Tag Archives: carbon monoxide

Soy and cellulose come together for a bionano air filter

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A Jan. 18, 2017 news item on Nanowerk describes research into an environmentally friendly air filter from Washington State University,

Washington State University researchers have developed a soy-based air filter that can capture toxic chemicals, such as carbon monoxide and formaldehyde, which current air filters can’t.

The research could lead to better air purifiers, particularly in regions of the world that suffer from very poor air quality. …

Working with researchers from the University of Science and Technology Beijing, the WSU team, including Weihong (Katie) Zhong, professor in the School of Mechanical and Materials Engineering, and graduate student Hamid Souzandeh, used a pure soy protein along with bacterial cellulose for an all-natural, biodegradable, inexpensive air filter.

Here’s an image the researchers have made available,

Bionano air filter before and after filtration. Courtesy: Washington State University

A Jan. 12, 2017 Washington State University news release by Tilda Hilding, which originated the news item, expands on the theme,

Poor air quality causes health problems worldwide and is a factor in diseases such as asthma, heart disease and lung cancer. Commercial air purifiers aim for removing the small particles that are present in soot, smoke or car exhaust because these damaging particles are inhaled directly into the lungs.

With many sources of pollution in some parts of the world, however, air pollution also can contain a mix of hazardous gaseous molecules, such as carbon monoxide, formaldehyde, sulfur dioxide and other volatile organic compounds.

Typical air filters, which are usually made of micron-sized fibers of synthetic plastics, physically filter the small particles but aren’t able to chemically capture gaseous molecules. Furthermore, they’re most often made of glass and petroleum products, which leads to secondary pollution, Zhong said.

Soy captures nearly all pollutants

The WSU and Chinese team developed a new kind of air filtering material that uses natural, purified soy protein and bacterial cellulose – an organic compound produced by bacteria. The soy protein and cellulose are cost effective and already used in numerous applications, such as adhesives, plastic products, tissue regeneration materials and wound dressings.

Soy contains a large number of functional chemical groups – it includes 18 types of amino groups. Each of the chemical groups has the potential to capture passing pollution at the molecular level. The researchers used an acrylic acid treatment to disentangle the very rigid soy protein, so that the chemical groups can be more exposed to the pollutants.

The resulting filter was able to remove nearly all of the small particles as well as chemical pollutants, said Zhong.

Filters are economical, biodegradable

Especially in very polluted environments, people might be breathing an unknown mix of pollutants that could prove challenging to purify. But, with its large number of functional groups, the soy protein is able to attract a wide variety of polluting molecules.

“We can take advantage from those chemical groups to grab the toxics in the air,” Zhong said.

The materials are also cost-effective and biodegradable. Soybeans are among the most abundant plants in the world, she added.

Zhong occasionally visits her native China and has personally experienced the heavy pollution in Beijing as sunny skies turn to gray smog within a few days.

“Air pollution is a very serious health issue,” she said. “If we can improve indoor air quality, it would help a lot of people.”

Patents filed on filters, paper towels

In addition to the soy-based filters, the researchers have also developed gelatin- and cellulose-based air filters. They are also applying the filter material on top of low-cost and disposable paper towel to reinforce it and to improve its performance. They have filed patents on the technology and are interested in commercialization opportunities.

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

Soy protein isolate/bacterial cellulose composite membranes for high efficiency particulate air filtration by Xiaobing Liu, Hamid Souzandeh, Yudong Zheng, Yajie Xie, Wei-Hong Zhong, Cai Wang. Composites Science and Technology Volume 138, 18 January 2017, Pages 124–133         http://dx.doi.org/10.1016/j.compscitech.2016.11.022

This paper is behind a paywall.

The volatile lithium-ion battery

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On the heels of Samsung’s Galaxy Note 7 recall due to fires (see Alex Fitzpatrick’s Sept. 9, 2016 article for Time magazine for a good description of lithium-ion batteries and why they catch fire; see my May 29, 2013 posting on lithium-ion batteries, fires [including the airplane fires], and nanotechnology risk assessments), there’s new research on lithium-ion batteries and fires from China. From an Oct. 21, 2016 news item on Nanotechnology Now,

Dozens of dangerous gases are produced by the batteries found in billions of consumer devices, like smartphones and tablets, according to a new study. The research, published in Nano Energy, identified more than 100 toxic gases released by lithium batteries, including carbon monoxide.

An Oct. 20, 2016 Elsevier Publishing press release (also on EurekAlert), which originated the news item, expands on the theme,

The gases are potentially fatal, they can cause strong irritations to the skin, eyes and nasal passages, and harm the wider environment. The researchers behind the study, from the Institute of NBC Defence and Tsinghua University in China, say many people may be unaware of the dangers of overheating, damaging or using a disreputable charger for their rechargeable devices.

