Tag Archives: phosphorus

Gold nanoparticles not always always biologically stable

It’s usually silver nanoparticles (with a nod to titanium dioxide as another problem nanoparticle) which star in scenarios regarding environmental concerns, especially with water. According to an Aug. 28, 2018 news item on Nanowerk, gold nanoparticles under certain conditions could also pose problems,

It turns out gold isn’t always the shining example of a biologically stable material that it’s assumed to be, according to environmental engineers at Duke’s Center for the Environmental Implications of NanoTechnology (CEINT).

In a nanoparticle form, the normally very stable, inert, noble metal actually gets dismantled by a microbe found on a Brazilian aquatic weed.

While the findings don’t provide dire warnings about any unknown toxic effects of gold, they do provide a warning to researchers on how it is used in certain experiments.

Here’s an image of one of the researchers standing in the test bed where they made their discovery (the caption will help to make sense of the reference to mesocosms in the news release, which follows,,

Mark Wiesner stands with rows of mesocosms—small, manmade structures containing different plants and microorganisms meant to represent a natural environment with experimental controls. Courtesy: Duke University

An August 28, 2018 Duke University news release (also on EurekAlert) by Ken Kingery, which originated the news item, provides more detail about gold nanoparticle instability,

CEINT researchers from Duke, Carnegie Mellon and the University of Kentucky were running an experiment to investigate how nanoparticles used as a commercial pesticide affect wetland environments in the presence of added nutrients. Although real-world habitats often receive doses of both pesticides and fertilizers, most studies on the environmental effects of such compounds only look at a single contaminant at a time.

For nine months, the researchers released low doses of nitrogen, phosphorus and copper hydroxide nanoparticles into wetland mesocosms [emphasis mine]– small, manmade structures containing different plants and microorganisms meant to represent a natural environment with experimental controls. The goal was to see where the nanoparticle pesticides ended up and how they affected the plant and animal life within the mesocosm.

The researchers also released low doses of gold nanoparticles as tracers, assuming the biologically inert nanoparticles would remain stable while migrating through the ecosystem. This would help the researchers interpret data on the pesticide particles that partly dissolve by showing them how a solid metal particle acts within the system.

But when the researchers went to analyze their results, they found that many of the gold nanoparticles had been oxidized and dissolved.

“We were taken completely by surprise,” said Mark Wiesner, the James B. Duke Professor and chair of civil and environmental engineering at Duke. “The nanoparticles that were supposed to be the most stable turned out to be the least stable of all.”

After further inspection, the researchers found the culprit — the microbiome growing on a common Brazilian waterweed called Egeria densa. Many bacteria secrete chemicals to essentially mine metallic nutrients from their surroundings. With their metabolism spiked by the experiment’s added nutrients, the bacteria living on the E. densa were catalyzing the reaction to dissolve the gold nanoparticles.

This process wouldn’t pose any threat [emphasis mine] to humans or other animal species in the wild. But when researchers design experiments with the assumption that their gold nanoparticles will remain intact, the process can confound the interpretation of their results.

“The assumption that gold is inert did not hold in these experiments,” said Wiesner. “This is a good lesson that underscores how real, complex environments, that include for example the bacteria growing on leaves, can give very different results from experiments run in a laboratory setting that do not include these complexities.”

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

Gold nanoparticle biodissolution by a freshwater macrophyte and its associated microbiome by Astrid Avellan, Marie Simonin, Eric McGivney, Nathan Bossa, Eleanor Spielman-Sun, Jennifer D. Rocca, Emily S. Bernhardt, Nicholas K. Geitner, Jason M. Unrine, Mark R. Wiesner, & Gregory V. Lowry. Nature Nanotechnology (2018) DOI: https://doi.org/10.1038/s41565-018-0231-y Published

This paper is behind a paywall.

Nanoparticles for sustainable ways to grow crops

An April 29, 2016 news item on Nanowerk celebrates research into food production,

Scientists are working diligently to prepare for the expected increase in global population — and therefore an increased need for food production— in the coming decades. A team of engineers at Washington University in St. Louis has found a sustainable way to boost the growth of a protein-rich bean by improving the way it absorbs much-needed nutrients.

Ramesh Raliya, a research scientist, and Pratim Biswas, the Lucy & Stanley Lopata Professor and chair of the Department of Energy, Environmental & Chemical Engineering, both in the School of Engineering & Applied Science, discovered a way to reduce the use of fertilizer made from rock phosphorus and still see improvements in the growth of food crops by using zinc oxide nanoparticles.

