The new theory suggests positively charged holes that propagate at catalytic sites can spread out and trigger catalysis in neighboring sectors. Image: Bhawakshi Punia and Srabanti Chaudhury/IISER Pune.New research suggests that catalysis appears to function because of holes. Rather than the physical kind, however, these are quasiparticles known as electron holes, which can be viewed as effective positive particles in the absence of negative electrons. According to researchers at Rice University, the action and propagation of these holes on heterogeneous catalyst particles allows the chemical reactions to happen.
The Rice lab of chemist Anatoly Kolomeisky, working with Srabanti Chaudhury at the Indian Institute of Science Education and Research (IISER) Pune, used computational models to reveal that greater control over catalytic reactions might be gained by applying electric fields that prompt holes to migrate. This could lead to improvements in the ubiquitous process.
“Despite the fact that we’ve known about catalysis for 200 years – it goes back to cellars in the 19th century – we still don’t understand what’s happening on a catalyst,” said Kolomeisky, a professor and chair of Rice’s Department of Chemistry and a professor of chemical and biomolecular engineering. “But a couple of years ago I saw a series of intriguing papers from people at Cornell [University] who were able to see co-catalytic cooperation involving positively charged particles.”
The Rice and IISER researchers set out to explain what the Cornell team saw, and found that their theory matched the experiments. Their models show that holes are produced when a catalytic site activates; these holes then spread to adjacent sites, activating them before recombining with electrons and dying. The researchers report their findings in a paper in the Proceedings of the National Academy of Sciences.
According to Kolomeisky, the game-changing innovation by the Cornell team was making the products of the catalyzed reactions they investigated fluorescent, so they could track them over time and space. “They realized to their surprise that if a reaction happens in one segment of a nanorod, it’s much more probable for the same reaction to happen on an adjacent segment. This cooperativity weakens down with distance, but it’s still surprising,” he said.
The new work suggests that each catalytic site on a nanorod probably makes positively charged holes during redox chemical reactions, which involve the transfer of charged particles like electrons. As the local concentration of holes increases, they want to move to less-crowded areas. Wherever they settle, they trigger more catalysis and then die. The new catalytic site then makes more holes that further spread into neighboring regions.
“Our model is still highly speculative, because there is a clearly very complex underlying quantum mechanical phenomena here, and we don’t know what it is,” said Kolomeisky. “But our models quantitatively match the experiments. This should stimulate more investigations of these intriguing phenomena.
“If our theoretical predictions are valid, it will be possible to create an artificial density of holes in a controllable way, or create structures where holes might diffuse faster, and it might open a lot of channels for applications. We might design new catalysts in the most efficient way.”
This story is adapted from material from Rice University, with editorial changes made by Materials Today. The views expressed in this article do not necessarily represent those of Elsevier. Link to original source.