Development of renewable energy technologies has been a significant area of research amongst scientists with the aim of attaining a sustainable world society Solar thermal fuels that can capture, convert, store, and release solar energy in the form of heat through reversible photoisomerization of molecular photoswitches such as azobenzene derivatives are currently in the limelight of research Herein, we provide a state-of-the-art account on the recent advancements in solar thermal fuels based on azobenzene photoswitches We begin with an overview on the importance of azobenzene-based solar thermal fuels and their fundamentals Then, we highlight the recent advances in diverse azobenzene materials for solar thermal fuels such as pure azobenzene derivatives, nanocarbon-templated azobenzene, and polymer-templated azobenzene The basic design concepts of these advanced solar energy storage materials are discussed, and their promising applications are highlighted We then introduce the recent endeavors in the molecular design of azobenzene derivatives toward efficient solar thermal fuels, and conclude with new perspectives on the future scope, opportunities and challenges It is expected that continuous pioneering research involving scientists and engineers from diverse technological backgrounds could trigger the rapid advancement of this important interdisciplinary field, which embraces chemistry, physics, engineering, nanoscience, nanotechnology, materials science, polymer science, etc

Azobenzene-based solar thermal fuels: design, properties, and applications

Large-scale utilization of solar-energy resources will require considerable advances in energy-storage technologies to meet ever-increasing global energy demands. Other than liquid fuels, existing energy-storage materials do not provide the requisite combination of high energy density, high stability, easy handling, transportability and low cost. New hybrid solar thermal fuels, composed of photoswitchable molecules on rigid, low-mass nanostructures, transcend the physical limitations of molecular solar thermal fuels by introducing local sterically constrained environments in which interactions between chromophores can be tuned. We demonstrate this principle of a hybrid solar thermal fuel using azobenzene-functionalized carbon nanotubes. We show that, on composite bundling, the amount of energy stored per azobenzene more than doubles from 58 to 120 kJ mol(-1), and the material also maintains robust cyclability and stability. Our results demonstrate that solar thermal fuels composed of molecule-nanostructure hybrids can exhibit significantly enhanced energy-storage capabilities through the generation of template-enforced steric strain.

Templated assembly of photoswitches significantly increases the energy-storage capacity of solar thermal fuels

This review analyzes the inherent scientific challenges of realizing the potential of storing solar energy by photochemical generation of high-energy metastable compounds whose subsequent thermal isomerization releases large amounts of low-temperature (<500 K) heat. Such compounds may be stored at room temperature for days or months, regenerated using sunlight, and may be cycled many times without significant degradation. After highlighting some of the general challenges of solar energy conversion and storage, we discuss how recent advances in understanding the effect of molecular strain on the thermal and photochemical reactivity of small molecules offers new opportunities for a systematic approach to the molecular design of solar thermal fuels, defining the molecular properties which determine the fundamental limits of such a material's performance characteristics.

Chemical solutions for the closed-cycle storage of solar energy

Review on synthesis and properties of high-energy-density liquid fuels: Hydrocarbons, nanofluids and energetic ionic liquids

http://publications.lib.chalmers.se/records/fulltext/214130/local_214130.pdf

Designing photoswitches for molecular solar thermal energy storage

The results of studies on intramolecular interconversions in systems of norbornadiene quadricyclane and their derivatives are classified and discussed. The mechanisms of the forward photoreaction and reverse thermal process in relation to the nature of the substituents and carbocycles, type of sensitiser and catalyst, and properties of the medium are discussed in detail and classified. An analysis is made of the influence of these factors on the spectroscopic, kinetic, and thermodynamic properties of this system as an accumulator and converter of light energy. Methods of improving its characteristics — light absorption, the quantum yield of the photoreaction, and stability of the photoproduct — have been established. The bibliography includes 188 references.

https://iopscience.iop.org/article/10.1070/RC1991v060n05ABEH001088/pdf

Norbornadiene-quadricyclane — an effective molecular system for the storage of solar energy

Data on the valence isomerisation of norbornadiene and its derivatives into the corresponding quadricyclanes published between 1990 and 2001 are considered and described systematically. The applicability of this reaction for the storage of solar energy is discussed. The bibliography includes 112 references.

Norbornadiene–quadricyclane as an abiotic system for the storage of solar energy

A series of novel 3-phenyhorbornadienes with conjugated substituents in 2- position (carbaldimine, carbaldoxime, amide, aroylvinyl and heterocyclic groups) have been synthesized. All the compounds obtained absorb in the 310-420 nm spectral region and under UV-Vis-irradiation form corresponding quadricyclanes with quantum yields in the range of 0.1-0.7. The back reaction proceeds almost quantitative yield under homogeneous and heterogeneous catalysis or on heating.

Photoinitiated Rearrangements of 3-Phenylnorbornadiene with conjugated Substituents in 2-Position

Novel biphotochromic systems containing two norbornadiene moieties in one molecule or one norbornadienyl group in 2-N-(3-phenylnorbornadiene-2-carbonyl)]-N-arylaminomethylene-(2H) benzo[b]thiophenones have been prepared Under UV/VIS irradiation the latter compounds undergo Z/E-isomerktion acompanied by N → O acyl rearrangement and valence isomerization in the norbornadiene fragment Bis-norbornadienyl derivatives upon irradiation convert through stepwise isomerization into corresponding quadricyclanes The back reactions are catalyzed with trifluoroacetic acid at room temperature

Biphotochromic norbornadiene systems

3-(4-Nitrophenyl)bicyclo[2.2.1]hepta-2,5-diene-2-carbaldehyde and its derivatives at the formyl group were synthesized. By reduction of the nitro group the corresponding 3-(4-aminophenyl)-substituted compounds were obtained, as well as 4,4'-bis(bicyclo[2.2.1]hepta-2,5-dien-2-yl)azobenzenes. Irradiation of the resulting norbornadiene derivatives in the region of their absorption maxima resulted in valence isomerization with formation of the corresponding quadricyclanes. The reverse transformations are promoted by molybdenum(VI) oxide as heterogeneous catalyst. 4,4'-Bis(bicyclo[2.2.1]hepta-2,5-dien-2-yl)azobenzenes undergo reversible (on heating) photochemical EZ/ isomerization at the NIN bond.

Synthesis and Photoinitiated Isomerizations of 3-(4-Nitrophenyl)-and 3-(4-Aminophenyl)bicyclo[2.2.1]hepta-2,5-diene-2-carbaldehyde and -2-carboxylic acid Derivatives

V. A. Chernoivanov

Papers

Norbornadiene-quadricyclane — an effective molecular system for the storage of solar energy

Norbornadiene–quadricyclane as an abiotic system for the storage of solar energy

Photoinitiated Rearrangements of 3-Phenylnorbornadiene with conjugated Substituents in 2-Position

Biphotochromic norbornadiene systems

Synthesis and Photoinitiated Isomerizations of 3-(4-Nitrophenyl)-and 3-(4-Aminophenyl)bicyclo[2.2.1]hepta-2,5-diene-2-carbaldehyde and -2-carboxylic acid Derivatives