Tag Archives: desalination

Spooling strips of graphene

An April 18, 2018 news item on phys.org highlights an exciting graphene development at the Massachusetts Institute of Technology (MIT),

MIT engineers have developed a continuous manufacturing process that produces long strips of high-quality graphene.

The team’s results are the first demonstration of an industrial, scalable method for manufacturing high-quality graphene that is tailored for use in membranes that filter a variety of molecules, including salts, larger ions, proteins, or nanoparticles. Such membranes should be useful for desalination, biological separation, and other applications.

A new manufacturing process produces strips of graphene, at large scale, for use in membrane technologies and other applications. Image: Christine Daniloff, MIT

An April 17, 2018 MIT news release (also on EurekAlert) by Jennifer Chu, which originated the news item,. provides more detail,

“For several years, researchers have thought of graphene as a potential route to ultrathin membranes,” says John Hart, associate professor of mechanical engineering and director of the Laboratory for Manufacturing and Productivity at MIT. “We believe this is the first study that has tailored the manufacturing of graphene toward membrane applications, which require the graphene to be seamless, cover the substrate fully, and be of high quality.”

Hart is the senior author on the paper, which appears online in the journal Applied Materials and Interfaces. The study includes first author Piran Kidambi, a former MIT postdoc who is now an assistant professor at Vanderbilt University; MIT graduate students Dhanushkodi Mariappan and Nicholas Dee; Sui Zhang of the National University of Singapore; Andrey Vyatskikh, a former student at the Skolkovo Institute of Science and Technology who is now at Caltech; and Rohit Karnik, an associate professor of mechanical engineering at MIT.

Growing graphene

For many researchers, graphene is ideal for use in filtration membranes. A single sheet of graphene resembles atomically thin chicken wire and is composed of carbon atoms joined in a pattern that makes the material extremely tough and impervious to even the smallest atom, helium.

Researchers, including Karnik’s group, have developed techniques to fabricate graphene membranes and precisely riddle them with tiny holes, or nanopores, the size of which can be tailored to filter out specific molecules. For the most part, scientists synthesize graphene through a process called chemical vapor deposition, in which they first heat a sample of copper foil and then deposit onto it a combination of carbon and other gases.

Graphene-based membranes have mostly been made in small batches in the laboratory, where researchers can carefully control the material’s growth conditions. However, Hart and his colleagues believe that if graphene membranes are ever to be used commercially they will have to be produced in large quantities, at high rates, and with reliable performance.

“We know that for industrialization, it would need to be a continuous process,” Hart says. “You would never be able to make enough by making just pieces. And membranes that are used commercially need to be fairly big – some so big that you would have to send a poster-wide sheet of foil into a furnace to make a membrane.”

A factory roll-out

The researchers set out to build an end-to-end, start-to-finish manufacturing process to make membrane-quality graphene.

The team’s setup combines a roll-to-roll approach – a common industrial approach for continuous processing of thin foils – with the common graphene-fabrication technique of chemical vapor deposition, to manufacture high-quality graphene in large quantities and at a high rate. The system consists of two spools, connected by a conveyor belt that runs through a small furnace. The first spool unfurls a long strip of copper foil, less than 1 centimeter wide. When it enters the furnace, the foil is fed through first one tube and then another, in a “split-zone” design.

While the foil rolls through the first tube, it heats up to a certain ideal temperature, at which point it is ready to roll through the second tube, where the scientists pump in a specified ratio of methane and hydrogen gas, which are deposited onto the heated foil to produce graphene.

“Graphene starts forming in little islands, and then those islands grow together to form a continuous sheet,” Hart says. “By the time it’s out of the oven, the graphene should be fully covering the foil in one layer, kind of like a continuous bed of pizza.”

As the graphene exits the furnace, it’s rolled onto the second spool. The researchers found that they were able to feed the foil continuously through the system, producing high-quality graphene at a rate of 5 centimers per minute. Their longest run lasted almost four hours, during which they produced about 10 meters of continuous graphene.

“If this were in a factory, it would be running 24-7,” Hart says. “You would have big spools of foil feeding through, like a printing press.”

Flexible design

Once the researchers produced graphene using their roll-to-roll method, they unwound the foil from the second spool and cut small samples out. They cast the samples with a polymer mesh, or support, using a method developed by scientists at Harvard University, and subsequently etched away the underlying copper.

“If you don’t support graphene adequately, it will just curl up on itself,” Kidambi says. “So you etch copper out from underneath and have graphene directly supported by a porous polymer – which is basically a membrane.”

The polymer covering contains holes that are larger than graphene’s pores, which Hart says act as microscopic “drumheads,” keeping the graphene sturdy and its tiny pores open.

The researchers performed diffusion tests with the graphene membranes, flowing a solution of water, salts, and other molecules across each membrane. They found that overall, the membranes were able to withstand the flow while filtering out molecules. Their performance was comparable to graphene membranes made using conventional, small-batch approaches.

The team also ran the process at different speeds, with different ratios of methane and hydrogen gas, and characterized the quality of the resulting graphene after each run. They drew up plots to show the relationship between graphene’s quality and the speed and gas ratios of the manufacturing process. Kidambi says that if other designers can build similar setups, they can use the team’s plots to identify the settings they would need to produce a certain quality of graphene.

“The system gives you a great degree of flexibility in terms of what you’d like to tune graphene for, all the way from electronic to membrane applications,” Kidambi says.

Looking forward, Hart says he would like to find ways to include polymer casting and other steps that currently are performed by hand, in the roll-to-roll system.

“In the end-to-end process, we would need to integrate more operations into the manufacturing line,” Hart says. “For now, we’ve demonstrated that this process can be scaled up, and we hope this increases confidence and interest in graphene-based membrane technologies, and provides a pathway to commercialization.”

Here’s a link to and a citation for the paper,

A Scalable Route to Nanoporous Large-Area Atomically Thin Graphene Membranes by Roll-to-Roll Chemical Vapor Deposition and Polymer Support Casting by Piran R. Kidambi, Dhanushkodi D. Mariappan, Nicholas T. Dee, Andrey Vyatskikh, Sui Zhang, Rohit Karnik, and A. John Hart. ACS Appl. Mater. Interfaces, 2018, 10 (12), pp 10369–10378 DOI: 10.1021/acsami.8b00846 Publication Date (Web): March 19, 2018

Copyright © 2018 American Chemical Society

This paper is behind a paywall.

Finally, there is a video of the ‘graphene spooling out’ process,

Carbon nanotubes for water desalination

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.

The second Aug. 24, 2017 news item on ScienceDaily offers a more technical  perspective,

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

An Aug. 24, 2017 LLNL news release (also on EurekAlert), which originated the second news item, proceeds

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 [2017]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.

Here’s a link to and a citation for the paper,

Enhanced water permeability and tunable ion selectivity in subnanometer carbon nanotube porins by Ramya H. Tunuguntla, Robert Y. Henley, Yun-Chiao Yao, Tuan Anh Pham, Meni Wanunu, Aleksandr Noy. Science 25 Aug 2017: Vol. 357, Issue 6353, pp. 792-796 DOI: 10.1126/science.aan2438

This paper is behind a paywall.

