First-row Metal Complexes for Photo-induced Electron Transfer: Fundamental Issues and Applications in Energy Science
Professor James McCusker (Michigan State University, Department of Chemistry)
Host: Professor Michael Therien
Thursday, October 19, 2017 - 11:40am to 1:10pm
Location: French Family Science Center 2231
Rosenthal, Janet

Link for Professor McCusker

Abstract:  The conversion of light to chemical energy is one of the most fundamental processes on Earth. It is the basis of photosynthesis, in which light absorption results in the separation of charge that ultimately creates the chemical potential needed to drive ATP synthesis; an advantageous by-product of this process is, of course, O2 production. Ironically, photosynthesis is also the source of the biomass from which the fossil fuels that constitute the basis of society’s energy infrastructure are derived. The overwhelming majority of climate scientists are in agreement that it is the burning of these fossil fuels – in effect the rerelease of what was sequestered carbon into the atmosphere – that is driving global climate change.  Options for shifting away from fossil fuels as our primary energy source generally revolve around
renewables such as wind, solar, biomass, nuclear, geothermal, and hydro: of these, the only renewable energy source that is limitless and carbon-free (at least in principle) is solar. The energy flux hitting the Earth is 120,000 TW: integrated over a 24-hour period, this translates to humankind’s total energy budget for an entire year. Despite the progress that has been made in the implementation of solar energy (due primarily to reductions in the cost of silicon), the intermittent nature of solar energy, the balance of systems costs that continue to represent a significant economic obstacle, combined with the fact that electricity constitutes only ~30% of the global energy footprint all underscore the need for continued research in solar energy conversion science.

Fundamental research on solar energy conversion – which will ultimately lead to the next generation of solar energy technologies – has sought to replicate Nature’s solution through the creation of artificial constructs that mimic various aspect of photosynthesis. When considering large-scale (i.e., global) implementation of any solar energy conversion scheme, material availability becomes a critically important consideration in the lightcapture part of the problem, particularly given the projected two- to three-fold increase in energy demand over the next 30-40 years. Unfortunately, virtually all of the molecule-based approaches for solar energy conversion that have been proven successful to date rely on some of the least abundant elements on earth.

An obvious alternative is to employ chromophores based on earth-abundant materials: for transition metal-based approaches, this means moving away from the second- and third-row transition series elements (e.g., ruthenium) and develop photoredox-active chromophores based on first-row, widely available metals like iron. As our group first demonstrated in 2000, the central problem with this approach is that the charge-transfer excited states that lie at the heart of photo-induced electron transfer chemistry exhibit sub-picosecond lifetimes (as compared to the microsecond lifetimes of their 2nd- and 3rd-row congeners). Our research program therefore focuses on understanding the factors that determine the dynamics associated with the excited states of first-row transition metal-based chromophores, with the ultimate goal of circumventing and/or redefining their intrinsic photophysical properties in order to make feasible their use as light-harvesting components in solar energy conversion schemes. This seminar will describe the key experimental results establishing this paradigm, as well as survey several approaches that we are pursuing in an effort to broaden the utility of this class of chromophores for applications not only in solar energy conversion, but any process for which photo-induced charge separation is required.