Tag Archives: nano titanium dioxide

Sandia National Laboratories looking for commercial partners to bring titanium dioxide nanoparticles (5 nm in diameter) to market

Sandia National Laboratories (Sandia Labs) doesn’t  ask directly but I think the call for partners is more than heavily implied. Let’s start with a June 17, 2014 news item on ScienceDaily,

Sandia National Laboratories has come up with an inexpensive way to synthesize titanium-dioxide nanoparticles and is seeking partners who can demonstrate the process at industrial scale for everything from solar cells to light-emitting diodes (LEDs).

Titanium-dioxide (TiO2) nanoparticles show great promise as fillers to tune the refractive index of anti-reflective coatings on signs and optical encapsulants for LEDs, solar cells and other optical devices. Optical encapsulants are coverings or coatings, usually made of silicone, that protect a device.

Industry has largely shunned TiO2 nanoparticles because they’ve been difficult and expensive to make, and current methods produce particles that are too large.

Sandia became interested in TiO2 for optical encapsulants because of its work on LED materials for solid-state lighting.

Current production methods for TiO2 often require high-temperature processing or costly surfactants — molecules that bind to something to make it soluble in another material, like dish soap does with fat.

Those methods produce less-than-ideal nanoparticles that are very expensive, can vary widely in size and show significant particle clumping, called agglomeration.

Sandia’s technique, on the other hand, uses readily available, low-cost materials and results in nanoparticles that are small, roughly uniform in size and don’t clump.

“We wanted something that was low cost and scalable, and that made particles that were very small,” said researcher Todd Monson, who along with principal investigator Dale Huber patented the process in mid-2011 as “High-yield synthesis of brookite TiO2 nanoparticles.” [emphases mine]

A June 17, 2014 Sandia Labs news release, which originated the news item, goes on to describe the technology (Note: Links have been removed),

Their (Monson and Huber) method produces nanoparticles roughly 5 nanometers in diameter, approximately 100 times smaller than the wavelength of visible light, so there’s little light scattering, Monson said.

“That’s the advantage of nanoparticles — not just nanoparticles, but small nanoparticles,” he said.

Scattering decreases the amount of light transmission. Less scattering also can help extract more light, in the case of an LED, or capture more light, in the case of a solar cell.

TiO2 can increase the refractive index of materials, such as silicone in lenses or optical encapsulants. Refractive index is the ability of material to bend light. Eyeglass lenses, for example, have a high refractive index.

Practical nanoparticles must be able to handle different surfactants so they’re soluble in a wide range of solvents. Different applications require different solvents for processing.

“If someone wants to use TiO2 nanoparticles in a range of different polymers and applications, it’s convenient to have your particles be suspension-stable in a wide range of solvents as well,” Monson said. “Some biological applications may require stability in aqueous-based solvents, so it could be very useful to have surfactants available that can make the particles stable in water.”

The researchers came up with their synthesis technique by pooling their backgrounds — Huber’s expertise in nanoparticle synthesis and polymer chemistry and Monson’s knowledge of materials physics. The work was done under a Laboratory Directed Research and Development project Huber began in 2005.

“The original project goals were to investigate the basic science of nanoparticle dispersions, but when this synthesis was developed near the end of the project, the commercial applications were obvious,” Huber said. The researchers subsequently refined the process to make particles easier to manufacture.

Existing synthesis methods for TiO2 particles were too costly and difficult to scale up production. In addition, chemical suppliers ship titanium-dioxide nanoparticles dried and without surfactants, so particles clump together and are impossible to break up. “Then you no longer have the properties you want,” Monson said.

The researchers tried various types of alcohol as an inexpensive solvent to see if they could get a common titanium source, titanium isopropoxide, to react with water and alcohol.

The biggest challenge, Monson said, was figuring out how to control the reaction, since adding water to titanium isopropoxide most often results in a fast reaction that produces large chunks of TiO2, rather than nanoparticles. “So the trick was to control the reaction by controlling the addition of water to that reaction,” he said.

Some textbooks dismissed the titanium isopropoxide-water-alcohol method as a way of making TiO2 nanoparticles. Huber and Monson, however, persisted until they discovered how to add water very slowly by putting it into a dilute solution of alcohol. “As we tweaked the synthesis conditions, we were able to synthesize nanoparticles,” Monson said.

Whoever wrote the news release now makes the plea which isn’t quite a plea (Note: A link has been removed),

The next step is to demonstrate synthesis at an industrial scale, which will require a commercial partner. Monson, who presented the work at Sandia’s fall Science and Technology Showcase, said Sandia has received inquiries from companies interested in commercializing the technology.

“Here at Sandia we’re not set up to produce the particles on a commercial scale,” he said. “We want them to pick it up and run with it and start producing these on a wide enough scale to sell to the end user.”

Sandia would synthesize a small number of particles, then work with a partner company to form composites and evaluate them to see if they can be used as better encapsulants for LEDs, flexible high-index refraction composites for lenses or solar concentrators. “I think it can meet quite a few needs,” Monson said.

I wish them good luck.

