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Buckyballs on DNA for harvesting light

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Buckyballs on DNA for harvesting light

Organic molecules that capture photons and convert these into electricity have important applications for producing green energy. Light-harvesting complexes need two semiconductors, an electron donor and an acceptor. How well they work is measured by their quantum efficiency, the rate by which photons are converted into electron-hole pairs.

Quantum efficiency is lower than optimal if there is “self-quenching”, where one molecule excited by an incoming photon donates some of its energy to an identical non-excited molecule, yielding two molecules at an intermediate energy state too low to produce an electron-hole pair. But if electron donors and acceptors are better spaced out, self-quenching is limited, so that quantum efficiency improves.

In a new paper in Frontiers in Chemistry, researchers from the Karlsruhe Institute of Technology (KIT) synthesize a novel type of organic light-harvesting supramolecule based on DNA. The double helix of DNA acts as a scaffold to arrange chromophores (i.e. fluorescent dyes) – which function as electron donors – and “buckyballs” – electron acceptors – in three dimensions to avoid self-quenching.

“DNA is an attractive scaffold for building light-harvesting supramolecules: its helical structure, fixed distances between nucleobases, and canonical base pairing precisely control the position of the chromophores. Here we show that carbon buckyballs, bound to modified nucleosides inserted into the DNA helix, greatly enhance the quantum efficiency. We also show that the supramolecule’s 3D structure persists not only in the liquid phase but also in the solid phase, for example in future organic solar cells,” says lead author Dr Hans-Achim Wagenknecht, Professor for Organic Chemistry at Karlsruhe Institute of Technology (KIT).

DNA provides regular structure, like beads on a helical string

As scaffold, Wagenknecht and colleagues used single-stranded DNA, deoxyadenosine (A) and thymine (T) strands 20 nucleotides long. This length was chosen because theory suggests that shorter DNA oligonucleotides wouldn’t assemble orderly, while longer ones wouldn’t be soluble in water.

The chromophores were violet-fluorescent pyrene and red-fluorescent Nile red molecules, each bound noncovalently to a single synthetic uracil (U)-deoxyribose nucleoside. Each nucleoside was base-paired to the DNA scaffold, but the order of pyrenes and Nile reds was left to chance during self-assembly.

For the electron acceptors, Wagenknecht et al. tested two forms of “buckyballs” – also called fullerenes – which are known to have an excellent capacity for “quenching” (accepting electrons). Each buckyball was a hollow globe built from interlocking rings of five or six carbon atoms, for a total of 60 carbons per molecule. The first form of buckyball tested binds nonspecifically to the DNA through electrostatic charges.

The second form – not previously tested as an electron acceptor – was covalently bound via a malonic ester to two flanking U-deoxyribose nucleosides, which allowed it to be base-paired to an A nucleotide on the DNA.

High quantum efficiency, including in solid phase

The researchers confirmed experimentally that the 3D structure of the DNA-based supramolecule persists in solid phase: a crucial requirement for applications in solar cells. To this end, they tested supramolecules with either form of buckyballs as the active layer in a miniature solar cell.

The constructs showed excellent charge separation – the formation of a positive hole and negative electron charge in the chromophore and their acceptance by nearby buckyballs – with either form of buckyball, but especially for the second form.

The authors explain this from the more specific binding, through canonical base-pairing, to the DNA scaffold by the second form, which should result in a smaller distance between buckyball and chromophore. This means that the second form is the better schoice for use in solar cells.

Importantly, the authors also show that the DNA-dye-buckyball supramolecule has strong circular dichroism, that is, it is much more reactive to left- than to right-handed polarized light, due to its complex 3D helical structure – even in the solid phase.

“”I don’t expect that everyone will have solar cells with DNA on their roof soon. But the chirality of DNA will be interesting: DNA-based solar cells might sense circularly polarized light in specialized applications,” concludes Wagenknecht.

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Breakthrough new material brings affordable, sustainable future within grasp

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Breakthrough new material brings affordable, sustainable future within grasp


Breakthrough new material brings affordable, sustainable future within grasp

by Rashda Khan for Canepa News

Houston TX (SPX) Dec 23, 2024






While lithium-ion batteries have been the go-to technology for everything from smartphones and laptops to electric cars, there are growing concerns about the future because lithium is relatively scarce, expensive and difficult to source, and may soon be at risk due to geopolitical considerations. Scientists around the world are working to create viable alternatives.

