Caption: SEM images of MWCNT-PA (Multi-Walled Carbon Nanotube-Polyamide) nanocomposite membranes, for plain PA, and PA with 5, 9.5, 12.5, 15.5, 17 and 20 wt.% of MWCNT, where the typical lobe-like structures appear at the surface. Note the tendency towards a flatter membrane surface as the content of MWCNT increases. Scale bar corresponds to 1.0?μm for all the micrographs. Credit: Copyright 2018, Springer Nature, Licensed under CC BY 4.0
It seems unlikely that the image’s resemblance to a Japanese kimono on display is accidental. Either way, nicely done!
A research team of Shinshu University, Japan, has developed robust reverse osmosis membranes that can endure large-scale water desalination. The team published their results in early February  in Scientific Reports.
“Since more than 97 percent of the water in the world is saline water, reverse osmosis desalination plants for producing fresh water are increasingly important for providing a safe and consistent supply,” said Morinobu Endo, Ph.D., corresponding author on the paper. Endo is a distinguished professor of Shinshu University and the Honorary Director of the Institute of Carbon Science and Technology. “Even though reverse osmosis membrane technology has been under development for several decades, new threats like global warming and increasing clean water demand in populated urban centers challenge the conventional water supply systems.”
Reverse osmosis membranes typically consist of thin film composite systems, with an active layer of polymer film that restricts undesired substances, such as salt, from passing through a permeable porous substrate. Such membranes can turn seawater into drinkable water, as well as aid in agricultural and landscape irrigation, but they can be costly to operate and spend a large amount of energy.
To meet the demand of potable water at low cost, Endo says more robust membranes capable of withstanding harsh conditions, while remaining chemically stable to tolerate cleaning treatments, are necessary. The key lays in carbon nanotechnology.
Endo is a pioneer of carbon nanotubes [sic] synthesis by catalytic chemical vapor deposition. In this research, Endo and his team developed a multi-walled carbon nanotube-polyamide nanocomposite membrane, which is resistant to chlorine–one of the main cause of degradation or failure cases in reverse osmosis membranes. The added carbon nanotubes create a protective effect that stabilized the linked molecules of the polyamide against chlorine.
“Carbon nanotechnology has been expected to bring benefits, and this is one promising example of the contribution of carbon nanotubes to a very critical application: water purification,” Endo said. “Carbon nanotubes and fibers are already superb reinforcements for other applications in materials science and engineering, and this is yet another field where their exceptional properties can be used for improving conventional technologies.”
The researchers are working to stabilize and expand the production and processing of multi-walled carbon nanotube-polyamide nanocomposite membranes.
“We are currently working on scaling up our method of synthesis, which, in principle, is based on the same method used to prepare current polyamide membranes,” Endo said. He also noted that his team is planning a collaboration to produce commercial membranes.
In discussions about water desalination and carbon nanomaterials, it’s graphene that’s usually mentioned these days. By contrast, scientists from the US Department of Energy’s Lawrence Livermore National Laboratory (LLNL) have turned to carbon nanotubes,
There are two news items about the work at LLNL on ScienceDaily, this first one originated by the American Association for the Advancement of Science (AAAS) offers a succinct summary of the work (from an August 24, 2017 news item on ScienceDaily,
At just the right size, carbon nanotubes can filter water with better efficiency than biological proteins, a new study reveals. The results could pave the way to new water filtration systems, at a time when demands for fresh water pose a global threat to sustainable development.
A class of biological proteins, called aquaporins, is able to effectively filter water, yet scientists have not been able to manufacture scalable systems that mimic this ability. Aquaporins usually exhibit channels for filtering water molecules at a narrow width of 0.3 nanometers, which forces the water molecules into a single-file chain.
Here, Ramya H. Tunuguntla and colleagues experimented with nanotubes of different widths to see which ones are best for filtering water. Intriguingly, they found that carbon nanotubes with a width of 0.8 nanometers outperformed aquaporins in filtering efficiency by a factor of six.
These narrow carbon nanotube porins (nCNTPs) were still slim enough to force the water molecules into a single-file chain. The researchers attribute the differences between aquaporins and nCNTPS to differences in hydrogen bonding — whereas pore-lining residues in aquaporins can donate or accept H bonds to incoming water molecules, the walls of CNTPs cannot form H bonds, permitting unimpeded water flow.
The nCNTPs in this study maintained permeability exceeding that of typical saltwater, only diminishing at very high salt concentrations. Lastly, the team found that by changing the charges at the mouth of the nanotube, they can alter the ion selectivity. This advancement is highlighted in a Perspective [in Science magazine] by Zuzanna Siwy and Francesco Fornasiero.
Lawrence Livermore scientists, in collaboration with researchers at Northeastern University, have developed carbon nanotube pores that can exclude salt from seawater. The team also found that water permeability in carbon nanotubes (CNTs) with diameters smaller than a nanometer (0.8 nm) exceeds that of wider carbon nanotubes by an order of magnitude.
