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- Elholm, Jacob Lynge, et al.
(författare)
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High throughput screening of norbornadiene/quadricyclane derivates for molecular solar thermal energy storage
- 2022
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Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9084 .- 1463-9076. ; 24:47, s. 28956-28964
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Tidskriftsartikel (refereegranskat)abstract
- We present a procedure for performing high throughput screening of molecular compounds for molecular solar thermal energy storage devices using extended tight binding (xTB) methods. In order to validate our approach, we performed screening of 3230 norbornadiene/quadricyclane (NBD/QC) derivatives in terms of storage energies, activation barriers and absorption of solar radiation using our approach, and compared it to high level density functional theory (DFT) and cluster perturbation (CP) theory calculations. Our comparisons show that the xTB screening framework correlates very well with DFT and CP theory in that it predicts the same relative trends in the studied parameters although the storage energies and thermal reaction barriers are significantly offset. Utilizing the screening methodology, we have been able to locate compounds that would either be excellent candidates or compounds that should not be considered further for molecular solar thermal energy storage devices. This methodology can readily be extended and applied to screening other molecular motifs for molecular solar energy storage.
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| 2. |
- Quant, Maria, 1985, et al.
(författare)
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Synthesis, characterization and computational evaluation of bicyclooctadienes towards molecular solar thermal energy storage
- 2022
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Ingår i: Chemical Science. - : Royal Society of Chemistry (RSC). - 2041-6539 .- 2041-6520. ; 13:3, s. 834-841
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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