An international team of interdisciplinary researchers, including the Canepa Research Laboratory at the University of Houston, has developed a new type of material for sodium-ion batteries that could make them more efficient and boost their energy performance – paving the way for a more sustainable and affordable energy future.



The new material, sodium vanadium phosphate with the chemical formula NaxV2(PO4)3, improves sodium-ion battery performance by increasing the energy density – the amount of energy stored per kilogram – by more than 15%. With a higher energy density of 458 watt-hours per kilogram (Wh/kg) compared to the 396 Wh/kg in older sodium-ion batteries, this material brings sodium technology closer to competing with lithium-ion batteries.



“Sodium is nearly 50 times cheaper than lithium and can even be harvested from seawater, making it a much more sustainable option for large-scale energy storage,” said Pieremanuele Canepa, Robert Welch assistant professor of electrical and computer engineering at UH and lead researcher of the Canepa Lab. “Sodium-ion batteries could be cheaper and easier to produce, helping reduce reliance on lithium and making battery technology more accessible worldwide.”

From Theory to Reality

The Canepa Lab, which uses theoretical expertise and computational methods to discover new materials and molecules to help advance clean energy technologies, collaborated with the research groups headed by French researchers Christian Masquelier and Laurence Croguennec from the Laboratoire de Rea’ctivite’ et de Chimie des Solides, which is a CNRS laboratory part of the Universite’ de Picardie Jules Verne, in Amiens France, and the Institut de Chimie de la Matie`re Condense’e de Bordeaux, Universite’ de Bordeaux, Bordeaux, France for the experimental work on the project. This allowed theoretical modelling to go through experimental validation.

The researchers created a battery prototype using the new material, NaxV2(PO4)3, demonstrating significant energy storage improvements. NaxV2(PO4)3, part of a group called “Na superionic conductors” or NaSICONs, is designed to let sodium ions move smoothly in and out of the battery during charging and discharging.



Unlike existing materials, it has a unique way of handling sodium, allowing it to work as a single-phase system. This means it remains stable as it releases or takes in sodium ions. This allows the NaSICON to remain stable during charging and discharging while delivering a continuous voltage of 3.7 volts versus sodium metal, higher than the 3.37 volts in existing materials.



While this difference may seem small, it significantly increases the battery’s energy density or how much energy it can store for its weight. The key to its efficiency is vanadium, which can exist in multiple stable states, allowing it to hold and release more energy.



“The continuous voltage change is a key feature,” said Canepa. “It means the battery can perform more efficiently without compromising the electrode stability. That’s a game-changer for sodium-ion technology.”

Possibilities for a Sustainable Future

The implications of this work extend beyond sodium-ion batteries. The synthesis method used to create NaxV2(PO4)3 could be applied to other materials with similar chemistries, opening new possibilities for advanced energy storage technologies. That could in turn, impact everything from more affordable, sustainable batteries to power our devices to help us transition to a cleaner energy economy.



“Our goal is to find clean, sustainable solutions for energy storage,” Canepa said. “This material shows that sodium-ion batteries can meet the high-energy demands of modern technology while being cost-effective and environmentally friendly.”



A paper based on this work was published in the journal Nature Materials. Ziliang Wang, Canepa’s former student and now a postdoctoral fellow at Northwestern University, and Sunkyu Park, a former student of the French researchers and now a staff engineer at Samsung SDI in South Korea, performed much of the work on this project.



Research Report:Obtaining V2(PO4)3 by sodium extraction from single-phase NaxV2(PO4)3 (1 < x < 3) positive electrode materials


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Powering The World in the 21st Century at Energy-Daily.com





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Pioneering advancements in solid-state battery technology for energy storage

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Pioneering advancements in solid-state battery technology for energy storage


Pioneering advancements in solid-state battery technology for energy storage

by Riko Seibo

Tokyo, Japan (SPX) Dec 23, 2024






Recent strides in solid-state battery technology are setting the stage for a transformative era in energy storage. These advancements hold promise for revolutionizing electric vehicles and renewable energy systems through improved performance and safety. A focus on electrolyte innovation has been key to this progress, enabling the development of high-performance all-solid-state batteries (ASSBs).