The food under investigation is the mung bean,

Researchers at Washington University in St. Louis hope that nanoparticle technology can help reduce the need for fertilizer, creating a more sustainable way to grow crops such as mung beans. Courtesy: Washington University in St. Louis

Researchers at Washington University in St. Louis hope that nanoparticle technology can help reduce the need for fertilizer, creating a more sustainable way to grow crops such as mung beans. Courtesy: Washington University in St. Louis

An April 28, 2016 Washington University in St. Louis  news release (also on EurekAlert) by Beth Miller, which originated the news item, provides more detail,

The research was published April 7 [2016] in the Journal of Agricultural and Food Chemistry. Raliya said this is the first study to show how to mobilize native phosphorus in the soil using zinc oxide nanoparticles over the life cycle of the plant, from seed to harvest.

Food crops need phosphorus to grow, and farmers are using more and more phosphorus-based fertilizer as they increase crops to feed a growing world population. However, the plants can only use about 42 percent of the phosphorus applied to the soil, so the rest runs off into the water streams, where it grows algae that pollutes our water sources. In addition, nearly 82 percent of the world’s phosphorus is used as fertilizer, but it is a limited supply, Raliya says.

“If farmers use the same amount of phosphorus as they’re using now, the world’s supply will be depleted in about 80 years,” Raliya said. “Now is the time for the world to learn how to use phosphorus in a more sustainable manner.”

Raliya and his collaborators, including Jagadish Chandra Tarafdar at the Central Arid Zone Research Institute in Jodhpur, India, created zinc oxide nanoparticles from a fungus around the plant’s root that helps the plant mobilize and take up the nutrients in the soil. Zinc also is an essential nutrient for plants because it interacts with three enzymes that mobilize the complex form of phosphorus in the soil into a form that plants can absorb.

“Due to climate change, the daily temperature and rainfall amounts have changed,” Raliya said. “When they changed, the microflora in the soil are also changed, and once those are depleted, the soil phosphorus can’t mobilize the phosphorus, so the farmer applies more. Our goal is to increase the activity of the enzymes by several-fold, so we can mobilize the native phosphorus several-fold.”

When Raliya and the team applied the zinc nanoparticles to the leaves of the mung bean plant, it increased the uptake of the phosphorus by nearly 11 percent and the activity of the three enzymes by 84 percent to 108 percent. That leads to a lesser need to add phosphorus on the soil, Raliya said.

“When the enzyme activity increases, you don’t need to apply the external phosphorus, because it’s already in the soil, but not in an available form for the plant to uptake,” he said. “When we apply these nanoparticles, it mobilizes the complex form of phosphorus to an available form.”

The mung bean is a legume grown mainly in China, southeast Asia and India, where 60 percent of the population is vegetarian and relies on plant-based protein sources. The bean is adaptable to a variety of climate conditions and is very affordable for people to grow.

Raliya said 45 percent of the worldwide phosphorus use for agriculture takes place in India and China. Much of the phosphorus supply in developing countries is imported from the United States and Morocco-based rock phosphate mines.

“We hope that this method of using zinc oxide nanoparticles can be deployed in developing countries where farmers are using a lot of phosphorus,” Raliya said.

“These countries are dependent on the U.S. to export phosphorus to them, but in the future, the U.S. may have to help supply food, as well. If this crop can grow in a more sustainable manner, it will be helpful for everyone.”

“This is a broader effort under way at the nexus of food, energy and water,” Biswas said. “Nanoparticle technology enabled by aerosol science helps develop innovative solutions to address this global challenge problem that we face today.”

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

Enhancing the Mobilization of Native Phosphorus in the Mung Bean Rhizosphere Using ZnO Nanoparticles Synthesized by Soil Fungi by Ramesh Raliya, Jagadish Chandra Tarafdar, and Pratim Biswas. J. Agric. Food Chem., 2016, 64 (16), pp 3111–3118 DOI: 10.1021/acs.jafc.5b05224 Publication Date (Web): April 07, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.

Solar cells from the University of Alberta?

Trevor Robb’s Aug. 7, 2015 article for the Edmonton Sun (Alberta, Canada) features a research team dedicated to producing better solar cells and a facility (nanoFAB) at the University of Alberta,

But in an energy rich province like Alberta — known for its oil and gas sector — [JIllian] Buriak [chemistry professor at the University of Alberta, Canada Research chair of nanomaterials] is on a mission to shed some light on another form of energy Alberta is known for, solar energy.

So her team is dedicated to producing flexible, recyclable plastic solar cells that can be printed just like a newspaper.

In fact, they’ve already begun doing so.

