Unconventional low temperature decomposition of a saturated hydrocarbon over atomically-dispersed titanium-aluminum-boron catalyst

Abstract Sonochemically-synthesized atomically-dispersed titanium-aluminum-boron nanopowder (TiAlB NP) exhibits a remarkable low-temperature catalytic activation of aliphatic C-H bonds at 750 K followed by C-C bond activation thus emerging as a potent low-cost alternative to expensive platinum group...

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Main Authors: Souvick Biswas, Jack Cokas, Winston Gee, Dababrata Paul, Nureshan Dias, Harry W. T. Morgan, Matthew T. Finn, Bethany M. Hudak, Perrin M. Godbold, Christopher A. Klug, Albert Epshteyn, Anastassia N. Alexandrova, Musahid Ahmed, Ralf I. Kaiser
Format: Article
Language:English
Published: Nature Portfolio 2025-07-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-62112-2
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author Souvick Biswas
Jack Cokas
Winston Gee
Dababrata Paul
Nureshan Dias
Harry W. T. Morgan
Matthew T. Finn
Bethany M. Hudak
Perrin M. Godbold
Christopher A. Klug
Albert Epshteyn
Anastassia N. Alexandrova
Musahid Ahmed
Ralf I. Kaiser
author_facet Souvick Biswas
Jack Cokas
Winston Gee
Dababrata Paul
Nureshan Dias
Harry W. T. Morgan
Matthew T. Finn
Bethany M. Hudak
Perrin M. Godbold
Christopher A. Klug
Albert Epshteyn
Anastassia N. Alexandrova
Musahid Ahmed
Ralf I. Kaiser
author_sort Souvick Biswas
collection DOAJ
description Abstract Sonochemically-synthesized atomically-dispersed titanium-aluminum-boron nanopowder (TiAlB NP) exhibits a remarkable low-temperature catalytic activation of aliphatic C-H bonds at 750 K followed by C-C bond activation thus emerging as a potent low-cost alternative to expensive platinum group metals. Here, the model saturated hydrocarbon, exo-tetrahydrodicyclopentadiene (C10H16), undergoes catalytic decomposition on TiAlB NPs in a chemical microreactor to produce 1,3-cyclopentadiene (c-C5H6), cyclopentene (c-C5H8), and molecular hydrogen (H2) as detected in situ via isomer-selective, single-photon ionization time-of-flight mass spectrometry. Extensive electronic structure theory calculations on model clusters of the catalyst decode a unique synergy among the atomic constituents of the catalyst and chemical bonding in this stepwise, retro Diels Alder reaction: Ti, although insensitive to C-H activation in its metallic state, initiates the catalysis via chemisorption of the hydrocarbon, adjacent B centers readily abstract hydrogen atoms and store them during the catalytic cycle, while Al stabilizes the catalyst structure yet providing space for critical docking sites for the departing hydrocarbons.
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spelling doaj-art-05c7adcb679b44a89508bf7cc4d4298f2025-08-20T03:05:06ZengNature PortfolioNature Communications2041-17232025-07-0116111310.1038/s41467-025-62112-2Unconventional low temperature decomposition of a saturated hydrocarbon over atomically-dispersed titanium-aluminum-boron catalystSouvick Biswas0Jack Cokas1Winston Gee2Dababrata Paul3Nureshan Dias4Harry W. T. Morgan5Matthew T. Finn6Bethany M. Hudak7Perrin M. Godbold8Christopher A. Klug9Albert Epshteyn10Anastassia N. Alexandrova11Musahid Ahmed12Ralf I. Kaiser13Department of Chemistry, University of Hawaii at ManoaDepartment of Chemistry and Biochemistry, University of California, Los AngelesDepartment of Chemistry and Biochemistry, University of California, Los AngelesDepartment of Chemistry, University of Hawaii at ManoaChemical Sciences Division, Lawrence Berkeley National LaboratoryDepartment of Chemistry and Biochemistry, University of California, Los AngelesChemistry Division, U.S. Naval Research LaboratoryMaterials Science and Technology Division, U.S. Naval Research LaboratoryNRC Postdoctoral Associate, Chemistry Division, U.S. Naval Research LaboratoryChemistry Division, U.S. Naval Research LaboratoryChemistry Division, U.S. Naval Research LaboratoryDepartment of Chemistry and Biochemistry, University of California, Los AngelesChemical Sciences Division, Lawrence Berkeley National LaboratoryDepartment of Chemistry, University of Hawaii at ManoaAbstract Sonochemically-synthesized atomically-dispersed titanium-aluminum-boron nanopowder (TiAlB NP) exhibits a remarkable low-temperature catalytic activation of aliphatic C-H bonds at 750 K followed by C-C bond activation thus emerging as a potent low-cost alternative to expensive platinum group metals. Here, the model saturated hydrocarbon, exo-tetrahydrodicyclopentadiene (C10H16), undergoes catalytic decomposition on TiAlB NPs in a chemical microreactor to produce 1,3-cyclopentadiene (c-C5H6), cyclopentene (c-C5H8), and molecular hydrogen (H2) as detected in situ via isomer-selective, single-photon ionization time-of-flight mass spectrometry. Extensive electronic structure theory calculations on model clusters of the catalyst decode a unique synergy among the atomic constituents of the catalyst and chemical bonding in this stepwise, retro Diels Alder reaction: Ti, although insensitive to C-H activation in its metallic state, initiates the catalysis via chemisorption of the hydrocarbon, adjacent B centers readily abstract hydrogen atoms and store them during the catalytic cycle, while Al stabilizes the catalyst structure yet providing space for critical docking sites for the departing hydrocarbons.https://doi.org/10.1038/s41467-025-62112-2
spellingShingle Souvick Biswas
Jack Cokas
Winston Gee
Dababrata Paul
Nureshan Dias
Harry W. T. Morgan
Matthew T. Finn
Bethany M. Hudak
Perrin M. Godbold
Christopher A. Klug
Albert Epshteyn
Anastassia N. Alexandrova
Musahid Ahmed
Ralf I. Kaiser
Unconventional low temperature decomposition of a saturated hydrocarbon over atomically-dispersed titanium-aluminum-boron catalyst
Nature Communications
title Unconventional low temperature decomposition of a saturated hydrocarbon over atomically-dispersed titanium-aluminum-boron catalyst
title_full Unconventional low temperature decomposition of a saturated hydrocarbon over atomically-dispersed titanium-aluminum-boron catalyst
title_fullStr Unconventional low temperature decomposition of a saturated hydrocarbon over atomically-dispersed titanium-aluminum-boron catalyst
title_full_unstemmed Unconventional low temperature decomposition of a saturated hydrocarbon over atomically-dispersed titanium-aluminum-boron catalyst
title_short Unconventional low temperature decomposition of a saturated hydrocarbon over atomically-dispersed titanium-aluminum-boron catalyst
title_sort unconventional low temperature decomposition of a saturated hydrocarbon over atomically dispersed titanium aluminum boron catalyst
url https://doi.org/10.1038/s41467-025-62112-2
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