Anatase and rutile titanium dioxide and nanosunscreens

The American Chemical Society (ACS) features some research into nanoscreens and the anatase form of titanium dioxide in a Sept. 25, 2013 news release,,

Using a particular type of titanium dioxide — a common ingredient in cosmetics, food products, toothpaste and sunscreen — could reduce the potential health risks associated with the widely used compound. The report on the substance, produced by the millions of tons every year for the global market, appears in the ACS journal Chemical Research in Toxicology.
Francesco Turci and colleagues explain that titanium dioxide (TiO2) is generally considered a safe ingredient in commercially available skin products because it doesn’t penetrate healthy skin. But there’s a catch. Research has shown that TiO2 can cause potentially toxic effects when exposed to ultraviolet light, which is in the sun’s rays and is the same kind of light that the compound is supposed to offer protection against. To design a safer TiO2 for human use, the researchers set out to test different forms of the compound, each with its own architecture.

They tested titanium dioxide powders on pig skin (which often substitutes for human skin in these kinds of tests) with indoor lighting, which has very little ultraviolet light in it. They discovered that one of the two most commonly used crystalline forms of TiO2, called rutile, easily washes off and has little effect on skin. Anatase, the other commonly used form, however, was difficult to wash off and damaged the outermost layer of skin — even in low ultraviolet light. It appears to do so via “free radicals,” which are associated with skin aging. “The present findings strongly encourage the use of the less reactive, negatively charged rutile to produce safer TiO2-based cosmetic and pharmaceutical products,” the researchers conclude.

It should be noted that the researchers used pig skin, i.e., the skin was not on a pig and, therefore, not part of a living organism with its various biological systems coming into play. As well, the testing was done indoors not under direct sunlight which is the condition under which most of us use sunscreen. This research points to problems  with using anatase nanoscale titanium dioxide in sunscreens but it doesn’t provide unequivocal proof.

The Danish Environmental Protection Agency report (this Oct. 3, 2013 posting of mine) on the state of the art of research into nanomateial dermal absorption does refer to research in this area, although it does not include Turci’s work (Note: The numbers n the excerpted text are reference numbers for the bibliography)),

When looking at bulk composition and the level of dermal penetration noted in studies using a specific material type, there appears to be very little pattern between bulk composition and penetration depth. Taking for example TiO2 as one of the most widely studied nanoparticles, we see reports of penetration no further than the SC [subcutaneous skin layer] 78, 86, 91 but also several studies suggesting deeper penetration (basal cell layer) and even penetration into the dermis 63, 84 although this is often reported as being a very small fraction/infrequent. Another compositional issue in relation to nanoparticles and in particular TiO2 is the crystalline structure. TiO2 is often used in either its anatase or rutile form or as mixture of both. Within the literature, there are studies using both the anatase form 86, 94, the rutile form 91, 114 or a mixture 84, 114 although we were unable to find any studies which appear to systematically evaluate the role of crystal form in TiO2 absorption into the skin. [emphasis mine] (p. 44 of this report: Dermal Absorption of Nanomaterials Part of the ”Better control of nano” initiative 2012 – 2015 Environmental Project No. 1504, 2013).

For those who would like to read Turci’s research for themselves,

Crystalline Phase Modulates the Potency of Nanometric TiO2 to Adhere to and Perturb the Stratum Corneum of Porcine Skin under Indoor Light by Francesco Turci, Elena Peira, Ingrid Corazzari, Ivana Fenoglio, Michele Trotta, and Bice Fubini. Chem. Res. Toxicol., Article ASAP DOI: 10.1021/tx400285j Publication Date (Web): September 12, 2013
Copyright © 2013 American Chemical Society

This research is behind a paywall.

Czech nanotechnology efforts in China

There’s a Sept. 27, 2013 news item about the Czech Republic’s latest technology mission to China on the Nanowerk website,

This week [Sept.  23 - 27, 2013], the representatives of Czech nanotechnology firms, two famous technical universities and CzechInvest took part in a technology mission to China, where they met Chinese counterparts and discussed the further strengthening of cooperation in the field of nanotechnology. This technology mission to China, together with activities of some Czech nanotechnology companies, which have also been extensively supported by the Czech embassy in Beijing in recent months, has brought new opportunities for investment and the further collaboration of highly innovative technologies originated in the Czech Republic.

The Sept. 25, 2013 Czechinvest news release, which originated the news item,  offers more details about the mission,

“The Czech Republic is a world leader in the field of nanotechnology, which has an impact on numerous industrial sectors and places major demands on research. Czech nanotechnology firms are highly respected on the Chinese market,” says Marian Piecha, CEO of CzechInvest.

Representatives of CzechInvest, the Technical University of Liberec, Brno University of Technology and the Czech nanotechnology firms NAFIGATE Corporation, Elmarco, ACT Nami and Noen are taking part in CHINanoForum 2013, which is being held from 24 to 27 September in Jiangsu province. Within the forum’s accompanying programme, CzechInvest and NAFIGATE Corporation conducted a seminar title Nanosolutions for Green Economy – Investment Opportunity in China on 24 September. On 27 September the Czech delegates and their Chinese counterparts will be at the Czech embassy in Beijing to discuss the topic of using nanotechnologies in water treatment, among other things.

“China offers tremendous space for introducing new high-tech products to the market,” says Ladislav Mareš, chairman of the board of directors of NAFIGATE Corporation. “This technology mission therefore has major significance for supporting Czech exports to the Chinese market. Presentation of the potential of Czech nanotechnologies is also a signal for Chinese investors.”