And, Northeastern University issued an August 25, 2017 news release (also on EurekAlert) by Allie Nicodemo,

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 [2016] 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.

Masdar Institute and rainmaking

Water security, of course, is a key issue and of particular concern in many parts of the world including the Middle East. (In the Pacific Northwest, an area described as a temperate rain forest, there tends to be less awareness but even we are sometimes forced to ration water.) According to a July 5, 2017 posting by Bhok Thompson (on the Green Prophet website) scientists at the Masdar Institute of Science and Technology (in Abu Dhabi, United Arab Emirates [UA]E) have applied for a patent on a new technique for rainmaking,

Umbrella sales in the UAE may soon see a surge in pricing. Researchers at the Masdar Institute have filed for a provisional patent with the United States Patent and Trademark Office for their discovery – and innovative cloud seeding material that moves them closer to their goal of producing rain on demand. It appears to be a more practical approach than building artificial mountains.

Dr. Linda Zou is leading the project. A professor of chemical and environmental engineering, she is one of the first scientists to explore nanotechnology to enhance a cloud seeding material’s ability to produce rain. By filing a patent, the team is paving a way to commercialize their discovery, and aligning with Masdar Institute’s aim to position the UAE as a world leader in science and tech, specifically in the realm of environmental sustainability.

A January 31, 2017 posting by Erica Solomon for the Masdar Institute reveals more about the project,

The Masdar Institute research team that was one of the inaugural recipients of the US$ 5 million grant from the UAE Research Program for Rain Enhancement Science last year has made significant progress in their work as evidenced by the filing a provisional patent with the United States Patent and Trademark Office (USPTO).

By filing a patent on their innovative cloud seeding material, the research team is bringing the material in the pathway for commercialization, thereby supporting Masdar Institute’s goal of bolstering the United Arab Emirates’ local intellectual property, which is a key measure of the country’s innovation drive. It also signifies a milestone towards achieving greater water security in the UAE, as rainfall enhancement via cloud seeding can potentially increase rainfall between 10% to 30%, helping to refresh groundwater reserves, boost agricultural production, and reduce the country’s heavy reliance on freshwater produced by energy-intensive seawater desalination.

Masdar Institute Professor of Chemical and Environmental Engineering, Dr. Linda Zou, is the principal investigator of this research project, and one of the first scientists in the world to explore the use of nanotechnology to enhance a cloud seeding material’s ability to produce rain.

“Using nanotechnology to accelerate water droplet formation on a typical cloud seeding material has never been researched before. It is a new approach that could revolutionize the development of cloud seeding materials and make them significantly more efficient and effective,” Dr. Zou remarked.

Conventional cloud seeding materials are small particles such as pure salt crystals, dry ice and silver iodide. These tiny particles, which are a few microns (one-thousandth of a millimeter) in size, act as the core around which water condenses in the clouds, stimulating water droplet growth. Once the air in the cloud reaches a certain level of saturation, it can no longer hold in that moisture, and rain falls. Cloud seeding essentially mimics what naturally occurs in clouds, but enhances the process by adding particles that can stimulate and accelerate the condensation process.

Dr. Zou and her collaborators, Dr. Mustapha Jouiad, Principal Research Scientist in Mechanical and Materials Engineering Department, postdoctoral researcher Dr. Nabil El Hadri and PhD student Haoran Liang, explored ways to improve the process of condensation on a pure salt crystal by layering it with a thin coating of titanium dioxide.

The extremely thin coating measures around 50 nanometers, which is more than one thousand times thinner than a human hair. Despite the coating’s miniscule size, the titanium dioxide’s effect on the salt’s condensation efficiency is significant. Titanium dioxide is a hydrophilic photocatalyst, which means that when in contact with water vapor in the cloud, it helps to initiate and sustain the water vapor adsorption and condensation on the nanoparticle’s surface. This important property of the cloud seeding material speeds up the formation of large water droplets for rainfall.

Dr. Zou’s team found that the titanium dioxide coating improved the salt’s ability to adsorb and condense water vapor over 100 times compared to a pure salt crystal. Such an increase in condensation efficiency could improve a cloud’s ability to produce more precipitation, making rain enhancement operations more efficient and effective. The research will now move to the next stage of simulated cloud and field testing in the future.

Dr. Zou’s research grant covers two more years of research. During this time, her team will continue to study different design concepts and structures for cloud seeding materials inspired by nanotechnology.

To give you a sense of the urgent need for these technologies, here’s the title from my Aug. 24, 2015 posting, The Gaza is running out of water by 2016 if the United Nations predictions are correct. I’ve not come across any updates on the situation in the Gaza Strip but both Israel and Palestine have recently signed a deal concerning water. Dalia Hatuqa’s August 2017 feature on the water deal for Al Jazeera is critical primarily of Israel (as might be expected) but there are one or two subtle criticisms of Palestine too,

Critics have also warned that the plan does not address Israeli restrictions on Palestinian access to water and the development of infrastructure needed to address the water crisis in the occupied West Bank.

Palestinians in the West Bank consume only 70 litres of water per capita per day, well below what the World Health Organization recommends as a minimum (100).

In the most vulnerable communities in Area C – those not connected to the water network – that number further drops to 20, according to EWASH, a coalition of Palestinian and international organisations working on water and sanitation in the Palestinian territories.

The recent bilateral agreement, which does not increase the Palestinians’ quota of water in the Jordan River, makes an untenable situation permanent and guarantees Israel a lion’s share of its water, thus reinforcing the status quo, Buttu [Diana Buttu, a former adviser to the Palestinian negotiating team] said.

“They have moved away from the idea that water is a shared resource and instead adopted the approach that Israel controls and allocates water to Palestinians,” she added. “Israel has been selling water to Palestinians for a long time, but this is enshrining it even further by saying that this is the way to alleviate the water problem.”

Israeli officials say that water problems in the territories could have been addressed had the Palestinians attended the meetings of the joint committee. Palestinians attribute their refusal to conditions set by their counterparts, namely that they must support Israeli settlement water projects for any Palestinian water improvements to be approved.

According to Israeli foreign ministry spokesman Emmanuel Nahshon, “There are many things to be done together to upgrade the water infrastructure in the PA. We are talking about old, leaking pipes, and a more rational use of water.” He also pointed to the illegal tapping into pipes, which he maintained Palestinians did because they did not want to pay for water. “This is something we’ve been wanting to do over the years, and the new water agreement is one of the ways to deal with that. The new agreement … is not only about water quotas; it’s also about more coherent and better use of water, in order to address the needs of the Palestinians.”

But water specialists say that the root cause of the problem is not illegal activity, but the unavailability of water resources to Palestinians and the mismanagement and diversion of the Jordan River.

Access to water is gong to be of increasing urgency should temperatures continue to rise as they have. In many parts of the world, potable water is not easy to find and if temperatures continue to rise areas that did have some water security will lose it and the potential for conflict rises hugely. Palestine and Israel may be a harbinger of what’s to come. As for the commodification of water, I have trouble accepting it; I think everyone has a right to water.

