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From coal, cheap quantum dots in one step

"Coal is the cheapest material you can get for producing GQDs, and we found we can get a 20 percent yield," says James Tour. "So this discovery…is going to show the world that inside of coal are these very interesting structures that have real value." Above, vials of graphene quantum dots drawn from bituminous coal, anthracite and coke glow under a fluorescent lamp. (Credit: Jeff Fitlow/Rice University)

Chemists have discovered how to reduce three kinds of coal into graphene quantum dots (GQDs) that could be used for medical imaging as well as sensing, electronic, and photovoltaic applications.

Band gaps determine how a semiconducting material carries an electric current. In quantum dots, microscopic discs of atom-thick graphene oxide, band gaps are responsible for their fluorescence and can be tuned by changing the dots’ size.

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The new process, described in the journal Nature Communications, allows a measure of control over their size, generally from 2 to 20 nanometers, depending on the source of the coal.

There are many ways to make GQDs now, but most are expensive and produce very small quantities, says James Tour, chair in chemistry and professor of mechanical engineering and materials science and of computer science at Rice University.

Earlier research found a way last year to make GQDs from relatively cheap carbon fiber, but coal promises greater quantities of GQDs made even cheaper in one chemical step.

“We wanted to see what’s there in coal that might be interesting, so we put it through a very simple oxidation procedure,” Tour says. That involved crushing the coal and bathing it in acid solutions to break the bonds that hold the tiny graphene domains together. “You can’t just take a piece of graphene and easily chop it up this small.”

Different coal, different dots

Tour worked with co-author Angel Martí, assistant professor of chemistry and bioengineering, to characterize the product. It turns out different types of coal produce different types of dots. GQDs were derived from bituminous coal, anthracite, and coke, a byproduct of oil refining.

The coals were each sonicated in nitric and sulfuric acids and heated for 24 hours. Bituminous coal produced GQDs between 2 and 4 nanometers wide. Coke produced GQDs between 4 and 8 nanometers, and anthracite made stacked structures from 18 to 40 nanometers, with small round layers atop larger, thinner layers. (Just to see what would happen, the researchers treated graphite flakes with the same process and got mostly smaller graphite flakes.)

The dots are water-soluble, and early tests have shown them to be nontoxic, offering the promise that GQDs may serve as effective antioxidants, Tour says.

Medical imaging could also benefit greatly, as the dots show robust performance as fluorescent agents.

Quantum dots resist bleaching

“One of the problems with standard probes in fluorescent spectroscopy is that when you load them into a cell and hit them with high-powered lasers, you see them for a fraction of a second to upwards of a few seconds, and that’s it,” Martí says. “They’re still there, but they have been photo-bleached. They don’t fluoresce anymore.”

Testing in the Martí lab showed GQDs resist bleaching. After hours of excitation, the photoluminescent response of the coal-sourced GQDs was barely affected. That could make them suitable for use in living organisms. “Because they’re so stable, they could theoretically make imaging more efficient,” he says.

A small change in the size of a quantum dot—as little as a fraction of a nanometer—changes its fluorescent wavelengths by a measurable factor, and that proved true for the coal-sourced GQDs, Martí says.

Low cost will also be a draw, Tour says.

“Graphite is $2,000 a ton for the best there is, from the UK. Cheaper graphite is $800 a ton from China. And coal is $10 to $60 a ton.

“Coal is the cheapest material you can get for producing GQDs, and we found we can get a 20 percent yield. So this discovery can really change the quantum dot industry. It’s going to show the world that inside of coal are these very interesting structures that have real value.”

The Air Force Office of Scientific Research and the Office of Naval Research funded the work through their Multidisciplinary University Research Initiatives.

Source: Rice University