According to the news release, a memorandum of understanding will be signed,

Technological cooperation between the two countries will also be supported by the signing of a Memorandum of Understanding between the Technology Agency of the Czech Republic and the Suzhou Industrial Park Administrative Committee. The signing of the memorandum, which will facilitate cooperation between Czech and Chinese firms with a high technological profile, will be attended by representatives of CzechInvest and His Excellency Libor Sečka, the Czech ambassador in China.

Earlier this years,  in June 2013, Nafigate signed a letter of intent with its Chinese partner, Guodian Technology & Environment Group Corporation Limited, regarding the development of a green nanotechnology centre. From a June 21, 2013 news release on PR newswire,

In the last few days, Czech nanotechnology pioneers have been presenting possible ways of utilizing Czech nanotechnology with specific examples taken from the Clean Air Nanosolution and Clean Water Nanosolution projects to representatives of the most significant Chinese companies at the Embassy of the Czech Republic in Beijing. “There is a lot of interest in the new technology because it solves fundamental problems in air and water cleaning. At the same time the Czech Republic is the world leader in the field of nanofibers and has much to offer China, from cooperation in research and development to putting specific innovative approaches into practice. Cooperation in this field could become an important new branch of mutual trade and scientific and technological exchanges and bring qualitative changes in the life of Chinese society,” said H. E. Mr. Libor Secka, Ambassador of the Czech Republic to the People’s Republic of China.

The signing of the Letter of Intent between NAFIGATE China (a subsidiary of the Czech company NAFIGATE Corporation JSC) and their Chinese partner Guodian Technology & Environment Group Corporation Limited (a subsidiary of one of the most prominent Chinese energy companies) is a significant milestone in Czech-Chinese cooperation in nanotechnology sector. Since January 2013 both companies have been preparing the foundation of the NANODEC (Nanofiber Development Center) project for the development of final applications for water and air cleaning.

The establishment of the center will be a major breakthrough with a global impact in the field of nanofiber applications. The aim of this initiative is to build a center of excellence which will utilize the best available worldwide know-how, the technological and infrastructural potential of one of the most significant Chinese companies and the potential of the market for new low carbon and green technologies. The Letter of Intent specifies the steps required to open the center according to the schedule in the last quarter of 2013.

For those interested in the overall nanotechnology scene in the Czech Republic, I found a 2012 article in the New York Times and a paper (2009?)  written for the National Information Centre For European Research (NICER) and located on the Organization of Economic Cooperation and Development.

Here’s some of what Jacy Meyer wrote for the New York Times in a May 22, 2012 article,

Industries based on nanotechnology are a rapidly growing niche in the economy of the Czech Republic, which, although small, is widely respected for its technical prowess. In February, the country had its own pavilion at the International Nanotechnology Trade Fair, Nanotech 2012, in Tokyo. Ten Czech companies took part.

One was Advanced Materials-JTJ, which produces photocatalytic coating materials incorporating titanium dioxide nanoparticles, known as FN coatings. The semi-transparent, odorless coatings have the unusual property of purifying the air around them — removing viruses, bacteria, toxins, cigarette smoke and more through a light-activated catalytic process.

Over the course of a year, “one square meter of FN-painted facade will clean and decontaminate over three million cubic meters of air,” or 106 million cubic feet, removing several kilograms of pollution, Mr. Prochazka [Jan Prochazka, Advanced Materials-JTJ’s chief executive] said.

As well as cleaning the air, the coating protects the painted surfaces from mold, fungus and the slow accumulation of dirt deposits that cause erosion and discoloring, he said.

The process, activated by ultraviolet light — that is, sunshine — is both environmentally friendly and cost-effective.

“For many people nano is a question mark, but really, everything is nano, except for gravel, sand and a few other materials,” Mr. Prochazka said in an interview in Prague. “Take a cup of water; you can’t imagine how many nanoparticles are inside.”

The National Information Centre For European Research (NICER) report titled, Czech Experience in the International Nanotechnology Cooperation, by Jitka Kubatova on the OECD website offers an overview of the public funding of R&D and much more,

the total (public + private) expenditure on R&D:

in 2005
42,2 billion CZK(€1,58 billion)
1,41% GDP (gross domestic product)

in 2006
49,9 billion CZK (€1,87 billion)
1,55% GDP

in 2007
54,3 billion CZK, (€2,03 billion)
1,53% GDP (p. 3 of the PDF)

Combining bacteriorhodopsin with semiconducting nanoparticles to generate hydrogen

Scientists at the US Argonne National Laboratory have created a hybrid bio-assisted photocatalyst according to a July 19, 2013 news item on ScienceDaily,

A protein found in the membranes of ancient microorganisms that live in desert salt flats could offer a new way of using sunlight to generate environmentally friendly hydrogen fuel, according to a new study by researchers at the U.S. Department of Energy’s Argonne National Laboratory.

Argonne nanoscientist Elena Rozhkova and her colleagues combined a pigment called bacteriorhodopsin with semiconducting nanoparticles to create a system that uses light to spark a catalytic process that creates hydrogen fuel.

Before getting to the new hybrid the story starts with nano titanium dioxide (from the July 16, 2013 Argonne National Laboratory press release, which originated the news item),

Scientists have been aware of the potential of titanium dioxide nanoparticles for light-based reactions since the early 1970s, when Japanese researchers discovered that a titanium dioxide electrode exposed to bright ultraviolet light could split water molecules in a phenomenon that came to be known as the Honda-Fujishima effect. Since then, scientists have made continuous efforts to extend the light reactivity of titanium dioxide photocatalysts into the visible part of the spectrum. The promise of these photocatalysts prompted scientists to experiment with different modifications to their basic chemistry in hope of making the reaction more efficient, Rozhkova said.

