Molecular solar thermal energy storage in photoswitch oligomers increases energy densities and storage times.
ABSTRACT: Molecular photoswitches can be used for solar thermal energy storage by photoisomerization into high-energy, meta-stable isomers; we present a molecular design strategy leading to photoswitches with high energy densities and long storage times. High measured energy densities of up to 559?kJ?kg-1 (155?Wh?kg-1), long storage lifetimes up to 48.5 days, and high quantum yields of conversion of up to 94% per subunit are demonstrated in norbornadiene/quadricyclane (NBD/QC) photo-/thermoswitch couples incorporated into dimeric and trimeric structures. By changing the linker unit between the NBD units, we can at the same time fine-tune light-harvesting and energy densities of the dimers and trimers so that they exceed those of their monomeric analogs. These new oligomers thereby meet several of the criteria to be met for an optimum molecule to ultimately enter actual devices being able to undergo closed cycles of solar light-harvesting, energy storage, and heat release.
Project description:Devices that can capture and convert sunlight into stored chemical energy are attractive candidates for future energy technologies. A general challenge is to combine efficient solar energy capture with high energy densities and energy storage time into a processable composite for device application. Here, norbornadiene (NBD)-quadricyclane (QC) molecular photoswitches are embedded into polymer matrices, with possible applications in energy storing coatings. The NBD-QC photoswitches that are capable of absorbing sunlight with estimated solar energy storage efficiencies of up to 3.8% combined with attractive energy storage densities of up to 0.48 MJ kg<sup>-1</sup>. The combination of donor and acceptor units leads to an improved solar spectrum match with an onset of absorption of up to 529 nm and a lifetime (<i>t</i> <sub>1/2</sub>) of up to 10 months. The NBD-QC systems with properties matched to a daily energy storage cycle are further investigated in the solid state by embedding the molecules into a series of polymer matrices revealing that polystyrene is the preferred choice of matrix. These polymer devices, which can absorb sunlight and over a daily cycle release the energy as heat, are investigated for their cyclability, showing multicycle reusability with limited degradation that might allow them to be applied as window laminates.
Project description:Molecular photoswitches based on the norbornadiene-quadricylane (NBD-QC) couple have been proposed as key elements of molecular solar thermal energy storage schemes. To characterize the intrinsic properties of such systems, reversible isomerization of a charge-tagged NBD-QC carboxylate couple is investigated in a tandem ion mobility mass spectrometer, using light to induce intramolecular [2 + 2] cycloaddition of NBD carboxylate to form the QC carboxylate and driving the back reaction with molecular collisions. The NBD carboxylate photoisomerization action spectrum recorded by monitoring the QC carboxylate photoisomer extends from 290 to 360 nm with a maximum at 315 nm, and in the longer wavelength region resembles the NBD carboxylate absorption spectrum recorded in solution. Key structural and photochemical properties of the NBD-QC carboxylate system, including the gas-phase absorption spectrum and the energy storage capacity, are determined through computational studies using density functional theory.
Project description:Molecular photoswitches provide an extremely simple solution for solar energy conversion and storage. To convert stored energy to electricity, however, the photoswitch has to be coupled to a semiconducting electrode. In this work, we report on the assembly of an operational solar-energy-storing organic-oxide hybrid interface, which consists of a tailor-made molecular photoswitch and an atomically-defined semiconducting oxide film. The synthesized norbornadiene derivative 2-cyano-3-(4-carboxyphenyl)norbornadiene (CNBD) was anchored to a well-ordered Co<sub>3</sub>O<sub>4</sub>(111) surface by physical vapor deposition in ultrahigh vacuum. Using a photochemical infrared reflection absorption spectroscopy experiment, we demonstrate that the anchored CNBD monolayer remains operational, i.e., can be photo-converted to its energy-rich counterpart 2-cyano-3-(4-carboxyphenyl)quadricyclane (CQC). We show that the activation barrier for energy release remains unaffected by the anchoring reaction and the anchored photoswitch can be charged and discharged with high reversibility. Our atomically-defined solar-energy-storing model interface enables detailed studies of energy conversion processes at organic/oxide hybrid interfaces.
Project description:Current energy demand makes it compulsory to explore alternative energy sources beyond fossil fuels. Molecular solar thermal (MOST) systems have been proposed as a suitable technology for the use and storage of solar energy. Compounds used for this application need to fulfil a long series of requirements, being the absorption of sunlight and the energy stored some of the most critical. In this paper, we study different families of well-known molecular photoswitches from the point of view of their potential use as MOST. Starting from basic structures, we use density functional theory (DFT) computational modelling to propose two different strategies to increase the energy difference between isomers and to tune the absorption spectrum. The inclusion of a mechanical lock in the structure, via an alkyl chain and the presence of a hydrogen bonding are shown to directly influence the energy difference and the absorption spectra. Results shown here prove that these two approaches could be relevant for the design of new compounds with improved performance for MOST applications.
Project description:Molecular solar-thermal energy storage systems are based on molecular switches that reversibly convert solar energy into chemical energy. Herein, we report the synthesis, characterization, and computational evaluation of a series of low molecular weight (193-260?g?mol(-1) ) norbornadiene-quadricyclane systems. The molecules feature cyano acceptor and ethynyl-substituted aromatic donor groups, leading to a good match with solar irradiation, quantitative photo-thermal conversion between the norbornadiene and quadricyclane, as well as high energy storage densities (396-629?kJ?kg(-1) ). The spectroscopic properties and energy storage capability have been further evaluated through density functional theory calculations, which indicate that the ethynyl moiety plays a critical role in obtaining the high oscillator strengths seen for these molecules.