Using only sunlight to desalinate water

The researchers seem to believe that this new desalination technique could be a game changer. From a June 20, 2017 news item on Azonano,

An off-grid technology using only the energy from sunlight to transform salt water into fresh drinking water has been developed as an outcome of the effort from a federally funded research.

The desalination system uses a combination of light-harvesting nanophotonics and membrane distillation technology and is considered to be the first major innovation from the Center for Nanotechnology Enabled Water Treatment (NEWT), which is a multi-institutional engineering research center located at Rice University.

NEWT’s “nanophotonics-enabled solar membrane distillation” technology (NESMD) integrates tried-and-true water treatment methods with cutting-edge nanotechnology capable of transforming sunlight to heat. …

A June 19, 2017 Rice University news release, which originated the news item, expands on the theme,

More than 18,000 desalination plants operate in 150 countries, but NEWT’s desalination technology is unlike any other used today.

“Direct solar desalination could be a game changer for some of the estimated 1 billion people who lack access to clean drinking water,” said Rice scientist and water treatment expert Qilin Li, a corresponding author on the study. “This off-grid technology is capable of providing sufficient clean water for family use in a compact footprint, and it can be scaled up to provide water for larger communities.”

The oldest method for making freshwater from salt water is distillation. Salt water is boiled, and the steam is captured and run through a condensing coil. Distillation has been used for centuries, but it requires complex infrastructure and is energy inefficient due to the amount of heat required to boil water and produce steam. More than half the cost of operating a water distillation plant is for energy.

An emerging technology for desalination is membrane distillation, where hot salt water is flowed across one side of a porous membrane and cold freshwater is flowed across the other. Water vapor is naturally drawn through the membrane from the hot to the cold side, and because the seawater need not be boiled, the energy requirements are less than they would be for traditional distillation. However, the energy costs are still significant because heat is continuously lost from the hot side of the membrane to the cold.

“Unlike traditional membrane distillation, NESMD benefits from increasing efficiency with scale,” said Rice’s Naomi Halas, a corresponding author on the paper and the leader of NEWT’s nanophotonics research efforts. “It requires minimal pumping energy for optimal distillate conversion, and there are a number of ways we can further optimize the technology to make it more productive and efficient.”

NEWT’s new technology builds upon research in Halas’ lab to create engineered nanoparticles that harvest as much as 80 percent of sunlight to generate steam. By adding low-cost, commercially available nanoparticles to a porous membrane, NEWT has essentially turned the membrane itself into a one-sided heating element that alone heats the water to drive membrane distillation.

“The integration of photothermal heating capabilities within a water purification membrane for direct, solar-driven desalination opens new opportunities in water purification,” said Yale University ‘s Menachem “Meny” Elimelech, a co-author of the new study and NEWT’s lead researcher for membrane processes.

In the PNAS study, researchers offered proof-of-concept results based on tests with an NESMD chamber about the size of three postage stamps and just a few millimeters thick. The distillation membrane in the chamber contained a specially designed top layer of carbon black nanoparticles infused into a porous polymer. The light-capturing nanoparticles heated the entire surface of the membrane when exposed to sunlight. A thin half-millimeter-thick layer of salt water flowed atop the carbon-black layer, and a cool freshwater stream flowed below.

Li, the leader of NEWT’s advanced treatment test beds at Rice, said the water production rate increased greatly by concentrating the sunlight. “The intensity got up 17.5 kilowatts per meter squared when a lens was used to concentrate sunlight by 25 times, and the water production increased to about 6 liters per meter squared per hour.”

Li said NEWT’s research team has already made a much larger system that contains a panel that is about 70 centimeters by 25 centimeters. Ultimately, she said, NEWT hopes to produce a modular system where users could order as many panels as they needed based on their daily water demands.

“You could assemble these together, just as you would the panels in a solar farm,” she said. “Depending on the water production rate you need, you could calculate how much membrane area you would need. For example, if you need 20 liters per hour, and the panels produce 6 liters per hour per square meter, you would order a little over 3 square meters of panels.”

Established by the National Science Foundation in 2015, NEWT aims to develop compact, mobile, off-grid water-treatment systems that can provide clean water to millions of people who lack it and make U.S. energy production more sustainable and cost-effective. NEWT, which is expected to leverage more than $40 million in federal and industrial support over the next decade, is the first NSF Engineering Research Center (ERC) in Houston and only the third in Texas since NSF began the ERC program in 1985. NEWT focuses on applications for humanitarian emergency response, rural water systems and wastewater treatment and reuse at remote sites, including both onshore and offshore drilling platforms for oil and gas exploration.

There is a video but it is focused on the NEWT center rather than any specific water technologies,

For anyone interested in the technology, here’s a link to and a citation for the researchers’ paper,

Nanophotonics-enabled solar membrane distillation for off-grid water purification by Pratiksha D. Dongare, Alessandro Alabastri, Seth Pedersen, Katherine R. Zodrow, Nathaniel J. Hogan, Oara Neumann, Jinjian Wu, Tianxiao Wang, Akshay Deshmukh,f, Menachem Elimelech, Qilin Li, Peter Nordlander, and Naomi J. Halas. PNAS {Proceedings of the National Academy of Sciences] doi: 10.1073/pnas.1701835114 June 19, 2017

This paper appears to be open access.

Desalination of sea water with a graphene sieve

The proposed use of graphene membranes for water purification and remediation isn’t new (I have a July 20, 2015 posting which covers some of this field of interest). However, there’s this April 3, 2017 news item on ScienceDaily announcing some new work on graphene and desalination at the University of Manchester,

Graphene-oxide membranes have attracted considerable attention as promising candidates for new filtration technologies. Now the much sought-after development of making membranes capable of sieving common salts has been achieved.

New research demonstrates the real-world potential of providing clean drinking water for millions of people who struggle to access adequate clean water sources.

The new findings from a group of scientists at The University of Manchester were published today in the journal Nature Nanotechnology. Previously graphene-oxide membranes have shown exciting potential for gas separation and water filtration.

An April 3, 2017 University of Manchester press release (also on EurekAlert), which originated the news item, expands on the theme,

Graphene-oxide membranes developed at the National Graphene Institute have already demonstrated the potential of filtering out small nanoparticles, organic molecules, and even large salts. Until now, however, they couldn’t be used for sieving common salts used in desalination technologies, which require even smaller sieves.

Previous research at The University of Manchester found that if immersed in water, graphene-oxide membranes become slightly swollen and smaller salts flow through the membrane along with water, but larger ions or molecules are blocked.

The Manchester-based group have now further developed these graphene membranes and found a strategy to avoid the swelling of the membrane when exposed to water. The pore size in the membrane can be precisely controlled which can sieve common salts out of salty water and make it safe to drink.

As the effects of climate change continue to reduce modern city’s water supplies, wealthy modern countries are also investing in desalination technologies. Following the severe floods in California major wealthy cities are also looking increasingly to alternative water solutions.