“Titanium dioxide alone reacts with ultraviolet light, but not with visible light, so we used biological photoreactive molecules as a building block to create a hybrid system that could use visible light efficiently,” Rozhkova said.

Rozhkova and her colleagues turned to bacteriorhodopsin – which is responsible for the unusual purple color of a number of salt flats in California and Nevada – because it uses sunlight as an energy source that allows it to act as a “proton pump.”  Proton pumps are proteins that typically straddle a cellular membrane and transfer protons from inside the cell to the extracellular space.

Here’s an image of the purple membrane caused by bacteriorhodopsin (from University of Bari [Italy] Professor Angela Correlli’s webpage of Photorecptors and Olfactory Receptors,

Bacteriorhodopsin is the only protein of purple membranes, which contains few different lipids. [downloaded from the University of Bari: http://www.biologia.uniba.it/fisiologia/corcelli/en/ric2.html]

Bacteriorhodopsin is the only protein of purple membranes, which contains few different lipids. [downloaded from the University of Bari: http://www.biologia.uniba.it/fisiologia/corcelli/en/ric2.html]

The press release goes on to describe the hybrid system,

In the Argonne system, the protons provided by the bacteriorhodopsin are combined with free electrons at small platinum sites interspersed in the titanium dioxide matrix. “The platinum nanoparticles are essential for creating a distinct spot for the production of the hydrogen molecule,” said Peng Wang, an Argonne postdoctoral researcher in Rozhkova’s group at Argonne’s Center for Nanoscale Materials.

“It is interesting that in biology, bacteriorhodopsin does not naturally participate in these kind of reactions,” Rozhkova said. “Its natural function really doesn’t have much to do at all with creating hydrogen. But as part of this hybrid, it helps make hydrogen under white light and at environmentally friendly conditions.”

This bio-assisted hybrid photocatalyst outperforms many other similar systems in hydrogen generation and could be a good candidate for fabrication of green energy devices that consume virtually infinite sources — salt water and sunlight.

You can find the published paper with the link below,

High-Performance Bioassisted Nanophotocatalyst for Hydrogen Production by Shankar Balasubramanian, Peng Wang, Richard D. Schaller, Tijana Rajh, and Elena A. Rozhkova. Nano Lett., 2013, 13 (7), pp 3365–3371 DOI: 10.1021/nl4016655 Publication Date (Web): June 19, 2013
Copyright © 2013 American Chemical Society

The paper is behind a paywall.

*The head for this posting was corrected from Combining bacteriorhodopsin with semiconduction nanopartcles to generate hydrogen to Combining bacteriorhodopsin with semiconductor nanoparticles to generate hydrogen on July 22, 2013 at 3:03 pm PDT.

** I changed the head for this posting again from ‘semiconductor’ to ‘semiconducting’ on July 23, 2013 at 6:50 am PDT.

Gloves, Québec’s (Canada) Institut de recherche Robert-Sauvé en santé et en sécurité du travail, and a workplace nanotoxicity methodology report

A new report on a workplace health and safety issue in regard to nanoparticles (Development of a Method of Measuring Nanoparticle Penetration through Protective Glove Materials under Conditions Simulating Workplace Use)  was released in June 2013 by Québec’s Institut de recherche Robert-Sauvé en santé et en sécurité du travail (IRSST). Little research has been done on exposure through skin (cutaneous exposure), most research has focused on exposure by inhalation according to the report (en français version here),

In the workplace, the main pathway to NP exposure is inhalation (Ostiguy et al., 2008a). Exposure by the cutaneous route has not been studied much, partly because of the widely held belief that skin offers an impermeable barrier to NPs (Truchon et al., 2008). Yet a growing number of studies have pointed to the possible percutaneous absorption of NPs, such as in the case of skin damaged by abrasion (Zhang et al., 2008), repeated flexion (Rouse et al., 2007) or even through intact skin (Ryman-Rasmussen et al., 2006). Pores, hair follicles and sweat glands may also play a role in facilitating absorption of NPs through the skin (Hervé-Bazin, 2007). The nanoparticles are then carried throughout the body by the lymphatic circulatory system (Papp et al., 2008). Induced direct toxic effects have also been reported for epidermal keratinocyte cells exposed to carbon nanotubes and other types of NPs (Shvedova, 2003). [p. 17 PDF version; p. 1 print version; Note: See report bibliography for citations]

The researchers examined gloves made of four different types of material: nitrile, latex, neoprene, and butyl rubber under a number of different conditions. One type of nanoparticle was used for the study, titanium dioxide in powder and liquid forms. The report summary provides a bit more detail about the decision to develop a methodology and the testing methods,

With the exponential growth in industrial applications of nanotechnologies and the increased risk of occupational exposure to nanomaterials, the precautionary principle has been recommended. To apply this principle, and even though personal protective equipment against nanoparticles must be considered only as a last resort in the risk control strategy, this equipment must be available. To respond to the current lack of tools and knowledge in this area, a method was developed for measuring the penetration of nanoparticles through protective glove materials under conditions simulating workplace use.