Project description:Photoswitchable molecules-based solar thermal energy storage system (MOST) can potentially be a route to store solar energy for future use. Herein, the use of a multijunction MOST device that combines various photoswitches with different onsets of absorption to push the efficiency limit on solar energy collection and storage is explored. With a parametric model calculation, it is shown that the efficiency limit of MOST concept can be improved from 13.0% to 18.2% with a double-junction system and to 20.5% with a triple-junction system containing ideal, red-shifted MOST candidates. As a proof-of-concept, the use of a three-layered MOST device is experimentally demonstrated. The device uses different photoswitches including a norbornadiene derivative, a dihydroazulene derivative, and an azobenzene derivative in liquid state with different MOSTproperties, to increase the energy capture and storage behavior. This conceptional device introduces a new way of thinking and designing optimal molecular candidates for MOST, as much improvement can be made by tailoring molecules to efficiently store solar energy at specific wavelengths.
Project description:A major drawback of traditional photocatalysts like TiO2 is that they can only work under illumination, and the light has to be UV. As a solution for this limitation, visible-light-driven energy storage photocatalysts have been developed in recent years. However, energy storage photocatalysts that are full-sunlight-driven (UV-visible-NIR) and possess long-lasting energy storage ability are lacking. Here we report, a Pt-loaded and hydrogen-treated WO3 that exhibits a strong absorption at full-sunlight spectrum (300-1,000 nm), and with a super-long energy storage time of more than 300 h to have formaldehyde degraded in dark. In this new material system, the hydrogen treated WO3 functions as the light harvesting material and energy storage material simultaneously, while Pt mainly acts as the cocatalyst to have the energy storage effect displayed. The extraordinary full-spectrum absorption effect and long persistent energy storage ability make the material a potential solar-energy storage and an effective photocatalyst in practice.
Project description:Simultaneously harvesting, converting and storing solar energy in a single device represents an ideal technological approach for the next generation of power sources. Herein, we propose a device consisting of an integrated carbon-based perovskite solar cell module capable of harvesting solar energy (and converting it into electricity) and a rechargeable aqueous zinc metal cell. The electrochemical energy storage cell utilizes heterostructural Co<sub>2</sub>P-CoP-NiCoO<sub>2</sub> nanometric arrays and zinc metal as the cathode and anode, respectively, and shows a capacity retention of approximately 78% after 25000 cycles at 32 A/g. In particular, the battery cathode and perovskite material of the solar cell are combined in a sandwich joint electrode unit. As a result, the device delivers a specific power of 54 kW/kg and specific energy of 366 Wh/kg at 32 A/g and 2 A/g, respectively. Moreover, benefiting from its narrow voltage range (1.40-1.90 V), the device demonstrates an efficiency of approximately 6%, which is stable for 200 photocharge and discharge cycles.
Project description:Ultrathin transition metal carbides with high capacity, high surface area, and high conductivity are a promising family of materials for applications from energy storage to catalysis. However, large-scale, cost-effective, and precursor-free methods to prepare ultrathin carbides are lacking. Here, we demonstrate a direct pattern method to manufacture ultrathin carbides (MoC<sub>x</sub>, WC<sub>x</sub>, and CoC<sub>x</sub>) on versatile substrates using a CO<sub>2</sub> laser. The laser-sculptured polycrystalline carbides (macroporous, ~10-20?nm wall thickness, ~10?nm crystallinity) show high energy storage capability, hierarchical porous structure, and higher thermal resilience than MXenes and other laser-ablated carbon materials. A flexible supercapacitor made of MoC<sub>x</sub> demonstrates a wide temperature range (-50 to 300?°C). Furthermore, the sculptured microstructures endow the carbide network with enhanced visible light absorption, providing high solar energy harvesting efficiency (~72 %) for steam generation. The laser-based, scalable, resilient, and low-cost manufacturing process presents an approach for construction of carbides and their subsequent applications.
Project description:Efficient solar energy storage is a key challenge in striving toward a sustainable future. For this reason, molecules capable of solar energy storage and release through valence isomerization, for so-called molecular solar thermal energy storage (MOST), have been investigated. Energy storage by photoconversion of the dihydroazulene/vinylheptafulvene (DHA/VHF) photothermal couple has been evaluated. The robust nature of this system is determined through multiple energy storage and release cycles at elevated temperatures in three different solvents. In a nonpolar solvent such as toluene, the DHA/VHF system can be cycled more than 70?times with less than 0.01?% degradation per cycle. Moreover, the [Cu(CH<sub>3</sub> CN)<sub>4</sub> ]PF<sub>6</sub> -catalyzed conversion of VHF into DHA was demonstrated in a flow reactor. The performance of the DHA/VHF couple was also evaluated in prototype photoconversion devices, both in the laboratory by using a flow chip under simulated sunlight and under outdoor conditions by using a parabolic mirror. Device experiments demonstrated a solar energy storage efficiency of up to 0.13?% in the chip device and up to 0.02?% in the parabolic collector. Avenues for future improvements and optimization of the system are also discussed.