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Chemistry

Breaking Down Redox Reactions: Unraveling the Secrets of Proton-Coupled Electron Transfer with High Pressure

Chemists reveal method for differentiating PCET mechanisms — a key step for steering fundamental energy conversion and redox catalysis processes.

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Redox reactions are the backbone of many vital processes that sustain life on Earth. From cellular respiration to photosynthesis, these chemical reactions play a crucial role in harnessing energy and converting it into forms that can be used by living organisms. In addition to their importance in biology, redox reactions also have significant implications for various fields such as chemistry, biochemistry, and the use of light for energy generation.

A team of researchers led by Professor Ivana Ivanović-Burmazović from LMU Munich and Professor Dirk Guldi from FAU Erlangen-Nürnberg has made a groundbreaking discovery in understanding the fundamental principles of redox reactions. Using an innovative approach based on high pressures, they have successfully differentiated between two related reaction mechanisms: concerted and stepwise proton-coupled electron transfer (PCET).

In PCET reactions, electrons are transferred between molecules while protons are moved simultaneously to prevent changes in charge, making it the most efficient way for a redox reaction to occur. However, there were previously no direct methods to distinguish between the two mechanisms with certainty.

The researchers investigated the effect of pressure on the light-induced reaction of a photosensitive molecule in solution. They applied pressures up to 1,200 atmospheres and observed changes in the reaction rate. If the reaction rate remained unchanged under high pressure, it indicated a concerted mechanism, where electrons and protons are transferred simultaneously without changing the charge or solvation sphere.

Conversely, if the reaction rate changed under high pressure, it suggested a stepwise process, where electrons and protons were transferred separately, causing changes in the charge and solvation sphere. To their surprise, the researchers found that they could influence the process by increasing the pressure, steering the reaction from a stepwise mechanism toward a concerted one.

This breakthrough discovery has significant implications for research areas dealing with electron and proton motion, offering new insights into fundamental chemical processes. The findings could also contribute to advancing technologies concerned with converting and storing chemical energy, such as redox catalysis for solar fuel generation or hydrogen production.

Batteries

“Reviving ‘Dead’ Batteries: The Path to a Greener Future”

Lithium battery recycling offers a powerful solution to rising demand, with discarded batteries still holding most of their valuable materials. Compared to mining, recycling slashes emissions and resource use while unlocking major economic potential. Yet infrastructure, policy, and technology hurdles must still be overcome.

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As the world moves towards a cleaner energy future, the importance of recycling ‘dead’ batteries cannot be overstated. With the growing demand for electric vehicles, portable electronics, and renewable energy storage, lithium has become a critical mineral. According to new research from Edith Cowan University (ECU), tapping into used batteries as a secondary source of lithium not only helps reduce environmental impact but also secures access to this valuable resource, supporting a circular economy and ensuring long-term sustainability in the energy sector.

The global lithium-ion battery market size is projected to expand at a compound annual growth rate of 13 per cent, reaching $87.5 billion by 2027. However, only around 20 per cent of a lithium-ion battery’s capacity is used before the battery is no longer fit for use in electric vehicles, meaning those batteries ending up in storage or on the landfill retain nearly 80 per cent of their lithium capacity.

The Australian Department of Industry, Science and Resources has estimated that by 2035, Australia could be generating 137,000 t of lithium battery waste annually. For the end-of-life batteries, the obvious answer is recycling, said first author Mr Asad Ali, quoting figures from the government which estimates that the recycling industry could be worth between $603 million and $3.1 billion annually in just over a decade.

“By recycling these batteries, you can access not only the remaining lithium – which already purified to near 99 per cent – but you can also retrieve the nickel and the cobalt from these batteries,” Mr Ali noted.

While the lithium retrieved through the recycling process is unlikely to impact the lithium extraction or downstream sectors, the recycling process offered significant environmental benefits when compared with the mining industry. Recycling processes can significantly reduce the extensive use of land, soil contamination, ecological footprint, water footprint, carbon footprint, and harmful chemical release into the environment.

Mining emits up to 37% tons of CO2 per ton of lithium. Recycling processes produce up to 61 per cent less carbon emissions compared with mining and uses 83 per cent less energy and 79 per cent less water as compared to mining.

ECU lecturer and corresponding author Dr Muhammad Azhar said that while Australia holds one of the largest hard rock lithium reserves in the world, the recovery of lithium from end-of-life batteries could provide socio-economic benefits and fulfils environmental sustainability.

