Synthesis, characterization and computational evaluation of bicyclooctadienes towards molecular solar thermal energy storage
Journal article, 2022

Molecular solar-thermal energy storage (MOST) systems are based on photoswitches that reversibly convert solar energy into chemical energy. In this context, bicyclooctadienes (BODs) undergo a photoinduced transformation to the corresponding higher energy tetracyclooctanes (TCOs), but the photoswitch system has not until now been evaluated for MOST application, due to the short half-life of the TCO form and limited available synthetic methods. The BOD system degrades at higher temperature via a retro-Diels-Alder reaction, which complicates the synthesis of the compounds. We here report a cross-coupling reaction strategy that enables an efficient synthesis of a series of 4 new BOD compounds. We show that the BODs were able to switch to the corresponding tetracyclooctanes (TCOs) in a reversible way and can be cycled 645 times with only 0.01% degradation. Half-lives of the TCOs were measured, and we illustrate how the half-life could be engineered from seconds to minutes by molecular structure design. A density functional theory (DFT) based modelling framework was developed to access absorption spectra, thermal half-lives, and storage energies which were calculated to be 143-153 kJ mol(-1) (0.47-0.51 MJ kg(-1)), up to 76% higher than for the corresponding norbornadiene. The combined computational and experimental findings provide a reliable way of designing future BOD/TCO systems with tailored properties.

Author

Maria Quant

Chalmers, Chemistry and Chemical Engineering, Applied Chemistry

Andreas Erbs Hillers-Bendtsen

University of Copenhagen

Shima Ghasemi

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

Mate Erdelyi

Uppsala University

Zhihang Wang

Chalmers, Chemistry and Chemical Engineering, Applied Chemistry

Lidiya Musherefa Muhammad

Chalmers, Chemistry and Chemical Engineering, Applied Chemistry

Nina Kann

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

Kurt V. Mikkelsen

University of Copenhagen

Kasper Moth-Poulsen

Institute of Material Science of Barcelona (ICMAB)

Chalmers, Chemistry and Chemical Engineering, Applied Chemistry

Catalan Institution for Research and Advanced Studies

Chemical Science

2041-6520 (ISSN) 2041-6539 (eISSN)

Vol. 13 3 834-841

Driving Forces

Sustainable development

Subject Categories

Energy Engineering

Theoretical Chemistry

Organic Chemistry

Areas of Advance

Energy

DOI

10.1039/d1sc05791j

More information

Latest update

3/23/2022