Identifying signatures of thermal and non-thermal reaction pathways in plasmon induced H2 + D2 exchange reaction

In this work we demonstrate a strategy for identifying experimental signatures of thermal and non-thermal effects in plasmon mediated heterogeneous catalytic chemistry, a topic widely debated and discussed in the literature. Our method is based on monitoring the progress of plasmon-induced (or thermally-driven) reaction, carried out in a closed system, all the way to equilibrium. Initial part of evolution of the reaction provides information about kinetics, whereas at later times the equilibrium concentrations provide information about effective temperature at the reaction sites. Combining these two pieces of information we estimate the activation energies. Using this strategy on H 2 (g) + D 2 (g) <-->2 HD(g) isotope exchange reaction, catalyzed by Au nanoparticles under thermally-driven and light-induced conditions, we estimate the activation energies to be 0.75 ± 0.02 eV and 0.21 ± 0.02 eV, respectively. These vastly different activation energies observed are interpreted as a signature of different reaction pathways followed by the system under thermally-driven and light-induced conditions.

Silver Salt Enabled H/D Exchange at β Position of Thiophene Rings: Synthesis of Fully Deuterated Thiophene derivatives

We disclose a silver catalyzed H/D exchange reaction, which can introduce deuterium atom at β position of thiophene rings without the assisstance of any coordinating groups. The advantages of this...

COS-triggered Oxygen/Sulfur Exchange of Isatins: Chemoselective Synthesis of Functionalized Isoindigos and Spirothiopyrans via Self-condensation and Thio-Diels-Alder Reaction

Herein, we present the first organocatalytic oxygen/sulfur atom exchange reaction (O/S ER) of isatins by employing carbonyl sulfide (COS) as novel sulfuring reagent under mild reaction conditions. 8-Diazabicyclo[5.4.0] undec-7-ene (DBU),...

High-loading Ga-exchanged MFI zeolites as selective and coke-resistant catalysts for nonoxidative ethane dehydrogenation

In this paper, we investigated the effects of Ga loading amount and H2 treatment temperature for reductive solid-state ion-exchange reaction on the generated Ga species in Ga-exchanged MFI zeolites (Ga-MFIs)...

Colorimetric sensor array for rapid discrimination of edible oil species based on halogen ion exchange reaction between CsPbBr3 and iodide

Peroxides in edible oils, measured by peroxidation value for their amount, are closely related to human health. Long-term consumption of edible oils with high peroxidation values can lead to a...

Determining 88Sr/86Sr of barite using the Na2CO3 exchange method

This study presents a method of high precision stable Sr isotope measurement for barite using the Na2CO3 exchange reaction and MC-ICP-MS. The reliability of this method was strictly tested by...

Identifying signatures of thermal and non-thermal reaction pathways in plasmon induced H2 + D2 exchange reaction

In this work we demonstrate a strategy for identifying experimental signatures of thermal and non-thermal effects in plasmon mediated heterogeneous catalytic chemistry, a topic widely debated and discussed in the literature. Our method is based on monitoring the progress of plasmon induced (or thermally driven) reaction, carried out in a closed system, all the way to equilibrium. Initial part of evolution of the reaction provides information about kinetics, where as at later times the equilibrium concentrations provide information about effective temperature at the reaction sites. Combining these two pieces of information we estimate the activation energies. Using this strategy on H2 (g) + D2 (g) <--> 2 HD(g) isotope exchange reaction, catalyzed by Au nanoparticles under thermally driven and light induced conditions, we estimate the activation energies to be 0.75 ± 0.02 and 0.21 ± 0.02, respectively. These vastly different activation energies observed are interpreted as signatures of different reaction pathways followed by the system under thermally driven and light induced conditions.