The nanotubes, hollow structures made of carbon atoms in a unique arrangement, are more than 50,000 times thinner than a human hair. The super smooth inner surface of the nanotube is responsible for their remarkably high water permeability, while the tiny pore size blocks larger salt ions.
There’s a rather lovely illustration for this work,
An artist’s depiction of the promise of carbon nanotube porins for desalination. The image depicts a stylized carbon nanotube pipe that delivers clean desalinated water from the ocean to a kitchen tap. Image by Ryan Chen/LLNL
Increasing demands for fresh water pose a global threat to sustainable development, resulting in water scarcity for 4 billion people. Current water purification technologies can benefit from the development of membranes with specialized pores that mimic highly efficient and water selective biological proteins.
“We found that carbon nanotubes with diameters smaller than a nanometer bear a key structural feature that enables enhanced transport. The narrow hydrophobic channel forces water to translocate in a single-file arrangement, a phenomenon similar to that found in the most efficient biological water transporters,” said Ramya Tunuguntla, an LLNL postdoctoral researcher and co-author of the manuscript appearing in the Aug. 24 edition of Science.
Computer simulations and experimental studies of water transport through CNTs with diameters larger than 1 nm showed enhanced water flow, but did not match the transport efficiency of biological proteins and did not separate salt efficiently, especially at higher salinities. The key breakthrough achieved by the LLNL team was to use smaller-diameter nanotubes that delivered the required boost in performance.
“These studies revealed the details of the water transport mechanism and showed that rational manipulation of these parameters can enhance pore efficiency,” said Meni Wanunu, a physics professor at Northeastern University and co-author on the study.
“Carbon nanotubes are a unique platform for studying molecular transport and nanofluidics,” said Alex Noy, LLNL principal investigator on the CNT project and a senior author on the paper. “Their sub-nanometer size, atomically smooth surfaces and similarity to cellular water transport channels make them exceptionally suited for this purpose, and it is very exciting to make a synthetic water channel that performs better than nature’s own.”
This discovery by the LLNL scientists and their colleagues has clear implications for the next generation of water purification technologies and will spur a renewed interest in development of the next generation of high-flux membranes.
Earth is 70 percent water, but only a tiny portion—0.007 percent—is available to drink.
As potable water sources dwindle, global population increases every year. One potential solution to quenching the planet’s thirst is through desalinization—the process of removing salt from seawater. While tantalizing, this approach has always been too expensive and energy intensive for large-scale feasibility.
Now, researchers from Northeastern have made a discovery that could change that, making desalinization easier, faster and cheaper than ever before. In a paper published Thursday [August 24, 2017] in Science, the group describes how carbon nanotubes of a certain size act as the perfect filter for salt—the smallest and most abundant water contaminant.
Filtering water is tricky because water molecules want to stick together. The “H” in H2O is hydrogen, and hydrogen bonds are strong, requiring a lot of energy to separate. Water tends to bulk up and resist being filtered. But nanotubes do it rapidly, with ease.
A carbon nanotube is like an impossibly small rolled up sheet of paper, about a nanometer in diameter. For comparison, the diameter of a human hair is 50 to 70 micrometers—50,000 times wider. The tube’s miniscule size, exactly 0.8 nm, only allows one water molecule to pass through at a time. This single-file lineup disrupts the hydrogen bonds, so water can be pushed through the tubes at an accelerated pace, with no bulking.
“You can imagine if you’re a group of people trying to run through the hallway holding hands, it’s going to be a lot slower than running through the hallway single-file,” said co-author Meni Wanunu, associate professor of physics at Northeastern. Wanunu and post doctoral student Robert Henley collaborated with scientists at the Lawrence Livermore National Laboratory in California to conduct the research.
Scientists led by Aleksandr Noy at Lawrence Livermore discovered last year  that carbon nanotubes were an ideal channel for proton transport. For this new study, Henley brought expertise and technology from Wanunu’s Nanoscale Biophysics Lab to Noy’s lab, and together they took the research one step further.
In addition to being precisely the right size for passing single water molecules, carbon nanotubes have a negative electric charge. This causes them to reject anything with the same charge, like the negative ions in salt, as well as other unwanted particles.
“While salt has a hard time passing through because of the charge, water is a neutral molecule and passes through easily,” Wanunu said. Scientists in Noy’s lab had theorized that carbon nanotubes could be designed for specific ion selectivity, but they didn’t have a reliable system of measurement. Luckily, “That’s the bread and butter of what we do in Meni’s lab,” Henley said. “It created a nice symbiotic relationship.”
“Robert brought the cutting-edge measurement and design capabilities of Wanunu’s group to my lab, and he was indispensable in developing a new platform that we used to measure the ion selectivity of the nanotubes,” Noy said.
The result is a novel system that could have major implications for the future of water security. The study showed that carbon nanotubes are better at desalinization than any other existing method— natural or man-made.
To keep their momentum going, the two labs have partnered with a leading water purification organization based in Israel. And the group was recently awarded a National Science Foundation/Binational Science Foundation grant to conduct further studies and develop water filtration platforms based on their new method. As they continue the research, the researchers hope to start programs where students can learn the latest on water filtration technology—with the goal of increasing that 0.007 percent.
