalysts by evaluating different metal promoters.
View Article and Find Full Text PDFKinetic Insights into Boron-Based Materials Catalyzed Oxidative Dehydrogenation of Light Alkanes.
Precis Chem
May 2024
Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
Article Synopsis
- Boron-based materials show high selectivity for alkenes in oxidative dehydrogenation (ODH) of light alkanes, making them promising catalysts, although key reaction mechanisms remain debated due to difficulties in capturing short-lived intermediates.
- The review highlights the investigation of reaction orders and activation energies, which could provide insight into reactions involving radical intermediates, an area that hasn't been deeply explored yet.
- Common features among different boron-based catalysts include alkene selectivity and active site formation, attributed to shared radical-mediated reaction pathways, indicating that apparent reaction orders and activation energies are reliable measures for understanding these mechanisms in boron-catalyzed ODH.
Want AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!