Tag Archives: carbon dioxide

Low-cost carbon sequestration and eco-friendly manufacturing for chemicals with nanobio hybrid organisms

Years ago I was asked about carbon sequestration and nanotechnology and could not come up with any examples. At last I have something for the next time the question is asked. From a June 11, 2019 news item on ScienceDaily,

University of Colorado Boulder researchers have developed nanobio-hybrid organisms capable of using airborne carbon dioxide and nitrogen to produce a variety of plastics and fuels, a promising first step toward low-cost carbon sequestration and eco-friendly manufacturing for chemicals.

By using light-activated quantum dots to fire particular enzymes within microbial cells, the researchers were able to create “living factories” that eat harmful CO2 and convert it into useful products such as biodegradable plastic, gasoline, ammonia and biodiesel.

A June 11, 2019 University of Colorado at Boulder news release (also on EurekAlert) by Trent Knoss, which originated the news item, provides a deeper dive into the research,

“The innovation is a testament to the power of biochemical processes,” said Prashant Nagpal, lead author of the research and an assistant professor in CU Boulder’s Department of Chemical and Biological Engineering. “We’re looking at a technique that could improve CO2 capture to combat climate change and one day even potentially replace carbon-intensive manufacturing for plastics and fuels.”

The project began in 2013, when Nagpal and his colleagues began exploring the broad potential of nanoscopic quantum dots, which are tiny semiconductors similar to those used in television sets. Quantum dots can be injected into cells passively and are designed to attach and self-assemble to desired enzymes and then activate these enzymes on command using specific wavelengths of light.

Nagpal wanted to see if quantum dots could act as a spark plug to fire particular enzymes within microbial cells that have the means to convert airborne CO2 and nitrogen, but do not do so naturally due to a lack of photosynthesis.

By diffusing the specially-tailored dots into the cells of common microbial species found in soil, Nagpal and his colleagues bridged the gap. Now, exposure to even small amounts of indirect sunlight would activate the microbes’ CO2 appetite, without a need for any source of energy or food to carry out the energy-intensive biochemical conversions.

“Each cell is making millions of these chemicals and we showed they could exceed their natural yield by close to 200 percent,” Nagpal said.

The microbes, which lie dormant in water, release their resulting product to the surface, where it can be skimmed off and harvested for manufacturing. Different combinations of dots and light produce different products: Green wavelengths cause the bacteria to consume nitrogen and produce ammonia while redder wavelengths make the microbes feast on CO2 to produce plastic instead.

The process also shows promising signs of being able to operate at scale. The study found that even when the microbial factories were activated consistently for hours at a time, they showed few signs of exhaustion or depletion, indicating that the cells can regenerate and thus limit the need for rotation.

“We were very surprised that it worked as elegantly as it did,” Nagpal said. “We’re just getting started with the synthetic applications.”

The ideal futuristic scenario, Nagpal said, would be to have single-family homes and businesses pipe their CO2 emissions directly to a nearby holding pond, where microbes would convert them to a bioplastic. The owners would be able to sell the resulting product for a small profit while essentially offsetting their own carbon footprint.

“Even if the margins are low and it can’t compete with petrochemicals on a pure cost basis, there is still societal benefit to doing this,” Nagpal said. “If we could convert even a small fraction of local ditch ponds, it would have a sizeable impact on the carbon output of towns. It wouldn’t be asking much for people to implement. Many already make beer at home, for example, and this is no more complicated.”

The focus now, he said, will shift to optimizing the conversion process and bringing on new undergraduate students. Nagpal is looking to convert the project into an undergraduate lab experiment in the fall semester, funded by a CU Boulder Engineering Excellence Fund grant. Nagpal credits his current students with sticking with the project over the course of many years.

“It has been a long journey and their work has been invaluable,” he said. “I think these results show that it was worth it.”

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

Nanorg Microbial Factories: Light-Driven Renewable Biochemical Synthesis Using Quantum Dot-Bacteria Nanobiohybrids by Yuchen Ding, John R. Bertram, Carrie Eckert, Rajesh Reddy Bommareddy, Rajan Patel, Alex Conradie, Samantha Bryan, Prashant Nagpal. J. Am. Chem. Soc.2019XXXXXXXXXX-XXX DOI: https://doi.org/10.1021/jacs.9b02549 Publication Date:June 7, 2019
Copyright © 2019 American Chemical Society

This paper is behind a paywall.

Unusual appetite for gold

This bacterium (bacteria being the plural) loves gold, which is lucky for anyone trying to develop artificial photosynthesis.From an October 9, 2018 news item on ScienceDaily,

A bacterium named Moorella thermoacetica won’t work for free. But UC Berkeley [University of California at Berkeley] researchers have figured out it has an appetite for gold. And in exchange for this special treat, the bacterium has revealed a more efficient path to producing solar fuels through artificial photosynthesis.

An October 5, 2018 UC Berkeley news release by Theresa Duque (also on EurekAlert but published on October 9, 2018), which originated the news item, expands on the theme,

M. thermoacetica first made its debut as the first non-photosensitive bacterium to carry out artificial photosynthesis (link is external) in a study led by Peidong Yang, a professor in UC Berkeley’s College of Chemistry. By attaching light-absorbing nanoparticles made of cadmium sulfide (CdS) to the bacterial membrane exterior, the researchers turned M. thermoacetica into a tiny photosynthesis machine, converting sunlight and carbon dioxide into useful chemicals.

Now Yang and his team of researchers have found a better way to entice this CO2-hungry bacterium into being even more productive. By placing light-absorbing gold nanoclusters inside the bacterium, they have created a biohybrid system that produces a higher yield of chemical products than previously demonstrated. The research, funded by the National Institutes of Health, was published on Oct. 1 in Nature Nanotechnology (link is external).

For the first hybrid model, M. thermoacetica-CdS, the researchers chose cadmium sulfide as the semiconductor for its ability to absorb visible light. But because cadmium sulfide is toxic to bacteria, the nanoparticles had to be attached to the cell membrane “extracellularly,” or outside the M. thermoacetica-CdS system. Sunlight excites each cadmium-sulfide nanoparticle into generating a charged particle known as an electron. As these light-generated electrons travel through the bacterium, they interact with multiple enzymes in a process known as “CO2 reduction,” triggering a cascade of reactions that eventually turns CO2 into acetate, a valuable chemical for making solar fuels.

But within the extracellular model, the electrons end up interacting with other chemicals that have no part in turning CO2 into acetate. And as a result, some electrons are lost and never reach the enzymes. So to improve what’s known as “quantum efficiency,” or the bacterium’s ability to produce acetate each time it gains an electron, the researchers found another semiconductor: nanoclusters made of 22 gold atoms (Au22), a material that M. thermoacetica took a surprising shine to.

