The technical-sounding category of “light-driven charge-transfer reactions,” becomes more familiar to non-physicists when you just call it photosynthesis or solar electricity.
When a molecule (in a leaf or solar cell) is hit by an energetic photon of light, it first absorbs the little meteor’s energy, generating what chemists call an excited state. This excited state then almost immediately (like trillionths of a second) shuttles an electron away to a charge acceptor to lower its energy. That transference of charge is what drives plant life and photovoltaic current.
The energy of the excited state plays an important role in determining solar energy conversion efficiency. That is, the more of that photon’s energy that can be retained in the charge-separated state, the better. For most solar-electric devices, the excited state rapidly loses energy, resulting in less efficient devices.
But what if there were a way to create even more energetic excited states from that incoming photon?
Using a very efficient photosynthesizing bacterium as their inspiration, a team of Duke chemists that included graduate students Nick Polizzi and Ting Jiang, and faculty members David Beratan and Michael Therien, synthesized a “supermolecule” to help address this question.
“Nick and Ting discovered a really cool trick about electron transfer that we might be able to adapt to improving solar cells,” said Michael Therien, the William R. Kenan, Jr. Professor of Chemistry. “Biology figured this out eons ago,” he said.
“When molecules absorb light, they have more energy,” Therien said. “One of the things that these molecular excited states do is that they move charge. Generally speaking, most solar energy conversion structures that chemists design feature molecules that push electron density in the direction they want charge to move when a photon is absorbed. The solar-fueled microbe, Rhodobacter sphaeroides, however, does the opposite. What Nick and Ting demonstrated is that this could also be a winning strategy for solar cells.”
The chemists devised a clever synthetic molecule that shows the advantages of an excited state that pushes electron density in the direction opposite to where charge flows. In effect, this allows more of the energy harvested from a photon to be used in a solar cell.
“Nick and Ting’s work shows that there are huge advantages to pushing electron density in the exact opposite direction where you want charge to flow,” Therien said in his top-floor office of the French Family Science Center. “The biggest advantage of an excited state that pushes charge the wrong way is it stops a really critical pathway for excited state relaxation.”
“So, in many ways it’s a Rube Goldberg Like conception,” Therien said. “It is a design strategy that’s been maybe staring us in the face for several years, but no one’s connected the dots like Nick and Ting have here.”
In a July 2 commentary for the Proceedings of the National Academy of Sciences, Bowling Green State University chemist and photoscientist Malcom D.E. Forbes calls this work “a great leap forward,” and says it “should be regarded as one of the most beautiful experiments in physical chemistry in the 21st century.”
(Image by Nick Polizzi)
CITATION: “Engineering Opposite Electronic Polarization of Singlet and Triplet States Increases the Yield of High-Energy Photoproducts,” Nicholas Polizzi, Ting Jiang, David Beratan, Michael Therien. Proceedings of the National Academy of Sciences, June 10, 2019. DOI: 10.1073/pnas.1901752116 Online: https://www.pnas.org/content/early/2019/07/01/1908872116