In the new study, the researchers investigated a type of rechargeable battery, known as a “lithium-ion” battery, which is placed in two billion consumer devices every year.

“Nowadays, lithium-ion batteries are being actively promoted by many governments all over the world as a viable energy solution to power everything from electric vehicles to mobile devices. The lithium-ion battery is used by millions of families, so it is imperative that the general public understand the risks behind this energy source,” explained Dr. Jie Sun, lead author and professor at the Institute of NBC Defence.

The dangers of exploding batteries have led manufacturers to recall millions of devices: Dell recalled four million laptops in 2006 and millions of Samsung Galaxy Note 7 devices were recalled this month after reports of battery fires. But the threats posed by toxic gas emissions and the source of these emissions are not well understood.

Dr. Sun and her colleagues identified several factors that can cause an increase in the concentration of the toxic gases emitted. A fully charged battery will release more toxic gases than a battery with 50 percent charge, for example. The chemicals contained in the batteries and their capacity to release charge also affected the concentrations and types of toxic gases released.

Identifying the gases produced and the reasons for their emission gives manufacturers a better understanding of how to reduce toxic emissions and protect the wider public, as lithium-ion batteries are used in a wide range of environments.

“Such dangerous substances, in particular carbon monoxide, have the potential to cause serious harm within a short period of time if they leak inside a small, sealed environment, such as the interior of a car or an airplane compartment,” Dr. Sun said.

Almost 20,000 lithium-ion batteries were heated to the point of combustion in the study, causing most devices to explode and all to emit a range of toxic gases. Batteries can be exposed to such temperature extremes in the real world, for example, if the battery overheats or is damaged in some way.

The researchers now plan to develop this detection technique to improve the safety of lithium-ion batteries so they can be used to power the electric vehicles of the future safely.

“We hope this research will allow the lithium-ion battery industry and electric vehicle sector to continue to expand and develop with a greater understanding of the potential hazards and ways to combat these issues,” Sun concluded.

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

Toxicity, a serious concern of thermal runaway from commercial Li-ion battery by Jie Sun, Jigang Li, Tian Zhou, Kai Yang, Shouping Wei, Na Tang, Nannan Dang, Hong Li, Xinping Qiu, Liquan Chend. Nano Energy Volume 27, September 2016, Pages 313–319  http://dx.doi.org/10.1016/j.nanoen.2016.06.031

This paper appears to be open access.

Discovering why nanoscale gold has catalytic properties

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Gold’s glitter may have inspired poets and triggered wars, but its catalytic prowess has helped make chemical reactions greener and more efficient. (Image courtesy of iStock/sbayram) [downloaded from http://www1.lehigh.edu/news/scientists-uncover-secret-gold%E2%80%99s-catalytic-powers

Gold’s glitter may have inspired poets and triggered wars, but its catalytic prowess has helped make chemical reactions greener and more efficient. (Image courtesy of iStock/sbayram) [downloaded from http://www1.lehigh.edu/news/scientists-uncover-secret-gold%E2%80%99s-catalytic-powers

A Sept. 27, 2016 news item on phys.org describes a discovery made by scientists at Lehigh University (US),

Settling a decades-long debate, new research conclusively shows that a hierarchy of active species exists in gold on iron oxide catalysis designed for low temperature carbon monoxide oxidation; Nanoparticles, sub-nanometer clusters and dispersed atoms—as well as how the material is prepared—are all important for determining catalytic activity.

A Sept. 27, 2016 Lehigh University news release by Lori Friedman, which originated the news item, provides more information about the discovery that gold nanoparticles can be used in catalysis and about the discovery of why that’s possible,

Christopher J. Kiely calls the 1982 discovery by Masatake Haruta that gold (Au) possessed a high level of catalytic activity for carbon monoxide (CO) oxidation when deposited on a metal-oxide “a remarkable turn of events in nanotechnology”—remarkable because gold had long been assumed to be inert for catalysis.

Haruta showed that gold dispersed on iron oxide effectively catalyzed the conversion of harmful carbon monoxide into more benign carbon dioxide (CO2) at room temperatures—a reaction that is critical for the construction of fire fighters’ breathing masks and for removal of CO from hydrogen feeds for fuel cells. In fact, today gold catalysts are being exploited in a major way for the greening of many important reactions in the chemical industry, because they can lead to cleaner, more efficient reactions with fewer by-products.

Haruta and Graham J. Hutchings, who co-discovered the use of gold as a catalyst for different reactions, are noted as Thompson Reuters Citation Laureates and appear annually on the ScienceWatch Nobel Prize prediction list. Their pioneering work opened up a new area of scientific inquiry and kicked off a decades-long debate about which type of supported gold species are most effective for the CO oxidation reaction.