A single nanocluster of 22 gold atoms

Figure: A single nanocluster of 22 gold atoms – Au22 – is only 1 nanometer in diameter, allowing it to easily slip through the bacterial cell wall.

“We selected Au22 because it’s ideal for absorbing visible light and has the potential for driving the CO2 reduction process, but we weren’t sure whether it would be compatible with the bacteria,” Yang said. “When we inspected them under the microscope, we discovered that the bacteria were loaded with these Au22 clusters – and were still happily alive.”

Imaging of the M. thermoacetica-Au22 system was done at UC Berkeley’s Molecular Imaging Center (link is external).

The researchers also selected Au22 ­– dubbed by the researchers as “magic” gold nanoclusters – for its ultrasmall size: A single Au22nanocluster is only 1 nanometer in diameter, allowing each nanocluster to easily slip through the bacterial cell wall.

“By feeding bacteria with Au22 nanoclusters, we’ve effectively streamlined the electron transfer process for the CO2 reduction pathway inside the bacteria, as evidenced by a 2.86 percent quantum efficiency – or 33 percent more acetate produced within the M. thermoacetica-Au22 system than the CdS model,” Yang said.

The magic gold nanocluster is the latest discovery coming out of Yang’s lab, which for the past six years has focused on using biohybrid nanostructures to convert CO2 into useful chemicals as part of an ongoing effort to find affordable, abundant resources for renewable fuels, and potential solutions to thwart the effects of climate change.

“Next, we’d like to find a way to reduce costs, improve the lifetimes for these biohybrid systems, and improve quantum efficiency,” Yang said. “By continuing to look at the fundamental aspect of how gold nanoclusters are being photoactivated, and by following the electron transfer process within the CO2 reduction pathway, we hope to find even better solutions.”

Co-authors with Yang are UC Berkeley graduate student Hao Zhang and former postdoctoral fellow Hao Liu, now at Donghua University in Shanghai, China.

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

Bacteria photosensitized by intracellular gold nanoclusters for solar fuel production by Hao Zhang, Hao Liu, Zhiquan Tian, Dylan Lu, Yi Yu, Stefano Cestellos-Blanco, Kelsey K. Sakimoto, & Peidong Yang. Nature Nanotechnologyvolume 13, pages900–905 (2018). DOI: https://doi.org/10.1038/s41565-018-0267-z Published: 01 October 2018

This paper is behind a paywall.

For lovers of animation, the folks at UC Berkeley have produced this piece about the ‘gold-loving’ bacterium,

Colo(u)ring your carbon nanotubes

Finnish research is highlighted in an August 28, 2018 news item on phys.org,

A method developed at Aalto University, Finland, can produce large quantities of pristine single-walled carbon nanotubes in select shades of the rainbow. The secret is a fine-tuned fabrication process—and a small dose of carbon dioxide. The films could find applications in touch screen technologies or as coating agents for new types of solar cells.

An August 28, 2018 Aalto University press release (also on EurekAlert), which originated the news item, provides more detail,

Samples of the colourful carbon nanotube thin films, as produced in the fabrication reactor. Image: Aalto University.
 

Single-walled carbon nanotubes, or sheets of one atom-thick layers of graphene rolled up into different sizes and shapes, have found many uses in electronics and new touch screen devices. By nature, carbon nanotubes are typically black or a dark grey.

In their new study published in the Journal of the American Chemical Society (JACS), Aalto University researchers present a way to control the fabrication of carbon nanotube thin films so that they display a variety of different colours—for instance, green, brown, or a silvery grey.

The researchers believe this is the first time that coloured carbon nanotubes have been produced by direct synthesis. Using their invention, the colour is induced straight away in the fabrication process, not by employing a range of purifying techniques on finished, synthesized tubes.

With direct synthesis, large quantities of clean sample materials can be produced while also avoiding damage to the product in the purifying process—which makes it the most attractive approach for applications.

‘In theory, these coloured thin films could be used to make touch screens with many different colours, or solar cells that display completely new types of optical properties,’ says Esko Kauppinen, Professor at Aalto University.

To get carbon structures to display colours is a feat in itself. The underlying techniques needed to enable the colouration also imply finely detailed control of the structure of the nanotube structures. Kauppinen and his team’s unique method, which uses aerosols of metal and carbon, allows them to carefully manipulate and control the nanotube structure directly from the fabrication process.

‘Growing carbon nanotubes is, in a way, like planting trees: we need seeds, feeds, and solar heat. For us, aerosol nanoparticles of iron work as a catalyst or seed, carbon monoxide as the source for carbon, so feed, and a reactor gives heat at a temperature more than 850 degrees Celsius,’ says Dr. Hua Jiang, Senior Scientist at Aalto University.

Professor Kauppinen’s group has a long history of using these very resources in their singular production method. To add to their repertoire, they have recently experimented with administering small doses of carbon dioxide into the fabrication process.

‘Carbon dioxide acts as a kind of graft material that we can use to tune the growth of carbon nanotubes of various colors,’ explains Jiang.

With an advanced electron diffraction technique, the researchers were able to find out the precise atomic scale structure of their thin films. They found that they have very narrow chirality distributions, meaning that the orientation of the honeycomb-lattice of the tubes’ walls is almost uniform throughout the sample. The chirality more or less dictates the electrical properties carbon nanotubes can have, as well as their colour.

The method developed at Aalto University promises a simple and highly scalable way to fabricate carbon nanotube thin films in high yields.

‘Usually you have to choose between mass production or having good control over the structure of carbon nanotubes. With our breakthrough, we can do both,’ trusts Dr. Qiang Zhang, a postdoctoral researcher in the group.

Follow-up work is already underway.

‘We want to understand the science of how the addition of carbon dioxide tunes the structure of the nanotubes and creates colours. Our aim is to achieve full control of the growing process so that single-walled carbon nanotubes could be used as building blocks for the next generation of nanoelectronics devices,’ says professor Kauppinen.

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

Direct Synthesis of Colorful Single-Walled Carbon Nanotube Thin Films by Yongping Liao, Hua Jiang, Nan Wei, Patrik Laiho, Qiang Zhang, Sabbir A. Khan, and Esko I. Kauppinen. J. Am. Chem. Soc., 2018, 140 (31), pp 9797–9800 DOI: 10.1021/jacs.8b05151 Publication Date (Web): July 26, 2018

Copyright © 2018 American Chemical Society

This paper appears to be open access.

For the curious, here’s a peek at the coloured carbon nanotube films,

 

Caption: Samples of the colorful carbon nanotube thin films, as produced in the fabrication reactor. Credit: Authors / Aalto University

It’s a very ‘carbony’ time: graphene jacket, graphene-skinned airplane, and schwarzite

In August 2018, I been stumbled across several stories about graphene-based products and a new form of carbon.

