Showing posts sorted by relevance for query POLYMER. Sort by date Show all posts
Showing posts sorted by relevance for query POLYMER. Sort by date Show all posts

Sunday, November 07, 2021

Fractured artificial rock helps crack a 54-year-old mystery

Fractured artificial rock helps crack a 54-year-old mystery
Princeton researchers have developed a technique to better understand how polymers 
flow through small channels under pressure. Credit: David Kelly Crow

Princeton researchers have solved a 54-year-old puzzle about why certain fluids strangely slow down under pressure when flowing through porous materials, such as soils and sedimentary rocks. The findings could help improve many important processes in energy, environmental and industrial sectors, from oil recovery to groundwater remediation.

The fluids in question are called  solutions. These solutions—everyday examples of which include cosmetic creams and the mucus in our noses—contain dissolved polymers, or materials made of large molecules with many repeating subunits. Typically, when they're put under pressure, polymer solutions become less viscous and  faster. But when going through materials with lots of tiny holes and channels, the solutions tend to become more viscous and gunky, reducing their flow rates.

To get at the root of the problem, the Princeton researchers devised an innovative experiment using a see-through porous medium made of tiny glass beads—a transparent artificial rock. This lucid medium allowed the researchers to visualize a polymer solution's movement. The experiment revealed that the long-baffling increase in viscosity in porous media happens because the polymer solution's flow becomes chaotic, much like turbulent air on an airplane ride, swirling into itself and gumming up the works.

"Surprisingly, until now, it has not been possible to predict the viscosity of polymer solutions flowing in porous media," said Sujit Datta, an assistant professor of chemical and biological engineering at Princeton and senior author of the study appearing Nov. 5 in the journal Science Advances. "But in this paper, we've now finally shown these predictions can be made, so we've found an answer to a problem that has eluded researchers for over a half-century."

"With this study, we finally made it possible to see exactly what is happening underground or within other opaque, porous media when polymer solutions are being pumped through," said Christopher Browne, a Ph.D. student in Datta's lab and the paper's lead author.

Browne ran the experiments and built the experimental apparatus, a small rectangular chamber randomly packed with tiny borosilicate glass beads. The setup, akin to an artificial sedimentary rock, spanned only about half the length of a pinky finger. Into this faux rock, Browne pumped a common polymer solution laced with fluorescent latex microparticles to help see the solution's flow around the beads. The researchers formulated the polymer solution so the material's refractive index offset light distortion from the beads and made the whole setup transparent when saturated. Datta's lab has innovatively used this technique to create see-through soil for studying ways to counter agricultural droughts, among other investigations.

Browne then zoomed in with a microscope on the pores, or holes between the beads, which occur on the scale of 100 micrometers (millionths of a meter) in size, or similar to the width of a human hair, in order to examine the  through each pore. As the polymer solution worked its way through the porous medium, the fluid's flow became chaotic, with the fluid crashing back into itself and generating turbulence. What's surprising is that, typically, fluid flows at these speeds and in such tight pores are not turbulent, but "laminar": the fluid moves smoothly and steadily. As the polymers navigated the pore space, however, they stretched out, generating forces that accumulated and generated turbulent flow in different pores. This effect grew more pronounced when pushing the solution through at higher pressures.

"I was able to see and record all these patchy regions of instability, and these regions really impact the transport of the solution through the medium," said Browne.

Fractured artificial rock helps crack a 54-year-old mystery
Princeton researchers have developed a technique to better understand how polymers flow through small channels under pressure. Credit: David Kelly Crow

The Princeton researchers used data gathered from the experiment to formulate a way to predict the behavior of polymer solutions in real-life situations.

Gareth McKinley, a professor of mechanical engineering at the Massachusetts Institute of Technology who was not involved in the study, offered comments on its significance.

"This study shows definitively that the large increase in the macroscopically observable pressure drop across a porous medium has its microscopic physical origins in viscoelastic flow instabilities that occur on the pore scale of the porous medium," McKinley said.

Given that viscosity is one of the most fundamental descriptors of fluid flow, the findings not only help deepen understanding of polymer solution flows and chaotic flows in general, but also provide quantitative guidelines to inform their applications at large scales in the field.

"The new insights we have generated could help practitioners in diverse settings determine how to formulate the right polymer  and use the right pressures needed to carry out the task at hand," said Datta. "We're particularly excited about the findings' application in groundwater remediation."