In 2008, using electron microscopy technology that was not yet available in the 1980s and ’90 s, Hutchings, the director of the Cardiff Catalysis Institute at Cardiff University worked with Kiely, the Harold B. Chambers Senior Professor Materials Science and Engineering at Lehigh, examined the structure of supported gold at the nanoscale. One nanometer (nm) is equal to one one-billionth of a meter or about the diameter of five atoms.

Using what was then a rare piece of equipment—Lehigh’s aberration-corrected JEOL 2200 FS scanning transmission electron microscope (STEM)—the team identified the co-existence of three distinct gold species: facetted nanoparticles larger than one nanometer in size, sub-clusters containing less than 20 atoms and individual gold atoms strewn over the support. Because only the larger gold nanoparticles had previously been detected, this created debate as to which of these species were responsible for the good catalytic behavior.

Haruta, professor of applied chemistry at Tokyo Metropolitan University, Hutchings and Kiely have been working collaboratively on this problem over recent years and are now the first to demonstrate conclusively that it is not the particles or the individual atoms or the clusters which are solely responsible for the catalysis—but that they all contribute to different degrees. Their results have been published in an article in Nature Communications titled: “Population and hierarchy of active species in gold iron oxide catalysts for carbon monoxide oxidation.”

“All of the species tend to co-exist in conventionally prepared catalysts and show some level of activity,” says Kiely. “They all do something—but some less efficiently than others.”

Their research revealed the sub-nanometer clusters and 1-3nm nanoparticles to be the most efficient for catalyzing this CO oxidation reaction, while larger particles were less so and the atoms even less.  Nevertheless, Kiely cautions, all the species present need to be considered to fully explain the overall measured activity of the catalyst.

Among the team’s other key findings: the measured activity of gold on iron oxide catalysts is exquisitely dependent on exactly how the material is prepared. Very small changes in synthesis parameters  influence the relative proportion and spatial distribution of these various Au species on the support material and thus have a big impact on its overall catalytic performance.

A golden opportunity

Building on their earlier work (published in a 2008 Science article), the team sought to find a robust way to quantitatively analyze the relative population distributions of nanoparticles of various sizes, sub-nm clusters and highly dispersed atoms in a given gold on iron oxide sample. By correlating this information with catalytic performance measurements, they then hoped to determine which species distribution would be optimal to produce the most efficient catalyst, in order to utilize the precious gold component in the most cost effective way.

Ultimately, it was a catalyst synthesis problem the team faced that offered them a golden opportunity to do just that.

During the collaboration, Haruta’s and Hutchings’ teams each prepared gold on iron oxide samples in their home labs in Tokyo and Cardiff. Even though both groups nominally utilized the same ‘co-precipitation’ synthesis method, it turned out that a final heat treatment step was beneficial to the catalytic performance for one set of materials but detrimental to the other. This observation provided a fascinating scientific conundrum that detailed electron microscopy studies performed by Qian He, one of Kiely’s PhD students at the time, was key to solving. Qian He is now a University Research Fellow at Cardiff University leading their electron microscopy effort.

“In the end, there were subtle differences in the order and speed in which each group added in their ingredients while preparing the material,” explains He. “When examined under the electron microscope, it was clear that the two slightly different methods produced quite different distributions of particles, clusters and dispersed atoms on the support.”

“Very small variations in the preparation route or thermal history of the sample can alter the relative balance of supported gold nanoparticles-to-clusters-to-atoms in the material and this manifests itself in the measured catalytic activity,” adds Kiely.

The group was able to compare this set of materials and correlate the Au species distributions with catalytic performance measurements, ultimately identifying the species distribution that was associated with greater catalytic efficiency.

Now that the team has identified the catalytic activity hierarchy associated with these supported gold species, the next step, says Kiely, will be to modify the synthesis method to positively influence that distribution to optimize the catalyst performance while making the most efficient use of the precious gold metal content.

“As a next stage to this study we would like to be able to observe gold on iron oxide materials in-situ within the electron microscope while the reaction is happening,” says Kiely.

Once again, it is next generation microscopy facilities that may hold the key to fulfilling gold’s promise as a pivotal player in green technology.

Despite the link to the paper already in the news release, here’s one that includes a citation,

Identification of Active Gold Nanoclusters on Iron Oxide Supports for CO Oxidation by Andrew A. Herzing, Christopher J. Kiely, Albert F. Carley, Philip Landon, Graham J. Hutchings. Science  05 Sep 2008: Vol. 321, Issue 5894, pp. 1331-1335 DOI: 10.1126/science.1159639

This paper is currently behind a paywall but, if you can wait one year, free access can be gained if you register (for free) with Science.

Recycling carbon dioxide with gold nanoparticles

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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.