Graphene jacket

The company producing this jacket has as its goal “… creating bionic clothing that is both bulletproof and intelligent.” Well, ‘bionic‘ means biologically-inspired engineering and ‘intelligent‘ usually means there’s some kind of computing capability in the product. This jacket, which is the first step towards the company’s goal, is not bionic, bulletproof, or intelligent. Nonetheless, it represents a very interesting science experiment in which you, the consumer, are part of step two in the company’s R&D (research and development).

Onto Vollebak’s graphene jacket,

Courtesy: Vollebak

From an August 14, 2018 article by Jesus Diaz for Fast Company,

Graphene is the thinnest possible form of graphite, which you can find in your everyday pencil. It’s purely bi-dimensional, a single layer of carbon atoms that has unbelievable properties that have long threatened to revolutionize everything from aerospace engineering to medicine. …

Despite its immense promise, graphene still hasn’t found much use in consumer products, thanks to the fact that it’s hard to manipulate and manufacture in industrial quantities. The process of developing Vollebak’s jacket, according to the company’s cofounders, brothers Steve and Nick Tidball, took years of intensive research, during which the company worked with the same material scientists who built Michael Phelps’ 2008 Olympic Speedo swimsuit (which was famously banned for shattering records at the event).

The jacket is made out of a two-sided material, which the company invented during the extensive R&D process. The graphene side looks gunmetal gray, while the flipside appears matte black. To create it, the scientists turned raw graphite into something called graphene “nanoplatelets,” which are stacks of graphene that were then blended with polyurethane to create a membrane. That, in turn, is bonded to nylon to form the other side of the material, which Vollebak says alters the properties of the nylon itself. “Adding graphene to the nylon fundamentally changes its mechanical and chemical properties–a nylon fabric that couldn’t naturally conduct heat or energy, for instance, now can,” the company claims.

The company says that it’s reversible so you can enjoy graphene’s properties in different ways as the material interacts with either your skin or the world around you. “As physicists at the Max Planck Institute revealed, graphene challenges the fundamental laws of heat conduction, which means your jacket will not only conduct the heat from your body around itself to equalize your skin temperature and increase it, but the jacket can also theoretically store an unlimited amount of heat, which means it can work like a radiator,” Tidball explains.

He means it literally. You can leave the jacket out in the sun, or on another source of warmth, as it absorbs heat. Then, the company explains on its website, “If you then turn it inside out and wear the graphene next to your skin, it acts like a radiator, retaining its heat and spreading it around your body. The effect can be visibly demonstrated by placing your hand on the fabric, taking it away and then shooting the jacket with a thermal imaging camera. The heat of the handprint stays long after the hand has left.”

There’s a lot more to the article although it does feature some hype and I’m not sure I believe Diaz’s claim (August 14, 2018 article) that ‘graphene-based’ hair dye is perfectly safe ( Note: A link has been removed),

Graphene is the thinnest possible form of graphite, which you can find in your everyday pencil. It’s purely bi-dimensional, a single layer of carbon atoms that has unbelievable properties that will one day revolutionize everything from aerospace engineering to medicine. Its diverse uses are seemingly endless: It can stop a bullet if you add enough layers. It can change the color of your hair with no adverse effects. [emphasis mine] It can turn the walls of your home into a giant fire detector. “It’s so strong and so stretchy that the fibers of a spider web coated in graphene could catch a falling plane,” as Vollebak puts it in its marketing materials.

Not unless things have changed greatly since March 2018. My August 2, 2018 posting featured the graphene-based hair dye announcement from March 2018 and a cautionary note from Dr. Andrew Maynard (scroll down ab out 50% of the way for a longer excerpt of Maynard’s comments),

Northwestern University’s press release proudly announced, “Graphene finds new application as nontoxic, anti-static hair dye.” The announcement spawned headlines like “Enough with the toxic hair dyes. We could use graphene instead,” and “’Miracle material’ graphene used to create the ultimate hair dye.”

From these headlines, you might be forgiven for getting the idea that the safety of graphene-based hair dyes is a done deal. Yet having studied the potential health and environmental impacts of engineered nanomaterials for more years than I care to remember, I find such overly optimistic pronouncements worrying – especially when they’re not backed up by clear evidence.

These studies need to be approached with care, as the precise risks of graphene exposure will depend on how the material is used, how exposure occurs and how much of it is encountered. Yet there’s sufficient evidence to suggest that this substance should be used with caution – especially where there’s a high chance of exposure or that it could be released into the environment.

The full text of Dr. Maynard’s comments about graphene hair dyes and risk can be found here.

Bearing in mind  that graphene-based hair dye is an entirely different class of product from the jacket, I wouldn’t necessarily dismiss risks; I would like to know what kind of risk assessment and safety testing has been done. Due to their understandable enthusiasm, the brothers Tidball have focused all their marketing on the benefits and the opportunity for the consumer to test their product (from graphene jacket product webpage),

While it’s completely invisible and only a single atom thick, graphene is the lightest, strongest, most conductive material ever discovered, and has the same potential to change life on Earth as stone, bronze and iron once did. But it remains difficult to work with, extremely expensive to produce at scale, and lives mostly in pioneering research labs. So following in the footsteps of the scientists who discovered it through their own highly speculative experiments, we’re releasing graphene-coated jackets into the world as experimental prototypes. Our aim is to open up our R&D and accelerate discovery by getting graphene out of the lab and into the field so that we can harness the collective power of early adopters as a test group. No-one yet knows the true limits of what graphene can do, so the first edition of the Graphene Jacket is fully reversible with one side coated in graphene and the other side not. If you’d like to take part in the next stage of this supermaterial’s history, the experiment is now open. You can now buy it, test it and tell us about it. [emphasis mine]

How maverick experiments won the Nobel Prize

While graphene’s existence was first theorised in the 1940s, it wasn’t until 2004 that two maverick scientists, Andre Geim and Konstantin Novoselov, were able to isolate and test it. Through highly speculative and unfunded experimentation known as their ‘Friday night experiments,’ they peeled layer after layer off a shaving of graphite using Scotch tape until they produced a sample of graphene just one atom thick. After similarly leftfield thinking won Geim the 2000 Ig Nobel prize for levitating frogs using magnets, the pair won the Nobel prize in 2010 for the isolation of graphene.

Should you be interested, in beta-testing the jacket, it will cost you $695 (presumably USD); order here. One last thing, Vollebak is based in the UK.

Graphene skinned plane

An August 14, 2018 news item (also published as an August 1, 2018 Haydale press release) by Sue Keighley on Azonano heralds a new technology for airplans,

Haydale, (AIM: HAYD), the global advanced materials group, notes the announcement made yesterday from the University of Central Lancashire (UCLAN) about the recent unveiling of the world’s first graphene skinned plane at the internationally renowned Farnborough air show.

