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2D all-organic perovskites: potential use in 2D electronics

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2D all-organic perovskites: potential use in 2D electronics


Perovskites are among the most researched topics in materials science. Recently, a research team led by Prof. LOH Kian Ping, Chair Professor of Materials Physics and Chemistry and Global STEM Professor of the Department of Applied Physics of The Hong Kong Polytechnic University (PolyU), Dr Kathy LENG, Assistant Professor of the same department, together with Dr Hwa Seob CHOI, Postdoctoral Research Fellow and the first author of the research paper, has solved an age-old challenge to synthesise all-organic two-dimensional perovskites, extending the field into the exciting realm of 2D materials. This breakthrough opens up a new field of 2D all-organic perovskites, which holds promise for both fundamental science and potential applications. This research titled “Molecularly thin, two-dimensional all-organic perovskites” was recently published in the journal Science.

Perovskites are named after their structural resemblance to the mineral calcium titanate perovskite, and are well known for their fascinating properties that can be applied in wide-ranging fields such as solar cells, lighting and catalysis. With a fundamental chemical formula of ABX3, perovskites possess the ability to be finely tuned by adjusting the A and B cations as well as the X anion, paving the way for the development of high-performance materials.

While perovskite was first discovered as an inorganic compound, Prof. Loh’s team has focused their attention on the emerging class of all-organic perovskites. In this new family, A, B, and X constituents are organic molecules rather than individual atoms like metals or oxygen. The design principles for creating three-dimensional (3D) perovskites using organic components have only recently been established. Significantly, all-organic perovskites offer distinct advantages over their all-inorganic counterparts, as they are solution-processible and flexible, enabling cost-effective fabrication. Moreover, by manipulating the chemical composition of the crystal, valuable electromagnetic properties such as dielectric properties, which finds applications in electronics and capacitors, can be precisely engineered.

Traditionally, researchers face challenges in the synthesis of all-organic 3D perovskites due to the restricted selection of organic molecules that can fit with the crystal structure. Recognising this limitation, Prof. Loh and his team proposed an innovative approach: synthesising all-organic perovskites in the form of 2D layers instead of 3D crystals. This strategy aimed to overcome the constraints imposed by bulky molecules and facilitate the incorporation of a broader range of organic ions. The anticipated outcome was the emergence of novel and extraordinary properties in these materials.

Validating their prediction, the team developed a new general class of layered organic perovskites. Following the convention for naming perovskites, they called it the “Choi-Loh-v phase” (CL-v) after Dr Choi and Prof. Loh. These perovskites comprise molecularly thin layers held together by forces that hold graphite layers together, the so-called van der Waals forces — hence the “v” in CL-v. Compared with the previously studied hybrid 2D perovskites, the CL-v phase is stabilised by the addition of another B cation into the unit cell and has the general formula A2B2X4.

Using solution-phase chemistry, the research team prepared a CL-v material known as CMD-N-P2, in which the A, B and X sites are occupied by CMD (a chlorinated cyclic organic molecule), ammonium and PF6− ions, respectively. The expected crystal structure was confirmed by high-resolution electron microscopy carried out at cryogenic temperature. These molecularly thin 2D organic perovskites are fundamentally different from traditional 3D minerals, they are single crystalline in two dimensions and can be exfoliated as hexagonal flakes just a few nanometres thick — 20,000 times thinner than a human hair.

The solution-processibility of 2D organic perovskites presents exciting opportunities for their application in 2D electronics. The Poly U team conducted measurements on the dielectric constants of the CL-v phase, yielding values ranging from 4.8 to 5.5. These values surpass those of commonly used materials such as silicon dioxide and hexagonal boron nitride. This discovery establishes a promising avenue for incorporating CL-v phase as a dielectric layer in 2D electronic devices, as these devices often necessitate 2D dielectric layers with high dielectric constants, which are typically scarce. Team member Dr Leng successfully addressed the challenge of integrating 2D organic perovskites with 2D electronics. In their approach, the CL-v phase was employed as the top gate dielectric layer, while the channel material consisted of atomically thin Molybdenum Sulfide. By utilising the CL-v phase, the transistor achieved superior control over the current flow between the source and drain terminals, surpassing the capabilities of conventional silicon oxide dielectric layers.