This method consists of an experimental device for exposing glove samples to nanoparticles in powder form or in colloidal solution, while at the same time subjecting them to static or dynamic mechanical stresses and conditions simulating the microclimate in the gloves. This device is connected to a data control and acquisition system. To complete the method, a sampling protocol was developed and a series of nanoparticle detection techniques was selected.

Preliminary tests were performed using this method to measure the resistance of four models of protective gloves of different thicknesses made of nitrile, latex, neoprene and butyl to the passage of commercial TiO2 nanoparticles in powder form or colloidal solution. The results seem to indicate possible penetration of the nanoparticles in some types of gloves, particularly when subjected to repeated mechanical deformation and when the nanoparticles are in the form of colloidal solutions. Additional work is necessary to confirm these results, and consideration should be given to the selection of the configurations and values of the parameters that best simulate the different possible workplace situations. Nevertheless, a recommendation can already be issued regarding the need for regular replacement of gloves that have been worn, particularly with the thinnest gloves and when there has been exposure to nanoparticles in colloidal solution.

For interested parties, here’s a citation for and a link to the report (PDF),

Development of a Method of Measuring Nanoparticle Penetration through Protective Glove Materials under Conditions Simulating Workplace Use by Dolez, Patricia; Vinches, Ludwig; Perron, Gérald; Vu-Khanh, Toan; Plamondon, Philippe; L’Espérance, Gilles; Wilkinson, Kevin; Cloutier, Yves; Dion, Chantal; Truchon, Ginette
Studies and Research Projects / Report  R-785, Montréal, IRSST, 2013, 124 pages.

I last wrote about gloves and toxicity in a June 11, 2013 posting about gloves with sensors (they turned blue when exposed to toxic levels of chemicals). It would be interesting if they could find a way to create gloves with sensors that warn you when you are reaching dangerous levels of exposure through your gloves. Of course, first they’d have to determine what constitute a dangerous level of exposure. The US National Institute of Occupational Health and Safety (NIOSH) recently released its recommendations for exposure to carbon nanofibers and carbon nanotubes (my April 26, 2013 posting). In layperson’s terms, the recommended exposure is close to zero exposure. Presumably, the decision was based on the principle of being ‘safe rather than sorry’.

One final comment about exposure to engineered nanoparticles through skin, to date there has been no proof that there has been any significant exposure via skin. In fact, the first significant breach of the skin barrier was achieved for medical research, Chad Mirkin and his team at Northwestern University trumpeted their research breakthrough (pun intended) last year, from my July 4, 2012 posting,

Researchers at Northwestern University (Illinois, US) have found a way to deliver gene regulation technology using skin moisturizers. From the July 3, 2012 news item on Science Blog,

A team led by a physician-scientist and a chemist — from the fields of dermatology and nanotechnology — is the first to demonstrate the use of commercial moisturizers to deliver gene regulation technology that has great potential for life-saving therapies for skin cancers.

The topical delivery of gene regulation technology to cells deep in the skin is extremely difficult because of the formidable defenses skin provides for the body. The Northwestern approach takes advantage of drugs consisting of novel spherical arrangements of nucleic acids. These structures, each about 1,000 times smaller than the diameter of a human hair, have the unique ability to recruit and bind to natural proteins that allow them to traverse the skin and enter cells.

This goes a long way to explaining why primary occupational health and safety research has focused on exposure via inhalation rather than skin.  That said, I think ensuring safety means minimizing exposure by all routes until more is known about the hazards.

Self-cleaning products dangerous?

For anyone else out there who hates housecleaning, this is heartbreaking research. Personally, I’m not sure I can ever forgive Professor Jonathan Raff at Indian University for this (from a June 12, 2103 Indiana University news release; also on EurekAlert),

Research by Indiana University [IU] environmental scientists shows that air-pollution-removal technology used in “self-cleaning” paints and building surfaces may actually cause more problems than they solve.

The study finds that titanium dioxide coatings, seen as promising for their role in breaking down airborne pollutants on contact, are likely in real-world conditions to convert abundant ammonia to nitrogen oxide, the key precursor of harmful ozone pollution.

“As air quality standards become more stringent, people are going to be thinking about other technologies that can reduce pollution,” said Jonathan D. Raff, assistant professor in the School of Public and Environmental Affairs at IU Bloomington and an author of the study. “Our research suggests that this may not be one of them.”

Here’s a link to and a citation for this published study,

Photooxidation of Ammonia on TiO2 as a Source of NO and NO2 under Atmospheric Conditions by Mulu A. Kebede, Mychel E. Varner ‡, Nicole K. Scharko, R. Benny Gerber, and Jonathan D. Raff. J. Am. Chem. Soc., 2013, 135 (23), pp 8606–8615 DOI: 10.1021/ja401846x Publication Date (Web): May 30, 2013

Copyright © 2013 American Chemical Society

This research is behind a paywall.

The news release goes on to explain what makes this latest discovery about titanium dioxide particularly relevant,

The findings are timely because the Environmental Protection Agency is developing stricter regulations for ground-level ozone, a primary component in photochemical smog. The pollution is linked to serious health problems, including breathing difficulties and heart and lung disease.

Ozone is produced by reactions involving nitrogen oxides (NOx), which come primarily from motor vehicle emissions, and volatile organic compounds resulting from industrial processes. Equipping cars with catalytic converters has been effective at reducing ozone in urban areas. But different technologies may be needed to meet tighter air-quality standards of the future.

