One-Step Catalyst Turns Nitrates into Water and Air

Date: January 4, 2018
Source: Rice University
Summary: Engineers have found a catalyst the cleans toxic nitrates from drinking water by converting them into air and water.

Rice University's indium-palladium nanoparticle catalysts clean nitrates from drinking water by converting the toxic molecules into air and water.
Credit: Jeff Fitlow/Rice University

The research is available online in the American Chemical Society journal ACS Catalysis.

"Nitrates come mainly from agricultural runoff, which affects farming communities all over the world," said Rice chemical engineer Michael Wong, the lead scientist on the study. "Nitrates are both an environmental problem and health problem because they're toxic. There are ion-exchange filters that can remove them from water, but these need to be flushed every few months to reuse them, and when that happens, the flushed water just returns a concentrated dose of nitrates right back into the water supply."

Wong's lab specializes in developing nanoparticle-based catalysts, submicroscopic bits of metal that speed up chemical reactions. In 2013, his group showed that tiny gold spheres dotted with specks of palladium could break apart nitrites, the more toxic chemical cousins of nitrates.

"Nitrates are molecules that have one nitrogen atom and three oxygen atoms," Wong explained. "Nitrates turn into nitrites if they lose an oxygen, but nitrites are even more toxic than nitrates, so you don't want to stop with nitrites. Moreover, nitrates are the more prevalent problem.

"Ultimately, the best way to remove nitrates is a catalytic process that breaks them completely apart into nitrogen and oxygen, or in our case, nitrogen and water because we add a little hydrogen," he said. "More than 75 percent of Earth's atmosphere is gaseous nitrogen, so we're really turning nitrates into air and water."

Nitrates are toxic to infants and pregnant women and may also be carcinogenic. Nitrate pollution is common in agricultural communities, especially in the U.S. Corn Belt and California's Central Valley, where fertilizers are heavily used, and some studies have shown that nitrate pollution is on the rise due to changing land-use patterns.

Both nitrates and nitrites are regulated by the Environmental Protection Agency, which sets allowable limits for safe drinking water. In communities with polluted wells and lakes, that typically means pretreating drinking water with ion-exchange resins that trap and remove nitrates and nitrites without destroying them.

From their previous work, Wong's team knew that gold-palladium nanoparticles were not good catalysts for breaking apart nitrates. Co-author Kim Heck, a research scientist in Wong's lab, said a search of published scientific literature turned up another possibility: indium and palladium.

"We were able to optimize that, and we found that covering about 40 percent of a palladium sphere's surface with indium gave us our most active catalyst," Heck said. "It was about 50 percent more efficient than anything else we found in previously published studies. We could have stopped there, but we were really interested in understanding why it was better, and for that we had to explore the chemistry behind this reaction."

In collaboration with chemical engineering colleagues Jeffrey Miller of Purdue University and Lars Grabow of the University of Houston, the Rice team found that the indium speeds up the breakdown of nitrates while the palladium apparently keeps the indium from being permanently oxidized.

"Indium likes to be oxidized," Heck said. "From our in situ studies, we found that exposing the catalysts to solutions containing nitrate caused the indium to become oxidized. But when we added hydrogen-saturated water, the palladium prompted some of that oxygen to bond with the hydrogen and form water, and that resulted in the indium remaining in a reduced state where it's free to break apart more nitrates."

Wong said his team will work with industrial partners and other researchers to turn the process into a commercially viable water-treatment system.

"That's where NEWT comes in," he said. "NEWT is all about taking basic science discoveries and getting them deployed in real-world conditions. This is going to be an example within NEWT where we have the chemistry figured out, and the next step is to create a flow system to show proof of concept that the technology can be used in the field."

NEWT is a multi-institutional engineering research center based at Rice that was established by the National Science Foundation in 2015 to develop compact, mobile, off-grid water-treatment systems that can provide clean water to millions of people and make U.S. energy production more sustainable and cost-effective. NEWT is expected to leverage more than $40 million in federal and industrial support by 2025 and is focused on applications for humanitarian emergency response, rural water systems and wastewater treatment and reuse at remote sites, including both onshore and offshore drilling platforms for oil and gas exploration.