Because polymer solutions are inherently goopy, environmental engineers inject the solutions into the ground at highly contaminated sites such as abandoned chemical factories and industrial plants. The viscous solutions help push out trace contaminants from the affected soils. Polymer solutions likewise aid in oil recovery by pushing oil out of the pores in underground rocks. On the remediation side, polymer solutions enable "pump and treat," a common method for cleaning up groundwater polluted with industrial chemicals and metals that involves bringing the water to a surface treatment station. "All these applications of polymer solutions, and more, such as in separations and manufacturing processes, stand to benefit from our findings," said Datta.

Overall, the new findings on  flow rates in  brought together ideas from multiple fields of scientific inquiry, ultimately disentangling what had started out as a long-frustrating, complex problem.

"This work draws connections between studies of polymer physics, turbulence, and geoscience, following the flow of fluids in rocks underground as well as through aquifers," said Datta. "It's a lot of fun sitting at the interface between all these different disciplines."

Tiny polymer springs give a boost to environmental cleanup
More information: Christopher A. Browne et al, Elastic turbulence generates anomalous flow resistance in porous media, Science Advances (2021). DOI: 10.1126/sciadv.abj2619. www.science.org/doi/10.1126/sciadv.abj2619
Journal information: Science Advances 
Provided by Princeton University 

Saturday, April 01, 2023

 

Closed loop for circular economy: New polymer recycling strategy ensures both high stability and complete recyclability

Closed loop for circular economy: new polymer recycling strategy ensures both high stability and complete recyclability
In a new study, researchers from Japan proposed a new recycling strategy that facilitates
 material recycling without any loss in their properties. In “closed-loop” recycling, a polymer 
film composed of polyacrylate-based microparticles is disassembled into individual 
microparticles, which can be reassembled to form the film without losing any properties.
 This process could also be applied to recycle polymer microparticles in composite 
materials. Credit: Daisuke Suzuki from Shinshu University

The ever-increasing generation of plastic solid waste has resulted in global plastic pollution both on land and in the oceans. Projections show that plastic waste will double in the next 20 years, causing further environmental problems. Large amounts of plastic waste are, at present, incinerated or deposited in landfills. This not only degrades the environment but also depletes valuable resources.

In this light,  plastics such as polymers is a promising sustainable alternative for waste management. But this involves the breaking of chemical bonds between monomers (building blocks of polymers), which diminishes their overall stability and quality. Addressing this concern, researchers have developed methods to recycle polymers in a "," that is, without the loss of these properties. However, these methods are complicated and expensive and require specialized monomers, necessitating further innovation.

In this direction, a group of researchers led by Daisuke Suzuki, an Associate Professor at Shinshu University, has recently proposed a closed-loop recycling process based on  microparticles. Their work, co-authored by Dr. Takumi Watanabe and Dr. Haruka Minato of Shinshu University, has been published in Green Chemistry.

Prof. Suzuki briefly explains the rationale behind their strategy: "Recycling materials without deterioration (closed-loop recycling) is attractive in terms of reducing anthropogenic waste. However, this currently remains very difficult given that there usually is a trade-off between mechanical stability and degradability of polymer materials."

"Our material recycling concept with microparticles enables the recycling of a huge amount of functional polymer materials that we use in our day-to-day lives and has the potential to solve the problems of resource depletion and environmental pollution."

In their study, the authors prepared polymer microparticles via the aqueous emulsion polymerization of methyl acrylate (MA) monomers in water, which resulted in . These aggregated to form a solution containing uniform spherical poly-MA microparticles. The solution was then dried to get a thin polymer film with physical (as opposed to chemical) cross-linking among the microparticles, which could be reobtained by dissolving the film in ethanol. These recycled microparticles, in turn, could be reused to form various recycled materials.

The films synthesized in this work exhibit several desirable properties, which they retain upon recycling. They have high mechanical stability and fracture energy, which is an indicator of their toughness. The latter property increases with the interfacial thickness between the poly-MA microparticles. This, in turn, decreases with the degree of interparticle cross-linking but increases upon heating the film.

The researchers further enhanced the fracture energy of the polymer films by mixing the microparticles with silica nanofillers. Moreover, adding colored pigments gave the resulting composite films tunable optical properties, which did not diminish upon recycling. These results suggest that closed-loop recycling based on polymer microparticles will enable resource circulation for polymers as well as numerous other  that contain polymer microparticles to create adhering interfaces between their different layers.