When the common salts are dissolved in water, they always form a ‘shell’ of water molecules around the salts molecules. This allows the tiny capillaries of the graphene-oxide membranes to block the salt from flowing along with the water. Water molecules are able to pass through the membrane barrier and flow anomalously fast which is ideal for application of these membranes for desalination.

Professor Rahul Nair, at The University of Manchester said: “Realisation of scalable membranes with uniform pore size down to atomic scale is a significant step forward and will open new possibilities for improving the efficiency of desalination technology.

“This is the first clear-cut experiment in this regime. We also demonstrate that there are realistic possibilities to scale up the described approach and mass produce graphene-based membranes with required sieve sizes.”

Mr. Jijo Abraham and Dr. Vasu Siddeswara Kalangi were the joint-lead authors on the research paper: “The developed membranes are not only useful for desalination, but the atomic scale tunability of the pore size also opens new opportunity to fabricate membranes with on-demand filtration capable of filtering out ions according to their sizes.” said Mr. Abraham.

By 2025 the UN expects that 14% of the world’s population will encounter water scarcity. This technology has the potential to revolutionise water filtration across the world, in particular in countries which cannot afford large scale desalination plants.

It is hoped that graphene-oxide membrane systems can be built on smaller scales making this technology accessible to countries which do not have the financial infrastructure to fund large plants without compromising the yield of fresh water produced.

Courtesy of the University of Manchester

I believe the previous image is an artist’s rendering of the graphene-oxide membrane trapping salt as water moves through it.

Here’s a link to and a citation for the paper,

Tunable sieving of ions using graphene oxide membranes by Jijo Abraham, Kalangi S. Vasu, Christopher D. Williams, Kalon Gopinadhan, Yang Su, Christie T. Cherian, James Dix, Eric Prestat, Sarah J. Haigh, Irina V. Grigorieva, Paola Carbone, Andre K. Geim, & Rahul R. Nair. Nature Nanotechnology (2017) doi:10.1038/nnano.2017.21 Published online 03 April 2017

This paper is open access provided you sign up (or have already signed up) for a free registration with nature.com.

Oil spill cleanup nanotechnology-enabled solution from A*STAR

A*STAR (Singapore’s Agency for Science Technology and Research) has developed a new technology for cleaning up oil spills according to an Oct. 11, 2016 news item on Nanowerk,

Oceanic oil spills are tough to clean up. They dye feathers a syrupy sepia and tan fish eggs a toxic tint. The more turbulent the waters, the farther the slick spreads, with inky droplets descending into the briny deep.

Now technology may be able to succeed where hard-working volunteers have failed in the past. Researchers at the A*STAR Institute of Bioengineering and Nanotechnology (IBN) are using nanotechnology to turn an oil spill into a floating mass of brown jelly that can be scooped up before it can make its way into the food chain.

“Nanoscience makes it possible to tailor the essential structures of materials at the nanometer scale to achieve specific properties,” says chemist Yugen Zhang at IBN, who is developing some of the technologies. “Structures and materials in the nanometer size range often take on distinctive properties that are not seen in other size ranges,” adds Huaqiang Zeng, another chemist at IBN.

An Oct. 11, 2016 A*STAR press release, which originated the news item, describes some of problematic solutions before describing the new technology,

There are many approaches to cleaning an oil spill, and none are completely effective. Fresh, thick grease can be set ablaze or contained by floating barriers for skimmers to scoop out. The slick can also be inefficiently hardened, messily absorbed, hazardously dispersed, or slowly consumed by oil-grazing bacteria. All of these are deficient on a large scale, especially in rough waters.

Organic molecules with special gelling abilities offer a cheap, simple and environmentally friendly alternative for cleaning up the mess. Zeng has developed several such molecules that turn crude oil into jelly within minutes.

To create his ‘supergelators’, Zeng designed the molecules to associate with each other without forming physical bonds. When sprayed on contaminated seawater, the molecules immediately bundle into long fibers between 40 and 800 nanometers wide. These threads create a web that traps the interspersed oil in a giant blob that floats on the water’s surface. The gunk can then be swiftly sieved out of the ocean. Valuable crude oil can later be reclaimed using a common technique employed by petroleum refineries called fractional distillation.

Zeng tested the supergelators on four types of crude oil with different densities, viscosities and sulfur levels in a small round dish. The results were impressive. “The supergelators solidified both freshly spilled crude oil and highly weathered crude oil 37 to 60 times their own weight,” says Zeng. The materials used to produce these organic molecules are cheap and non toxic, which make them a commercially viable solution for managing accidents out at sea. Zeng hopes to work with industrial partners to test the nanomolecules on a much larger scale.

Zeng and his colleagues have developed other other ‘water’ applications as well,

Unsalty water

Scientists at IBN are also using nanoscience to remove salt from seawater and heavy metals from contaminated water.

With dwindling global fresh and ground water reserves, many countries are looking to desalination as a viable source of drinking water. Desalination is expected to meet 30 per cent of the water demand of Singapore by 2060, which will mean tripling the country’s current desalination capacity. But desalination demands huge energy consumption and reverse osmosis, the mainstream technology it depends on, has a relatively high cost. Reverse osmosis works by using extreme pressures to squeeze water molecules through tightly knit membranes.

An emerging alternative solution mimics the way proteins embedded in cell membranes, known as aquaporins, channel water in and out. Some research groups have even created membranes made of fatty lipid molecules that can accommodate natural aquaporins. Zeng has developed a cheaper and more resilient replacement.

His building blocks consist of helical noodles with sticky ends that connect to form long spirals. Water molecules can flow through the 0.3 nanometer openings at the center of the spirals, but all the other positively and negatively charged ions that make up saltwater are too bulky to pass. These include sodium, potassium, calcium, magnesium, chlorine and sulfur oxide. “In water, all of these ions are highly hydrated, attached to lots of water molecules, which makes them too large to go through the channels,” says Zeng.

The technology could lead to global savings of up to US$5 billion a year, says Zeng, but only after several more years of testing and tweaking the lipid membrane’s compatibility and stability with the nanospirals. “This is a major focus in my group right now,” he says. “We want to get this done, so that we can reduce the cost of water desalination to an acceptable level.”

Stick and non-stick

Nanomaterials also offer a low-cost, effective and sustainable way to filter out toxic metals from drinking water.

Heavy metal levels in drinking water are stringently regulated due to the severe damage the substances can cause to health, even at very low concentrations. The World Health Organization requires that levels of lead, for example, remain below ten parts per billion (ppb). Treating water to these standards is expensive and extremely difficult.

Zhang has developed an organic substance filled with pores that can trap and remove toxic metals from water to less than one ppb. Each pore is ten to twenty nanometers wide and packed with compounds, known as amines that stick to the metals.

Exploiting the fact that amines lose their grip over the metals in acidic conditions, the valuable and limited resource can be recovered by industry, and the polymers reused.

The secret behind the success of Zhang’s polymers is the large surface area covered by the pores, which translates into more opportunities to interact with and trap the metals. “Other materials have a surface area of about 100 square meters per gram, but ours is 1,000 square meters per gram,” says Zhang. “It is 10 times higher.”