Prof. Loh’s research not only establishes an entirely new class of all-organic perovskites but also demonstrates how they can be solution-processed in conjunction with advanced fabrication technique to enhance the performance of 2D electronic devices. These developments open up new possibilities for the creation of more efficient and versatile electronic systems.



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Simple food swaps could cut greenhouse gas emissions from household groceries by a quarter

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Simple food swaps could cut greenhouse gas emissions from household groceries by a quarter


Switching food and drink purchases to very similar but more environmentally friendly alternatives could reduce the greenhouse gas emissions from household groceries by more than a quarter (26%), according to a new Australian study from The George Institute for Global Health and Imperial College London published today in Nature Food.

Making bigger changes — like swapping a frozen meat lasagne for the vegetarian option — could push the reduction to as much as 71%.

To make this happen will require on-pack labelling of greenhouse gas emissions for every packaged food product so that consumers can make informed choices.

This is the most detailed analysis ever conducted on the environmental impacts of a country’s food purchasing behaviour, involving comprehensive data on greenhouse gas emissions and sales for tens of thousands of supermarket products, typical of the Western diet of many countries globally.

Lead author and epidemiologist Dr Allison Gaines, who conducted the analysis for The George Institute and Imperial College London, said, “Dietary habits need to change significantly if we are to meet global emissions targets, particularly in high-income countries like Australia, the UK, and US.

“But while consumers are increasingly aware of the environmental impact of the food system and willing to make more sustainable food choices, they lack reliable information to identify the more environmentally friendly options.”

Researchers calculated the projected emissions of annual grocery purchases from 7,000 Australian households using information on ingredients, weights and production life cycles in The George Institute’s FoodSwitch database and global environmental impact datasets. More than 22,000 products were assigned to major, minor and sub-categories of foods (e.g. ‘bread and bakery’, ‘bread’ and ‘white bread’, respectively) to quantify emissions saved by switching both within and between groups.

Making switches within the same sub-categories of foods could lead to emission reductions of 26% in Australia, equivalent to taking over 1.9 million cars off the road.2 Switches within minor categories of foods could lead to even bigger emission reductions of 71%.

“The results of our study show the potential to significantly reduce our environmental impact by switching like-for-like products. This is also something consumers in the UK could, and would probably like, to do if we put emissions information onto product labels,” said Dr Gaines.

Dr Gaines added that the switches would not compromise food healthiness overall: “We showed that you can switch to lower emissions products while still enjoying nutritious foods. In fact, we found it would lead to a slight reduction in the proportion of ultra-processed foods purchased, which is a positive outcome because they’re generally less healthy,” she said.

The purchase analysis also showed that meat products contributed almost half (49%) of all greenhouse gas emissions, but only 11% of total purchases.Conversely, fruit, vegetables, nuts and legumes represented one quarter (25%) of all purchases, but were responsible for just 5% of emissions.

It is estimated that around one-third of global greenhouse gas emissions are attributable to the food and agriculture sector, and the combined health and environmental costs of the global food system are estimated to be 10-14 trillion USD (8-11 trillion GBP) per year.3,4,5 More than 12 million deaths per year could be prevented if the system transitioned to deliver healthy, low-emission diets.3

Prof Bruce Neal, Executive Director at The George Institute Australia and Professor of Clinical Epidemiology at Imperial College London, said that as a global community, we are taking too long to improve the sustainability of the food system, endangering the prospect of a net-zero future.

“There is currently no standardised framework for regulating the climate or planetary health parameters of our food supply, and voluntary measures have not been widely adopted by most countries. This research shows how innovative ways of approaching the problem could enable consumers to make a real impact,” he said.

“With this in mind, we have developed a free app called ecoSwitch, currently available in Australia, which is based on this research. Shoppers can use their device to scan a product barcode and check its ‘Planetary Health Rating’, a measure of its emissions shown as a score between half a star (high emissions) to five stars (low emissions).”

The George Institute plans to extend the ecoSwitch algorithm to integrate other environmental indicators such as land and water use, and biodiversity, and to introduce the tool to other countries.

“While ecoSwitch is a much-needed first step in providing environmental transparency for grocery shoppers, the vision is for mandatory display of a single, standardised sustainability rating system on all supermarket products,” concluded Prof Neal.