Prof. Suzuki says, "Our concept can lead to the production of fully recyclable films with high fracture energy. Therefore, it will enable the recycling of huge amounts of various polymer materials, thus reducing  waste and potentially solving the problems of environmental degradation and plastic pollution."

The "closed"-loop recycling strategy certainly "opens" new doors for the efficient and sustainable recycling of polymer !

More information: Takumi Watanabe et al, Closed-loop recycling of microparticle-based polymers, Green Chemistry (2023). DOI: 10.1039/D3GC00090G


Journal information: Green Chemistry 


Provided by Shinshu UniversityTechnology transforms plastic waste bottles into polymers for lithium-ion batteries

Tuesday, October 27, 2020

 

Stay focused: Algae-inspired polymers light the way for enhanced night vision

Researchers from the University of Tsukuba synthesize an elastic polymer from low-cost, sustainable materials, that can be used it to fabricate lenses that help keep infrared cameras focused in the dark

UNIVERSITY OF TSUKUBA

Research News

Tsukuba, Japan - In a study recently published in ACS Applied Polymer Materials, researchers from the University of Tsukaba synthesized an infrared-transmitting polymer--based on low-cost, widely available materials--that retains its shape after stretching. The properties of this polymer are highly applicable to the preparation of cheaper night-vision lenses that retain focus while imaging at variable distances.

Cameras that function in the dark are common in many fields, including the military, security, firefighting, and wildlife tracking. However, infrared night-vision lenses are typically expensive, and the camera images tend to appear flat. Consequently, there is a need for lenses based on commonly available, cheap materials that are useful for more realistic vision in three dimensions.

The researchers' polymer is based on sulfur and compounds derived from algae and plants. The polymer is easy to prepare using a chemical process called inverse vulcanization: simply mix the constituent compounds together and stir while heating. As a first step, the researchers designed a polymer that is elastic--that is, reverts to its original shape--after being repeatedly restretched by 20%.

"Inverse vulcanization is an ideal synthetic approach for our polymers," explains lead author Professor Junpei Kuwabara. "Squalene and other long unsaturated hydrocarbons help optimize the cross-linking structure and give the polymers a desirable elasticity."

Next, the researchers needed to determine whether lenses constructed from their polymers are at least partially transparent to infrared light, for nighttime imaging. Lens construction was easy: simply pour the polymer into a lens-shaped silicone mold and heat for a few hours. Even a 3.3-millimeter-thick lens transmitted 10% of incoming infrared light.

"The lenses have two wavelength ranges that are infrared-transparent," says senior author Professor Takaki Kanbara. "No lens is completely transparent; 10% transmission is an excellent value for these materials."

Furthermore, the researchers confirmed that the polymer has variable-focus properties. By projecting an image through the lens, and monitoring the resulting image that came through while elongating the lens, much of the transmitted image remained in focus.

"The lens retained 54% of the focus variation, which is sufficient for practical uses," explains Dr. Takashi Fukuda, senior researcher, National Institute of Advanced Industrial Science and Technology (AIST). "The lens also retained its full initial focus after contracting back to its original shape."

The fabrication of conventional infrared night-vision lenses, in a way that allows users to easily change focus from one position to another, is typically difficult. Without a variable-focus capability, details that are pertinent to criminal or research investigations, for example, may be lost. The researchers of this study are overcoming current lens design limitations by using cheap, sustainable materials, and fabrication procecures that any researcher can carry out in their laboratory. Development of new materials in this area may benefit a range of sectors including emergency personnel and environmental researchers

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The article, "Algae-inspired, sulfur-based polymer with infrared transmission and elastic function," was published in ACS Applied Polymer Materials at DOI: 10.1021/acsapm.0c00924.

Monday, April 15, 2024

 

Using CO2 and biomass, FAMU-FSU researchers find path to more environmentally friendly recyclable plastics



FLORIDA STATE UNIVERSITY
Researchers 

IMAGE: 

FROM LEFT, ASSOCIATE PROFESSOR HOYONG CHUNG AND POSTDOCTORAL RESEARCHER ARIJIT GHORAI DISPLAY THE TWO PHASES OF THEIR DEGRADABLE POLYMER AT THE DITTMER CHEMISTRY LAB AT FLORIDA STATE UNIVERSITY.

view more 

CREDIT: SCOTT HOLSTEIN/FAMU-FSU COLLEGE OF ENGINEERING





Modern life relies on plastic. This lightweight, adaptable product is a cornerstone of packaging, medical equipment, the aerospace and automotive industries and more. But plastic waste remains a problem as it degrades in landfills and pollutes oceans.