Additional study co-authors include Sujin Guo, Huifeng Qian and Zhun Zhao, all of Rice, and Sashank Kasiraju of the University of Houston. The research was funded by the National Science Foundation, the Department of Energy and the China Scholarship Council.

Source: Rice University. "One-step catalyst turns nitrates into water and air." ScienceDaily. ScienceDaily, 4 January 2018. www.sciencedaily.com/releases/2018/01/180104160819.htm

Structure of 'Concrete Disease' Solved

Previously undocumented sheet-silicate crystal structure

Date: November 5, 2015
Source: Swiss Federal Laboratories for Materials Science and Technology (EMPA)
Summary: When bridges, dam walls and other structures made of concrete are streaked with dark cracks after a few decades, the culprit is AAR: the alkali-aggregate reaction. AAR damages concrete structures all over the world and makes complex renovations or reconstructions necessary. Researchers have now solved the structure of the material produced in the course of AAR at atomic Level.


Researchers from the Paul Scherrer Institute (PSI) teamed up with colleagues from the Swiss Materials Science Lab Empa to study a degenerative sign of ageing in concrete: the so-called alkali-aggregate reaction (AAR). In the course of AAR, a material forms that takes up more space than the original concrete and thus gradually cracks the concrete from within as the decades go by.

The researchers have now explored the exact structure of this material. They managed to demonstrate that its atoms are arranged extremely regularly, making it a crystal. They also showed that the structure of this crystal is a so-called sheet-silicate structure. This specific structure had never been observed before. The researchers made their discovery thanks to measurements at the Swiss Light Source SLS at PSI. The research results could help towards the development of more durable concrete in future.

A Global Problem

AAR is a chemical reaction that affects outdoor concrete structures all over the world. It happens when concrete is exposed to water or moisture. For instance, numerous bridges and up to twenty per cent of the dam walls in Switzerland are affected by AAR. With AAR, the basic ingredients in the concrete are actually the problem: cement -- the main component of concrete -- contains alkali metals such as sodium and potassium. Any moisture infiltrating the concrete -- stemming for example from rainwater -- reacts with these alkali metals, leading to an alkaline solution.

The second main ingredient in concrete is sand and gravel, which in turn are composed of minerals, such as quartz or feldspar. Chemically speaking, these minerals are so-called silicates. The alkaline water reacts with these silicates and forms a so-called alkali calcium silicate hydrate. This is itself able to absorb more moisture, which causes it to expand and gradually crack the concrete from within. This entire process is referred to as AAR.

AAR takes place extremely slowly, so that the cracks are initially only tiny and invisible to the naked eye. Over the course of three or four decades, however, the cracks widen significantly and eventually jeopardise the durability of the entire concrete structure.

A New Crystal

Even if the chemical processes involved in AAR have long been known, nobody had identified the physical structure of the alkali calcium silicate hydrate formed in the course of AAR. The researchers at PSI and Empa have now managed to fill this knowledge gap. They studied the substance of a Swiss bridge constructed in 1969, which has been affected heavily by AAR. Researchers from Empa cut out a material sample from the bridge and ground down a small piece of it until they were left with a wafer-thin sample that was merely 0.02 millimetres thick. The sample was then taken to the Swiss Light Source SLS and irradiated with an extremely narrow x-ray beam, fifty times thinner than a human hair. Performing so-called diffraction measurements and a complex data analysis, the PSI researchers were eventually able to determine the crystal structure of the material with pinpoint precision.

They found that the alkali calcium silicate hydrate has a previously undocumented sheet-silicate crystal structure. "Normally, discovering an uncatalogued crystal structure means you get to name it," explains Rainer Dähn, the first author of the study. "But it has to be a crystal found in nature, therefore we didn't get that honour," says the researcher with a smile. Andreas Leemann, Head of the Concrete Technology Group at Empa, had the idea for the current study. The researchers from PSI then brought their knowledge of the x-ray beam method to the table. "In principle, it's possible to add organic materials to the concrete that are able to reduce the build-up of tension," explains materials scientist Leemann. "Our new results provide a scientific basis for these considerations and could pave the way for the development of new materials.

Story Source: Swiss Federal Laboratories for Materials Science and Technology (EMPA). "Structure of 'concrete disease' solved: Previously undocumented sheet-silicate crystal structure." ScienceDaily. ScienceDaily, 5 November 2015. .