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Florida fossil porcupine solves a prickly dilemma 10-million years in the making

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Florida fossil porcupine solves a prickly dilemma 10-million years in the making


There’s a longstanding debate simmering among biologists who study porcupines. There are 16 porcupine species in Central and South America, but only one in the United States and Canada. DNA evidence suggests North America’s sole porcupine belongs to a group that originated 10 million years ago, but fossils seem to tell a different story. Some paleontologists think they may have evolved just 2.5 million years ago, at the beginning of the ice ages.

A new study published in the journal Current Biology claims to have reconciled the dispute, thanks to an exceptionally rare, nearly complete porcupine skeleton discovered in Florida. The authors reached their conclusion by studying key differences in bone structure between North and South American porcupines, but getting there wasn’t easy. It took an entire class of graduate and undergraduate students and several years of careful preparation and study.

“Even for a seasoned curator with all the necessary expertise, it takes an incredible amount of time to fully study and process an entire skeleton,” said lead author Natasha Vitek. While studying as a doctoral student at the Florida Museum of Natural History, Vitek teamed up with vertebrate paleontology curator Jonathan Bloch to create a college course in which students got hands-on research experience by studying porcupine fossils.

Ancient radiation gave rise to world’s largest rodents

Porcupines are a type of rodent, and their ancestors likely originated in Africa more than 30 million years ago. Their descendants have since wandered into Asia and parts of Europe by land, but their journey to South America is a particularly defining event in the history of mammals. They crossed the Atlantic Ocean — likely by rafting — when Africa and South America were much closer together than they are today. They were the first rodents to ever set foot on the continent, where they evolved into well-known groups like guinea pigs, chinchillas, capybaras and porcupines.

Some took on giant proportions. There were lumbering, rat-like animals up to five feet long, equipped with a tiny brain that weighed less than a plum. Extinct relatives of the capybara grew to the size of cows.

Porcupines remained relatively small and evolved adaptations for life in the treetops of South America’s lush rainforests. Today, they travel through the canopy with the aid of long fingers capped with blunt, sickle-shaped claws perfectly angled for gripping branches. Many also have long, prehensile tails capable of bearing their weight, which they use while climbing and reaching for fruit.

Despite their excellent track record of getting around, South America was a dead end for many millions of years. A vast seaway with swift currents separated North and South America, and most animals were unable to cross — with a few notable exceptions.

Beginning about 5 million years ago, the Isthmus of Panama rose above sea level, cutting off the Pacific from the Atlantic. This land bridge became the ancient equivalent of a congested highway a few million years later, with traffic flowing in both directions.

Prehistoric elephants, saber-toothed cats, jaguars, llamas, peccaries, deer, skunks and bears streamed from North America to South. The reverse trek was made by four different kinds of ground sloths, oversized armadillos, terror birds, capybaras and even a marsupial.

The two groups met with radically different fates. Those mammals migrating south did fairly well; many became successfully established in their new tropical environments and survived to the present. But nearly all lineages that ventured north into colder environments have gone extinct. Today, there are only three survivors: the nine-banded armadillo, the Virginia opossum and the North American porcupine.

New fossils catch evolution in the act

Animals that traveled north had to contend with new environments that bore little resemblance to the ones they left behind. Warm, tropical forests gave way to open grasslands, deserts and cold deciduous forests. For porcupines, this meant coping with brutal winters, fewer resources and coming down from the trees to walk on land. They still haven’t quite gotten the hang of the latter; North American porcupines have a maximum ground speed of about 2 mph.

South American porcupines are equipped with a menacing coat of hollow, overlapping quills, which offer a substantial amount of protection but do little to regulate body temperature. North American porcupines replaced these with a mix of insulating fur and long, needle-like quills that can be raised when they feel threatened. They also had to modify their diet, which changed the shape of their jaw.

“In winter, when their favorite foods are not around, they will bite into tree bark to get at the softer tissue underneath. It’s not great food, but it’s better than nothing,” Vitek said. “We think this type of feeding selected for a particular jaw structure that makes them better at grinding.”

They also lost their prehensile tails. Although North American porcupines still like climbing, it’s not their forte. Museum specimens often show evidence of healed bone fractures, likely caused by falling from trees.

Many of these traits can be observed in fossils. The problem is there aren’t many fossils to go around. According to Vitek, most are either individual teeth or jaw fragments, and researchers often lump them in with South American porcupines. Those that are considered to belong to the North American group lack the critical features that would provide paleontologists with clues to how they evolved.