The need has sparked interest in titanium dioxide, a common mineral that is used as a whitening agent in paints and surface coatings. The compound acts as a photocatalyst, breaking down nitrogen oxides, ammonia and other pollutants in the presence of sunlight. “Self-cleaning” surfaces coated with titanium dioxide can break down chemical grime that will otherwise adhere to urban buildings. News stories have celebrated “smog-eating” tiles and concrete surfaces coated with the compound.

But Raff and his colleagues show that, in normal environmental conditions, titanium dioxide also catalyzes the incomplete breakdown of ammonia into nitrogen oxides. Ammonia is an abundant constituent in motor vehicle emissions, and its conversion to nitrogen oxides could result in increases in harmful ozone concentrations.

“We show that uptake of atmospheric NH3 (ammonia) onto surfaces containing TiO2 (titanium dioxide) is not a permanent removal process, as previously thought, but rather a photochemical route for generating reactive oxides of nitrogen that play a role in air pollution and are associated with significant health effects,” the authors write.

Raff, who is also an adjunct professor of chemistry in the IU College of Arts and Sciences, said other studies missed the effect on ammonia because they investigated reactions that occur with high levels of emissions under industrial conditions, not the low levels and actual humidity levels typically present in urban environments.

The findings also call into question other suggestions for using titanium dioxide for environmental remediation — for example, to remove odor-causing organic compounds from emissions produced by confined livestock feeding operations. Titanium dioxide has also been suggested as a geo-engineering substance that could be injected into the upper atmosphere to reflect sunlight away from the Earth and combat global warming.

Further studies in Raff’s lab are aimed at producing better understanding of the molecular processes involved when titanium dioxide catalyzes the breakdown of ammonia. The results could suggest approaches for developing more effective pollution-control equipment as well as improvements in industrial processes involving ammonia.

It’ll be interesting to see how that resolves itself. I imagine some of the civil society groups are going to get very excited about this research.

NanoSustain published four case studies: zinc oxide, titanium dioxide, carbon nanotubes, and nanocellulose

A May 17, 2013 news item on Nanowerk highlight a European Commission-funded project, NanoSustain and its publication of a fact sheet and four case studies,,

NanoSustain, a €2.5 million NMP small collaborative project (2010-2013) funded by the European Union under FP7, has published a fact sheet and four case studies addressing these issues.

How do nanotechnology-based products impact human health and the environment?
Can they be recycled?
Can they be safely disposed of?
How can you find out?

The March 20, 2013 NanoSustain news release, which originated the news item, goes on to explain,

… the EC-funded NanoSustain project has been developing new sustainable solutions through an investigation of the life-cycle of nanotechnology-based products, in particular the physical and chemical characteristics of materials, hazard and exposure aspects, and end-of-life disposal or recycling to determine the fate and impact of nanomaterials.

A summary of the different materials and products tested within NanoSustain:

• Case Study #1: Titanium dioxide for paints
• Case Study #2: Zinc oxide for glazing products
• Case Study #3: Carbon nanotubes epoxy resins for plastics
- for structural or electrical/antistatic applications
• Case Study #4: Nanocellulose for advanced paper applications

Information about the individual experimental approaches

Descriptions of the different techniques developed

How these techniques have been successfully applied in physical-chemical characterisation; life-cycle analysis; final disposal; recycling.

Getting access to the case case studies and the fact sheet requires filling out a form but once you’ve done that you get instant access to the materials.

Here’s some information from EuroSustain’s fact sheet,


Analytical Techniques

Development of sustainable solutions for nanotechnology-based products based on hazard characterization and LCA1 The primary goal of the NanoSustain project is to develop new technical solutions for the sustainable design and use, recycling and final treatment of selected nanotechnology-based products.

To achieve this the project has the following objectives: 1) to assess the hazard of selected nanomaterials based on a comprehensive data survey and generation concerning their physicochemical (PC) and toxicological properties, exposure probabilities, etc., and the adaptation, evaluation, validation and use of existing analytical, testing and life-cycle assessment (LCA) methods; 2) to assess the impact of selected products during their life cycle in relation to material and energy flows (LCA); 3) to assess possible exposure routes and risks associated with the handling of these materials, their transformation and final fate; and 4) to explore the feasibility and sustainability of new technical solutions for end-of=life processes, such as reuse/recycling, final treatment or disposal.

Within NanoSustain an assessment has been made of the PC properties, exposure and toxicity, energy and material inputs and outputs at relevant stages of a material or product’s life-cycle. This means: material production, processing, manufacturing, use, transportation, and end-of-life (recycling/disposal). At each stage potential risks to human health and the environment have also been assessed, through a number of experimental models and test systems using materials that would be expected to be released from products containing nanomaterials.

Four nanomaterials were investigated that either already feature in commercial products or are expected to be commercialized on a large scale: titanium dioxide (TiO2) in paint, zinc oxide (ZnO) as a coating for glass, multi-walled carbon nanotubes (MWCNT) in epoxy resins, and nanocellulose in paper.

Detailed information on the nanomaterials have been summarized in internal project material datasheets (MDS), and will be made available as part of peer-reviewed publications on release studies and toxicological investigations. [emphases mine]

Having looked at the four case studies, each of which is two pages, I would describe them as teasers. There’s not a lot of information in them as to the results of the testing which makes sense when you see that they will be publishing in various publications.