In order to produce the sheet-like solar cells, Buriak and her team use nothing more than simple commercial laminators and a spray gun, not unlike something you would use to paint a car.

“We run them through this laminator that squeezes them down and turns them from something that’s not conducting to something that’s really conducting,” said Buriak.

“You could incorporate it into clothing, you could incorporate it into books, into window blinds, or unroll it on a tent when you’re camping,” said Buriak. “You could use it anywhere. Anything from simple funny things to cafe umbrellas that could allow you to charge electronic devices, to large scale things in developing countries; large scale solar cells that you could simply carry on your backpack, unroll at a medical clinic, and suddenly you have instant power.”

There are more details about Buriak’s work and information about nanoFAB in Robb’s article. As for technical information, the best I can find is in an Aug. 29, 2013 University of Alberta news release (also on EurekAlert),

University of Alberta researchers have found that abundant materials in the Earth’s crust can be used to make inexpensive and easily manufactured nanoparticle-based solar cells.

The discovery, several years in the making, is an important step forward in making solar power more accessible to parts of the world that are off the traditional electricity grid or face high power costs, such as the Canadian North, said researcher Jillian Buriak, a chemistry professor and senior research officer of the National Institute for Nanotechnology based on the U of A campus.
Buriak and her team have designed nanoparticles that absorb light and conduct electricity from two very common elements: phosphorus and zinc. Both materials are more plentiful than scarce materials such as cadmium and are free from manufacturing restrictions imposed on lead-based nanoparticles.

Buriak collaborated with U of A post-doctoral fellows Erik Luber of the U of A Faculty of Engineering and Hosnay Mobarok of the Faculty of Science to create the nanoparticles. The team was able to develop a synthetic method to make zinc phosphide nanoparticles, and demonstrated that the particles can be dissolved to form an ink and processed to make thin films that are responsive to light.

Buriak and her team are now experimenting with the nanoparticles, spray-coating them onto large solar cells to test their efficiency. The team has applied for a provisional patent and has secured funding to enable the next step to scale up manufacture.

I wonder if this news article by Robb is an attempt by Buriak to attract interest from potential investors?

A race to find substitutes for graphene?

I have two items concerning research which seeks to replace graphene in one application or other.

Black phosporus and the École Polytechniqe de Montréal

A June 2, 2015 news item on Nanotechnology Now features work on developing a two-dimensional black phosphorus material, 2D phosphane,

A team of researchers from Universite de Montreal, Polytechnique Montreal and the Centre national de la recherche scientifique (CNRS) in France is the first to succeed in preventing two-dimensional layers of black phosphorus from oxidating. In so doing, they have opened the doors to exploiting their striking properties in a number of electronic and optoelectronic devices. …

Black phosphorus, a stable allotrope of phosphorus that presents a lamellar structure similar to that of graphite, has recently begun to capture the attention of physicists and materials researchers. It is possible to obtain single atomic layers from it, which researchers call 2D phosphane. A cousin of the widely publicized graphene, 2D phosphane brings together two very sought-after properties for device design.

A June 2, 2015 École Polytechniqe de Montréal news release, which originated the news item, expands on why 2D phosphane is an appealing material,

First, 2D phosphane is a semiconductor material that provides the necessary characteristics for making transistors and processors. With its high-mobility, it is estimated that 2D phosphane could form the basis for electronics that is both high-performance and low-cost.

Furthermore, this new material features a second, even more distinctive, characteristic: its interaction with light depends on the number of atomic layers used. One monolayer will emit red light, whereas a thicker sample will emit into the infrared. This variation makes it possible to manufacture a wide range of optoelectronic devices, such as lasers or detectors, in a strategic fraction of the electromagnetic spectrum.

The news release goes on to describe an important issue with phosphane and how the scientists addressed it,

Until now, the study of 2D phosphane’s properties was slowed by a major problem: in ambient  conditions, very thin layers of the material would degrade, to the point of compromising its future in the industry despite its promising potential.

As such, the research team has made a major step forward by succeeding in determining the physical mechanisms at play in this degradation, and in identifying the key elements that lead to the layers’ oxidation.

“We have demonstrated that 2D phosphane undergoes oxidation under ambient conditions, caused jointly by the presence of oxygen, water and light. We have also characterized the phenomenon’s evolution over time by using electron beam spectroscopy and Raman spectroscopy,” reports Professor Richard Martel of Université de Montréal’s Department of Chemistry.

Next, the researchers developed an efficient procedure for producing these very fragile single-atom layers and keeping them intact.