The prepreg material, developed by Haydale, has potential value for fuselage and wing surfaces in larger scale aero and space applications especially for the rapidly expanding drone market and, in the longer term, the commercial aerospace sector. By incorporating functionalised nanoparticles into epoxy resins, the electrical conductivity of fibre-reinforced composites has been significantly improved for lightning-strike protection, thereby achieving substantial weight saving and removing some manufacturing complexities.

Before getting to the photo, here’s a definition for pre-preg from its Wikipedia entry (Note: Links have been removed),

Pre-preg is “pre-impregnated” composite fibers where a thermoset polymer matrix material, such as epoxy, or a thermoplastic resin is already present. The fibers often take the form of a weave and the matrix is used to bond them together and to other components during manufacture.

Haydale has supplied graphene enhanced prepreg material for Juno, a three-metre wide graphene-enhanced composite skinned aircraft, that was revealed as part of the ‘Futures Day’ at Farnborough Air Show 2018. [downloaded from https://www.azonano.com/news.aspx?newsID=36298]

A July 31, 2018 University of Central Lancashire (UCLan) press release provides a tiny bit more (pun intended) detail,

The University of Central Lancashire (UCLan) has unveiled the world’s first graphene skinned plane at an internationally renowned air show.

Juno, a three-and-a-half-metre wide graphene skinned aircraft, was revealed on the North West Aerospace Alliance (NWAA) stand as part of the ‘Futures Day’ at Farnborough Air Show 2018.

The University’s aerospace engineering team has worked in partnership with the Sheffield Advanced Manufacturing Research Centre (AMRC), the University of Manchester’s National Graphene Institute (NGI), Haydale Graphene Industries (Haydale) and a range of other businesses to develop the unmanned aerial vehicle (UAV), which also includes graphene batteries and 3D printed parts.

Billy Beggs, UCLan’s Engineering Innovation Manager, said: “The industry reaction to Juno at Farnborough was superb with many positive comments about the work we’re doing. Having Juno at one the world’s biggest air shows demonstrates the great strides we’re making in leading a programme to accelerate the uptake of graphene and other nano-materials into industry.

“The programme supports the objectives of the UK Industrial Strategy and the University’s Engineering Innovation Centre (EIC) to increase industry relevant research and applications linked to key local specialisms. Given that Lancashire represents the fourth largest aerospace cluster in the world, there is perhaps no better place to be developing next generation technologies for the UK aerospace industry.”

Previous graphene developments at UCLan have included the world’s first flight of a graphene skinned wing and the launch of a specially designed graphene-enhanced capsule into near space using high altitude balloons.

UCLan engineering students have been involved in the hands-on project, helping build Juno on the Preston Campus.

Haydale supplied much of the material and all the graphene used in the aircraft. Ray Gibbs, Chief Executive Officer, said: “We are delighted to be part of the project team. Juno has highlighted the capability and benefit of using graphene to meet key issues faced by the market, such as reducing weight to increase range and payload, defeating lightning strike and protecting aircraft skins against ice build-up.”

David Bailey Chief Executive of the North West Aerospace Alliance added: “The North West aerospace cluster contributes over £7 billion to the UK economy, accounting for one quarter of the UK aerospace turnover. It is essential that the sector continues to develop next generation technologies so that it can help the UK retain its competitive advantage. It has been a pleasure to support the Engineering Innovation Centre team at the University in developing the world’s first full graphene skinned aircraft.”

The Juno project team represents the latest phase in a long-term strategic partnership between the University and a range of organisations. The partnership is expected to go from strength to strength following the opening of the £32m EIC facility in February 2019.

The next step is to fly Juno and conduct further tests over the next two months.

Next item, a new carbon material.

Schwarzite

I love watching this gif of a schwarzite,

The three-dimensional cage structure of a schwarzite that was formed inside the pores of a zeolite. (Graphics by Yongjin Lee and Efrem Braun)

An August 13, 2018 news item on Nanowerk announces the new carbon structure,

The discovery of buckyballs [also known as fullerenes, C60, or buckminsterfullerenes] surprised and delighted chemists in the 1980s, nanotubes jazzed physicists in the 1990s, and graphene charged up materials scientists in the 2000s, but one nanoscale carbon structure – a negatively curved surface called a schwarzite – has eluded everyone. Until now.

University of California, Berkeley [UC Berkeley], chemists have proved that three carbon structures recently created by scientists in South Korea and Japan are in fact the long-sought schwarzites, which researchers predict will have unique electrical and storage properties like those now being discovered in buckminsterfullerenes (buckyballs or fullerenes for short), nanotubes and graphene.

An August 13, 2018 UC Berkeley news release by Robert Sanders, which originated the news item, describes how the Berkeley scientists and the members of their international  collaboration from Germany, Switzerland, Russia, and Italy, have contributed to the current state of schwarzite research,

The new structures were built inside the pores of zeolites, crystalline forms of silicon dioxide – sand – more commonly used as water softeners in laundry detergents and to catalytically crack petroleum into gasoline. Called zeolite-templated carbons (ZTC), the structures were being investigated for possible interesting properties, though the creators were unaware of their identity as schwarzites, which theoretical chemists have worked on for decades.

Based on this theoretical work, chemists predict that schwarzites will have unique electronic, magnetic and optical properties that would make them useful as supercapacitors, battery electrodes and catalysts, and with large internal spaces ideal for gas storage and separation.

UC Berkeley postdoctoral fellow Efrem Braun and his colleagues identified these ZTC materials as schwarzites based of their negative curvature, and developed a way to predict which zeolites can be used to make schwarzites and which can’t.

“We now have the recipe for how to make these structures, which is important because, if we can make them, we can explore their behavior, which we are working hard to do now,” said Berend Smit, an adjunct professor of chemical and biomolecular engineering at UC Berkeley and an expert on porous materials such as zeolites and metal-organic frameworks.

Smit, the paper’s corresponding author, Braun and their colleagues in Switzerland, China, Germany, Italy and Russia will report their discovery this week in the journal Proceedings of the National Academy of Sciences. Smit is also a faculty scientist at Lawrence Berkeley National Laboratory.

Playing with carbon

Diamond and graphite are well-known three-dimensional crystalline arrangements of pure carbon, but carbon atoms can also form two-dimensional “crystals” — hexagonal arrangements patterned like chicken wire. Graphene is one such arrangement: a flat sheet of carbon atoms that is not only the strongest material on Earth, but also has a high electrical conductivity that makes it a promising component of electronic devices.

schwarzite carbon cage

The cage structure of a schwarzite that was formed inside the pores of a zeolite. The zeolite is subsequently dissolved to release the new material. (Graphics by Yongjin Lee and Efrem Braun)

Graphene sheets can be wadded up to form soccer ball-shaped fullerenes – spherical carbon cages that can store molecules and are being used today to deliver drugs and genes into the body. Rolling graphene into a cylinder yields fullerenes called nanotubes, which are being explored today as highly conductive wires in electronics and storage vessels for gases like hydrogen and carbon dioxide. All of these are submicroscopic, 10,000 times smaller than the width of a human hair.

