4.6 Article

Controlled Grafting Synthesis of Silica-Supported Boron for Oxidative Dehydrogenation Catalysis

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JOURNAL OF PHYSICAL CHEMISTRY C
卷 125, 期 23, 页码 12636-12649

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AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.1c01899

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资金

  1. National Science Foundation [CBET-1916809]
  2. Alfred P. Sloan Foundation
  3. UW2020 fund

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The study focused on the controlled grafting synthesis of pinacolborane on amorphous silica, revealing that the silica pretreatment dehydration temperature can control the formation of hydrogen bonds. Thermal treatment under vacuum showed that boron on the silica surface is highly mobile at elevated temperatures, and the catalysts exhibited expected activity. However, the kinetic behavior of these supported catalysts deviates from that of bulk boron materials, prompting further research into reaction kinetics.
We present the controlled grafting synthesis of pinacolborane on amorphous silica. B-11 solid-state NMR and IR spectroscopies reveal that the precursor molecule anchors monopodally to the surface and can form hydrogen-bonding interactions with neighboring unreacted silanol groups. The extent of hydrogen bonding can be controlled by the silica pretreatment dehydration temperature. Thermal treatment of the grafted boron materials under vacuum generates clusters of oxidized/hydrolyzed boron regardless of boron weight loading, illustrating that boron is highly mobile on the silica surface at elevated temperatures. The materials exhibit propane oxidative dehydrogenation activity expected for silica-supported boron catalysts. Interestingly, the kinetic behavior of these supported catalysts deviates from that of previously reported bulk boron materials, prompting further studies into the reaction kinetics over these materials. The synthetic and catalytic insights gained here can inform future studies of improved synthesis routes and reaction kinetics.

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