So when Florida Museum paleontologist Art Poyer found an exquisitely preserved porcupine skeleton in a Florida limestone quarry, they were well aware of its significance.

“When they first brought it in, I was amazed,” said Bloch, senior author of the study. “It is so rare to get fossil skeletons like this with not only a skull and jaws, but many associated bones from the rest of the body. It allows for a much more complete picture of how this extinct mammal would have interacted with its environment. Right away we noticed that it was different from modern North American porcupines in having a specialized tail for grasping branches.”

By comparing the fossil skeleton with bones from modern porcupines, Bloch and Vitek were confident they could determine its identity. But the amount of work this would require was more than one person could do on their own in a short amount of time. So they co-created a paleontology college course, in which the only assignment for the entire semester was studying porcupine bones.

“It’s the kind of thing that could only be taught at a place like the Florida Museum, where you have both collections and enough students to study them,” Vitek said. “We focused on details of the jaw, limbs, feet and tails. It required a very detailed series of comparisons that you might not even notice on the first pass.”

The results were surprising. The fossil lacked the reinforced bark-gnawing jaws and possessed a prehensile tail, making it appear more closely related to South American porcupines. But, Vitek said, other traits bore a stronger similarity to North American porcupines, including the shape of the middle ear bone as well as the shapes of the lower front and back teeth.

With all the data combined, analyses consistently provided the same answer. The fossils belonged to an extinct species of North American porcupine, meaning this group has a long history that likely began before the Isthmus of Panama had formed. But questions remain as to how many species once existed in this group or why they went extinct.

“One thing that isn’t resolved by our study is whether these extinct species are direct ancestors of the North American porcupine that is alive today,” Vitek said. “It’s also possible porcupines got into temperate regions twice, once along the Gulf Coast and once out west. We’re not there yet.”

Jennifer Hoeflich, Isaac Magallanes, Sean Moran, Rachel Narducci, Victor Perez, Jeanette Pirlo, Mitchell Riegler, Molly Selba, María Vallejo-Pareja, Michael Ziegler, Michael Granatosky and Richard Hulbert of the Florida Museum of Natural History are also authors on the paper.



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Charge your laptop in a minute or your EV in 10? Supercapacitors can help

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Charge your laptop in a minute or your EV in 10? Supercapacitors can help


Imagine if your dead laptop or phone could charge in a minute or if an electric car could be fully powered in 10 minutes.

While not possible yet, new research by a team of CU Boulder scientists could potentially lead to such advances.

Published today in the Proceedings of the National Academy of Sciences, researchers in Ankur Gupta’s lab discovered how tiny charged particles, called ions, move within a complex network of minuscule pores. The breakthrough could lead to the development of more efficient energy storage devices, such as supercapacitors, said Gupta, an assistant professor of chemical and biological engineering.

“Given the critical role of energy in the future of the planet, I felt inspired to apply my chemical engineering knowledge to advancing energy storage devices,” Gupta said. “It felt like the topic was somewhat underexplored and as such, the perfect opportunity.”

Gupta explained that several chemical engineering techniques are used to study flow in porous materials such as oil reservoirs and water filtration, but they have not been fully utilized in some energy storage systems.

The discovery is significant not only for storing energy in vehicles and electronic devices but also for power grids, where fluctuating energy demand requires efficient storage to avoid waste during periods of low demand and to ensure rapid supply during high demand.

Supercapacitors, energy storage devices that rely on ion accumulation in their pores, have rapid charging times and longer life spans compared to batteries.

“The primary appeal of supercapacitors lies in their speed,” Gupta said. “So how can we make their charging and release of energy faster? By the more efficient movement of ions.”

Their findings modify Kirchhoff’s law, which has governed current flow in electrical circuits since 1845 and is a staple in high school students’ science classes. Unlike electrons, ions move due to both electric fields and diffusion, and the researchers determined that their movements at pore intersections are different from what was described in Kirchhoff’s law.

Prior to the study, ion movements were only described in the literature in one straight pore. Through this research, ion movement in a complex network of thousands of interconnected pores can be simulated and predicted in a few minutes.

“That’s the leap of the work,” Gupta said. “We found the missing link.”



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