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Electrocatalytic Energy Release of Norbornadiene‐Based Molecular Solar Thermal Systems: Tuning the Electrochemical Stability by Molecular Design
Author(s) -
Franz Evanie,
Krappmann Daniel,
Fromm Lukas,
Luchs Tobias,
Görling Andreas,
Hirsch Andreas,
Brummel Olaf,
Libuda Jörg
Publication year - 2022
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.202201483
Subject(s) - norbornadiene , quadricyclane , chemistry , cyclic voltammetry , electrochemistry , energy transformation , thermal decomposition , electrochemical energy conversion , energy conversion efficiency , thermal stability , molecule , electrode , materials science , photochemistry , chemical engineering , organic chemistry , thermodynamics , optoelectronics , physics , catalysis , engineering
Molecular solar thermal (MOST) systems, such as the norbornadiene/quadricyclane (NBD/QC) couple, combine solar energy conversion, storage, and release in a simple one‐photon one‐molecule process. Triggering the energy release electrochemically enables high control of the process, high selectivity, and reversibility. In this work, the influence of the molecular design of the MOST couple on the electrochemically triggered back‐conversion reaction was addressed for the first time. The MOST systems phenyl‐ethyl ester‐NBD/QC (NBD1/QC1) and p ‐methoxyphenyl‐ethyl ester‐NBD/QC (NBD2/QC2) were investigated by in‐situ photoelectrochemical infrared spectroscopy, voltammetry, and density functional theory modelling. For QC1, partial decomposition (40 %) was observed upon back‐conversion and along with a voltammetric peak at 0.6 V fc , which was assigned primarily to decomposition. The back‐conversion of QC2, however, occurred without detectable side products, and the corresponding peak at 0.45 V fc was weaker by a factor of 10. It was concluded that the electrochemical stability of a NBD/QC couple is easy tunable by simple structural changes. Furthermore, the charge input and, therefore, the current for the electrochemically triggered energy release is very low, which ensures a high overall efficiency of the MOST system.