Hangman Catalysis for Photo–and Photoelectro–Chemical Activation of Water Proton-Coupled Electron Transfer Mechanisms of Small Molecule Activation
- Harvard Univ., Cambridge, MA (United States)
The weakest link for the large-scale deployment of solar energy and for that matter, any renewable energy source, is its storage. The energy needs of future society demands are so large that storage must be in the form of fuels owing to their high energy density. Indeed, society has intuitively understood this disparity in energy density as it has developed over the last century as all large-scale energy storage in our society is in the form of fuels. But these fuels are carbon-based. The imperative for the discipline of chemistry, and more generally science, is to develop fuel storage methods that are easily scalable, carbon-neutral and sustainable. These methods demand the creation of catalysts to manage the multi-electron, multi-proton transformations of the conversion of small molecules into fuels. The splitting of water using solar light is a fuel-forming reaction that meets the imperative of large scale energy storage. As light does not directly act on water to engender its splitting into its elemental components, we have designed “hangman” catalysts to effect the energy conversion processes needed for the fuel forming reactions. The hangman construct utilizes a pendant acid/base functionality within the secondary coordination sphere that is “hung” above the redox platform onto which substrate binds. In this way, we can precisely control the delivery of a proton to the substrate, thus ensuring efficient coupling between the proton and electron. An emphasis was on the coupling of electron and proton in the hydrogen evolution reaction (HER) on Ni, Co and Fe porphyrin platforms. Electrokinetic rate laws were developed to define the proton-coupled electron transfer (PCET) mechanism. The HER of Co and Fe porphyrins was metal-centered. Surprisingly, HER this was not the case for Ni porphyrins. In this system, the PCET occurred at the porphyrin platform to give rise to a phlorin. This is one of the first examples of an HER occurring via ligand non-innocence. The program was expanded to include other macrocycles with a focus on corroles. The photophyscial and electrochemical properties of a number of new metal- and free-base corroles were defined. Finally, the reaction chemistry of a new platform designed for oxygen evolution and reduction reactions. The hexacarboxamide cryptands was shown to be an ideal binucleating ligand for studies of oxygen. The electron transfer reaction of native oxygen in the absence of protons and metals was enabled for the first time, thus allowing us to observe new reactions of reduced oxygen with carbon dioxide. These results have had important consequence in shedding light on Li air batteries, and why these batteries cannot be recharged. This is the key issue impeding the technology development of Li-air batteries and therefore these results should be enlightening to the commercial development of Li-air batteries. Together, this portfolio of experiments provides a powerful insight to the crucial steps for the efficient conversion of small molecules to fuels and their subsequent use. To this end, the research program provides basic science to enable the low cost solar production of hydrogen from water and the reverse fuel cell reaction.
- Research Organization:
- Harvard Univ., Cambridge, MA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- DOE Contract Number:
- SC0009758
- OSTI ID:
- 1367667
- Report Number(s):
- DE-SC0009758
- Country of Publication:
- United States
- Language:
- English
Similar Records
Theoretical Analysis of Cobalt Hangman Porphyrins: Ligand Dearomatization and Mechanistic Implications for Hydrogen Evolution
Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins