The Korea Advanced Institute of Science and Technology (KAIST
Scientists have taken a major step toward a circular carbon economy by developing a long-lasting, economical catalyst that recycles greenhouse gases into ingredients that can be used in fuel, hydrogen gas, and other chemicals. The results could be revolutionary in the effort to reverse global warming, according to the researchers. The study was published on February 14 in Science.
“We set out to develop an effective catalyst that can convert large amounts of the greenhouse gases carbon dioxide and methane without failure,” said Cafer T. Yavuz, paper author and associate professor of chemical and biomolecular engineering and of chemistry at KAIST.
The catalyst, made from inexpensive and abundant nickel, magnesium, and molybdenum, initiates and speeds up the rate of reaction that converts carbon dioxide and methane into hydrogen gas. It can work efficiently for more than a month.
This conversion is called ‘dry reforming’, where harmful gases, such as carbon dioxide, are processed to produce more useful chemicals that could be refined for use in fuel, plastics, or even pharmaceuticals. It is an effective process, but it previously required rare and expensive metals such as platinum and rhodium to induce a brief and inefficient chemical reaction.
Other researchers had previously proposed nickel as a more economical solution, but carbon byproducts would build up and the surface nanoparticles would bind together on the cheaper metal, fundamentally changing the composition and geometry of the catalyst and rendering it useless.
“The difficulty arises from the lack of control on scores of active sites over the bulky catalysts surfaces because any refinement procedures attempted also change the nature of the catalyst itself,” Yavuz said.
The researchers produced nickel-molybdenum nanoparticles under a reductive environment in the presence of a single crystalline magnesium oxide. As the ingredients were heated under reactive gas, the nanoparticles moved on the pristine crystal surface seeking anchoring points. The resulting activated catalyst sealed its own high-energy active sites and permanently fixed the location of the nanoparticles — meaning that the nickel-based catalyst will not have a carbon build up, nor will the surface particles bind to one another. (Article continues below **)
This schematic shows the electrolyzer developed at Rice to reduce carbon dioxide, a greenhouse gas, to valuable fuels. At left is a catalyst that selects for carbon dioxide and reduces it to a negatively charged formate, which is pulled through a gas diffusion layer (GDL) and the anion exchange membrane (AEM) into the central electrolyte. At the right, an oxygen evolution reaction (OER) catalyst generates positive protons from water and sends them through the cation exchange membrane (CEM). The ions recombine into formic acid or other products that are carried out of the system by deionized (DI) water and gas. Illustration by Chuan Xia and Demin Liu
(** New catalyst recycles greenhouse gases into fuel and hydrogen gas continues)
“It took us almost a year to understand the underlying mechanism,” said first author Youngdong Song, a graduate student in the Department of Chemical and Biomolecular Engineering at KAIST. “Once we studied all the chemical events in detail, we were shocked.”
The researchers dubbed the catalyst Nanocatalysts on Single Crystal Edges (NOSCE). The magnesium-oxide nanopowder comes from a finely structured form of magnesium oxide, where the molecules bind continuously to the edge. There are no breaks or defects in the surface, allowing for uniform and predictable reactions.
“Our study solves a number of challenges the catalyst community faces,” Yavuz said. “We believe the NOSCE mechanism will improve other inefficient catalytic reactions and provide even further savings of greenhouse gas emissions.”
This work was supported, in part, by the Saudi-Aramco-KAIST CO2 Management Center and the National Research Foundation of Korea.
Other contributors include Ercan Ozdemir, Sreerangappa Ramesh, Aldiar Adishev, and Saravanan Subramanian, all of whom are affiliated with the Graduate School of Energy, Environment, Water and Sustainability at KAIST; Aadesh Harale, Mohammed Albuali, Bandar Abdullah Fadhel, and Aqil Jamal, all of whom are with the Research and Development Center in Saudi Arabia; and Dohyun Moon and Sun Hee Choi, both of whom are with the Pohang Accelerator Laboratory in Korea. Ozdemir is also affiliated with the Institute of Nanotechnology at the Gebze Technical University in Turkey; Fadhel and Jamal are also affiliated with the Saudi-Armco-KAIST CO2 Management Center in Korea.
Materials provided by The Korea Advanced Institute of Science and Technology (KAIST). Note: Content may be edited for style and length.
- Youngdong Song, Ercan Ozdemir, Sreerangappa Ramesh, Aldiar Adishev, Saravanan Subramanian, Aadesh Harale, Mohammed Albuali, Bandar Abdullah Fadhel, Aqil Jamal, Dohyun Moon, Sun Hee Choi, Cafer T. Yavuz. Dry reforming of methane by stable Ni–Mo nanocatalysts on single-crystalline MgO. Science, 2020; 367 (6479): 777 DOI: 10.1126/science.aav2412
During embryonic development, the entire nervous system, the skin and the sensory organs emerge from a single sheet of cells known as the ectoderm. While there have been extensive studies of how this sheet forms all these derivatives, it hasn’t been possible to study the process in humans – until now.
Rice bioscientist Aryeh Warmflash, graduate student George Britton and their colleagues have created a system in which all of the major cell types of ectoderm are formed in a culture dish in a pattern similar to that seen in embryos.This technique, based on controlling the geometry of stem cell colonies with microscale patterns, has helped them make the most comprehensive analysis yet of signaling pathways that drive patterning of human ectoderm.
“There are very few possible signals the embryo uses to generate the wide variety of cell types that arise,” Britton said. “We want to understand the timing of these signals and how the cells interpret them in time to generate this variety.”
It revealed that the balance between two signaling pathways, BMP and Wnt, are both critical, and even a bit adaptable as they orchestrate patterning in the ectoderm. The logic they employ ultimately drives ectodermal cells to their fates, but the research showed they can take more than one road to get there.
Britton said the micro-patterned plates and a better understanding of how the signaling pathways work let them manipulate stem cell colonies to form unusual patterns at the start, but ultimately they always seemed to converge at the same place. “We found different trajectories of the signals that arrived at the same pattern,” he said. That suggested the system by which stem cells become neurons, neural crest cells, neurogenic placodes and epidermis cells is pretty robust.
“A lot of people are interested in the transcription factor network that directs neural crest emergence, so this is a powerful system to dissect the signals that contribute to that logic,” Britton said. “That was one thing we feel we contributed to the field.
“There’s also the idea that cells that have the ability to interpret relative levels of BMP and Wnt to incorporate the appropriate fate decision,” he said. “In the embryo, cells are moving around quite a bit in a space where signals and the ligands they’re exposed to are also moving around. It might be that cells are reading the relative levels to determine a certain fate.”
The researchers observed that the relative activity of BMP and Wnt signaling determines cells’ decisions to become either neural crest or placodal cells, while BMP alone initiates and controls the size of the surface ectoderm, all within about the first four days.
“Four days is about right in the sense that cells are starting to make decisions: ‘I’m going to be a placodal cell, I’m going to be a neural crest cell, I’m going to be neural fate and I’m going to an epidermal fate,” Britton said.
“We see that approximately a day or two after BMP treatment. But it’s hard to put a finger on whether these are the final patterns,” he said. “We’d have to do a more careful observation to make sure those placodal cells don’t change to neural crest cells, or vice versa. That will give us information on how these lineages and fates settle into a final pattern, maybe by day 6 or 7.”
He said future studies will further refine their understanding of how signaling patterns work, as well as how the development of all the germ layers collaborate.
“Until now, studies of human stem cells differentiating to ectodermal fates were mostly about how to get all the cells in your culture dish to become a particular cell type; for example, how to make a dish full of neurons,” Warmflash said. “We are interested in a different question: How do cells interact with each other to make patterns of different cell fates? The system we developed does this outside the embryo and is allowing us to begin to tackle this question.”
A toothpaste-like composite with hexagonal boron nitride developed by researchers at Rice University is an effective electrolyte and separator in lithium-ion batteries intended for high-temperature applications in a number of industries, including aerospace and oil and gas. (Source: Jeff Fitlow/Rice University)
One major and dangerous problem with lithium-ion batteries is that they can catch fire when heated to high temperatures, an issue that has caused damage and even death when devices ignited without warning.
Now researchers at Rice University have come up with a solution to this very serious safety problem in the form of a combined electrolyte and separator for rechargeable lithium-ion batteries that supplies energy at usable voltages and in high temperatures. The material is a toothpaste-like composite that is capable of performing well at and withstanding high temperatures without combusting.
The problem with most current lithium-battery chemistries is that they present safety concerns when heated beyond 50C (122F) due to the electrolyte/separator combination used in them, explained Marco-Tulio Rodrigues, a Rice graduate student and one of the authors of a paper on the research published in Advanced Materials Science.
The work of the Rice team addresses both the issue of developing a separator that will not cause a short circuit and an electrolyte that doesn’t have the tendency to catch fire, he said.
The batteries made with the components they developed functioned as intended in temperatures of 50C (122F) for more than a month without losing efficiency, according to researchers. Moreover, test batteries consistently operated from room temperature to 150C (302F), setting one of the widest temperature ranges ever reported for such devices, they said.
To solve the electrolyte problem, researchers used solutions based on ionic liquids in the electrolytes, which have largely been proposed as substitutes for organic solvents in the electrolyte of lithium-ion batteries because they present a much higher thermal stability, Rodrigues explained.
“These chemicals are basically special salts with a very low melting point, in such a way that they are liquid at room temperatures,” he said. “They are completely nonflammable and they do not evaporate at all until they decompose, which occurs beyond 350C (662F).”
With the electrolyte situation solved, researchers turned their attention to finding a new separator, which they addressed with a material called hexagonal boron nitride, also known as white graphene.
Rice lab discovers simple technique to make biocompatible ‘turn-on’ dyes
It only took the replacement of one atom for Rice University scientists to give new powers to biocompatible fluorescent molecules.
The Rice lab of chemist Han Xiao reported in the Journal of the American Chemical Society it has developed a single-atom switch to turn fluorescent dyes used in biological imaging on and off at will. The technique will enable high-resolution imaging and dynamic tracking of biological processes in living cells, tissues and animals.
The Rice lab developed a minimally modified probe that can be triggered by a broad range of visible light. The patented process could replace existing photoactivatable fluorophores that may only be activated with ultraviolet light or require toxic chemicals to turn on the fluorescence, characteristics that limit their usefulness.
The researchers took advantage of a phenomenon known as photo-induced electron transfer (PET), which was already known to quench fluorescent signals.
They put fluorophores in cages of thiocarbonyl, the moeity responsible for quenching. With one-step organic synthesis, they replaced an oxygen atom in the cage with one of sulfur. That enabled them to induce the PET effect to quench fluorescence.
Triggering the complex again with visible light near the fluorescent molecule’s preferred absorbance oxidized the cage in turn. That knocked out the sulfur and replaced it with an oxygen atom, restoring fluorescence.
“All it takes to make these is a little chemistry and one step,” said Xiao, who joined Rice in 2017 with funding from the Cancer Prevention and Research Institute of Texas (CPRIT). “We demonstrated in the paper that it works the same for a range of fluorescent dyes. Basically, one reaction solves a lot of problems.”
Researchers worldwide use fluorescent molecules to tag and track cells or elements within cells. Activating the tags with low-powered visible light rather than ultraviolet is much less damaging to the cells being studied, Xiao said, and makes the long exposures of living cells required by super-resolution imaging possible.
Super-resolution experiments by Theodore Wensel, the Robert A. Welch Chair in Chemistry at Baylor College of Medicine, and his team confirmed their abilities, he said.
“We feel this will be a really good probe for living-cell imaging,” Xiao said. “People also use photoactivatable dye to track the dynamics of proteins, to see where and how far and how fast they travel. Our work was to provide a simple, general way to generate this dye.”
The researchers found their technique worked on a wide range of common fluorescent tags and could even be mixed for multicolor imaging of targeted molecules in a single cell.
Rice postdoctoral researcher Juan Tang is lead author of the paper. Co-authors are Rice graduate students Kuan-Lin Wu and Jingqi Pei; postdoctoral fellow Michael Robichaux of Baylor; and graduate student Nhung Nguyen and Yubin Zhou, an assistant professor at the Center for Translational Cancer Research at Texas A&M University. Xiao is the Norman Hackerman-Welch Young Investigator and an assistant professor of chemistry, biosciences, and bioengineering.
CPRIT, the Robert A. Welch Foundation, a Hamill Innovation Award, a John S. Dunn Foundation Collaborative Research Award and the National Institutes of Health supported the research.
Scientists at Texas Heart Institute (THI) report they have used biocompatible fibers invented at Rice University in studies that showed sewing them directly into damaged tissue can restore electrical function to hearts.
“Instead of shocking and defibrillating, we are actually correcting diseased conduction of the largest major pumping chamber of the heart by creating a bridge to bypass and conduct over a scarred area of a damaged heart,” said Dr. Mehdi Razavi, a cardiologist and director of Electrophysiology Clinical Research and Innovations at THI, who co-led the study with Rice chemical and biomolecular engineer Matteo Pasquali.
“Today there is no technology that treats the underlying cause of the No. 1 cause of sudden death, ventricular arrhythmias,” Razavi said. “These arrhythmias are caused by the disorganized firing of impulses from the heart’s lower chambers and are challenging to treat in patients after a heart attack or with scarred heart tissue due to such other conditions as congestive heart failure or dilated cardiomyopathy.”
Results of the studies on preclinical models appear as an open-access Editor’s Pick in the American Heart Association’s Circulation: Arrhythmia and Electrophysiology. The association helped fund the research with a 2015 grant.
The research springs from the pioneering 2013 invention by Pasquali’s lab of a method to make conductive fibers out of carbon nanotubes. The lab’s first threadlike fibers were a quarter of the width of a human hair, but contained tens of millions of microscopic nanotubes. The fibers are also being studied for electrical interfaces with the brain, for use in cochlear implants, as flexible antennas and for automotive and aerospace applications.
The experiments showed the nontoxic, polymer-coated fibers, with their ends stripped to serve as electrodes, were effective in restoring function during month-long tests in large preclinical models as well as rodents, whether the initial conduction was slowed, severed or blocked, according to the researchers. The fibers served their purpose with or without the presence of a pacemaker, they found.
In the rodents, they wrote, conduction disappeared when the fibers were removed.
“The reestablishment of cardiac conduction with carbon nanotube fibers has the potential to revolutionize therapy for cardiac electrical disturbances, one of the most common causes of death in the United States,” said co-lead author Mark McCauley, who carried out many of the experiments as a postdoctoral fellow at THI. He is now an assistant professor of clinical medicine at the University of Illinois College of Medicine.
“Our experiments provided the first scientific support for using a synthetic material-based treatment rather than a drug to treat the leading cause of sudden death in the U.S. and many developing countries around the world,” Razavi added.
Many questions remain before the procedure can move toward human testing, Pasquali said. The researchers must establish a way to sew the fibers in place using a minimally invasive catheter, and make sure the fibers are strong and flexible enough to serve a constantly beating heart over the long term. He said they must also determine how long and wide fibers should be, precisely how much electricity they need to carry and how they would perform in the growing hearts of young patients.
“Flexibility is important because the heart is continuously pulsating and moving, so anything that’s attached to the heart’s surface is going to be deformed and flexed,” said Pasquali, who has appointments at Rice’s Brown School of Engineering and Wiess School of Natural Sciences.
“Good interfacial contact is also critical to pick up and deliver the electrical signal,” he said. “In the past, multiple materials had to be combined to attain both electrical conductivity and effective contacts. These fibers have both properties built in by design, which greatly simplifies device construction and lowers risks of long-term failure due to delamination of multiple layers or coatings.”
Razavi noted that while there are many effective antiarrhythmic drugs available, they are often contraindicated in patients after a heart attack. “What is really needed therapeutically is to increase conduction,” he said. “Carbon nanotube fibers have the conductive properties of metal but are flexible enough to allow us to navigate and deliver energy to a very specific area of a delicate, damaged heart.”
In Vivo Restoration of Myocardial Conduction With Carbon Nanotube Fibers
Mark D. McCauley, Flavia Vitale, J. Stephen Yan, Colin C. Young, Brian Greet, Marco Orecchioni, Srikanth Perike, Abdelmotagaly Elgalad, Julia A. Coco, Mathews John, Doris A. Taylor, Luiz C. Sampaio, Lucia G. Delogu, Mehdi Razavi, Matteo Pasquali
Circulation: Arrhythmia and Electrophysiology Vol. 12, No. 8
Professor of Chemical and Biomolecular Engineering at Rice University
Cardiologist, Associate Professor of Medicine-Cardiology at Baylor College of Medicine and Director of Electrophysiology Clinical Research and Innovations at THI
Rice University’s solar-powered approach for purifying salt water with sunlight and nanoparticles is even more efficient than its creators first believed.
Researchers in Rice’s Laboratory for Nanophotonics (LANP) this week showed they could boost the efficiency of their solar-powered desalination system by more than 50% simply by adding inexpensive plastic lenses to concentrate sunlight into “hot spots.” The results are available online in the Proceedings of the National Academy of Sciences.
“The typical way to boost performance in solar-driven systems is to add solar concentrators and bring in more light,” said Pratiksha Dongare, a graduate student in applied physics at Rice’s Brown School of Engineering and co-lead author of the paper. “The big difference here is that we’re using the same amount of light. We’ve shown it’s possible to inexpensively redistribute that power and dramatically increase the rate of purified water production.”
In conventional membrane distillation, hot, salty water is flowed across one side of a sheetlike membrane while cool, filtered water flows across the other. The temperature difference creates a difference in vapor pressure that drives water vapor from the heated side through the membrane toward the cooler, lower-pressure side. Scaling up the technology is difficult because the temperature difference across the membrane—and the resulting output of clean water—decreases as the size of the membrane increases. Rice’s “nanophotonics-enabled solar membrane distillation” (NESMD) technology addresses this by using light-absorbing nanoparticles to turn the membrane itself into a solar-driven heating element.
Dongare and colleagues, including study co-lead author Alessandro Alabastri, coat the top layer of their membranes with low-cost, commercially available nanoparticles that are designed to convert more than 80% of sunlight energy into heat. The solar-driven nanoparticle heating reduces production costs, and Rice engineers are working to scale up the technology for applications in remote areas that have no access to electricity.
Alabastri, a physicist and Texas Instruments Research Assistant Professor in Rice’s Department of Electrical and Computer Engineering, used a simple mathematical example to describe the difference between a linear and nonlinear relationship. “If you take any two numbers that equal 10—seven and three, five and five, six and four—you will always get 10 if you add them together. But if the process is nonlinear, you might square them or even cube them before adding. So if we have nine and one, that would be nine squared, or 81, plus one squared, which equals 82. That is far better than 10, which is the best you can do with a linear relationship.”
In the case of NESMD, the nonlinear improvement comes from concentrating sunlight into tiny spots, much like a child might with a magnifying glass on a sunny day. Concentrating the light on a tiny spot on the membrane results in a linear increase in heat, but the heating, in turn, produces a nonlinear increase in vapor pressure. And the increased pressure forces more purified steam through the membrane in less time.
“We showed that it’s always better to have more photons in a smaller area than to have a homogeneous distribution of photons across the entire membrane,” Alabastri said.
Halas, a chemist and engineer who’s spent more than 25 years pioneering the use of light-activated nanomaterials, said, “The efficiencies provided by this nonlinear optical process are important because water scarcity is a daily reality for about half of the world’s people, and efficient solar distillation could change that.
“Beyond water purification, this nonlinear optical effect also could improve technologies that use solar heating to drive chemical processes like photocatalysis,” Halas said.
For example, LANP is developing a copper-based nanoparticle for converting ammonia into hydrogen fuel at ambient pressure.
Halas is the Stanley C. Moore Professor of Electrical and Computer Engineering, director of Rice’s Smalley-Curl Institute and a professor of chemistry, bioengineering, physics and astronomy, and materials science and nanoengineering.
NESMD is in development at the Rice-based Center for Nanotechnology Enabled Water Treatment (NEWT) and won research and development funding from the Department of Energy’s Solar Desalination program in 2018.
Houston, TX | Posted on May 29th, 2019
Researchers at Rice University, Durham (U.K.) University and North Carolina State University reported their success at activating the motors with precise two-photon excitation via near-infrared light. Unlike the ultraviolet light they first used to drive the motors, the new technique does not damage adjacent, healthy cells.
The team’s results appear in the American Chemical Society journal ACS Nano.
The research led by chemists James Tour of Rice, Robert Pal of Durham and Gufeng Wang of North Carolina may be best applied to skin, oral and gastrointestinal cancer cells that can be reached for treatment with a laser.
In a 2017 Nature paper, the same team reported the development of molecular motors enhanced with small proteins that target specific cancer cells.
Once in place and activated with light, the paddlelike motors spin up to 3 million times a second, allowing the molecules to drill through the cells’ protective membranes and killing them in minutes.
Since then, researchers have worked on a way to eliminate the use of damaging ultraviolet light. In two-photon absorption, a phenomenon predicted in 1931 and confirmed 30 years later with the advent of lasers, the motors absorb photons in two frequencies and move to a higher energy state, triggering the paddles.
A video produced in 2017 explains the basic concept of cell death via molecular motors. Video produced by Brandon Martin/Rice University.
“Multiphoton activation is not only more biocompatible but also allows deeper tissue penetration and eliminates any unwanted side effects that may arise with the previously used UV light,” Pal said.
The researchers tested their updated motors on skin, breast, cervical and prostate cancer cells in the lab. Once the motors found their targets, lasers activated them with a precision of about 200 nanometers.
In most cases, the cells were dead within three minutes, they reported. They believe the motors also drill through chromatin and other components of the diseased cells, which could help slow metastasis.
Because the motors target specific cells, Tour said work is underway to adapt them to kill antibiotic-resistant bacteria as well.
“We continue to perfect the molecular motors, aiming toward ones that will work with visible light and provide even higher efficacies of kill toward the cellular targets,” he said.
Rice postdoctoral researcher Dongdong Liu is lead author of the paper. Co-authors are Rice alumni Victor Garcia-López, Lizanne Nilewski and Amir Aliyan, visiting research scientist Richard Gunasekera, and senior research scientist Lawrence Alemany and graduate student Tao Jin of North Carolina State.
Wang is an assistant professor of chemistry at North Carolina State. Pal is an assistant professor of chemistry at Durham. Tour is the T.T. and W.F. Chao Chair in Chemistry as well as a professor of computer science and of materials science and nanoengineering at Rice.
The Royal Society, the United Kingdom’s Engineering and Physical Sciences Research Council, the Discovery Institute, the Pensmore Foundation and North Carolina State supported the research.
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A nanocomposite invented at Rice University’s Brown School of Engineering promises to be a superior high-temperature dielectric material for flexible electronics, energy storage and electric devices.
The nanocomposite combines one-dimensional polymer nanofibers and two-dimensional boron nitride nanosheets. The nanofibers reinforce the self-assembling material while the “white graphene” nanosheets provide a thermally conductive network that allows it to withstand the heat that breaks down common dielectrics, the polarized insulators in batteries and other devices that separate positive and negative electrodes.
The discovery by the lab of Rice materials scientist Pulickel Ajayan is detailed in Advanced Functional Materials.
Research scientist M.M. Rahman and postdoctoral researcher Anand Puthirath of the Ajayan lab led the study to meet the challenge posed by next-generation electronics: Dielectrics must be thin, tough, flexible and able to withstand harsh environments.
“Ceramic is a very good dielectric, but it is mechanically brittle,” Rahman said of the common material. “On the other hand, polymer is a good dielectric with good mechanical properties, but its thermal tolerance is very low.”
Boron nitride is an electrical insulator, but happily disperses heat, he said. “When we combined the polymer nanofiber with boron nitride, we got a material that’s mechanically exceptional, and thermally and chemically very stable,” Rahman said.
The 12-to-15-micron-thick material acts as an effective heat sink up to 250 degrees Celsius (482 degrees Fahrenheit), according to the researchers. Tests showed the polymer nanofibers-boron nitride combination dispersed heat four times better than the polymer alone.
In its simplest form, a single layer of polyaramid nanofibers binds via van der Waals forces to a sprinkling of boron nitride flakes, 10% by weight of the final product. The flakes are just dense enough to form a heat-dissipating network that still allows the composite to retain its flexibility, and even foldability, while maintaining its robustness. Layering polyaramid and boron nitride can make the material thicker while still retaining flexibility, according to the researchers.
“The 1D polyaramid nanofiber has many interesting properties except thermal conductivity,” Rahman said. “And boron nitride is a very interesting 2-D material right now. They both have different independent properties, but when they are together, they make something very unique.”
Rahman said the material is scalable and should be easy to incorporate into manufacturing.
Stronger and more flexible than graphene, a single-atom layer of boron could revolutionize sensors, batteries, and catalytic chemistry.
From MIT Technology Review March 2019