To date, however, only positively curved fullerenes and graphene, which has zero curvature, have been synthesized, feats rewarded by Nobel Prizes in 1996 and 2010, respectively.

In the 1880s, German physicist Hermann Schwarz investigated negatively curved structures that resemble soap-bubble surfaces, and when theoretical work on carbon cage molecules ramped up in the 1990s, Schwarz’s name became attached to the hypothetical negatively curved carbon sheets.

“The experimental validation of schwarzites thus completes the triumvirate of possible curvatures to graphene; positively curved, flat, and now negatively curved,” Braun added.

Minimize me

Like soap bubbles on wire frames, schwarzites are topologically minimal surfaces. When made inside a zeolite, a vapor of carbon-containing molecules is injected, allowing the carbon to assemble into a two-dimensional graphene-like sheet lining the walls of the pores in the zeolite. The surface is stretched tautly to minimize its area, which makes all the surfaces curve negatively, like a saddle. The zeolite is then dissolved, leaving behind the schwarzite.

soap bubble schwarzite structure

A computer-rendered negatively curved soap bubble that exhibits the geometry of a carbon schwarzite. (Felix Knöppel image)

“These negatively-curved carbons have been very hard to synthesize on their own, but it turns out that you can grow the carbon film catalytically at the surface of a zeolite,” Braun said. “But the schwarzites synthesized to date have been made by choosing zeolite templates through trial and error. We provide very simple instructions you can follow to rationally make schwarzites and we show that, by choosing the right zeolite, you can tune schwarzites to optimize the properties you want.”

Researchers should be able to pack unusually large amounts of electrical charge into schwarzites, which would make them better capacitors than conventional ones used today in electronics. Their large interior volume would also allow storage of atoms and molecules, which is also being explored with fullerenes and nanotubes. And their large surface area, equivalent to the surface areas of the zeolites they’re grown in, could make them as versatile as zeolites for catalyzing reactions in the petroleum and natural gas industries.

Braun modeled ZTC structures computationally using the known structures of zeolites, and worked with topological mathematician Senja Barthel of the École Polytechnique Fédérale de Lausanne in Sion, Switzerland, to determine which of the minimal surfaces the structures resembled.

The team determined that, of the approximately 200 zeolites created to date, only 15 can be used as a template to make schwarzites, and only three of them have been used to date to produce schwarzite ZTCs. Over a million zeolite structures have been predicted, however, so there could be many more possible schwarzite carbon structures made using the zeolite-templating method.

Other co-authors of the paper are Yongjin Lee, Seyed Mohamad Moosavi and Barthel of the École Polytechnique Fédérale de Lausanne, Rocio Mercado of UC Berkeley, Igor Baburin of the Technische Universität Dresden in Germany and Davide Proserpio of the Università degli Studi di Milano in Italy and Samara State Technical University in Russia.

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

Generating carbon schwarzites via zeolite-templating by Efrem Braun, Yongjin Lee, Seyed Mohamad Moosavi, Senja Barthel, Rocio Mercado, Igor A. Baburin, Davide M. Proserpio, and Berend Smit. PNAS August 14, 2018. 201805062; published ahead of print August 14, 2018. https://doi.org/10.1073/pnas.1805062115

This paper appears to be open access.

Creating cheap, small carbon nanotubes

The excitement fairly crackles off the video,

A May 24, 2018 news item on Nanowerk announces the research,

Imagine a box you plug into the wall that cleans your toxic air and pays you cash.

That’s essentially what Vanderbilt University researchers produced after discovering the blueprint for turning the carbon dioxide into carbon nanotubes with small diameters.

Carbon nanotubes are supermaterials that can be stronger than steel and more conductive than copper. The reason they’re not in every application from batteries to tires is that these amazing properties only show up in the tiniest nanotubes, which are extremely expensive. Not only did the Vanderbilt team show they can make these materials from carbon dioxide sucked from the air, but how to do this in a way that is much cheaper than any other method out there.

I’m not sure what ‘small’ means in this context. I’ve heard of long and short carbon nanotubes (CNTs) and also of single-walled, multi-walled, and double-walled CNTs. I wish there’d been an an explanation and measurements for ‘small diameter CNTs’. That nitpick aside, a May 23, 2018 Vanderbilt University news release by Heidi Hall adds a few more technical details,

These materials, which Assistant Professor of Mechanical Engineering Cary Pint calls “black gold,” could steer the conversation from the negative impact of emissions to how we can use them in future technology.

“One of the most exciting things about what we’ve done is use electrochemistry to pull apart carbon dioxide into elemental constituents of carbon and oxygen and stitch together, with nanometer precision, those carbon atoms into new forms of matter,” Pint said. “That opens the door to being able to generate really valuable products with carbon nanotubes.

“These could revolutionize the world.”

In a report published today in ACS [American Chemical Society] Applied Materials and Interfaces, Pint, interdisciplinary material science Ph.D. student Anna Douglas and their team describe how tiny nanoparticles 10,000 times smaller than a human hair can be produced from coatings on stainless steel surfaces. The key was making them small enough to be valuable.

“The cheapest carbon nanotubes on the market cost around $100-200 per kilogram,” Douglas said. “Our research advance demonstrates a pathway to synthesize carbon nanotubes better in quality than these materials with lower cost and using carbon dioxide captured from the air.”

But making small nanotubes is no small task. The research team showed that a process called Ostwald ripening — where the nanoparticles that grow the carbon nanotubes change in size to larger diameters — is a key contender against producing the infinitely more useful size. The team showed they could partially overcome this by tuning electrochemical parameters to minimize these pesky large nanoparticles.

side-by-side photos showing stainless steel plate becoming covered in carbon nanotubes (which look like lumps of ash or mud)
Small diameter carbon nanotubes grown on a stainless steel surface. (Pint Lab/Vanderbilt University)

This core technology led Pint and Douglas to co-found SkyNano LLC, a company focused on building upon the science of this process to scale up and commercialize products from these materials.

“What we’ve learned is the science that opens the door to now build some of the most valuable materials in our world, such as diamonds and single-walled carbon nanotubes, from carbon dioxide that we capture from air through our process,” Pint said.

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

Toward Small-Diameter Carbon Nanotubes Synthesized from Captured Carbon Dioxide: Critical Role of Catalyst Coarsening by Anna Douglas, Rachel Carter, Mengya Li, and Cary L. Pint. ACS Appl. Mater. Interfaces, Article ASAP DOI: 10.1021/acsami.8b02834 Publication Date (Web): May 1, 2018

Copyright © 2018 American Chemical Society

This paper is behind a paywall.

Regarding the start-up, SkyNano, which Douglas and Pint have co-founded, it looks to be at a  very early stage.