“We were able to study the vibration modes of the atoms in this new material. Since earlier studies had been carried out on heavily degraded materials, we revealed the as-yet-unsuspected effects of quantum confinement on atoms’ vibration modes,” notes Professor Sébastien Francoeur of Polytechnique’s Department of Engineering Physics.

The study’s results will help the world scientific community develop 2D phosphane’s very special properties with the aim of developing new nanotechnologies that could give rise to high-performance microprocessors, lasers, solar cells and more.

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

Photooxidation and quantum confinement effects in exfoliated black phosphorus by Alexandre Favron, Etienne Gaufrès, Frédéric Fossard, Anne-Laurence Phaneuf-L’Heureux, Nathalie Y-W. Tang, Pierre L. Lévesque, Annick Loiseau, Richard Leonelli, Sébastien Francoeur, & Richard Martel. Nature Materials (2015)  doi:10.1038/nmat4299 Published online 25 May 2015

This paper is behind a paywall.

Now. for the second item about replacing graphene.

China’s new aerogel, a rival to graphene aerogels?

A June 2, 2015 American Institute of Physics news release (also on EurekAlert) describes research into an alternative to expensive graphene aerogels,

The electromagnetic radiation discharged by electronic equipment and devices is known to hinder their smooth operation. Conventional materials used today to shield from incoming electromagnetic waves tend to be sheets of metal or composites, which rely on reflection as a shielding mechanism.

But now, materials such as graphene aerogels are gaining traction as more desirable alternatives because they act as electromagnetic absorbers. They’re widely expected to improve energy storage, sensors, nanoelectronics, catalysis and separations, but graphene aerogels are prohibitively expensive and difficult to produce for large-scale applications because of the complicated purification and functionalization steps involved in their fabrication.

So a team of researchers in China set out to design a cheaper material with properties similar to a graphene aerogel–in terms of its conductivity, as well as a lightweight, anticorrosive, porous structure. In the journal Applied Physics Letters, from AIP Publishing, the researchers describe the new material they created and its performance.

Aming Xie, an expert in organic chemistry, and Fan Wu, both affiliated with PLA University of Science and Technology, worked with colleagues at Nanjing University of Science and Technology to tap into organic chemistry and conducting polymers to fabricate a three-dimensional (3-D) polypyrrole (PPy) aerogel-based electromagnetic absorber.

They chose to concentrate on this method because it enables them to “regulate the density and dielectric property of conducting polymers through the formation of pores during the oxidation polymerization of the pyrrole monomer,” explained Wu.

And the fabrication process is a simple one. “It requires only four common chemical reagents: pyrrole, ferric chloride (FeCl3), ethanol and water — which makes it cheap enough and enables large-scale fabrication,” Wu said. “We’re also able to pour the FeCl3 solution directly into the pyrrole solution — not drop by drop — to force the pyrrole to polymerize into a 3-D aerogel rather than PPy particles.”

In short, the team’s 3-D PPy aerogel is designed to exhibit “desirable properties such as a porous structure and low density,” Wu noted.

Beyond that, its electromagnetic absorption performance — with low loss — shows great promise. “We believe a ‘wide’ absorption range is more useful than high absorption within one frequency,” Wu said. Compared with previous works, the team’s new aerogel has the lowest adjunction and widest effective bandwidth — with a reflection loss below -10 decibels.

In terms of applications, based on the combination of low adjunction and a “wide” effective bandwidth, the researchers expect to see their 3-D PPy aerogel used in surface coatings for aircraft.

Another potential application is as coatings within the realm of corrosion prevention and control. “Common anticorrosion coatings contain a large amount of zinc (70 to 80 percent by weight), and these particles not only serve as a cathode by corroding to protect the iron structure but also to maintain a suitable conductivity for the electrochemistry process,” Wu pointed out. “If our 3-D PPy aerogel could build a conductivity network in this type of coating, the loss of zinc particles could be rapidly reduced.”

The team is now taking their work a step further by pursuing a 3-D PPy/PEDOT-based (poly(3,4-ethylenedioxythiophene) electromagnetic absorber. “Our goal is to grow solid-state polymerized PEDOT particles in the holes of the 3-D PPy aerogel formed by PPy chains,” Wu added.

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

Self-assembled ultralight three-dimensional polypyrrole aerogel for effective electromagnetic absorption by Aming Xie, Fan Wu, Mengxiao Sun, Xiaoqing Dai, Zhuanghu Xu, Yanyu Qiu, Yuan Wang, and Mingyang Wang. Appl. Phys. Lett. 106, 222902 (2015); http://dx.doi.org/10.1063/1.4921180

This paper is open access.