A new review paper provides a comprehensive summary of advancements in inorganic solid electrolytes (ISEs), materials that are central to ASSBs. Researchers examined the roles of oxides, sulfides, hydroborates, antiperovskites, and halides not only as electrolytes but also as catholytes and interface layers, which collectively enhance battery performance and safety.



“We highlighted the recent breakthroughs in synthesizing these materials, honing our attention on the innovative techniques that enable the precise tuning of their properties to meet the demanding requirements of ASSBs,” said Eric Jianfeng Cheng, associate professor at Tohoku University’s Advanced Institute for Materials Research (AIMR). “Precise tuning is crucial for developing batteries with higher energy densities, longer life cycles, and better safety profiles than conventional liquid-based batteries.”



The review also delves into the electrochemical properties of ISEs, including ionic conductivity, stability, and electrode compatibility. Researchers evaluated current ASSB models and suggested emerging strategies that could drive the next generation of energy storage solutions.



However, challenges persist in the development of ASSBs, notably the limited compatibility between ISEs and electrodes, which can trigger interfacial reactions. Addressing these compatibility issues is vital to improving battery efficiency and longevity. The review outlines these challenges and provides insights into efforts aimed at overcoming them.



“Our comprehensive review underscores the importance of continued research and development in the field of solid-state batteries. By developing new materials, improving synthesis methods, and overcoming compatibility issues, current efforts are driving innovation toward practical ASSBs that could transform how we store and use energy,” Cheng added.



Research Report:Inorganic solid electrolytes for all-solid-state lithium/sodium-ion batteries: recent developments and applications


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Powering The World in the 21st Century at Energy-Daily.com





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Buried interface engineering drives advances in tin-lead perovskite solar cell efficiency

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Buried interface engineering drives advances in tin-lead perovskite solar cell efficiency


Buried interface engineering drives advances in tin-lead perovskite solar cell efficiency

by Simon Mansfield

Sydney, Australia (SPX) Dec 20, 2024






A team led by Prof. Meng Li from Henan University’s School of Nanoscience and Materials Engineering has unveiled an innovative approach to overcoming stability and efficiency challenges in tin-lead (Sn-Pb) perovskite solar cells. The researchers’ work focuses on optimizing the buried hole-selective interface using a specially designed self-assembled material, offering major implications for single-junction and tandem solar cell technologies.

Tin-lead perovskites are valued for their narrow bandgap properties, which position them as key materials for producing high-efficiency solar cells. However, energy level mismatches and degradation at the buried interface have constrained both their performance and long-term stability. Addressing these issues, Prof. Meng’s team designed a boronic acid-anchored hole-selective contact material, 4-(9H-carbazole-9-yl)phenylboronic acid (4PBA).



Compared to conventional materials, 4PBA demonstrated superior stability and compatibility at the substrate surface. Its high adsorption energy of -5.24 eV and significant molecular dipole moment (4.524 D) improved energy level alignment between the substrate and perovskite layer, facilitating efficient charge extraction. Additionally, the interface engineered using 4PBA improved perovskite crystallization and substrate contact, reducing defects and non-radiative recombination.



These advancements enabled Sn-Pb perovskite solar cells incorporating 4PBA to achieve a power conversion efficiency (PCE) of 23.45%. The material’s reduced corrosiveness also mitigated the degradation effects typically caused by PEDOT:PSS, a widely used hole-transport material, enhancing chemical stability and storage durability. The cells retained 93.5% of their initial efficiency after 2,000 hours of shelf storage.



“This approach offers a practical path to enhancing both the efficiency and stability of Sn-Pb perovskite solar cells, addressing energy level mismatches and interfacial stability concerns,” the research team commented.



The findings provide a foundation for advancing efficient and stable Sn-Pb perovskite solar cells and highlight the importance of interface engineering in next-generation photovoltaic technologies.



Research Report:Buried Hole-Selective Interface Engineering for High-Efficiency Tin-Lead Perovskite Solar Cells with Enhanced Interfacial Chemical Stability


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Henan University

All About Solar Energy at SolarDaily.com





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