FAMU-FSU College of Engineering researchers have created a potential alternative to traditional petroleum-based plastic that is made from carbon dioxide (CO2) and lignin, a component of wood that is a low-cost byproduct of paper manufacturing and biofuel production. Their research was published in Advanced Functional Materials.

“Our study takes the harmful greenhouse gas CO2 and makes it into a useful raw material to produce degradable polymers or plastics,” said Hoyong Chung, an associate professor in chemical and biomedical engineering at the college. “We are not only reducing CO2 emissions, but we are producing a sustainable polymer product using the CO2.”

This study is the first to demonstrate the direct synthesis of what’s known as a cyclic carbonate monomer — a molecule made of carbon and oxygen atoms that can be linked with other molecules — made from CO2 and lignin.

By linking multiple monomers together, scientists can create synthetic polymers, long-chained molecules that can be designed to fill all manner of applications.

The material developed by Chung and his research team is fully degradable at the end of its life without producing microplastics and toxic substances. It can be synthesized at lower pressures and temperatures. And the polymer can be recycled without losing its original properties.

Using depolymerization, the researchers can convert polymers to pure monomers, which are the building blocks of polymers. This is the key to the high quality of the recycled material. The monomers can be recycled indefinitely and produce a high-quality polymer as good as the original, an improvement over previously developed and currently used polymer materials in which repeated heat exposure from melting reduces quality and allows for limited recycling.

“We can readily degrade the polymer via depolymerization, and the degraded product can synthesize the same polymer again,” Chung said. “This is more cost effective and keeps it from losing original properties of polymers over multiple recycling. This is considered a breakthrough in material science, as it enables the realization of a true circular economy.”

The newly developed material could be used for low-cost, short lifespan plastic products in such sectors as construction, agriculture, packaging, cosmetics, textiles, diapers and disposable kitchenware. With further development, Chung anticipates its use in highly specialized polymers for biomedical and energy storage applications.

The FSU Office of Commercialization provided valuable foundational support for Chung’s research. Support from an internal funding program helped previous work with lignin-based polymers, and with the help of the office, he has received patents for other polymer research.

The project was supported by federal funds awarded to the State of Florida from the United States Department of Agriculture, National Institute of Food and Agriculture and support from the FAMU-FSU College of Engineering. Postdoctoral researcher Arijit Ghorai was the lead author of the study.

A closer view of the polymer developed by Chung’s research team in monomer and polymer phases.

CREDIT

Scott Holstein/FAMU-FSU College of Engineering

Wednesday, February 15, 2023

New compound that withstands extreme heat and electricity could lead to next-generation energy storage devices

Flexible polymers made with a new generation of the Nobel-winning “click chemistry” reaction find use in capacitors and other applications

Peer-Reviewed Publication

DOE/LAWRENCE BERKELEY NATIONAL LABORATORY

Featured image 

IMAGE: A NEW TYPE OF POLYSULFATE COMPOUND CAN BE USED TO MAKE POLYMER FILM CAPACITORS THAT STORE AND DISCHARGE HIGH DENSITY OF ELECTRICAL ENERGY WHILE TOLERATING HEAT AND ELECTRIC FIELDS BEYOND THE LIMITS OF EXISTING POLYMER FILM CAPACITORS. view more 

CREDIT: YI LIU AND HE (HENRY) LI/BERKELEY LAB

– By Rachel Berkowitz

Society’s growing demand for high-voltage electrical technologies – including pulsed power systems, cars and electrified aircraft, and renewable energy applications – requires a new generation of capacitors that store and deliver large amounts of energy under intense thermal and electrical conditions. Researchers at the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) and Scripps Research have now developed a new polymer-based device that efficiently handles record amounts of energy while withstanding extreme temperatures and electric fields. The device is composed of materials synthesized via a next-generation version of the chemical reaction for which three scientists won the 2022 Nobel Prize in Chemistry.

Polymer film capacitors are electrical components that store and release energy within an electric field using a thin plastic layer as the insulating layer. They make up 50% of the global high voltage capacitor market and offer advantages including light weight, low cost, mechanical flexibility, and robust cyclability. But state-of-the-art polymer film capacitors decrease dramatically in performance with increasing temperature and voltages. Developing new materials with improved tolerance for heat and electric fields is paramount; and creating polymers with near-perfect chemistry offers a way to do so.