Zhang tested his nanoporous polymers on water contaminated with lead. He sprinkled a powdered version of the polymer into a slightly alkaline liquid containing close to 100 ppb of lead. Within seconds, lead levels reduced to below 0.2 ppb. Similar results were observed for cadmium, copper and palladium. Washing the polymers in acid released up to 93 per cent of the lead.

With many companies keen to scale these technologies for real-world applications, it won’t be long before nanoscience treats the Earth for its many maladies.

I wonder if the researchers have found industrial partners (who could be named) to bring these solutions for oil spill cleanups, desalination, and water purification to the market.

The Gaza is running out of water by 2016 if the United Nations predictions are correct

If the notion that people are in imminent danger of dying from thirst isn’t compelling enough, there’s this account of the situation and a possible solution in an August 24, 2015 posting by observers, Abou Assi and Majdi Fathi, with journalist, Dorothée Myriam Kellou for observers.france24.com,

Each year, Gaza’s population uses 180 million cubic metres of water but only has capacity for 60 million cubic metres of water usage per year. Running out of water is a constant fear for Gazans.

To understand the context of the crisis, we first spoke to our Observer Majdi Fathi, a photographer who lives in Gaza. He described the daily struggles of living in a place with a shortage of potable water.

The water that comes out of the taps in Gaza is too salty to drink. We only use it for washing. We have to buy bottled water to drink. Each family goes to water vendors. [Editor’s note : Often, families buy water from private companies who run desalination plants with little regulation. Though the water quality is often criticised, it’s still very expensive]. People frequently pay about $2 for 500 litres of water. There are ten people in my family and we can live on 500 litres for about 25 days. Though the authorities give some free water to the very poorest, it’s not enough.

We are all worried about the water shortage. Often, the taps run dry and we end up having to use the drinking water that we purchased for cleaning. Buying water from vendors is not a long-term, sustainable solution!

In a June 25, 2013 posting, I included (in an update) some information about the Gaza situation in the context of water issues in Israel and a special project with the University of Chicago designed to address those issues,

ETA June 27, 2013: There is no hint in the University of Chicago news releases that these water projects will benefit any parties other than Israel and the US but it is tempting to hope that this work might also have an impact in Palestine given its current water crisis there as described in a June 26, 2013 news item in the World Bulletin (Note: Links have been removed),

A tiny wedge of land jammed between Israel, Egypt and the Mediterranean sea, the Gaza Strip is heading inexorably into a water crisis that the United Nations says could make the Palestinian enclave unliveable in just a few years.

With 90-95 percent of the territory’s only aquifer contaminated by sewage, chemicals and seawater, neighbourhood desalination facilities and their public taps are a lifesaver for some of Gaza’s 1.6 million residents.

But these small-scale projects provide water for only about 20 percent of the population, forcing many more residents in the impoverished Gaza Strip to buy bottled water at a premium.

“There is a crisis. There is a serious deficit in the water resources in Gaza and there is a serious deterioration in the water quality,” said Rebhi El Sheikh, deputy chairman of the Palestinian Water Authority (PWA).

A NASA study of satellite data released this year showed that between 2003 and 2009 the region lost 144 cubic km of stored freshwater – equivalent to the amount of water held in the Dead Sea – making an already bad situation much worse.

But the situation in Gaza is particularly acute, with the United Nations warning that its sole aquifer might be unusable by 2016, with the damage potentially irreversible by 2020.

Abou Assi, a Palestinian engineer, thinks he may have a solution (from the observers.france24.com Aug. 24, 2015 posting),

The water table, which is the main source of drinking water in Gaza, is being over-exploited and is also polluted by both nitrates used in agriculture and by sea water. Gaza’s groundwater could run out as soon as next year, according to the United Nations.

While I was working on my masters in engineering at the Islamic University in Gaza, I started looking for a radical solution to the problem. Seeing as Gaza is located on the shores of the Mediterranean, I started considering a filtration system that could desalinate sea water.

There are seven different desalination plants in Gaza. They each produce between 45 and 80 cubic metres of water an hour. The problem is that all of these factories use the reverse osmosis procedure [Editor’s note: This is a water purification system that uses a semipermeable membrane to remove larger particles, including salt molecules, from water molecules].

Even though the method is ingenious, it requires a lot of energy. This is a problem in Gaza, because we also have a major energy shortage. Our power plant, which provides Gaza with about a third of its energy, regularly stops working due to fuel shortages.

My team and I conducted 170 experiments in 14 months before we managed to create a machine that reduced the salinity of the seawater enough to make it drinkable.

The machine is very simple: it pumps sea water very quickly through iron pipes. The water passes through electrical boxes that push the water through membranes made from nanomaterials. The membranes have tiny, microscopic pores that block the sodium chloride (salt) molecules but allow the water molecules to go through. After the water is filtered, the useful minerals are re-injected. After all this, the water that comes out of the taps is clean enough to drink!

With this machine, it’s possible to treat one cubic metre of water per day, using 60% less energy than with the old system. The water meets the quality standards of the World Health Organisation, which puts limits on a number of substances, including chlorine, limestone, lead, nitrates, pesticides and bacteria. For now, some so-called “drinkable” water in Gaza has nitrate levels that can reach up to 220 mg per litre even though the WHO recommends a limit of 50 mg per litre. Poorly treated drinking water can cause many health problems, especially for children. [Editor’s note: The WHO recently noted an increase in cases of children with diarrhea in Gaza].

Assi has gone into debt to finance his research despite the fact he has received grants for this work (from the observers.france24.com Aug. 24, 2015 posting),

In order to transition from the prototype to a practical application, I need more financial support. I would like to create a model of a smaller version that could be put into people’s homes in Gaza. In order to develop this, all I need is about $20,000.

That said, in order to really resolve the drinking water crisis across Gaza, we would need to build a desalination plant that uses this technique. That would be expensive — about $300,000 million – and there would always be the fear that the plant would be bombed, like with the power plant.

We have attempted to discuss our ideas with officials in both Gaza and Ramallah but, for the time being, we have received no response. We hope for support both from Palestinian institutions and from the international community.

There doesn’t yet seem to be a website or Facebook page or other means of contacting and/or lending other kinds of support to Assi. Hopefully, he will have something soon.

In a February 24, 2014 posting, I featured a nanotechnology laboratory in Oman where they were studying and working to develop desalination technologies. (I noticed that Assi received a grant for his work from the  Middle East Desalination Research Center in Oman.)

Crowd computing for improved nanotechnology-enabled water filtration

This research is the product of a China/Israel/Switzerland collaboration on water filtration with involvement from the UK and Australia. Here’s some general information about the importance of water and about the collaboration in a July 5, 2015 news item on Nanowerk (Note: A link has been removed),

Nearly 800 million people worldwide don’t have access to safe drinking water, and some 2.5 billion people live in precariously unsanitary conditions, according to the Centers for Disease Control and Prevention. Together, unsafe drinking water and the inadequate supply of water for hygiene purposes contribute to almost 90% of all deaths from diarrheal diseases — and effective water sanitation interventions are still challenging scientists and engineers.

