Simultaneous Harvesting of Multiple Hot Holes via Visible-Light Excitation of Plasmonic Gold Nanospheres for Selective Oxidative Bond Scission of Olefins to Carbonyls
Swathi Swaminathan
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016 Uttar Pradesh, India
Contribution: Conceptualization (supporting), Data curation (lead), Formal analysis (lead), Investigation (lead), Methodology (lead), Validation (lead), Writing - original draft (lead)
Search for more papers by this authorProf. Jitendra K. Bera
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016 Uttar Pradesh, India
Contribution: Supervision (supporting), Writing - review & editing (supporting)
Search for more papers by this authorCorresponding Author
Dr. Manabendra Chandra
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016 Uttar Pradesh, India
Contribution: Conceptualization (lead), Funding acquisition (lead), Investigation (supporting), Methodology (supporting), Resources (lead), Supervision (lead), Writing - review & editing (lead)
Search for more papers by this authorSwathi Swaminathan
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016 Uttar Pradesh, India
Contribution: Conceptualization (supporting), Data curation (lead), Formal analysis (lead), Investigation (lead), Methodology (lead), Validation (lead), Writing - original draft (lead)
Search for more papers by this authorProf. Jitendra K. Bera
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016 Uttar Pradesh, India
Contribution: Supervision (supporting), Writing - review & editing (supporting)
Search for more papers by this authorCorresponding Author
Dr. Manabendra Chandra
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016 Uttar Pradesh, India
Contribution: Conceptualization (lead), Funding acquisition (lead), Investigation (supporting), Methodology (supporting), Resources (lead), Supervision (lead), Writing - review & editing (lead)
Search for more papers by this authorAbstract
Using visible photoexcitation of gold nanospheres we successfully demonstrate the simultaneous harvesting of plasmon-induced multiple hot holes in the complete oxidative scission of the C=C bond in styrene at room temperature to selectively form benzaldehyde and formaldehyde, which is a reaction that requires activation of multiple substrates. Our results reveal that, while extraction of hot holes becomes efficient for interband excitation, harvesting of multiple hot holes from the excited Au nanospheres becomes prevalent only beyond a threshold light intensity. We show that the alkene oxidation proceeded via a sequence of two consecutive elementary steps; namely, a binding step and a cyclic oxometallate transition state as the rate-determining step. This demonstration of plasmon-excitation-mediated harvesting of multiple hot holes without the use of an extra hole transport media opens exciting possibilities, notably for difficult catalytic transformations involving multielectron oxidation processes.
Conflict of interest
The authors declare no conflict of interest.
Open Research
Data Availability Statement
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