“Our work adds a new class of electrically robust polymers to the table. It opens many possibilities to the exploration of more robust, high performing materials,” said Yi Liu, a chemist at Berkeley Lab and senior author on the Joule study reporting the work. Liu is the Facility Director of Organic and Macromolecular Synthesis at the Molecular Foundry, a DOE Office of Science user facility at Berkeley Lab.

In addition to remaining stable when subjected to high temperatures, a capacitor needs to be a strong “dielectric” material, meaning that it remains a strong insulator when subjected to high voltages. However, few known materials systems exist that deliver both thermal stability and dielectric strength. This scarcity is due to a lack of reliable and convenient synthesis methods, as well as a lack of fundamental understanding of the relationship between polymer structure and properties. “Improving the thermal stability of existing films while retaining their electrical insulating strength is an ongoing materials challenge,” said Liu.

A long-term collaboration between researchers at the Molecular Foundry and Scripps Research Institute has now met that challenge. They used a simple and quick chemical reaction developed in 2014 that swaps out fluorine atoms in compounds that contain sulfur-fluoride bonds, to yield long polymer chains of sulfate molecules called polysulfates. This Sulfur-Fluoride Exchange (SuFEx) reaction is a next-generation version of the click chemistry reaction pioneered by K. Barry Sharpless, a chemist at Scripps Research and two-time Nobel laureate in Chemistry, along with Peng Wu, also a chemist at Scripps Research. The near-perfect yet easy-to-run reactions join separate molecular entities through strong chemical bonds that form between different reactive groups. Liu’s team had originally used a variety of thermal analysis tools to examine the basic thermal and mechanical properties of these new materials.

As part of a Berkeley Lab program to synthesize and identify novel materials that could be useful in energy storage, Liu and his colleagues now find that, surprisingly, the polysulfates have outstanding dielectric properties, especially at high electric fields and temperatures. “Several commercial and lab-generated polymers are known for their dielectric properties, but polysulfates had never been considered. The marriage between polysulfates and dielectrics is one of the novelties here,” said He Li, a postdoctoral researcher in the Molecular Foundry and in Berkeley Lab’s Materials Sciences Division, and lead author of the study. 

Inspired by the excellent baseline dielectric properties offered by polysulfates, the researchers deposited extremely thin layers of aluminum oxide (Al2O3) onto thin films of the material to engineer capacitor devices with enhanced energy storage performance. They discovered that the fabricated capacitors exhibited excellent mechanical flexibility, withstood electric fields of more than 750 million volts per meter, and performed efficiently at temperatures up to 150 degrees Celsius. In comparison, today’s benchmark commercial polymer capacitors only function reliably at temperatures lower than 120 degrees Celsius. Above that temperature, they can only withstand electric fields smaller than 500 million volts per meter, and the energy efficiency severely drops by over half. 

The work opens new possibilities for exploring robust, high performing materials for energy storage. “We have provided deep insight into the underlying mechanisms that contribute to the material’s excellent performance,” said Wu.

The polymer strikes a balance of electrical, thermal, and mechanical properties, likely due to the sulfate linkages introduced by the click chemistry reaction. Because modular chemistry accommodates extraordinary structural diversity and scalability, the same route could offer a viable path to new polymers with higher performance that meet even more demanding operational conditions.

The polysulfates are strong contenders to become new state-of-the-art polymer dielectrics. Once researchers overcome barriers in large-scale manufacturing processes for thin film materials, the devices could greatly improve the energy efficiency of integrated power systems in electric vehicles and enhance their operational reliability. 

“Who could have imagined that a wispy sulfate polymer film could fend off lightning and fire, two of the most destructive forces in the universe?!” said Sharpless. 

“We’re continuously pushing the envelope of thermal and electrical properties, and accelerating the lab-to-market transition,” Liu added.

The technology is now available for licensing by contacting ipo@lbl.gov.

The work received funding from the Department of Energy’s Office of Science, the National Science Foundation, and the National Institute of Health. The work was carried out at the Molecular Foundry. 

Polysulfates with excellent thermal properties are casted into flexible free-standing films. High-temperature, high-voltage capacitors based on such films show state-of-the-art energy storage properties at 150 oC. Such power capacitors are promising for improving the energy efficiency and reliability of integrated power systems in demanding applications such as electrified transportation.

CREDIT

Credit: Yi Liu and He (Henry) Li/Berkeley Lab

Founded in 1931 on the belief that the biggest scientific challenges are best addressed by teams, Lawrence Berkeley National Laboratory and its scientists have been recognized with 16 Nobel Prizes. Today, Berkeley Lab researchers develop sustainable energy and environmental solutions, create useful new materials, advance the frontiers of computing, and probe the mysteries of life, matter, and the universe. Scientists from around the world rely on the Lab’s facilities for their own discovery science. Berkeley Lab is a multiprogram national laboratory, managed by the University of California for the U.S. Department of Energy’s Office of Science.

DOE’s Office of Science is the single largest supporter of basic research in the physical sciences in the United States, and is working to address some of the most pressing challenges of our time. For more information, please visit energy.gov/science.

Tuesday, September 05, 2023

 

A solid battery electrolyte with high performance


Peer-Reviewed Publication

PNAS NEXUS

reaction path Li et al 

IMAGE: INTRINSIC POLYMER ELECTROLYTE POLYMERIZATION REACTION PATH. view more 

CREDIT: LI ET AL.




A truly solid, highly conductive electrolyte has been designed, bringing solid-state lithium batteries within reach. Batteries store energy chemically and rely on the movement of charged ions between a cathode and an anode, through an electrolyte. For most of battery history, this electrolyte has been a liquid, although research has long sought a solid alternative. Polyethylene oxide (PEO)-based solid polymer electrolytes were developed in the 1970s, and have many attractive properties, including safety. (Unlike today’s lithium ion batteries, batteries with polymer electrolytes are less likely to burst into flames inside electric cars or in airplane holds if damaged.) Unfortunately, the ion conductivity at room temperature of polymer electrolytes is just too low to be practical. Other electrolytes that have recently been produced and described as “solid-state” actually contain gels. Quanfeng Dong and colleagues designed and synthesized a solid-state electrolyte from a cross-linked polymer composed of 1,3-dioxolane (DOL) and pentaerythritol glycidyl ether (PEG). This intrinsic polymer electrolyte (IPE) has a three-dimensional(3D) mesh structure, which has ionic conductivity up to 0.49 millisiemens per cm at room temperature—far higher than PEO. The intrinsic polymer electrolyte achieves lithium ion migration numbers of up to 0.85. Batteries built with intrinsic polymer electrolytes retain more than 90% of their storage capacity after 300 charge-discharge cycles. The material may be a good choice for next-generation high energy-density all solid-state lithium-based batteries, according to the authors.

Friday, November 10, 2023

 

Cornell chemists image basic blocks of synthetic polymers


Peer-Reviewed Publication

CORNELL UNIVERSITY



ITHACA, N.Y. -- Synthetic polymers are everywhere in our society – from nylon and polyester clothing to Teflon cookware and epoxy glue. At the molecular level, these polymers’ molecules are made of long chains of monomer building blocks, the complexity of which increases functionality in many such materials.

In particular, copolymers, which consist of different types of monomers in the same chain, allow for fine-tuning of the material’s properties, said Peng Chen, the Peter J.W. Debye Professor of Chemistry in the College of Arts and Sciences (A&S). The monomer sequence plays a critical role in a material’s properties, but scientists until now have lacked a method for sequencing synthetic copolymers.

Chen and colleagues have developed CREATS (Coupled REaction Approach Toward Super-resolution imaging), which allows them to image polymerization catalysis reactions at single-monomer resolution and, through fluorescent signaling, to differentiate monomers from one another. Both are important steps in discovering the molecular composition of a synthetic polymer.

They describe the technique and the first discoveries they’ve made with it in “Optical Sequencing of Single Synthetic Polymers,” published Nov. 9 in Nature Chemistry.

Co-lead authors are Rong Ye, Xiangcheng Sun and Xianwen Mao, all former postdoctoral researchers in the Chen group. Co-authors are former Chen group postdoctoral researchers Susil Baral and Chunming Liu, current postdoctoral researcher Felix Alfonso, and Geoffrey Coates, the Tisch University Professor in chemistry and chemical biology (A&S).

“Synthetic polymers are made of monomer units linked together like a string of beads,” Chen said. In the simplest polymers, the monomers are identical, but more complex properties arise when polymers contain monomers of different sorts – called copolymers. The precise arrangement of the monomers in a copolymer plays an important role in its properties, such as stiffness or flexibility.

Sequence plays a role in the properties of natural polymers, too, Chen said. A protein, for example, is made of 20 amino acid monomers arranged in a very specific sequence.

“In a natural polymer, nature has control,” Chen said. “In synthetic polymers, humans are making the arrangements, and the chemists generally don’t have that precise control.”

Sequencing copolymers is so difficult in large part because of heterogeneity in synthetic polymers, Chen said. Individual chains differ in length, composition and sequence, which requires single-polymer sequencing methods that can resolve and identify individual monomers.

Some modern methods allow scientists to control the arrangement of monomers in a chain, Chen said, but only for very short polymers – 10 to 20 monomers long.

Using CREATS, the researchers can determine the sequence of a polymer as it is made, one monomer at a time, by imaging and identifying every single monomer as it is added to the polymer. To make the monomers visible, CREATS couples the polymerization reaction with another reaction that produces fluorescent signals.

“Every monomer that goes in gives off a puff of light,” Chen said. “The light is induced by a laser, and the puff of light has a color. In our case, it’s either green or yellow. By seeing whether it’s yellow or green, we see what monomer goes in.”

The lab is already equipped to measure synthetic polymer properties. Now that they can determine the sequence of an individual polymer, a next step is to combine the two experiments to correlate structure and function, ultimately providing guiding principles for polymer design to achieve certain properties.

“If you know how sequence controls property, you can really think about designing whatever sequence you want to achieve a certain property,” Chen said. “This knowledge presumably can help people tailor their materials for a desired application.”

The research was funded by the Polymer Chemistry program of Army Research Office, a directorate of the U.S. Army Combat Capabilities Development Command Army Research Laboratory.

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Saturday, February 13, 2021

 

Producing more sustainable hydrogen with composite polymer dots

UPPSALA UNIVERSITY

Research News

Hydrogen for energy use can be extracted in an environmentally friendly way from water and sunlight, using photocatalytic composite polymer nanoparticles developed by researchers at Uppsala University. In laboratory tests, these "polymer dots" showed promising performance and stability alike. The study has been published in the Journal of the American Chemical Society.

How we are to meet future demand for sustainable energy is a much-debated question. One feasible way to go is hydrogen, which can be produced from renewable resources: water and solar energy. But the process requires what are known as photocatalysts. Traditionally, these have been made of metal-based materials that are often toxic. Instead, a research group headed by Haining Tian at Uppsala University's Ångström Laboratory is working to develop nano-sized organic photocatalysts - "polymer dots" - designed to be both environmentally friendly and cost-effective.

Since polymer dots (Pdots) are so tiny, they are evenly distributed in water. Compared with traditional photocatalysts, this provides a larger reaction surface, which means that more light can be stored in the form of hydrogen gas. The research group has now developed a Pdot containing three components. In tests, the particle has shown very good catalytic performance and stability.

"Combining several components that absorb light at different wavelengths is the easiest way to create a system in which all the visible surfaces capture light. But getting these components to work well together in a photocatalytic system is challenging," says Haining Tian, Associate Professor (Docent) of Physical Chemistry at Uppsala University.

To investigate how well the various components work together, Tian and his colleagues used spectroscopic techniques in which the Pdot was exposed to light for a certain length of time. They were thus able to follow how photochemical intermediates were created and, under illumination, disappeared.

"It's exciting to see that both ultrafast energy transfer and electron transfer take place in one particle, and that this helps the system to make use of the light and separate the charge for the catalytic process," says the study's lead author Aijie Liu, a postdoctoral researcher at the Department of Chemistry - Ångström Laboratory.

The researchers have succeeded in optimising the system of triple-component polymer dots so that it catalyses the conversion of solar energy into hydrogen with a 7% efficiency rate at 600 nanometres (nm). This is significantly better than the 0.3% at 600 nm obtained by the group when they were working on Pdots consisting of only one component. One problem has previously been that the photocatalysts degrade prematurely, but now the researchers were unable to discern any distinct degradation even after 120 hours' testing.

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Aijie Liu et al. (2020), Panchromatic Ternary Polymer Dots Involving Sub-Picosecond Energy and Charge Transfer for Efficient and Stable Photocatalytic Hydrogen Evolution, Journal of the American Chemical Society. DOI: 10.1021/jacs.0c12654