A new study published in Nature Nanotechnology (“Water transport inside carbon nanotubes mediated by phonon-induced oscillating friction”) proposes a novel nanotechnology-based strategy to improve water filtration. The research project involves the minute vibrations of carbon nanotubes called “phonons,” which greatly enhance the diffusion of water through sanitation filters. The project was the joint effort of a Tsinghua University-Tel Aviv University research team and was led by Prof. Quanshui Zheng of the Tsinghua Center for Nano and Micro Mechanics and Prof. Michael Urbakh of the TAU School of Chemistry, both of the TAU-Tsinghua XIN Center, in collaboration with Prof. Francois Grey of the University of Geneva.

A July 5, 2015 American Friends of Tel Aviv University news release (also on EurekAlert), which originated the news item, provides more details about the work,

“We’ve discovered that very small vibrations help materials, whether wet or dry, slide more smoothly past each other,” said Prof. Urbakh. “Through phonon oscillations — vibrations of water-carrying nanotubes — water transport can be enhanced, and sanitation and desalination improved. Water filtration systems require a lot of energy due to friction at the nano-level. With these oscillations, however, we witnessed three times the efficiency of water transport, and, of course, a great deal of energy saved.”

The research team managed to demonstrate how, under the right conditions, such vibrations produce a 300% improvement in the rate of water diffusion by using computers to simulate the flow of water molecules flowing through nanotubes. The results have important implications for desalination processes and energy conservation, e.g. improving the energy efficiency for desalination using reverse osmosis membranes with pores at the nanoscale level, or energy conservation, e.g. membranes with boron nitride nanotubes.

Crowdsourcing the solution

The project, initiated by IBM’s World Community Grid, was an experiment in crowdsourced computing — carried out by over 150,000 volunteers who contributed their own computing power to the research.

“Our project won the privilege of using IBM’s world community grid, an open platform of users from all around the world, to run our program and obtain precise results,” said Prof. Urbakh. “This was the first project of this kind in Israel, and we could never have managed with just four students in the lab. We would have required the equivalent of nearly 40,000 years of processing power on a single computer. Instead we had the benefit of some 150,000 computing volunteers from all around the world, who downloaded and ran the project on their laptops and desktop computers.

“Crowdsourced computing is playing an increasingly major role in scientific breakthroughs,” Prof. Urbakh continued. “As our research shows, the range of questions that can benefit from public participation is growing all the time.”

The computer simulations were designed by Ming Ma, who graduated from Tsinghua University and is doing his postdoctoral research in Prof. Urbakh’s group at TAU. Ming catalyzed the international collaboration. “The students from Tsinghua are remarkable. The project represents the very positive cooperation between the two universities, which is taking place at XIN and because of XIN,” said Prof. Urbakh.

Other partners in this international project include researchers at the London Centre for Nanotechnology of University College London; the University of Geneva; the University of Sydney and Monash University in Australia; and the Xi’an Jiaotong University in China. The researchers are currently in discussions with companies interested in harnessing the oscillation knowhow for various commercial projects.

 

Here’s a link to and a citation for the paper,

Water transport inside carbon nanotubes mediated by phonon-induced oscillating friction by Ming Ma, François Grey, Luming Shen, Michael Urbakh, Shuai Wu,    Jefferson Zhe Liu, Yilun Liu, & Quanshui Zheng. Nature Nanotechnology (2015) doi:10.1038/nnano.2015.134 Published online 06 July 2015

This paper is behind a paywall.

Final comment, I find it surprising that they used labour and computing power from 150,000 volunteers and didn’t offer open access to the paper. Perhaps the volunteers got their own copy? I certainly hope so.

Sealing graphene’s defects to make a better filtration device

Making a graphene filter that allows water to pass through while screening out salt and/or noxious materials has been more challenging than one might think. According to a May 7, 2015 news item on Nanowerk, graphene filters can be ‘leaky’,

For faster, longer-lasting water filters, some scientists are looking to graphene –thin, strong sheets of carbon — to serve as ultrathin membranes, filtering out contaminants to quickly purify high volumes of water.

Graphene’s unique properties make it a potentially ideal membrane for water filtration or desalination. But there’s been one main drawback to its wider use: Making membranes in one-atom-thick layers of graphene is a meticulous process that can tear the thin material — creating defects through which contaminants can leak.

Now engineers at MIT [Massachusetts Institute of Technology], Oak Ridge National Laboratory, and King Fahd University of Petroleum and Minerals (KFUPM) have devised a process to repair these leaks, filling cracks and plugging holes using a combination of chemical deposition and polymerization techniques. The team then used a process it developed previously to create tiny, uniform pores in the material, small enough to allow only water to pass through.

A May 8, 2015 MIT news release (also on EurkeAlert), which originated the news item, expands on the theme,

Combining these two techniques, the researchers were able to engineer a relatively large defect-free graphene membrane — about the size of a penny. The membrane’s size is significant: To be exploited as a filtration membrane, graphene would have to be manufactured at a scale of centimeters, or larger.

In experiments, the researchers pumped water through a graphene membrane treated with both defect-sealing and pore-producing processes, and found that water flowed through at rates comparable to current desalination membranes. The graphene was able to filter out most large-molecule contaminants, such as magnesium sulfate and dextran.

Rohit Karnik, an associate professor of mechanical engineering at MIT, says the group’s results, published in the journal Nano Letters, represent the first success in plugging graphene’s leaks.

“We’ve been able to seal defects, at least on the lab scale, to realize molecular filtration across a macroscopic area of graphene, which has not been possible before,” Karnik says. “If we have better process control, maybe in the future we don’t even need defect sealing. But I think it’s very unlikely that we’ll ever have perfect graphene — there will always be some need to control leakages. These two [techniques] are examples which enable filtration.”

Sean O’Hern, a former graduate research assistant at MIT, is the paper’s first author. Other contributors include MIT graduate student Doojoon Jang, former graduate student Suman Bose, and Professor Jing Kong.

A delicate transfer

“The current types of membranes that can produce freshwater from saltwater are fairly thick, on the order of 200 nanometers,” O’Hern says. “The benefit of a graphene membrane is, instead of being hundreds of nanometers thick, we’re on the order of three angstroms — 600 times thinner than existing membranes. This enables you to have a higher flow rate over the same area.”

O’Hern and Karnik have been investigating graphene’s potential as a filtration membrane for the past several years. In 2009, the group began fabricating membranes from graphene grown on copper — a metal that supports the growth of graphene across relatively large areas. However, copper is impermeable, requiring the group to transfer the graphene to a porous substrate following fabrication.

However, O’Hern noticed that this transfer process would create tears in graphene. What’s more, he observed intrinsic defects created during the growth process, resulting perhaps from impurities in the original material.