The benefits of lithium-ion battery recycling seem obvious, but there are still some challenges to be addressed. The rate of innovation significantly outstrips policy development, and the chemical make-up of the batteries also continuously evolve, which makes the recycling of these batteries more complicated.

However, there is a definite need for investment into the right infrastructure in order to create this circular economy. Several Australian companies are looking at the best ways to approach this, and ECU is exploring the second life of retired lithium batteries, providing a promising future for a greener tomorrow.

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Biochemistry

Shape-Shifting Catalysts: Revolutionizing Green Chemistry with a Single Atom

A team in Milan has developed a first-of-its-kind single-atom catalyst that acts like a molecular switch, enabling cleaner, more adaptable chemical reactions. Stable, recyclable, and eco-friendly, it marks a major step toward programmable sustainable chemistry.

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The scientific community has witnessed a groundbreaking development in sustainable chemistry with the creation of a shape-shifting single-atom catalyst at the Politecnico di Milano. This innovative material has demonstrated the capability to selectively adapt its chemical activity, paving the way for more efficient and programmable industrial processes.

Published in the Journal of the American Chemical Society, one of the world’s most esteemed scientific journals in chemistry, this study marks a significant breakthrough in the field of single-atom catalysts. For the first time, scientists have successfully designed a material that can change its catalytic function depending on the chemical environment, much like a ‘molecular switch.’ This allows complex reactions to be performed more cleanly and efficiently, using less energy than conventional processes.

The research focuses on a palladium-based catalyst in atomic form encapsulated in a specially designed organic structure. This unique setup enables the material to ‘switch’ between two essential reactions in organic chemistry – bioreaction and carbon-carbon coupling – simply by varying the reaction conditions. The team has successfully demonstrated this phenomenon, showcasing the potential for more intelligent, selective, and sustainable chemical transformations.

Lead researcher Gianvito Vilé, lecturer at the Politecnico di Milano’s ‘Giulio Natta’ Department of Chemistry, Materials and Chemical Engineering, emphasizes the significance of their discovery: “We have created a system that can modulate catalytic reactivity in a controlled manner, paving the way for more intelligent, selective, and sustainable chemical transformations.”

The new catalyst stands out not only for its reaction flexibility but also for its stability, recyclability, and reduced environmental impact. ‘Green’ analyses conducted by the team reveal a substantial decrease in waste and hazardous reagents, making it an exemplary model for sustainable chemistry.

This study is the result of an international collaboration with esteemed institutions from around the world, including the University of Milan-Bicocca, the University of Ostrava (Czech Republic), the University of Graz (Austria), and Kunsan National University (South Korea). The joint efforts of these researchers have led to a groundbreaking achievement that has far-reaching implications for the field of green chemistry.

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Chemistry

Scientists Confirm a Fundamental Quantum Rule for the First Time

Scientists have, for the first time, experimentally proven that angular momentum is conserved even when a single photon splits into two, pushing quantum physics to its most fundamental limits. Using ultra-precise equipment, the team captured this elusive process—comparable to finding a needle in a haystack—confirming a cornerstone law of nature at the photon level.

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Scientists at Tampere University and their international collaborators have made a groundbreaking discovery in the field of quantum physics. They have experimentally confirmed that angular momentum is conserved when a single photon is converted into a pair, validating a key principle of physics at the quantum level for the first time. This breakthrough has significant implications for creating complex quantum states useful in computing, communication, and sensing.

In essence, the researchers have tested the conservation laws of rotating objects to see if they also apply to light. They found that when a photon with zero orbital angular momentum is split into two photons, the OAM quanta of both photons must add to zero. This means that if one of the newly generated photons has one OAM quanta, its partner photon must have the opposite, i.e., negative OAM quanta.

The researchers used an extremely stable optical setup and delicate measurements to record enough successful conversions such that they could confirm the fundamental conservation law. They also observed first indications of quantum entanglement in the generated photon pairs, which suggests that the technique can be extended to create more complex photonic quantum states.

This work is not only of fundamental importance but also takes us a significant step closer to generating novel quantum states, where the photons are entangled in all possible ways. The researchers plan to improve the overall efficiency of their scheme and develop better strategies for measuring the generated quantum state such that in the future these photonic needles can be found easier in the laboratory haystack.

The confirmation of this fundamental quantum rule opens new possibilities for creating complex quantum states useful in computing, communication, and sensing. It also takes us a significant step closer to generating novel quantum states, where the photons are entangled in all possible ways, i.e., in space, time, and polarization.

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