Tag Archives: greenhouse gas

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.

Cleaning up carbon dioxide pollution in the oceans and elsewhere

I have a mini roundup of items (3) concerning nanotechnology and environmental applications with a special focus on carbon materials.

Carbon-capturing motors

First up, there’s a Sept. 23, 2015 news item on ScienceDaily which describes work with tiny carbon-capturing motors,

Machines that are much smaller than the width of a human hair could one day help clean up carbon dioxide pollution in the oceans. Nanoengineers at the University of California, San Diego have designed enzyme-functionalized micromotors that rapidly zoom around in water, remove carbon dioxide and convert it into a usable solid form.

The proof of concept study represents a promising route to mitigate the buildup of carbon dioxide, a major greenhouse gas in the environment, said researchers. …

A Sept 22, 2015 University of California at San Diego (UCSD) news release by Liezel Labios, which originated the news release, provides more details about the scientists’ hopes and the technology,

“We’re excited about the possibility of using these micromotors to combat ocean acidification and global warming,” said Virendra V. Singh, a postdoctoral scientist in Wang’s [nanoengineering professor and chair Joseph Wang] research group and a co-first author of this study.

In their experiments, nanoengineers demonstrated that the micromotors rapidly decarbonated water solutions that were saturated with carbon dioxide. Within five minutes, the micromotors removed 90 percent of the carbon dioxide from a solution of deionized water. The micromotors were just as effective in a sea water solution and removed 88 percent of the carbon dioxide in the same timeframe.

“In the future, we could potentially use these micromotors as part of a water treatment system, like a water decarbonation plant,” said Kevin Kaufmann, an undergraduate researcher in Wang’s lab and a co-author of the study.

The micromotors are essentially six-micrometer-long tubes that help rapidly convert carbon dioxide into calcium carbonate, a solid mineral found in eggshells, the shells of various marine organisms, calcium supplements and cement. The micromotors have an outer polymer surface that holds the enzyme carbonic anhydrase, which speeds up the reaction between carbon dioxide and water to form bicarbonate. Calcium chloride, which is added to the water solutions, helps convert bicarbonate to calcium carbonate.

The fast and continuous motion of the micromotors in solution makes the micromotors extremely efficient at removing carbon dioxide from water, said researchers. The team explained that the micromotors’ autonomous movement induces efficient solution mixing, leading to faster carbon dioxide conversion. To fuel the micromotors in water, researchers added hydrogen peroxide, which reacts with the inner platinum surface of the micromotors to generate a stream of oxygen gas bubbles that propel the micromotors around. When released in water solutions containing as little as two to four percent hydrogen peroxide, the micromotors reached speeds of more than 100 micrometers per second.

However, the use of hydrogen peroxide as the micromotor fuel is a drawback because it is an extra additive and requires the use of expensive platinum materials to build the micromotors. As a next step, researchers are planning to make carbon-capturing micromotors that can be propelled by water.

“If the micromotors can use the environment as fuel, they will be more scalable, environmentally friendly and less expensive,” said Kaufmann.

The researchers have provided an image which illustrates the carbon-capturing motors in action,

Nanoengineers have invented tiny tube-shaped micromotors that zoom around in water and efficiently remove carbon dioxide. The surfaces of the micromotors are functionalized with the enzyme carbonic anhydrase, which enables the motors to help rapidly convert carbon dioxide to calcium carbonate. Image credit: Laboratory for Nanobioelectronics, UC San Diego Jacobs School of Engineering.

Nanoengineers have invented tiny tube-shaped micromotors that zoom around in water and efficiently remove carbon dioxide. The surfaces of the micromotors are functionalized with the enzyme carbonic anhydrase, which enables the motors to help rapidly convert carbon dioxide to calcium carbonate. Image credit: Laboratory for Nanobioelectronics, UC San Diego Jacobs School of Engineering.

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

Micromotor-Based Biomimetic Carbon Dioxide Sequestration: Towards Mobile Microscrubbers by Murat Uygun, Virendra V. Singh, Kevin Kaufmann, Deniz A. Uygun, Severina D. S. de Oliveira, and oseph Wang. Angewandte Chemie DOI: 10.1002/ange.201505155 Article first published online: 4 SEP 2015

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This article is behind a paywall.

Carbon nanotubes for carbon dioxide capture (carbon capture)

In a Sept. 22, 2015 posting by Dexter Johnson on his Nanoclast blog (located on the IEEE [Institute for Electrical and Electronics Engineers] website) describes research where carbon nanotubes are being used for carbon capture,

Now researchers at Technische Universität Darmstadt in Germany and the Indian Institute of Technology Kanpur have found that they can tailor the gas adsorption properties of vertically aligned carbon nanotubes (VACNTs) by altering their thickness, height, and the distance between them.

“These parameters are fundamental for ‘tuning’ the hierarchical pore structure of the VACNTs,” explained Mahshid Rahimi and Deepu Babu, doctoral students at the Technische Universität Darmstadt who were the paper’s lead authors, in a press release. “This hierarchy effect is a crucial factor for getting high-adsorption capacities as well as mass transport into the nanostructure. Surprisingly, from theory and by experiment, we found that the distance between nanotubes plays a much larger role in gas adsorption than the tube diameter does.”

Dexter provides a good and brief summary of the research.

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

Double-walled carbon nanotube array for CO2 and SO2 adsorption by Mahshid Rahimi, Deepu J. Babu, Jayant K. Singh, Yong-Biao Yang, Jörg J. Schneider, and Florian Müller-Plathe. J. Chem. Phys. 143, 124701 (2015); http://dx.doi.org/10.1063/1.4929609

This paper is open access.

The market for nanotechnology-enabled environmental applications

Coincident with stumbling across these two possible capture solutions, I found this Sept. 23, 2015 BCC Research news release,

A groundswell of global support for developing nanotechnology as a pollution remediation technique will continue for the foreseeable future. BCC Research reveals in its new report that this key driver, along with increasing worldwide concerns over removing pollutants and developing alternative energy sources, will drive growth in the nanotechnology environmental applications market.

The global nanotechnology market in environmental applications is expected to reach $25.7 billion by 2015 and $41.8 billion by 2020, conforming to a five-year (2015-2020) compound annual growth rate (CAGR) of 10.2%. Air remediation as a segment will reach $10.2 billion and $16.7 billion in 2015 and 2020, respectively, reflecting a five-year CAGR of 10.3%. Water remediation as a segment will grow at a five-year CAGR of 12.4% to reach $10.6 billion in 2020.

As nanoparticles push the limits and capabilities of technology, new and better techniques for pollution control are emerging. Presently, nanotechnology’s greatest potential lies in air pollution remediation.

“Nano filters could be applied to automobile tailpipes and factory smokestacks to separate out contaminants and prevent them from entering the atmosphere. In addition, nano sensors have been developed to sense toxic gas leaks at extremely low concentrations,” says BCC research analyst Aneesh Kumar. “Overall, there is a multitude of promising environmental applications for nanotechnology, with the main focus area on energy and water technologies.”

You can find links to the report, TOC (table of contents), and report overview on the BCC Research Nanotechnology in Environmental Applications: The Global Market report webpage.

Recycling carbon dioxide with gold nanoparticles

Researchers at Brown University (in Providence, Rhode Island) have developed a technique using gold nanoparticles to capture carbon dioxide and turn it into carbon monoxide (from the Oct. 24, 2013 Brown University news release [also on EurekAlert]),

It’s a 21st-century alchemist’s dream: turning Earth’s superabundance of carbon dioxide — a greenhouse gas — into fuel or useful industrial chemicals. Researchers from Brown have shown that finely tuned gold nanoparticles can do the job. The key is maximizing the particles’ long edges, which are the active sites for the reaction.[This paragraph is present only on the Brown website news release]

By tuning gold nanoparticles to just the right size, researchers from Brown University have developed a catalyst that selectively converts carbon dioxide (CO2) to carbon monoxide (CO), an active carbon molecule that can be used to make alternative fuels and commodity chemicals.

“Our study shows potential of carefully designed gold nanoparticles to recycle CO2 into useful forms of carbon,” said Shouheng Sun, professor of chemistry and one of the study’s senior authors. “The work we’ve done here is preliminary, but we think there’s great potential for this technology to be scaled up for commercial applications.”

The scientists were trying to solve a major problem with recycling carbon dioxide when using gold (from the news release),

Converting CO2 to CO isn’t easy. Prior research has shown that catalysts made of gold foil are active for this conversion, but they don’t do the job efficiently. The gold tends to react both with the CO2 and with the water in which the CO2 is dissolved, creating hydrogen byproduct rather than the desired CO.

The Brown research team decided to try gold nanoparticles and had a surprising result (from the news release),

The Brown experimental group, led by Sun and Wenlei Zhu, a graduate student in Sun’s group, wanted to see if shrinking the gold down to nanoparticles might make it more selective for CO2. They found that the nanoparticles were indeed more selective, but that the exact size of those particles was important. Eight nanometer particles had the best selectivity, achieving a 90-percent rate of conversion from CO2 to CO. Other sizes the team tested — four, six, and 10 nanometers — didn’t perform nearly as well.

“At first, that result was confusing,” said Andrew Peterson, professor of engineering and also a senior author on the paper. “As we made the particles smaller we got more activity, but when we went smaller than eight nanometers, we got less activity.”

The researchers investigated further and found a relationship between size and shape which affects the gold nanoparticles’ performance (from the news release),

To understand what was happening, Peterson and postdoctoral researcher Ronald Michalsky used a modeling method called density functional theory. They were able to show that the shapes of the particles at different sizes influenced their catalytic properties.

“When you take a sphere and you reduce it to smaller and smaller sizes, you tend to get many more irregular features — flat surfaces, edges and corners,” Peterson said. “What we were able to figure out is that the most active sites for converting CO2 to CO are the edge sites, while the corner sites predominantly give the by-product, which is hydrogen. So as you shrink these particles down, you’ll hit a point where you start to optimize the activity because you have a high number of these edge sites but still a low number of these corner sites. But if you go too small, the edges start to shrink and you’re left with just corners.”

Now that they understand exactly what part of the catalyst is active, the researchers are working to further optimize the particles. “There’s still a lot of room for improvement,” Peterson said. “We’re working on new particles that maximize these active sites.”

The researchers believe these findings could be an important new avenue for recycling CO2 on a commercial scale.

“Because we’re using nanoparticles, we’re using a lot less gold than in a bulk metal catalyst,” Sun said. “That lowers the cost for making such a catalyst and gives the potential to scale up.”

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

Monodisperse Au Nanoparticles for Selective Electrocatalytic Reduction of CO2 to CO by Wenlei Zhu, Ronald Michalsky, Önder Metin, Haifeng Lv, Shaojun Guo, Christopher J. Wright, Xiaolian Sun, Andrew A. Peterson, and Shouheng Sun. J. Am. Chem. Soc., DOI: 10.1021/ja409445p Publication Date (Web): October 24, 2013
Copyright © 2013 American Chemical Society

This article is behind a paywall.