Plugging graphene’s leaks

To plug graphene’s leaks, the team came up with a technique to first tackle the smaller intrinsic defects, then the larger transfer-induced defects. For the intrinsic defects, the researchers used a process called “atomic layer deposition,” placing the graphene membrane in a vacuum chamber, then pulsing in a hafnium-containing chemical that does not normally interact with graphene. However, if the chemical comes in contact with a small opening in graphene, it will tend to stick to that opening, attracted by the area’s higher surface energy.

The team applied several rounds of atomic layer deposition, finding that the deposited hafnium oxide successfully filled in graphene’s nanometer-scale intrinsic defects. However, O’Hern realized that using the same process to fill in much larger holes and tears — on the order of hundreds of nanometers — would require too much time.

Instead, he and his colleagues came up with a second technique to fill in larger defects, using a process called “interfacial polymerization” that is often employed in membrane synthesis. After they filled in graphene’s intrinsic defects, the researchers submerged the membrane at the interface of two solutions: a water bath and an organic solvent that, like oil, does not mix with water.

In the two solutions, the researchers dissolved two different molecules that can react to form nylon. Once O’Hern placed the graphene membrane at the interface of the two solutions, he observed that nylon plugs formed only in tears and holes — regions where the two molecules could come in contact because of tears in the otherwise impermeable graphene — effectively sealing the remaining defects.

Using a technique they developed last year, the researchers then etched tiny, uniform holes in graphene — small enough to let water molecules through, but not larger contaminants. In experiments, the group tested the membrane with water containing several different molecules, including salt, and found that the membrane rejected up to 90 percent of larger molecules. However, it let salt through at a faster rate than water.

The preliminary tests suggest that graphene may be a viable alternative to existing filtration membranes, although Karnik says techniques to seal its defects and control its permeability will need further improvements.

“Water desalination and nanofiltration are big applications where, if things work out and this technology withstands the different demands of real-world tests, it would have a large impact,” Karnik says. “But one could also imagine applications for fine chemical- or biological-sample processing, where these membranes could be useful. And this is the first report of a centimeter-scale graphene membrane that does any kind of molecular filtration. That’s exciting.”

De-en Jiang, an assistant professor of chemistry at the University of California at Riverside, sees the defect-sealing technique as “a great advance toward making graphene filtration a reality.”

“The two-step technique is very smart: sealing the defects while preserving the desired pores for filtration,” says Jiang, who did not contribute to the research. “This would make the scale-up much easier. One can produce a large graphene membrane first, not worrying about the defects, which can be sealed later.”

I have featured graphene and water desalination work before  from these researchers at MIT in a Feb. 27, 2014 posting. Interestingly, there was no mention of problems with defects in the news release highlighting this previous work.

Here’s a link to and a citation for the latest paper,

Nanofiltration across Defect-Sealed Nanoporous Monolayer Graphene by Sean C. O’Hern, Doojoon Jang, Suman Bose, Juan-Carlos Idrobo, Yi Song §, Tahar Laoui, Jing Kong, and Rohit Karnik. Nano Lett., Article ASAP DOI: 10.1021/acs.nanolett.5b00456 Publication Date (Web): April 27, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

Water desalination by graphene and water purification by sapwood

I have two items about water. The first concerns a new technique from MIT (Massachusetts Institute of Technology) for desalination using graphene and sapwood, respectively*. From a Feb. 25, 2014 news release by David Chandler on EurekAlert,

Researchers have devised a way of making tiny holes of controllable size in sheets of graphene, a development that could lead to ultrathin filters for improved desalination or water purification.

The team of researchers at MIT, Oak Ridge National Laboratory, and in Saudi Arabia succeeded in creating subnanoscale pores in a sheet of the one-atom-thick material, which is one of the strongest materials known. …

The concept of using graphene, perforated by nanoscale pores, as a filter in desalination has been proposed and analyzed by other MIT researchers. The new work, led by graduate student Sean O’Hern and associate professor of mechanical engineering Rohit Karnik, is the first step toward actual production of such a graphene filter.

Making these minuscule holes in graphene — a hexagonal array of carbon atoms, like atomic-scale chicken wire — occurs in a two-stage process. First, the graphene is bombarded with gallium ions, which disrupt the carbon bonds. Then, the graphene is etched with an oxidizing solution that reacts strongly with the disrupted bonds — producing a hole at each spot where the gallium ions struck. By controlling how long the graphene sheet is left in the oxidizing solution, the MIT researchers can control the average size of the pores.

A big limitation in existing nanofiltration and reverse-osmosis desalination plants, which use filters to separate salt from seawater, is their low permeability: Water flows very slowly through them. The graphene filters, being much thinner, yet very strong, can sustain a much higher flow. “We’ve developed the first membrane that consists of a high density of subnanometer-scale pores in an atomically thin, single sheet of graphene,” O’Hern says.

For efficient desalination, a membrane must demonstrate “a high rejection rate of salt, yet a high flow rate of water,” he adds. One way of doing that is decreasing the membrane’s thickness, but this quickly renders conventional polymer-based membranes too weak to sustain the water pressure, or too ineffective at rejecting salt, he explains.

With graphene membranes, it becomes simply a matter of controlling the size of the pores, making them “larger than water molecules, but smaller than everything else,” O’Hern says — whether salt, impurities, or particular kinds of biochemical molecules.

The permeability of such graphene filters, according to computer simulations, could be 50 times greater than that of conventional membranes, as demonstrated earlier by a team of MIT researchers led by graduate student David Cohen-Tanugi of the Department of Materials Science and Engineering. But producing such filters with controlled pore sizes has remained a challenge. The new work, O’Hern says, demonstrates a method for actually producing such material with dense concentrations of nanometer-scale holes over large areas.

“We bombard the graphene with gallium ions at high energy,” O’Hern says. “That creates defects in the graphene structure, and these defects are more chemically reactive.” When the material is bathed in a reactive oxidant solution, the oxidant “preferentially attacks the defects,” and etches away many holes of roughly similar size. O’Hern and his co-authors were able to produce a membrane with 5 trillion pores per square centimeter, well suited to use for filtration. “To better understand how small and dense these graphene pores are, if our graphene membrane were to be magnified about a million times, the pores would be less than 1 millimeter in size, spaced about 4 millimeters apart, and span over 38 square miles, an area roughly half the size of Boston,” O’Hern says.

With this technique, the researchers were able to control the filtration properties of a single, centimeter-sized sheet of graphene: Without etching, no salt flowed through the defects formed by gallium ions. With just a little etching, the membranes started allowing positive salt ions to flow through. With further etching, the membranes allowed both positive and negative salt ions to flow through, but blocked the flow of larger organic molecules. With even more etching, the pores were large enough to allow everything to go through.

Scaling up the process to produce useful sheets of the permeable graphene, while maintaining control over the pore sizes, will require further research, O’Hern says.

Karnik says that such membranes, depending on their pore size, could find various applications. Desalination and nanofiltration may be the most demanding, since the membranes required for these plants would be very large. But for other purposes, such as selective filtration of molecules — for example, removal of unreacted reagents from DNA — even the very small filters produced so far might be useful.

“For biofiltration, size or cost are not as critical,” Karnik says. “For those applications, the current scale is suitable.”

