Triggering the energy release in molecular solar thermal systems: Norbornadiene-functionalized trioxatriangulen on Au(111)

Eschenbacher, Roman; Xu, Tian-Bing; Franz, Evanie; Löw, Roland; Moje, Tobias; Fromm, Lukas; Görling, Andreas; Brummel, Olaf; Herges, Rainer; Libuda, Jörg

doi:10.1016/j.nanoen.2022.107007

Cited by 14 publications

(33 citation statements)

References 57 publications

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“…Note that the metastable QC′ in the absence of a catalyst has a half-life time of 29 days and is reductively stable down to 2.0 V fc (see Chapter 9 in the Supporting Information), and the oxidative reaction channel triggered electrochemically occurs at much higher potentials (>0.0 V fc ). , Therefore, the experiment clearly demonstrates that the Au surface is highly active for the catalytically triggered back-conversion of QC′ to NBD′. In a recent study, we showed that the catalytic back-conversion requires direct electronic contact with Au . This observation is compatible with the singlet–triplet mechanism proposed previously by Herges, Tuczek, Magnussen, and coworkers, which differs significantly from the radical chain mechanism in the electrocatalytic reaction channel …”

Section: Resultsmentioning

confidence: 62%

“…Fascinatingly, it has also been demonstrated that gold has a remarkable influence on the photochemical properties of molecular switches. , Recently, Herges and coworkers showed that Au triggers the back-conversion in azobenzene photoswitches and proposed a singlet–triplet–singlet spin-change mechanism . In a very recent surface science study, we were able to demonstrate that Au also catalyzes the energy release from tailor-made NBD derivatives, directly linked to the Au surface. , …”

Section: Introductionmentioning

confidence: 63%

“…This surprising finding opens a completely new and quite easy-to-implement pathway for controlling the energy release rate from the catalytic MOST reactor. We propose that the effect originates from the electronic contact of the QC′ with the Au catalyst, which changes as a function of the potential applied, for example, due to potential-dependent adsorption of ions (i.e., blocking of active sites), potential-dependent orientation of the reactants, or potential-dependent changes in the electronic structure.…”

Section: Resultsmentioning

confidence: 99%

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Tunable Energy Release in a Reversible Molecular Solar Thermal System

et al. 2022

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Molecular solar thermal (MOST) systems open application fields for solar energy conversion as they combine conversion, storage, and release in one single molecule. For energy release, catalysts must be controllable, selective, and stable over many operation cycles. Here, we present a MOST/catalyst couple, which combines all these properties. We explore solar energy storage in a tailor-made MOST system (cyano-3-(3,4-dimethoxyphenyl)-norbornadiene/quadricyclane; NBD′/QC′) and the energy release heterogeneously catalyzed at a Au(111) surface. By photoelectrochemical infrared reflection absorption spectroscopy (PEC-IRRAS) and scanning tunneling microscopy, we show that Au triggers the energy release with very high activity. Most remarkably, the release rate of the heterogeneously catalyzed process can be tuned by applying an external potential. Our durability tests show that the MOST/catalyst system is stable over 1000 storage cycles without any decomposition. The surface structure of the catalyst is preserved, and its activity decreases by only 0.1% per storage cycle.

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Section: Resultsmentioning

confidence: 62%

Section: Introductionmentioning

confidence: 63%

Section: Resultsmentioning

confidence: 99%

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Tunable Energy Release in a Reversible Molecular Solar Thermal System

et al. 2022

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“…There are different ways to overcome these drawbacks, for example, molecular design [24,25] or choosing an appropriate trigger to release the energy. Commonly used triggers are metal complex catalysts, [26–31] copper(II) or tin(II) salts, [32] or heterogeneous catalysts [33–36] …”

Section: Introductionmentioning

confidence: 99%

“…Commonly used triggers are metal complex catalysts, [26][27][28][29][30][31] copper(II) or tin(II) salts, [32] or heterogeneous catalysts. [33][34][35][36] A particular intriguing concept is to initiate the heat release electrochemically. [7,[37][38][39][40][41] For the NBD/QC system, the electrochemically triggered back-conversion occurs via a hole-catalyzed (oxidative) reaction pathway.…”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic Energy Release of Norbornadiene‐Based Molecular Solar Thermal Systems: Tuning the Electrochemical Stability by Molecular Design

et al. 2022

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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 Vfc, which was assigned primarily to decomposition. The back‐conversion of QC2, however, occurred without detectable side products, and the corresponding peak at 0.45 Vfc 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.

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Unveiling the Potential of Heterogeneous Catalysts for Molecular Solar Thermal Systems

Gimenez‐Gomez,

Rollins,

Steele

et al. 2023

Chemistry A European J

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Solar energy utilization has gained considerable attention due to its abundance and renewability. However, its intermittent nature presents a challenge in harnessing its full potential. The development of energy storing compounds capable of capturing and releasing solar energy on demand has emerged as a potential solution. These compounds undergo a photochemical transformation that results in a high‐energy metastable photoisomer, which stores solar energy in the form of chemical bonds and can release it as heat when required. Such systems are referred to as MOlecular Solar Thermal (MOST)‐systems. Although the photoisomerization of MOST systems has been vastly studied, its back‐conversion, particularly using heterogeneous catalysts, is still underexplored and the development of effective catalysts for releasing stored energy is crucial. Herein we compare the performance of 27 heterogeneous catalysts releasing the stored energy in an efficient Norbornadiene/Quadricyclane (NBD/QC) MOST system. We report the first benchmarking of heterogeneous catalysts for a MOST system using a robust comparison method of the catalysts’ activity and monitoring the conversion using UV‐Visible (UV‐Vis) spectroscopy. Our findings provide insights into the development of effective catalysts for MOST systems. We anticipate that our assay will reveal the necessity of further investigation on heterogeneous catalysis.

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Triggering the energy release in molecular solar thermal systems: Norbornadiene-functionalized trioxatriangulen on Au(111)

Cited by 14 publications

References 57 publications

Tunable Energy Release in a Reversible Molecular Solar Thermal System

Tunable Energy Release in a Reversible Molecular Solar Thermal System

Electrocatalytic Energy Release of Norbornadiene‐Based Molecular Solar Thermal Systems: Tuning the Electrochemical Stability by Molecular Design

Unveiling the Potential of Heterogeneous Catalysts for Molecular Solar Thermal Systems

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