I find the inclusion of titanium dioxide, zinc oxide and carbon nanotubes for life-cycle assessments easily understandable as they  have been integrated into many consumer products. However, it’s my understanding that nanocellulose has not reached that level of product integration. Still, given the number of times I’ve been told this is a ‘safe’ product, it’s interesting to see what NanoSustain has to say about its toxicity (from the NanoSustain’s nanocellulose case study),

Work in NanoSustain has provided new data and information on the physicochemical properties, potential human and environmental hazard and risk associated with relevant stages of the life-cycle of nanocellulose based products as well as on the overall energy and material input/output that may happen during manufacturing, use and disposal. Initial results indicate that the nanocellulose degrades efficiently under standard composting conditions, but does not in aquatic environments. Furthermore nanocellulose does not demonstrate any ecotoxicity. Unfortunately nanocellulose forms a gel when suspended in media for inhalation studies, and so no toxicology experiments could be performed (as for the other engineered nanomaterials studied in NanoSustain). Final results will be made available once published in peer-reviewed journals.

I have written many times about nanocellulose, a topic featuring some interesting and confusing nomenclature and taking this opportunity to highlight a couple of responses from folks who took the time to clarify things for me (from my Aug. 2, 2012 posting),

KarenS says:

Hi Maryse!

From my understanding, nanocrystaline cellulose (NCC), cellulose nanocrystals (CNC), cellulose whiskers (CW) and cellulose nanowhiskers (CNW) are all the same stuff: cylindrical rods of crystalline cellulose (diameter: 5-10 nm; length: 20-1000 nm). Cellulose nanofibers or nanofibrils (CNF), on the contrary, are less crystalline and are in the form of long fibers (diameter: 20-50 nm; length: up to several micrometers).

There is still a lot of confusion on the nomenclature of cellulose nanoparticles, but nice explanations (and pictures!) are given here (and also in other papers from the same conference):


and there’s this from my Sept. 26, 2012 posting,

Gary Chinga Carrasco says:

The definition of cellulose nanofibrils as “diameter: 20-50 nm; length: up to several micrometers)” is somewhat simplified. For terminology on MFC terms you may want to take a look at: http://www.nanoscalereslett.com/content/6/1/417

Bringing this piece back to where I started, I look forward to seeing the NanoSustain case studies published with more details in the future.

Note: Since the folks at NanoSustain are likely using their form to collect data, I’m not linking back to the factsheet or nanocellulose case study as I would usually. So, if you want to look at the material, you do need to register via the form.

Disorder engineering turns ‘white’ nanoparticles to ‘black’ nanoparticles for clean energy

Titanium dioxide crystals are white, except when they’re black. According to an Apr. 10, 2013 news item on Nanowerk, researchers at the Lawrence Berkeley National Laboratory (US) have found a way to change white titanium dioxide crystals to black thereby changing some of their properties,

A unique atomic-scale engineering technique for turning low-efficiency photocatalytic “white” nanoparticles of titanium dioxide into high-efficiency “black” nanoparticles could be the key to clean energy technologies based on hydrogen.

Samuel Mao, a scientist who holds joint appointments with Berkeley Lab’s Environmental Energy Technologies Division and the University of California at Berkeley, leads the development of a technique for engineering disorder into the nanocrystalline structure of the semiconductor titanium dioxide. This turns the naturally white crystals black in color, a sign that the crystals are now able to absorb infrared as well as visible and ultraviolet light. The expanded absorption spectrum substantially improves the efficiency with which black titanium dioxide can use sunlight to split water molecules for the production of hydrogen.

The Apr. 10, 2013 Berkeley Lab news release, which originated the news item, provides more detail about how this discovery might have an impact on clean energy efforts,

The promise of hydrogen in batteries or fuels is a clean and renewable source of energy that does not exacerbate global climate change. The challenge is cost-effectively mass-producing it. Despite being the most abundant element in the universe, pure hydrogen is scarce on Earth because hydrogen combines with just about any other type of atom. Using solar energy to split the water molecule into hydrogen and oxygen is the ideal way to produce pure hydrogen. This, however, requires an efficient photocatalyst that water won’t corrode. Titanium dioxide can stand up to water but until the work of Mao and his group was only able to absorb ultraviolet light, which accounts for barely ten percent of the energy in sunlight.In his ACS [American Chemical Society]  talk [at the 245th meeting, Apr. 7 - 11, 2013], titled “Disorder Engineering: Turning Titanium Dioxide Nanoparticles Black,” Mao described how he developed the concept of “disorder engineering,” and how the introduction of hydrogenated disorders creates mid-band gap energy states above the valence band maximum to enhance hydrogen mobility. His studies have not only yielded a promising new photocatalyst for generating hydrogen, but have also helped dispel some widely held scientific beliefs.

“Our tests have shown that a good semiconductor photocatalyst does not have to be a single crystal with minimal defects and energy levels just beneath the bottom of conduction band,” Mao said.

Characterization studies at Berkeley Lab’s Advanced Light Source also helped answer the question of how much of the hydrogen  detected in their experiments comes from the photocatalytic reaction, and how much comes from hydrogen absorbed in the titanium oxide during the hydrogenation synthesis process.

“Our measurements indicate that only a very small amount of hydrogen is absorbed in black titanium dioxide, about 0.05 milligrams, as compared to the 40 milligrams of hydrogen detected during a 100 hour solar-driven hydrogen production experiment,” Mao said.