Dexter Johnson in a Feb. 26,2014 posting provides some context for and insight into the work (from the Nanoclast blog on the IEEE [Institute of Electrical and Electronics Engineers]), Note: Links have been removed,

About 18 months ago, I wrote about an MIT project in which computer models demonstrated that graphene could act as a filter in the desalination of water through the reverse osmosis (RO) method. RO is slightly less energy intensive than the predominantly used multi-stage-flash process. The hope was that the nanopores of the graphene material would make the RO method even less energy intensive than current versions by making it easier to push the water through the filter membrane.

The models were promising, but other researchers in the field said at the time it was going to be a long road to translate a computer model to a real product.

It would seem that the MIT researchers agreed it was worth the effort and accepted the challenge to go from computer model to a real device as they announced this week that they had developed a method for creating selective pores in graphene that make it suitable for water desalination.

Here’s a link to and a citation for the paper,

Selective Ionic Transport through Tunable Subnanometer Pores in Single-Layer Graphene Membranes by Sean C. O’Hern, Michael S. H. Boutilier, Juan-Carlos Idrobo, Yi Song, Jing Kong, Tahar Laoui, Muataz Atieh, and Rohit Karnik. Nano Lett., Article ASAP DOI: 10.1021/nl404118f Publication Date (Web): February 3, 2014

Copyright © 2014 American Chemical Society

This article is behind a paywall.

The second item is also from MIT and concerns a low-tech means of purifying water. From a Feb. 27, 2014 news item on Azonano,

If you’ve run out of drinking water during a lakeside camping trip, there’s a simple solution: Break off a branch from the nearest pine tree, peel away the bark, and slowly pour lake water through the stick. The improvised filter should trap any bacteria, producing fresh, uncontaminated water.

In fact, an MIT team has discovered that this low-tech filtration system can produce up to four liters of drinking water a day — enough to quench the thirst of a typical person.

In a paper published this week in the journal PLoS ONE, the researchers demonstrate that a small piece of sapwood can filter out more than 99 percent of the bacteria E. coli from water. They say the size of the pores in sapwood — which contains xylem tissue evolved to transport sap up the length of a tree — also allows water through while blocking most types of bacteria.

Co-author Rohit Karnik, an associate professor of mechanical engineering at MIT, says sapwood is a promising, low-cost, and efficient material for water filtration, particularly for rural communities where more advanced filtration systems are not readily accessible.

“Today’s filtration membranes have nanoscale pores that are not something you can manufacture in a garage very easily,” Karnik says. “The idea here is that we don’t need to fabricate a membrane, because it’s easily available. You can just take a piece of wood and make a filter out of it.”

The Feb. 26, 2014 news release on EurekAlert, which originated the news item, describes current filtration techniques and the advantages associated with this new low-tech approach,

There are a number of water-purification technologies on the market today, although many come with drawbacks: Systems that rely on chlorine treatment work well at large scales, but are expensive. Boiling water to remove contaminants requires a great deal of fuel to heat the water. Membrane-based filters, while able to remove microbes, are expensive, require a pump, and can become easily clogged.

Sapwood may offer a low-cost, small-scale alternative. The wood is comprised of xylem, porous tissue that conducts sap from a tree’s roots to its crown through a system of vessels and pores. Each vessel wall is pockmarked with tiny pores called pit membranes, through which sap can essentially hopscotch, flowing from one vessel to another as it feeds structures along a tree’s length. The pores also limit cavitation, a process by which air bubbles can grow and spread in xylem, eventually killing a tree. The xylem’s tiny pores can trap bubbles, preventing them from spreading in the wood.

“Plants have had to figure out how to filter out bubbles but allow easy flow of sap,” Karnik observes. “It’s the same problem with water filtration where we want to filter out microbes but maintain a high flow rate. So it’s a nice coincidence that the problems are similar.”

The news release also describes the experimental procedure the scientists followed (from the news release),

To study sapwood’s water-filtering potential, the researchers collected branches of white pine and stripped off the outer bark. They cut small sections of sapwood measuring about an inch long and half an inch wide, and mounted each in plastic tubing, sealed with epoxy and secured with clamps.

Before experimenting with contaminated water, the group used water mixed with red ink particles ranging from 70 to 500 nanometers in size. After all the liquid passed through, the researchers sliced the sapwood in half lengthwise, and observed that much of the red dye was contained within the very top layers of the wood, while the filtrate, or filtered water, was clear. This experiment showed that sapwood is naturally able to filter out particles bigger than about 70 nanometers.

However, in another experiment, the team found that sapwood was unable to separate out 20-nanometer particles from water, suggesting that there is a limit to the size of particles coniferous sapwood can filter.

Finally, the team flowed inactivated, E. coli-contaminated water through the wood filter. When they examined the xylem under a fluorescent microscope, they saw that bacteria had accumulated around pit membranes in the first few millimeters of the wood. Counting the bacterial cells in the filtered water, the researchers found that the sapwood was able to filter out more than 99 percent of E. coli from water.

Karnik says sapwood likely can filter most types of bacteria, the smallest of which measure about 200 nanometers. However, the filter probably cannot trap most viruses, which are much smaller in size.

The researchers have future plans (from the news release),

Karnik says his group now plans to evaluate the filtering potential of other types of sapwood. In general, flowering trees have smaller pores than coniferous trees, suggesting that they may be able to filter out even smaller particles. However, vessels in flowering trees tend to be much longer, which may be less practical for designing a compact water filter.

Designers interested in using sapwood as a filtering material will also have to find ways to keep the wood damp, or to dry it while retaining the xylem function. In other experiments with dried sapwood, Karnik found that water either did not flow through well, or flowed through cracks, but did not filter out contaminants.

“There’s huge variation between plants,” Karnik says. “There could be much better plants out there that are suitable for this process. Ideally, a filter would be a thin slice of wood you could use for a few days, then throw it away and replace at almost no cost. It’s orders of magnitude cheaper than the high-end membranes on the market today.”

Here’s a link to and a citation for the paper,

Water Filtration Using Plant Xylem by Michael S. H. Boutilier, Jongho Lee, Valerie Chambers, Varsha Venkatesh, & Rohit Karnik. PLOS One Published: February 26, 2014 DOI: 10.1371/journal.pone.0089934

This paper is open access.

One final observation, two of the researchers (Michael S. H. Boutilier & Rohit Karnik) listed as authors on the graphene/water desalination paper are also listed on the low-tech sapwood paper solution.*

* The first sentence of the this post originally stated both items were graphene-related, it has been changed to say 1… using graphene and sapwood, respectively*’ on May 8, 2015.

The last sentence of this post was changed from

‘One final observation, two of the researchers listed as authors on the graphene/water desalination paper are also listed on the low-tech sapwood paper (Michael S. H. Boutilier & Rohit Karnik).’

to this

‘One final observation, two of the researchers (Michael S. H. Boutilier & Rohit Karnik) listed as authors on the graphene/water desalination paper are also listed on the low-tech sapwood paper solution.*’ for clarity on May 8, 2015.