Historic and other buildings get protection from pollution?

This Sept. 15, 2017 news item on Nanowerk announces a new product for protecting buildings from pollution,

The organic pollution decomposing properties of titanium dioxide (TiO2 ) have been known for about half a century. However, practical applications have been few and hard to develop, but now a Greek paint producer claims to have found a solution

A Sept. 11, 2017 Youris (European Research Media Center) press release by Koen Mortelmans which originated the news item expands on the theme,

The photocatalytic properties of anatase, one of the three naturally occurring forms of titanium dioxide, were discovered in Japan in the late 1960s. Under the influence of the UV-radiation in sunlight, it can decompose organic pollutants such as bacteria, fungi and nicotine, and some inorganic materials into carbon dioxide. The catalytic effect is caused by the nanostructure of its crystals.

Applied outdoors, this affordable and widely available material could represent an efficient self-cleaning solution for buildings. This is due to the chemical reaction, which leaves a residue on building façades, a residue then washed away when it rains. Applying it to monuments in urban areas may save our cultural heritage, which is threatened by pollutants.

However, “photocatalytic paints and additives have long been a challenge for the coating industry, because the catalytic action affects the durability of resin binders and oxidizes the paint components,” explains Ioannis Arabatzis, founder and managing director of NanoPhos, based in the Greek town of Lavrio, in one of the countries home to some of the most important monuments of human history. The Greek company is testing a paint called Kirei, inspired by a Japanese word meaning both clean and beautiful.

According to Arabatzis, it’s an innovative product because it combines the self-cleaning action of photocatalytic nanoparticles and the reflective properties of cool wall paints. “When applied on exterior surfaces this paint can reflect more than 94% of the incident InfraRed radiation (IR), saving energy and reducing costs for heating and cooling”, he says. “The reflection values are enhanced by the self-cleaning ability. Compared to conventional paints, they remain unchanged for longer.”

The development of Kirei has been included in the European project BRESAER (BREakthrough Solutions for Adaptable Envelopes in building Refurbishment) which is studying a sustainable and adaptable “envelope system” to renovate buildings. The new paint was tested and subjected to quality controls following ISO standard procedures at the company’s own facilities and in other independent laboratories. “The lab results from testing in artificial, accelerated weathering conditions are reliable,” Arabatzis claims. “There was no sign of discolouration, chalking, cracking or any other paint defect during 2,000 hours of exposure to the simulated environmental conditions. We expect the coating’s service lifetime to be at least ten years.”

Many studies are being conducted to exploit the properties of titanium dioxide. Jan Duyzer, researcher at the Netherlands Organisation for Applied Scientific Research (TNO) in Utrecht, focused on depollution: “There is no doubt about the ability of anatase to decrease the levels of nitrogen oxides in the air. But in real situations, there are many differences in pollution, wind, light, and temperature. We were commissioned by the Dutch government specifically to find a way to take nitrogen oxides out of the air on roads and in traffic tunnels. We used anatase coated panels. Our results were disappointing, so the government decided to discontinue the research. Furthermore, we still don’t know what caused the difference between lab and life. Our best current hypothesis is that the total surface of the coated panels is very small compared to the large volumes of polluted air passing over them,” he tells youris.com.

Experimental deployment of titanium dioxide panels on an acoustic wall along a Dutch highway – Courtesy of Netherlands Organisation for Applied Scientific Research (TNO)

“In laboratory conditions the air is blown over the photocatalytic surface with a certain degree of turbulence. This results in the NOx-particles and the photocatalytic material coming into full contact with one another,” says engineer Anne Beeldens, visiting professor at KU Leuven, Belgium. Her experience with photocatalytic TiO2 is also limited to nitrogen dioxide (NOx) pollution.

In real applications, the air stream at the contact surface becomes laminar. This results in a lower velocity of the air at the surface and a lower depollution rate. Additionally, not all the air will be in contact with the photocatalytic surfaces. To ensure a good working application, the photocatalytic material needs to be positioned so that all the air is in contact with the surface and flows over it in a turbulent manner. This would allow as much of the NOx as possible to be in contact with photocatalytic material. In view of this, a good working application could lead to a reduction of 5 to 10 percent of NOx in the air, which is significant compared to other measures to reduce pollutants.”

The depollution capacity of TiO2 is undisputed, but most applications and tests have only involved specific kinds of substances. More research and measurements are required if we are to benefit more from the precious features of this material.

I think the most recent piece here on protecting buildings, i.e., the historic type, from pollution is an Oct. 21, 2014 posting: Heart of stone.

Cyborg bacteria to reduce carbon dioxide

This video is a bit technical but then it is about work being presented to chemists at the American Chemical Society’s (ACS) at the 254th National Meeting & Exposition Aug. 20 -24, 2017,

For a more plain language explanation, there’s an August 22, 2017 ACS news release (also on EurekAlert),

Photosynthesis provides energy for the vast majority of life on Earth. But chlorophyll, the green pigment that plants use to harvest sunlight, is relatively inefficient. To enable humans to capture more of the sun’s energy than natural photosynthesis can, scientists have taught bacteria to cover themselves in tiny, highly efficient solar panels to produce useful compounds.

“Rather than rely on inefficient chlorophyll to harvest sunlight, I’ve taught bacteria how to grow and cover their bodies with tiny semiconductor nanocrystals,” says Kelsey K. Sakimoto, Ph.D., who carried out the research in the lab of Peidong Yang, Ph.D. “These nanocrystals are much more efficient than chlorophyll and can be grown at a fraction of the cost of manufactured solar panels.”

Humans increasingly are looking to find alternatives to fossil fuels as sources of energy and feedstocks for chemical production. Many scientists have worked to create artificial photosynthetic systems to generate renewable energy and simple organic chemicals using sunlight. Progress has been made, but the systems are not efficient enough for commercial production of fuels and feedstocks.

Research in Yang’s lab at the University of California, Berkeley, where Sakimoto earned his Ph.D., focuses on harnessing inorganic semiconductors that can capture sunlight to organisms such as bacteria that can then use the energy to produce useful chemicals from carbon dioxide and water. “The thrust of research in my lab is to essentially ‘supercharge’ nonphotosynthetic bacteria by providing them energy in the form of electrons from inorganic semiconductors, like cadmium sulfide, that are efficient light absorbers,” Yang says. “We are now looking for more benign light absorbers than cadmium sulfide to provide bacteria with energy from light.”

Sakimoto worked with a naturally occurring, nonphotosynthetic bacterium, Moorella thermoacetica, which, as part of its normal respiration, produces acetic acid from carbon dioxide (CO2). Acetic acid is a versatile chemical that can be readily upgraded to a number of fuels, polymers, pharmaceuticals and commodity chemicals through complementary, genetically engineered bacteria.