As is usual in these cases there’s a fair degree of repetition but there’s always at least one nugget of new information, in this case, a link to Israel. As I noted many times, the Middle East is experiencing serious water issues. My most recent ‘water and the Middle East’ piece is an August 21, 2017 post about rainmaking at the Masdar Institute in United Arab Emirates. Approximately 50% of the way down the posting, I mention Israel and Palestine’s conflict over water.
EPFL researchers have developed a system that generates electricity from osmosis with unparalleled efficiency. Their work, featured in “Nature”, uses seawater, fresh water, and a new type of membrane just three atoms thick.
A July 13, 2016 news item on Nanowerk highlights research on osmotic power at École polytechnique fédérale de Lausanne (EPFL; Switzerland),
Proponents of clean energy will soon have a new source to add to their existing array of solar, wind, and hydropower: osmotic power. Or more specifically, energy generated by a natural phenomenon occurring when fresh water comes into contact with seawater through a membrane.
Researchers at EPFL’s Laboratory of Nanoscale Biology have developed an osmotic power generation system that delivers never-before-seen yields. Their innovation lies in a three atoms thick membrane used to separate the two fluids. …
The concept is fairly simple. A semipermeable membrane separates two fluids with different salt concentrations. Salt ions travel through the membrane until the salt concentrations in the two fluids reach equilibrium. That phenomenon is precisely osmosis.
If the system is used with seawater and fresh water, salt ions in the seawater pass through the membrane into the fresh water until both fluids have the same salt concentration. And since an ion is simply an atom with an electrical charge, the movement of the salt ions can be harnessed to generate electricity.
A 3 atoms thick, selective membrane that does the job
EPFL’s system consists of two liquid-filled compartments separated by a thin membrane made of molybdenum disulfide. The membrane has a tiny hole, or nanopore, through which seawater ions pass into the fresh water until the two fluids’ salt concentrations are equal. As the ions pass through the nanopore, their electrons are transferred to an electrode – which is what is used to generate an electric current.
Thanks to its properties the membrane allows positively-charged ions to pass through, while pushing away most of the negatively-charged ones. That creates voltage between the two liquids as one builds up a positive charge and the other a negative charge. This voltage is what causes the current generated by the transfer of ions to flow.
“We had to first fabricate and then investigate the optimal size of the nanopore. If it’s too big, negative ions can pass through and the resulting voltage would be too low. If it’s too small, not enough ions can pass through and the current would be too weak,” said Jiandong Feng, lead author of the research.
What sets EPFL’s system apart is its membrane. In these types of systems, the current increases with a thinner membrane. And EPFL’s membrane is just a few atoms thick. The material it is made of – molybdenum disulfide – is ideal for generating an osmotic current. “This is the first time a two-dimensional material has been used for this type of application,” said Aleksandra Radenovic, head of the laboratory of Nanoscale Biology
Powering 50’000 energy-saving light bulbs with 1m2 membrane
The potential of the new system is huge. According to their calculations, a 1m2 membrane with 30% of its surface covered by nanopores should be able to produce 1MW of electricity – or enough to power 50,000 standard energy-saving light bulbs. And since molybdenum disulfide (MoS2) is easily found in nature or can be grown by chemical vapor deposition, the system could feasibly be ramped up for large-scale power generation. The major challenge in scaling-up this process is finding out how to make relatively uniform pores.
Until now, researchers have worked on a membrane with a single nanopore, in order to understand precisely what was going on. ” From an engineering perspective, single nanopore system is ideal to further our fundamental understanding of 8=-based processes and provide useful information for industry-level commercialization”, said Jiandong Feng.
The researchers were able to run a nanotransistor from the current generated by a single nanopore and thus demonstrated a self-powered nanosystem. Low-power single-layer MoS2 transistors were fabricated in collaboration with Andras Kis’ team at at EPFL, while molecular dynamics simulations were performed by collaborators at University of Illinois at Urbana–Champaign
Harnessing the potential of estuaries
EPFL’s research is part of a growing trend. For the past several years, scientists around the world have been developing systems that leverage osmotic power to create electricity. Pilot projects have sprung up in places such as Norway, the Netherlands, Japan, and the United States to generate energy at estuaries, where rivers flow into the sea. For now, the membranes used in most systems are organic and fragile, and deliver low yields. Some systems use the movement of water, rather than ions, to power turbines that in turn produce electricity.
Once the systems become more robust, osmotic power could play a major role in the generation of renewable energy. While solar panels require adequate sunlight and wind turbines adequate wind, osmotic energy can be produced just about any time of day or night – provided there’s an estuary nearby.
Here’s a link to and a citation for the paper,
Single-layer MoS2 nanopores as nanopower generators by Jiandong Feng, Michael Graf, Ke Liu, Dmitry Ovchinnikov, Dumitru Dumcenco, Mohammad Heiranian, Vishal Nandigana, Narayana R. Aluru, Andras Kis, & Aleksandra Radenovic. Nature (2016) doi:10.1038/nature18593 Published online 13 July 2016