I must say, this ‘disorder engineering’ sounds much more appealing than some of the other disorders one hears about (e.g. personality disorders).

Natural and engineered nanoparticles in an Orion magazine podcast & in a NanoBosc machinima piece

The Jan. 16, 2013 Orion magazine podcast discussion (more about that later) regarding safety and engineered and natural nanoparticles arose from an article (worth reading) by Heather Millar in the magazine’s January/February 2013 issue, Pandora’s Boxes.

For anyone familiar with the term ‘Pandora’s box’, Millar’s and the magazine’s bias is made clear immediately, nanoparticles are small and threatening. From the Pandora’s box Wikipedia essay,

Today, the phrase “to open Pandora’s box” means to perform an action that may seem small or innocuous, but that turns out to have severe and far-reaching consequences. [emphases mine]

Millar’s article is well written and offers some excellent explanations. For example, there’s this from Pandora’s Boxes,

So chemistry and physics work differently if you’re a nanoparticle. You’re not as small as an atom or a molecule, but you’re also not even as big as a cell, so you’re definitely not of the macro world either. You exist in an undiscovered country somewhere between the molecular and the macroscopic. Here, the laws of the very small (quantum mechanics) merge quirkily with the laws of the very large (classical physics). Some say nanomaterials bring a third dimension to chemistry’s periodic table, because at the nano scale, long-established rules and groupings don’t necessarily hold up.

Then, she has some dodgier material,

Yet size seems to be a double-edged sword in the nanoverse. Because nanoparticles are so small, they can slip past the body’s various barriers: skin, the blood-brain barrier, the lining of the gut and airways. Once inside, these tiny particles can bind to many things. They seem to build up over time, especially in the brain. Some cause inflammation and cell damage. Preliminary research shows this can harm the organs of lab animals, though the results of some of these studies are a matter of debate.

Some published research has shown that inhaled nanoparticles actually become more toxic as they get smaller. Nano–titanium dioxide, one of the most commonly used nanoparticles (Pop-Tarts, sunblock), has been shown to damage DNA in animals and prematurely corrode metals. Carbon nanotubes seem to penetrate lungs even more deeply than asbestos. [emphases mine]

I think it’s worth ‘unpacking’ these two paragraphs, so here goes.  Slipping past the body’s barriers is a lot more difficult than Millar suggests in the first paragraph. My July 4, 2012 posting on breakthough research  where they penetrated the skin barrier includes this comment from me,

After all the concerns  about nanosunscreens and nanoparticles penetrating the skin raised by civil society groups, the Friends of the Earth in particular, it’s interesting to note that doctors and scientists consider penetration of the skin barrier to be extremely difficult. Of course, they seem to have solved [as of July 2012] that problem which means the chorus of concerns may rise to new heights.

I had a followup in my Oct.3, 2012 posting titled, Can nanoparticles pass through the skin or not?, suggesting there’s still a lot of confusion about this topic even within the scientific community.

Moving on to the other ‘breaches’. As I recall, there was a recent  (Autumn 2012?) nanomedicine research announcement that the blood-brain barrier was breached by nanoparticles. I haven’t yet encountered any mention of breaching the gut and I mention lungs in my next paragraph where I discuss carbon nanotubes.

As for that second paragraph, it’s an example of scaremongering. ‘Inhaled nanoparticles become more toxic as their size decreases’—ok. Why mention nano-titanium oxide in pop tarts and sunblocks, which are not inhaled, in the followup sentence? As for the reference to DNA damage and corroded metals further on, this is straight out of the Friends of the Earth literature which often cites research in a misleading fashion including those two pieces.  There is research supporting part of Millar’s statement about carbon nanotubes—provided they are long and multiwalled. In fact, as they get shorter, the resemblance to asbestos fibers in the lungs or elsewhere seems to disappear as per my Aug 22, 2012 posting and my Jan. 16, 2013 posting.

You don’t need to read the article before listening to the fascinating Jan. 16, 2013 Orion magazine podcast with Millar (reading portions of her article) and expert guests, Mark Wiesner from Duke University and director of their Center for Environmental Implications of Nano Technology (CEINT was first mentioned in my April 15, 2011 posting), Ronald Sandler from Northeastern University and author of Nanotechnology: The Social And Ethical Issues, and Jaydee Hanson, policy director for the International Center for Technology Assessment.

The discussion between Wiesner, Sandler, and Hanson about engineered and natural nanoparticles is why I’ve called the podcast fascinating. Hearing these experts ‘fence’ with each other highlights the complexities and subtleties inherent in discussions about emerging technologies (nano or other) and risk. Millar did not participate in that aspect of the conversation and I imagine that’s due to the fact that she has only been researching this area for six months while the other speakers all have several years worth experience individually and, I suspect, may have debated each other previously.

At the risk of enthusing too much about naturally occurring nanoparticles, I’m mentioning, again (my Feb. 1, 2013 posting), the recently published book by Nanowiki, Nanoparticles Before Nanotechnology, in the context of the stunning visual images used to illustrate the book. I commented previously about them and Victor Puntes of the Inorganic Nanoparticles Group at the Catalan Institute of Nanotechnology (ICN) and one of the creators of this imagery, kindly directed me to a machinima piece (derived from the NanoBosc Second Life community) which is the source for the imagery. Here it is,

NanoBosc from Per4mance MetaLES ..O.. on Vimeo.

Happy Weekend!