Chemical solutions for the closed-cycle storage of solar energy

Kucharski, Timothy J.; Tian, Yancong; Akbulatov, Sergey; Boulatov, Roman

doi:10.1039/c1ee01861b

Cited by 264 publications

(262 citation statements)

References 124 publications

(147 reference statements)

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“…Ideally both the photisomerization and heat release reactions reversibly occur in a closed-cycle without changing the chemical composition. 5 The clear advantage of such an approach is that the same material both converts and stores the sun's energy, providing a rechargeable fuel that can be safely transported and used ondemand; the materials used could, in principle, be cheap, nontoxic and abundant, and the cycle can be repeated thousands of times without any emission or waste.…”

Section: Section: Energy Conversion and Storage; Energy And Charge Trmentioning

confidence: 99%

Photoswitchable Molecular Rings for Solar-Thermal Energy Storage

Durgun

Grossman

2013

J. Phys. Chem. Lett.

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Solar-thermal fuels reversibly store solar energy in the chemical bonds of molecules by photoconversion, and can release this stored energy in the form of heat upon activation. Many conventional photoswichable molecules could be considered as solar thermal fuels, although they suffer from low energy density or short lifetime in the photoinduced high-energy metastable state, rendering their practical use unfeasible. We present a new approach to the design of chemistries for solar thermal fuel applications, wherein well-known photoswitchable molecules are connected by different linker agents to form molecular rings. This approach allows for a significant increase in both the amount of stored energy per molecule and the stability of the fuels. Our results suggest a range of possibilities for tuning the energy density and thermal stability as a function of the type of the photoswitchable molecule, the ring size, or the type of linkers. SECTION:Energy Conversion and Storage; Energy and Charge Transport E fficient utilization of the sun as a renewable and clean energy source is one of the greatest goals and challenges of this century due to the increasing demand for energy and its environmental impact. Numerous strategies exist to convert sunlight into useful forms of energy, including photocatalytic processes, artificial photosynthesis, 1,2 photothermal power plants, 3 and photovoltaic applications. 4 An alternative strategy to these is to convert and store the sun's energy directly in the chemical bonds of metastable photoisomers of suitable molecular systems. The stored energy can then be released as heat on demand by an external trigger. Ideally both the photisomerization and heat release reactions reversibly occur in a closed-cycle without changing the chemical composition. 5The clear advantage of such an approach is that the same material both converts and stores the sun's energy, providing a rechargeable fuel that can be safely transported and used ondemand; the materials used could, in principle, be cheap, nontoxic and abundant, and the cycle can be repeated thousands of times without any emission or waste.The idea of storing solar energy in chemical bonds was first introduced with the photoisomerization reactions of organic molecules (such as norbornadiene⇌quadricyclane 6,7 and the trans⇌cis isomers of azobenzene 8 ), although the concept was generally dismissed as unpractical 7 due to a number of reasons including degradation, instability of the photoinduced isomer (limited half-life or shelf life), low energy density, and cost. As such, the majority of recent experimental studies for such materials have focused on their photoswitchable properties, 9 as opposed to energy storage. The Ru-based organometallic complex (tetracarbonyl−diruthenium fulvalene) 10 has shown promise as a solar thermal fuel due to its high cyclability without degradation; however, substitutions for Ru must be found to reduce costs, and the volumetric energy density increased for practical applications. 11,12 Recently, a new s...

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Section: Section: Energy Conversion and Storage; Energy And Charge Trmentioning

confidence: 99%

Photoswitchable Molecular Rings for Solar-Thermal Energy Storage

Durgun

Grossman

2013

J. Phys. Chem. Lett.

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“…Such force-dependent reactivity is thought to account for the behaviour of polymeric materials, melts and solutions under load, may be exploited to yield new stress-responsive, actuating and energy transducing materials [1][2][3][4][5][6][7][8][9][10] and may even allow characterization of transition states. 11 Considerable theoretical, 3,[12][13][14][15][16][17][18][19] computational 13,[20][21][22][23][24][25][26] and experimental [27][28][29][30][31][32][33][34] effort has been devoted to refine and validate a model of forcedependent kinetics for elementary (single-barrier) reactions.…”

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confidence: 99%

Model studies of force-dependent kinetics of multi-barrier reactions

et al. 2013

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According to transition state theory, the rate of a reaction that traverses multiple energy barriers is determined by the least stable (rate-determining) transition state. The preceding ('inner') energy barriers are kinetically 'invisible' but mechanistically significant. Here we show experimentally and computationally that the reduction rate of organic disulphides by phosphines in water, which in the absence of force proceeds by an equilibrium formation of a thiophosphonium intermediate, measured as a function of force applied on the disulphide moiety yields a usefully accurate estimate of the height of the inner barrier. We apply varying stretching force to the disulphide by incorporating it into a series of increasingly strained macrocycles. This force accelerates the reduction, even though the strain-free rate-determining step is orthogonal to the pulling direction. The observed rate-force correlation is consistent with the simplest model of force-dependent kinetics of a multibarrier reaction.

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“…4 Thus, a molecule which upon excitation isomerizes to a more energetic metastable isomer, which in time will return to the more stable isomer by releasing energy as heat, may find use in lightharvesting energy storage devices. 3 In this context, the dihydroazulene/vinylheptafulvene (DHA/VHF) system 1/2 (Scheme 1), reported for the first time by Daub and co-workers in 1984, 5,6 is particularly interesting. DHA 1 is a yellow photochromic compound, which undergoes a light-induced 10-electron retro-electrocyclization to the red VHF 2.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3] Photo-and thermo-activated molecular switches are a family of compounds able to switch from one molecular structure to another upon light irradiation or changes in temperature, and whose characteristics depend on the nature of the functional groups that reside on the molecules. 4 Thus, a molecule which upon excitation isomerizes to a more energetic metastable isomer, which in time will return to the more stable isomer by releasing energy as heat, may find use in lightharvesting energy storage devices.…”

Section: Introductionmentioning

confidence: 99%

Synthetic protocols for the key functionalizations of the photochromic dihydroazulene scaffold

Cacciarini¹,

Broman²,

Nielsen³

2014

Arkivoc

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1,8a-Dihydroazulene-1,1-dicarbonitrile (DHA) is a photochromic molecule which upon irradiation undergoes ring-opening to a vinylheptafulvene (VHF). The system has many possible sites for functionalization and hence for tuning of its properties. In this account we summarize different synthetic protocols for attaching substituents at the ring carbon atoms of DHA as well as for replacing the cyano groups at position 1. In particular, positions 2 and 7 are most easily accessed, the latter from DHA by a regioselective bromination-elimination protocol.

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Chemical solutions for the closed-cycle storage of solar energy

Cited by 264 publications

References 124 publications

Photoswitchable Molecular Rings for Solar-Thermal Energy Storage

Photoswitchable Molecular Rings for Solar-Thermal Energy Storage

Model studies of force-dependent kinetics of multi-barrier reactions

Synthetic protocols for the key functionalizations of the photochromic dihydroazulene scaffold

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