When Sakimoto fed cadmium and the amino acid cysteine, which contains a sulfur atom, to the bacteria, they synthesized cadmium sulfide (CdS) nanoparticles, which function as solar panels on their surfaces. The hybrid organism, M. thermoacetica-CdS, produces acetic acid from CO2, water and light. “Once covered with these tiny solar panels, the bacteria can synthesize food, fuels and plastics, all using solar energy,” Sakimoto says. “These bacteria outperform natural photosynthesis.”

The bacteria operate at an efficiency of more than 80 percent, and the process is self-replicating and self-regenerating, making this a zero-waste technology. “Synthetic biology and the ability to expand the product scope of CO2 reduction will be crucial to poising this technology as a replacement, or one of many replacements, for the petrochemical industry,” Sakimoto says.

So, do the inorganic-biological hybrids have commercial potential? “I sure hope so!” he says. “Many current systems in artificial photosynthesis require solid electrodes, which is a huge cost. Our algal biofuels are much more attractive, as the whole CO2-to-chemical apparatus is self-contained and only requires a big vat out in the sun.” But he points out that the system still requires some tweaking to tune both the semiconductor and the bacteria. He also suggests that it is possible that the hybrid bacteria he created may have some naturally occurring analog. “A future direction, if this phenomenon exists in nature, would be to bioprospect for these organisms and put them to use,” he says.

For more insight into the work, check out Dexter Johnson’s Aug. 22, 2017 posting on his Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers] website),

“It’s actually a natural, overlooked feature of their biology,” explains Sakimoto in an e-mail interview with IEEE Spectrum. “This bacterium has a detoxification pathway, meaning if it encounters a toxic metal, like cadmium, it will try to precipitate it out, thereby detoxifying it. So when we introduce cadmium ions into the growth medium in which M. thermoacetica is hanging out, it will convert the amino acid cysteine into sulfide, which precipitates out cadmium as cadmium sulfide. The crystals then assemble and stick onto the bacterium through normal electrostatic interactions.”

I’ve just excerpted one bit, there’s more in Dexter’s posting.

Kinetic properties of cement at the nanoscale

There was a Vancouver-born architect, Arthur Erickson, who adored concrete as a building material. In fact, he gained an international reputation for his ‘concrete’ work. I have never been a fan, especially after attending Simon Fraser University (one of Erickson’s early triumphs) in Vancouver (Canada) and experiencing the joy of deteriorating concrete structures.

This somewhat related news concerns cement, (from a Dec.7, 2016 news item on ScienceDaily,

Bringing order to disorder is key to making stronger and greener cement, the paste that binds concrete.

Scientists at Rice University have decoded the kinetic properties of cement and developed a way to “program” the microscopic, semicrystalline particles within. The process turns particles from disordered clumps into regimented cubes, spheres and other forms that combine to make the material less porous and more durable.

A Dec. 7, 2016 Rice University news release, which originated the news item, explains further (Note: Links have been removed),

The technique may lead to stronger structures that require less concrete – and less is better, said Rice materials scientist and lead author Rouzbeh Shahsavari. Worldwide production of more than 3 billion tons of concrete a year now emits as much as 10 percent of the carbon dioxide, a greenhouse gas, released to the atmosphere.

Through extensive experiments, Shahsavari and his colleagues decoded the nanoscale reactions — or “morphogenesis” — of the crystallization within calcium-silicate hydrate (C-S-H) cement that holds concrete together.

For the first time, they synthesized C-S-H particles in a variety of shapes, including cubes, rectangular prisms, dendrites, core-shells and rhombohedra and mapped them into a unified morphology diagram for manufacturers and builders who wish to engineer concrete from the bottom up.

“We call it programmable cement,” he said. “The great advance of this work is that it’s the first step in controlling the kinetics of cement to get desired shapes. We show how one can control the morphology and size of the basic building blocks of C-S-H so that they can self-assemble into microstructures with far greater packing density compared with conventional amorphous C-S-H microstructures.”

He said the idea is akin to the self-assembly of metallic crystals and polymers. “It’s a hot area, and researchers are taking advantage of it,” Shahsavari said. “But when it comes to cement and concrete, it is extremely difficult to control their bottom-up assembly. Our work provides the first recipe for such advanced synthesis.

“The seed particles form first, automatically, in our reactions, and then they dominate the process as the rest of the material forms around them,” he said. “That’s the beauty of it. It’s in situ, seed-mediated growth and does not require external addition of seed particles, as commonly done in the industry to promote crystallization and growth.”

Previous techniques to create ordered crystals in C-S-H required high temperatures or pressures, prolonged reaction times and the use of organic precursors, but none were efficient or environmentally benign, Shahsavari said.

The Rice lab created well-shaped cubes and rectangles by adding small amounts of positive or negative ionic surfactants and calcium silicate to C-S-H and exposing the mix to carbon dioxide and ultrasonic sound. The crystal seeds took shape around surfactant micelles within 25 minutes. Decreasing the calcium silicate yielded more spherical particles and smaller cubes, while increasing it formed clumped spheres and interlocking cubes.

Once the calcite “seeds” form, they trigger the molecules around them to self-assemble into cubes, spheres and other shapes that are orders of magnitude larger. These can pack more tightly together in concrete than amorphous particles, Shahsavari said. Carefully modulating the precursor concentration, temperature and duration of the reaction varies the yield, size and morphology of the final particles.

The discovery is an important step in concrete research, he said. It builds upon his work as part of the Massachusetts Institute of Technology team that decoded cement’s molecular “DNA” in 2009. “There is currently no control over C-S-H shape,” Shahsavari said. “The concrete used today is an amorphous colloid with significant porosity that entails reduced strength and durability.”

Concrete is one focus of Shahsavari’s Rice lab, which has studied both its macroscale manufacture and intrinsic nanoscale properties. Because concrete is the world’s most common construction material and a significant source of atmospheric carbon dioxide, he is convinced of the importance of developing “greener” concrete.

The new technique has several environmental benefits, Shahsavari said. “One is that you need less of it (the concrete) because it is stronger. This stems from better packing of the cubic particles, which leads to stronger microstructures. The other is that it will be more durable. Less porosity makes it harder for unwanted chemicals to find a path through the concrete, so it does a better job of protecting steel reinforcement inside.”

The research required the team to develop a method to test microscopic concrete particles for strength. The researchers used a diamond-tipped nanoindenter to crush single cement particles with a flat edge.

They programmed the indenter to move from one nanoparticle to the next and crush it and gathered mechanical data on hundreds of particles of various shapes in one run. “Other research groups have tested bulk cement and concrete, but no group had ever probed the mechanics of single C-S-H particles and the effect of shape on mechanics of individual particles,” Shahsavari said.

He said strategies developed during the project could have implications for other applications, including bone tissue engineering, drug delivery and refractory materials, and could impact such other complex systems as ceramics and colloids.

