Supramolecules Get Time To Shine

What looks like a spongy ball wrapped in strands of yarn -- but a lot smaller -- could be key to unlocking better methods for catalysis, artificial photosynthesis or splitting water into hydrogen, according to Rice University chemists who have created a platform to analyze interactions between carbon nanotubes and a wide range of photoluminescent materials. The microscopic particles assembled in the lab of Angel Martí, an assistant professor of chemistry and bioengineering, combine single-walled carbon nanotubes with porous silicate materials that can absorb various molecules -- in this case, a ruthenium complex.

Martí, graduate student and lead author Avishek Saha and their colleagues reported their results today in the Royal Society of Chemistry journal Chemical Science.

The ability to immobilize individual carbon nanotubes on a solid surface is interesting enough, but combining supramolecular systems with nanomaterials to produce hybrids is unique, they said.

"This can be used as a general platform to study the interaction of not only ruthenium complexes, but most photoactive molecules can be encapsulated within these porous silicates in a very simple way without chemical modification, without anything," Marti said.

Saha endured trial and error at every step in bringing the new particles to fruition, first figuring out the best way to keep long, single-walled carbon nanotubes produced by the Rice-born HiPco process from aggregating into bundles while allowing them to adhere to the particles.

The solution suggested by co-author Matteo Pasquali, a Rice professor in chemical and biomolecular engineering and in chemistry, involved dissolving the bundles in chlorosulfonic acid, which added protons -- and thus a positive charge -- to each nanotube.

That was the key to making nanotubes attractive to the three types of silicate particles tested: a commercial version of MCM-41, a mesoporous material used as a molecular sieve; another version of MCM-41 synthesized at Rice by Saha, and microporous Zeolyte-Y.

"We don't fully understand the mechanism, but the truth is they have a very strong affinity to silicon oxide networks," said Marti, describing the nanotube-wrapped particles. "Once they're protonated, they just bind."

But that wasn't enough to create a proper platform because protonated nanoparticles are no longer photoluminescent, a quality the researchers required to "see" such tiny structures under a spectroscope. "Protonated nanotubes are cool, but we want to have pristine nanotubes," Martí said.

"We were stuck there for a while. We tried a lot of things," he said. Acetone, ammonia, chloroform and other substances would deprotonate the nanotubes, but would also release them from the silicate sponges and allow them to clump. But vinylpyrrolidone (VP) did the trick by giving the nanotubes a polymer-like coating while returning them to their pristine states.