4 research outputs found
Designing Efficient Solar-Thermal Fuels with [<i>n</i>.<i>n</i>](9,10)Anthracene Cyclophanes: A Theoretical Perspective
Molecular solar thermal storage (MOST)
systems have been largely
limited to three classes of molecular motifs: azo-benzene, norbornadiene,
and transition metal based fulvalene-tetracarbonyl systems. Photodimerization
of anthracene has been known for a century; however, this photoprocess
has not been successfully exploited for MOST purposes due to its poor
energy storage. Using well-calibrated theoretical methods on a series
of [<i>n</i>.<i>n</i>]Â(9,10)Âbis-anthracene cyclophanes,
we have exposed that they can store solar energy into chemical bonds
and can release in the form of heat energy on demand under mild conditions.
The storage is mainly attributed to the strain in the rings formed
by the alkyl linkers upon photoexcitation. Our results demonstrate
that the gravimetric energy storage density for longer alkyl-chain
linkers (<i>n</i> > 3) are comparable to those for the
best-known
candidates; however, it lacks some of the deleterious attributes of
known systems, thus making the proposed molecules desirable targets
for MOST applications
Photochemical Hydrogenation of CO<sub>2</sub> to CH<sub>3</sub>OH and Pyridine to 1,2-Dihydropyridine Using Plasmon-Facilitated Chemisorbed Hydrogen on Au Surface: Theoretical Perspective
CO<sub>2</sub> hydrogenation to methanol,
a renewable fuel, under
benign conditions and without the use of sacrificial agents is a rarity
and certainly a much sought after goal of present-day research. Herein,
we report using well calibrated computational tools the viability
of hydrogenating CO<sub>2</sub> to CH<sub>3</sub>OH and pyridine to
1,2-dihydropyridine, a renewable organohydride which can also reduce
CO<sub>2</sub> to CH<sub>3</sub>OH sustainably, using hydrogens chemisorbed
on Au(111) surface of Au<sub>20</sub> by photo-excitation.
Our studies predict that these hydrogenations can occur at appreciable
rates at room temperature. Thus, we reveal the untapped potential
of the chemisorbed hydrogens on Au(111) surface, achieved by hot-electron generation through photo-excitation, in facilitating endoergic hydrogenations akin
to those enabled by NADPH