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

Morphogenesis of Cement Hydrate by Sakineh E Moghaddam, vahid hejazi, Sung Hoon Hwang, Sreeprasad Srinavasan, Joseph B. Miller, Benhang Shi, Shuo Zhao, Irene Rusakova, Aali R. Alizadeh, Kenton Whitmire and Rouzbeh Shahsavari. J. Mater. Chem. A, 2016, DOI: 10.1039/C6TA09389B First published online 30 Nov 2016

I believe this paper is behind a paywall.

Nano-spike catalysts offer one step conversion of carbon dioxide to ethanol

An Oct. 12, 2016 news item on ScienceDaily makes an exciting announcement, if carbon-dixoide-conversion-to-fuel is one of your pet topics,

In a new twist to waste-to-fuel technology, scientists at the Department of Energy’s Oak Ridge National Laboratory [ORNL] have developed an electrochemical process that uses tiny spikes of carbon and copper to turn carbon dioxide, a greenhouse gas, into ethanol. Their finding, which involves nanofabrication and catalysis science, was serendipitous.

An Oct. 12, 2016 ORNL news release, which originated the news item, explains in greater detail,

“We discovered somewhat by accident that this material worked,” said ORNL’s Adam Rondinone, lead author of the team’s study published in ChemistrySelect. “We were trying to study the first step of a proposed reaction when we realized that the catalyst was doing the entire reaction on its own.”

The team used a catalyst made of carbon, copper and nitrogen and applied voltage to trigger a complicated chemical reaction that essentially reverses the combustion process. With the help of the nanotechnology-based catalyst which contains multiple reaction sites, the solution of carbon dioxide dissolved in water turned into ethanol with a yield of 63 percent. Typically, this type of electrochemical reaction results in a mix of several different products in small amounts.

“We’re taking carbon dioxide, a waste product of combustion, and we’re pushing that combustion reaction backwards with very high selectivity to a useful fuel,” Rondinone said. “Ethanol was a surprise — it’s extremely difficult to go straight from carbon dioxide to ethanol with a single catalyst.”

The catalyst’s novelty lies in its nanoscale structure, consisting of copper nanoparticles embedded in carbon spikes. This nano-texturing approach avoids the use of expensive or rare metals such as platinum that limit the economic viability of many catalysts.

“By using common materials, but arranging them with nanotechnology, we figured out how to limit the side reactions and end up with the one thing that we want,” Rondinone said.

The researchers’ initial analysis suggests that the spiky textured surface of the catalysts provides ample reactive sites to facilitate the carbon dioxide-to-ethanol conversion.

“They are like 50-nanometer lightning rods that concentrate electrochemical reactivity at the tip of the spike,” Rondinone said.

Given the technique’s reliance on low-cost materials and an ability to operate at room temperature in water, the researchers believe the approach could be scaled up for industrially relevant applications. For instance, the process could be used to store excess electricity generated from variable power sources such as wind and solar.

“A process like this would allow you to consume extra electricity when it’s available to make and store as ethanol,” Rondinone said. “This could help to balance a grid supplied by intermittent renewable sources.”

The researchers plan to refine their approach to improve the overall production rate and further study the catalyst’s properties and behavior.

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

High-Selectivity Electrochemical Conversion of CO2 to Ethanol using a Copper Nanoparticle/N-Doped Graphene Electrode by Yang Song, Rui Peng, Dale Hensley, Peter Bonnesen, Liangbo Liang, Zili Wu, Harry Meyer III, Miaofang Chi, Cheng Ma, Bobby Sumpter and Adam Rondinone. Chemistry Select DOI: 10.1002/slct.201601169 First published: 28 September 2016

This paper is open access.

Carbon capture with asphalt

I wish I could turn back the clock a few years, so I could mention this research from Rice University (Texas, US) on using asphalt for carbon capture (more on why at the end of this post). From a Sept. 13, 2016 news item on Nanowerk (Note: A link has been removed),

Rice University laboratory has improved its method to turn plain asphalt into a porous material that can capture greenhouse gases from natural gas.

In research detailed this month in Advanced Energy Materials (“Ultra-High Surface Area Activated Porous Asphalt for CO2 Capture through Competitive Adsorption at High Pressures”), Rice researchers showed that a new form of the material can sequester 154 percent of its weight in carbon dioxide at high pressures that are common at gas wellheads.

A Sept. 12, 2016 Rice University news release, which originated the news item, further describes the work (Note: Links have been removed),

Raw natural gas typically contains between 2 and 10 percent carbon dioxide and other impurities, which must be removed before the gas can be sold. The cleanup process is complicated and expensive and most often involves flowing the gas through fluids called amines that can soak up and remove about 15 percent of their own weight in carbon dioxide. The amine process also requires a great deal of energy to recycle the fluids for further use.

“It’s a big energy sink,” said Rice chemist James Tour, whose lab developed a technique last year to turn asphalt into a tough, sponge-like substance that could be used in place of amines to remove carbon dioxide from natural gas as it was pumped from ocean wellheads.

Initial field tests in 2015 found that pressure at the wellhead made it possible for that asphalt material to adsorb, or soak up, 114 percent of its weight in carbon at ambient temperatures.

Tour said the new, improved asphalt sorbent is made in two steps from a less expensive form of asphalt, which makes it more practical for industry.

“This shows we can take the least expensive form of asphalt and make it into this very high surface area material to capture carbon dioxide,” Tour said. “Before, we could only use a very expensive form of asphalt that was not readily available.”

The lab heated a common type asphalt known as Gilsonite at ambient pressure to eliminate unneeded organic molecules, and then heated it again in the presence of potassium hydroxide for about 20 minutes to synthesize oxygen-enhanced porous carbon with a surface area of 4,200 square meters per gram, much higher than that of the previous material.

The Rice lab’s initial asphalt-based porous carbon collected carbon dioxide from gas streams under pressure at the wellhead and released it when the pressure was released. The carbon dioxide could then be repurposed or pumped back underground while the porous carbon could be reused immediately.

In the latest tests with its new material, Tours group showed its new sorbent could remove carbon dioxide at 54 bar pressure. One bar is roughly equal to atmospheric pressure at sea level, and the 54 bar measure in the latest experiments is characteristic of the pressure levels typically found at natural gas wellheads, Tour said.

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

Ultra-High Surface Area Activated Porous Asphalt for CO2 Capture through Competitive Adsorption at High Pressures by Almaz S. Jalilov, Yilun Li, Jian Tian, James M. Tour.  Advanced Energy Materials DOI: 10.1002/aenm.201600693  First published [online]: 8 September 2016

This paper is behind a paywall.

Finishing the story I started at the beginning of this post, I was at an early morning political breakfast a few years back when someone seated at our table asked me if there were any nanotechnology applications for carbon sequestration/capture. At the time, I could not bring any such applications to mind. (Sigh) Now I have an answer.